Structural studies of organo-phosphorus (V) esters and thioesters
by Ronald Wade Warrant
A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of
DOCTOR OF PHILOSOPHY in Chemistry
Montana State University
© Copyright by Ronald Wade Warrant (1973)
Abstract:
The crystal and molecular structures of four organo-phosphorus (V) esters and thioesters were solved
by X-ray diffraction methods.
S, S, S-tri-p-tolyl phosphorotrithioate crystallizes in space group P2-1/n with a = 9.489(4) A, b.=
14.938(8) A, C = 14.916(8) A, β = 97.37(4)°, and Z = 4.
The structure was solved using symbolic addition procedures and all atoms lie in general positions. The
structure is analyzed for features pertinent to the compound's ability to show long-range coupling
effects in its 1H n.m.r. spectrum. The final R is 4.8% for 2144 observed intensities.
5-t-butyl-2-methoxy-2-oxo-1,3, 2-dioxaphosphorinane crystallizes in space group Pnma with a 6.123(4) A, b = 10.0.2(1) A, c = 17.65(1) A, and Z = 4. The structure was solved using the Patterson
synthesis and the molecule lies on a mirror plane at y = 1/4 and 3/4. The ring is a chair and the t-butyl
and methoxy groups are trahs to each other in axial positions. The final R is 5.9% for 585 observed
intensities.
5-t-butyl-2~phenyl-2-thio-l, 3,2-dioxaphosphorinane crystallizes in space group P21/n with a =
6.150(2) A, b - 11.036(3) A, c - 20.823(5) A, JS = 95.17(2)°, and Z = 4. The structure was solved using
the Patterson synthesis and all atoms lie in general positions. The ring is a chair with the t-butyl and
phenyl groups cis to each other on the ring. The t-butyl is equatorial and the phenyl axial.
The final R is 3.6% for 1259 observed intensities.
2, 5-t-butyl-l-thio-l, 3, 2-dioxaphosphorinane crystallizes in space group Pmcn with a = 10.077(3) A, b
= 10.662(3) A, c = 12.703(3) A, and Z = 4. The structure was solved using the Patterson synthesis and
the molecule lies on a mirror plane at x = 1/4 and 3/4. The ring is a chair and the t-butyl groups are cis
to each other with the t-butyl group on the C (5) position axial and equatorial on the P(2) position. The
final R is 4.8% for 763 observed intensities. STRUCTURAL STUDIES OF
'/
ORGANO-PHOSPHORUS (V) ESTERS AND THIOESTERS
by
RONALD WADE WARRANT
A th e s is subm itted to th e G raduate F aculty in p a rtia l
fu lfillm en t of the re q u ire m e n ts fo r the d eg ree
of
DOCTOR OF PHILOSOPHY
in
C h em istry
A pproved:
MONTANA STATE UNIVERSITY
B ozem an, M ontana
M arch, 1973
iii
ACKNOWLEDGMENTS
I w ish to thank D r 0 C h arles N, Caughlan and D r, G. D avid Smith fo r
th e ir help and guidance and o th e r m e m b e rs of the faculty of M ontana State U ni­
v e rs ity fo r th e ir help.
I w ish to acknowledge th e United S tates D ep artm en t of H ealth, E ducation
and W elfare fo r a fellow ship (NDEA) w hile w orking on the re s e a rc h .
Also I w ish
to thank the Computing C en ter of M ontana State U n iv ersity fo r g ra n ts of com ­
puting tim e ,
F in ally , I w ish to thank my p a re n ts fo r th e ir help in m y educational
e n d ea v o rs.
TABLE OF CONTENTS
Page
LIST OF T A B L E S ..................
v il
LIST OF FIGURES . .......................................................................................................
x
ABSTRACT ..............................................................................................................
xii
IN T R O D U C T IO N .....................
I
PART I
S ,S ,S - T r i-p -T o ly l P h o sp h o ro trith io ate
INTRODUCTION ....................................
3
THE CRYSTAL AND MOLECULAR STRUCTURE OF S ,S ,S -T R I-p TOLYL PHOSPHOROTRITHIOATE ...................................................
P r e p a r a tio n ............................. °
5
.
5
D ensity ...............................................
5
D eterm ination of ten tativ e cell dim ensions and space group . . . . .
5
D eterm in atio n of a cc u ra te unit c e ll dim ensions . . . . . . . . . . . .
6
D ata c o lle c tio n ................................
7
S tru ctu re d eterm in atio n ....................................................................................
10
R efinem ent ...............................................
H
D iscu ssio n of the s tru c tu re . ........................................
12
SUMMARY AND CONCLUSIONS.
\
. 32
V
PART II
I , 3 ,2 -D ioxaphosphorinanes
IN T R O D U C T IO N ..................
34
THE CRYSTAL AND MOLECULAR STRUCTURE OF 5 -t-B U T Y L 2-M ET H O X Y -2-O X O -1,3 , 2-D IO X A PH O SPH O RINA N E............................. 36
P r e p a r a tio n . .............................................................
36
D ensity
36
D eterm in atio n of ten tativ e cell dim ensions and space g r o u p .................. 36
D eterm in atio n of a cc u ra te cell dim ensions ................................................... 37
D ata collection
37
S tru ctu re d eterm in a tio n . .............................
39
R e f in e m e n t...........................................
..40
D iscu ssio n of the .stru c tu re , ................................................................................ 42
THE CRYSTAL AND MOLECULAR STRUCTURE OF 5 -t-B U T Y L 2 -P H E N Y L -2 -T H I0 -1 ,3 , 2-DIOXAPHOSPHORINANE .. . . . . . . . .
58
P r e p a r a tio n .........................
58
D e n s i t y ..................
58
D eterm in atio n of ten tativ e cell dim ensions and space g r o u p .................. 58
D eterm in atio n of a cc u ra te cell d i m e n s i o n s ................................................... 59
D ata collection ........................................................................................
59
S tru ctu re determ in atio n
61
vi
R e f in e m e n t................ .................................. ...................... ... .............................62
D iscu ssio n of the s tr u c tu r e .................. ... ................................
65
THE CRYSTAL AND MOLECULAR STRUCTURE OF 2 ,5 -t-B U T Y L 2 -T H IO -l, 3 , 2-DIC: 'APHOSPHORINANE
P re p a ra tio n .
..................................................... 78
................................. ......................................................... . 7 8
D ensity ...........................................................................................
78
D eterm in atio n of cell dim ensions and space group ................................. 78
D ata co llectio n . .................. ... ........................................................................ . 81
S tru ctu re d e term in a tio n
...................... ... . 84
Itelm em ent . . . . . . . . . . . . . . . . . . . . . . . . . . .
D iscu ssio n of s tr u c tu r e „ . . . . . . . . .
A
A
. . . . . . . . . . . . . .
COMPARISON OF THE 1 ,3 , 2-DIOXAPHOSPHORINANES
84
. 85
...............
100
SUMMARY AND CONCLUSIONS. ......................................................................... .
108
LITERATURE CITED .
. . no
LIST OF TABLES
Page
PART I
S, S, S - T r i-p -T o ly l P h o sp h o ro trith io ate
TABLE
I
C ry sta l D a t a .........................................
TABLE
2
O bserved and C alculated S tru ctu re F a c to rs . ................................. 14
TABLE
3
P ositional P a ra m e te rs of N on-hydrogen A to m s ...............................15
TABLE
4
T h e rm a l .P a ra m e te rs of N on-hydrogen At o ms . . . . . . . . .
8
16
TABLE 5
Hydrogen Atom P a r a m e t e r s ............................
...................... ... . 18
TABLE
6
Bond D istan ces
TABLE
7
Bond A ngles . . . . . . . . . . . . . . . . . . . . . . . . . . .
21
TABLE
8
L e a s t-s q u a re s P lanes ............................................
28
.......................................................
20
PART II
1 ,3 , 2-D ioxaphosphorinanes
5-t-B U T Y L~2-M ET H O X Y -2-O X O -l, 3 , 2-DIOXAPHOSPHORINANE
TABLE 9
C ry sta l D ata .............................................................................
38.
TABLE
10 O bserved and C alculated S tru ctu re F a c to rs .....................................43
TABLE
11 P ositional P a ra m e te rs of N on-hydrogen A tom s . .......................... 44
TABLE
12 T h e rm a l P a ra m e te rs of N on-hydrogen Atoms . ............................. 45
TABLE
13 C alculated Hydrogen Atom P a ra m e te rs '..............................
46
I
TABLE
14 Bond D is ta n c e s .........................................
48
viii
TABLE 15
Bond A ngles . . . . . . . . . . . . . . . . . . . . . . . . . . .
TABLE 16
Equations of P lanes ............................................
TABLE 17
T o rsio n a l A ngles. ..............................................................
49
i . „ . 52
53
5 -t-B U T Y L -2 -P H E N Y L -2 -T H IO -l, 3 , 2-DIOXAPHOSPHOB1NANE
TABLE 18
C ry sta l D a t a ..................
60
TABLE 19
O bserved and C alculated S tru ctu re F a c to rs ......................................63
TABLE 20
P o sitio n al P a ra m e te rs of N on-hydrogen A tom s . ..........................64
TABLE 21
T h e rm a l P a ra m e te rs of N on-hydrogen A to m s. . . ...................... 6 6
TABLE 22
H ydrogen Atom P a r a m e te r s ...................................................................... 67
TABLE 23
Bond D istan ces. . ..........................
TABLE 24
Bond A ngles . ................................................................................................ 70
TABLE 25
L e a s t-s q u a re s P l a n e s ..................
72
TABLE 26
T o rsio n a l A ngles. ..............................................................
73
69
2, 5- t -B U T Y L -2-T H IO -1, 3 ,2 -DIOXAPHOSPHORINANES
TABLE 27
C ry stal D ata .............................................................................
80
TABLE 28
O bserved and C alculated S tru ctu re F a c to rs ...................................... 8 6
TABLE 29
P o sitio n al P a ra m e te rs of N on-hydrogen A tom s . ...................’ . 87
TABLE 30
T h e rm a l P a ra m e te rs of N on-hydrogen A to m s. . . . . . . . .
88
TABLE 31 . H ydrogen Atom P a ra m e te rs . . .......................... ...
89
TABLE 32
Bond D istances. .............................................
91
TABLE 33
Bond A ngles ..............................................................................
92
ix
TABLE 34-
Equations of P lanes . ......................
TABLE 35
T o rsio n a l A ngles.................................
. . . . . . . . . . . . .
96
97
COMPARISON OF THE 1 , 3 , 2-DIOXAPHOSPHORINANES
TABLE 36
L ist of S tr u c t u r e s ..................
101
TABLE 37
C om parison of Bond D istan ces ............................................
103
TABLE 38
C om parison of Bond A ngles. . . . . . . . . . . . . . . . . .
104
LIST OF FIGURES
Page
PART I
S, S 5S - T r i-p -T o ly l P h o sp h o ro trith io ate
FIGURE I
S 5 S 5 S -T ri-P -T o ly l P h o s p h o ro trith io a te ......................
3
FIGURE 2
M olecular S tru ctu re and T h erm al E llip so id s.
FIGURE 3
Bond D istan ces and A n g le s ............................. ................................. 22
FIGURE 4
P h o sp h o ru s, C arbon O verlap
FIGURE 5.
D ihedral A ngles Between
............... ... . 19
.............................. ..................... . 25
77-E le c tro n
S ystem s and
the P-S-C . B o n d s........................................................................................ 27
FIGURE
6
FIGURE 7
D isto rtio n of the P-S Bonds. .............................................................. 29
S tereo g rap h ic Packing D ia g ra m . ...................................................
30
PART II
I 5 3, 2-D ioxaphosphorinanes
FIGURE
8
L ist of Compounds ........................................
35
5-t-B U T Y L -2-M E T H O X Y -2-O X O -l 5 3 ,2 -DIOXAPHOSPHORINANE
.FIGURE 9
M olecular S tru ctu re and T h e rm a l E llip so id s................................. 47
FIGURE 10
Bond D istan ces and A n g l e s ......................
FIGURE 11.
Newman P ro jec tio n Down the P(2)-0(13) Bond. .............................55
FIGURE 12
S tereo g rap h ic Packing D ia g ra m .............................
50
57
xi
5-t-B U T Y L ~2-P H E N Y L -2-O X O -l, 3 , 2-DIOXAPHOSPHORINANE
FIGURE 13
M olecular S tru ctu re and T h e rm a l E llip so id s. ............................... 6 8
FIGURE 14
Bond D istances and A ngles . . . . . . . . . . . . . . . . . .
71
FIGURE 15
Newman P ro jec tio n Down the C (ll)-P (2 ) Bond. . . . . . . .
75
FIGURE 16
S tereo g rap h ic Packing D ia g ra m . . . . . . . . . . . . . . . .
77
2, 5 -t-B U T Y L -2 -T H IO -l, 3, 2-DIOXAPHOSPHORINANE
FIGURE 17
Syntex Scale F a c to rs . .
^
. 82
FIGURE 18
M olecular S tru ctu re and T h e rm a l E llip so id s. . . . . . . . .
90
FIGURE 19
Bond D istan ces and Angles . . . . . . . . . . . . . . . . . .
94
FIGURE 20
S tereo g rap h ic Packing D ia g ra m . . . . . . . . . . . . . . . .
FIGURE 21
D ihedral A ngles B etw een the P lan es of the C h airs . . . .
99
109
ABSTRACT
The c ry s ta l and m o le c u lar s tru c tu re s of four o rg an o -p h o sp h o ru s(V) e s te r s
and th io e s te rs w e re solved by X -ra y d iffra ctio n m ethods.
S, S, S -tri-p -to ly l p h o sp h o ro trith io ate c ry s ta lliz e s in sp ace group P2-j_/n
w ith a = 9.489(4) A, b.= 14.938(8) A, c = 14.916(8) A, /3 = 97.37(4)°, and Z = 4.
The s tru c tu re w as solved using sym bolic addition p ro c e d u re s and all atom s lie
in g e n e ra l p o sitio n s. The s tru c tu re is analyzed fo r fe a tu re s p e rtin e n t to the
com pound's ability to show lo n g -ran g e coupling effects in its -*-Hn. m . r . sp ec tru m .
The final R is 4.8% fo r 2144 observ ed in te n sitie s.
5 - t -b u ty l- 2 -m ethoxy- 2 -oxo -1 ,3 , 2 -dioxaphosphorinane c ry s ta lliz e s in
sp ace group Pnm a w ith a - 6.123(4) A, b = 10.0.2(I) A, c = 17.65(1) A, and Z = 4.
The s tru c tu re w as solved using the P a tte rs o n sy n th esis and the m olecule lie s
on a m ir r o r plane at y = 1 /4 and 3 /4 . The rin g is a c h a ir and the t -butyl and
m ethoxy groups a re tr a h s to each o th er in axial p o sitio n s. The final R is 5.9%
fo r 585 o bserved in te n s itie s.
5 -t- b u ty l- 2 ~phenyl- 2 - t h i o - l , 3 , 2 -dioxaphosphorinane
c ry s ta lliz e s in space
group P21/ n w ith a - 6.150(2) A, b - 11.036(3) A, c - 20.823(5) A, g = 95.17(2)°,
and Z = 4. The s tru c tu re w as solved using the P a tte rs o n sy n th esis and all atom s
lie in g e n e ra l p o sitio n s. The rin g is a c h a ir w ith the t -butyl and phenyl groups
c is to each o th er on the rin g . The t-b u ty l is eq u ato rial and the phenyl axial.
The fin al R is 3.6% fo r 1259 observ ed in te n sitie s.
2, 5 - t- b u ty l- l- th io - l, 3, 2-dioxaphosphorinane c ry s ta lliz e s in space group
P m cn w ith a = 10.077(3) A, b = 10.662(3) A, C = 12.703(3) A, and Z = 4. The
s tru c tu re w as solved using th e P a tte rso n sy n th esis and the m o lecu le lie s on a
m ir r o r plane at x = 1 /4 and 3 /4 . The rin g is a ch air and the t-b u ty l groups a re
c is to each o th er w ith the t-b u ty l group on the C (5) p o sitio n ax ial and eq u ato rial
on the P (2) position. The final R is 4.8% fo r 763 observed in te n s itie s.
INTRODUCTION
T his d is s e rta tio n is p re se n te d in two p a rts .
P a rt I p re s e n ts the c ry s ta l
s tru c tu re of S, S, S -tri-p -to ly l p h o sp h o ro trith io ate , which c o n trib u tes to an
understanding of long range phosphorus-hydrogen coupling in aro m atic e s te r s
and th io e s te rs of phosphorus (V)„
P a rt II p re s e n ts th re e c ry s ta l s tru c tu re s : I) 5- t -b u ty l-2 -m eth o x y -2 o x o -1 ,3 ,2 -dioxaphosp h o rin a n e , 2) 5 -t-b u ty l-2 -p h e n y l-2 -th io -l, 3 , 2-dioxaphosp h o rinane, and 3) 2, 5 -i- b u ty l-2 -th io -l, 3 , 2-dioxaphosphorinane which contribute
to the knowledge of conform ations of six -m e m b e re d phosphorus h etero cy clic
rin g s.
PART I
S, S 5 S -T ri-p -T o ly l P h o sp h o ro trith io ate
INTRODUCTION
Solution of the s tru c tu re S, S, S -tri-p -to ly l p h o sp h o ro trith io ate, shown
in F ig u re I , w as undertaken in o rd e r to contribute to the explanation of longrange phosphorus-hydrogen coupling the compound shows in its n .m .r. sp ectru m .
CH3
FIGURE I
S, S, S -tri-p -to ly l phosphorotritM oate
R. A. Shaw (17) o bserved th a t the 1H n .m .r. s p e c tra of P(O) (SCgH^-pM e)g shows som e unusual lo ng-ran g e coupling effects.
The n .m .r. sp ectru m
of the p -m ethyl protons shows a doublet w ith a sep a ra tio n of 2.0 Hz in CCI4 .
Upon decoupling the phosphorus nucleus by irra d ia tio n w ith a second ra d io ­
frequency, the sp ec tru m a p p ea rs as a s h a rp sin g let.
Hence, the doublet m ust
be the re s u lt of sp in -sp in coupling in te ra c tio n over the seven bonds betw een the
phosphorus nucleus and the p -m eth y l p ro to n s (P-S-C =C -C =C -C -H ).
TMs is
believed to be the f ir s t exam ple of sp in -sp in coupling o v er seven bonds in a
phosphorus compound in which a su lfu r atom is an in terv em n g p a rt of the
4
bonding sy ste m (17).
S everal o th e r compounds (of the type P (Y) (XAr)n (ZR)m ; w here Y = O o r
S; X = O, C, o r S; and R = alkyl), also show lo n g -ran g e phosphorus -hydrogen
coupling (11). In review ing p o ssib le m ech an ism s which could explain the lo n g range sp in -sp in in te ra c tio n s fo r th e se com pounds, Sternhell (19) concluded th a t,
in g e n e ra l, a ^ -e le c tro n sy ste m is e ss e n tia l fo r tra n s m is s io n of lo ng-range
effe cts.
A ttem pts w ere m ade to explain coupling betw een the phosphorus and
the a ro m a tic sy ste m by hyperconjugation thus im p artin g TT-character into the
P-X -C bond, w here X = O, C, o r S.
T his approach w as discounted since t r i s -
p-tolylm ethylphosphonic dichlorid e (16), w here hyperconjugation is not p o ssib le ,
also exhibits pronounced lo n g -ran g e coupling.
G riffin and G ordon (11) explained
the sp in -sp in coupling through the P -X -C bond by using F is h e r-H ir s h fe ld e rT a y lo r m odels to show th a t fo r a benzyl phosphorus compound, the phosphorus
atom lie s over the in n e r c irc u m fe re n c e of the aro m atic rin g .
T h is configuration
m ay allow som e overlap betw een th e vacant d -o rb ita ls of the phosphorus and the
a ro m a tic TT-system and, th e re fo re , enhance tra n s m is sio n of lo n g -ran g e coupling.
Hence, the angle betw een phosphorus and the plane of the
(P -X -C ), m ay.be the key to the value of
77-e le c tro n
sy stem
7 Jp_y-.
In th is d is s e rta tio n the c ry s ta l and m o le c u lar s tru c tu re of S ,S , S - tr i- p tolyl phosphoro trith io ate is p re se n te d and the fe a tu re s p e rtin e n t to the proposed
ov erlap m odel a re d iscu ssed .
THE CRYSTAL AND MOLECULAR STRUCTURE OF
S, S ,S -T R I-p ara-T O L Y L PHOSPHOROTRITHIOATE, P(O) (SC6 H4 -P -M e ) 3
P re p a ra tio n
C ry sta ls of S 5 S5 S -tri-p -to ly l p h o sp h o ro trith io ate w e re supplied by R„ A.
Shaw and w e re p re p a re d as d e sc rib e d in the lite ra tu re (18),
The c ry s ta l used fo r X -ra y an aly sis is a c o lo rle s s , tra n s p a re n t, w e ll­
shaped p a ra lle le p ip e d w ith approxim ate dim ensions (0,5 m m )3 .
D ensity
The density of the c ry s ta ls w as m e a su re d by the flo tatio n method using
a solution of carb o n te tra c h lo rid e and
a c ry s ta l.
2 -m ethylbutane
ad ju sted to ju s t suspend
The calcu lated density w as b ased on four m o lecu les p e r unit cell,
deXp = 1.310 g / cm 3 and dca^c = 1.325 g /c m 3 .
D eterm ination of ten ta tiv e c ell dim ensions and space group
W eissenberg photographs of th e X -ra y d iffractio n p a tte rn of P(O) (SCgH^p-M e)g indicated m onoclinic sy m m etry .
m ounted w as designated as a.
The axis along w hich the c ry s ta l w as
The ten ta tiv e c ell dim ensions calcu lated from
the photographs w ere a = 9, b = 14, and c = 17 A 5 j5 was not d eterm in ed at th is
point.
A unit cell of th e se dim ensions would re q u ire four m o lecu les to ag ree
w ith its m e a su re d density.
6
The extinctions based on th is cell w ere:
hk£: No conditions
hOl: 4 ^ Zn
OkO: k f 2n.
T hese extinctions c o rre sp o n d to the sp ace group
w^ h the lb axis unique.
H ow ever, for any unit c ell of P g ^ /c sym m etry, a new unit c ell m ay be sele c ted
by choosing the diagonal of the a and
c_
axes as the
c
axis fo r the new cell.
doing so, the new unit c e ll w ill be in the space group P 2 ^yir
In
The convention
fo r deciding which choice of space group to m ak e, is to s e le c t th e space group
w hich m in im izes the angle (jS) betw een the a and c axes.
Upon d eterm in atio n
of m o re a cc u ra te c e ll dim ensions, the /3 angle fo r P 2 q /c was found to be 117.12°
and 97.37° fo r Pg-j/n*
Hence, by convention the space group P 2 l Zn Was a ssig n e d .
P 2 l Zn Iias the extinction s:
hkf: No conditions
hM : h + 1 Z 2 n
OkO: k Z Zn.
• D eterm in atio n of a cc u ra te unit c ell dim ensions
The d e term in atio n of acc u ra te cell p a ra m e te rs w as obtained by the
following m ethod which is stan d a rd fo r our G eneral E le c tric XRD-5 D iffracto ­
m e te r; the c ry s ta l is m ounted on th e d iffra c to m e te r and se ttin g s fo r se v e ra l
re c ip ro c a l la ttic e points a re located.
T w enty-four th re e -d im e n sio n a l re fle c ­
tions w ere then se le c te d fo r which p re c is e m e asu re m e n ts of the
+20
and -29
7
angles w ere m ade.
C ell dim ensions w ere th en refin ed by le a s t sq u a re s an aly sis
of the 2 9 's using our sta n d a rd c ry sta llo g ra p h ic com puting sy ste m .
The c ry s ta l
data a re lis te d in T able I .
D ata collection
D ata w ere co llected on the G eneral E le c tric XRD-5 D iffrac to m e te r
equipped w ith a scin tilla tio n coun ter, p u lse-h eig h t d is c rim in a to r, and G„ E.
single c ry s ta l o rie n te r, using 9-29 sca n technique and zirco n iu m filte re d
•molybdenum K0, ra d ia tio n .
to the spindle axis.
The c ry s ta l w as m ounted w ith the a axis p a ra lle l
E ach peak w as scanned fo r 60 seconds and the backgrounds
on each side of the peak w e re counted fo r 30 seconds.
A c h a rt reco rd in g of
in ten sity vs_. 29 w as m o n ito red during th e d ata collection as a check on the
cen terin g of the peak in the scan ran g e and fo r g en eral ap p earan ce of the peak
and backgrounds.
The scan ra te w as 2° p e r m inute w ith a takeoff angle of 4°.
In te n sitie s of 3518 unique re fle c tio n s w ere m e a su re d of which 2144
w ere co n sid ered observed, using the c rite rio n
13*2 . 5
a (I).
T h re e stan d ard
re fle c tio n s (133, 212, and 341 refle c tio n s) w e re checked approxim ately ev ery
two hours during d ata collection and re m a in ed constant w ith an average devi­
ation of 1 . 6 %, indicating no d e te rio ra tio n of the c ry s ta l.
S tru ctu re fa c to rs (F0) w ere calcu lated fro m the in te n sitie s by applying
the u su al L o ren tz -p o la riz a tio n c o rre c tio n , and w eights w ere calcu lated fro m
8
TABLE I
C ry sta l D ata
8 ,8
, S -tri-p -to ly l p h o sp h o ro trith io ate
C2 IP S 3 OH2 I
F(OOO) = 872
F .W . 418.46
Mono clinic, space group P 2 i/n
a = 9.489(4) A.
b = 14.938(8) .
90°
JS = 97.37(4)°
O
O
O)
Il
c = 14.916(8)
Ot -
Volume of the unit c ell =
2097 A3
Dexp = 1.310 g /c m '
M olecules /u n it cell - 4
DcaIc = 1.325 g /c n
9
stan d ard deviations as shown below.
E ach re fle c tio n was w eighted according to
the schem e d e sc rib e d by Stout and Jen se n fo r d iffra c to m e te r d ata (20), w here
w —I
/ , and
O-P = k /2 J I p
*
n/
N ^-N bgl-N gba
w here
w = the w eight,
op - the stan d a rd deviation in F 0 ,
k = the scale, constant
I/
JIp = the
L o re n tz -p o la riz a tio n c o rre c tio n ,
Np = the to ta l peak count,
N bgl and Nbgg = the background counts on e ith e r side of the peak, and
Npk “ the net peak count.
The w eighting is a m e a su re of the re lia b ility of an o b serv atio n .
]f p ro p erly
chosen, it has the effect of adjusting the contribution of each o b serv atio n to a
sy ste m of n o rm al equations in such a way as to produce th e m o st re lia b le
re s u lts .
No ab so rp tio n o r extinction c o rre c tio n s w ere m ade.
The lin e a r a b so rp ­
tio n coefficient of P(O) (SCgHq-p-Me)g fo r MoKa ra d ia tio n (X = 0.71069 A) is
jj,
= 4.27 cm""1. The tra n s m is s io n fa c to rs fo r X -ra y s p assin g through the
m axim um and m inim um dim ensions of th e c ry s ta l a re ap p ro x im ately 0.69 and
0.79 re sp e c tiv e ly ; th is range c o rre sp o n d s to approxim ately 7% v a ria tio n about
a m ean intensity value.
S catterin g fa c to rs fo r the non-hydrogen atom s and
10
anom alous s c a tte rin g c o rre c tio n s (^ f 1 and &£"),' fo r phosphorus and su lfu r w ere
tak en fro m the International T ables (12)„ S catterin g fa c to rs fo r hydrogen w ere
ta k en fro m Stew ard, e t. a l. (20).
S tru ctu re d e term in atio n
The s tru c tu re was solved and refin ed in space group
data w ere
then converted to the space group Pg^/m .
E ffo rts at solving the s tru c tu re by P a tte rs o n an aly sis •(2) failed; th e r e ­
fo re , th e m ethod of "sym bolic addition" (3) w as used.
The s tru c tu re fa c to rs
w ere n o rm alized and Z/g re la tio n s w ere calcu lated fo r th o se re fle c tio n s w ith
E 's g r e a te r than 1.50.
T h e re w e re 489 re fle c tio n s w ith E 's g r e a te r th an 1.50
w hich w ere u sed in the S g calcu latio n s.
The o rig in defining re fle c tio n s
se le c te d w ere:
H
K
L
sign
-3
7
6
+
0
3
5
+
-
1
1
0
+
Signs w ere d eterm in ed fo r 483 re fle c tio n s leaving only six a r b itr a r y choices of
sign.
U sing tills s e t of sig n s, an E -m ap (2) w as calcu lated fro m which positions
of the phosphorus, oxygen, and th re e su lfu rs w ere read ily found.
Using th ese
p o sitio n s, the s tru c tu re fa c to r calcu latio n gave an R -index of 0.39, w here
11
R - Z: IF n -F n I
R " S lF o l
A F o u rier m ap re v e ale d the positions of the rem aining non-
hydrogen atom s.
R efinem ent
R efinem ent w as begun using the fu ll m a trix le a s t sq u a re s m ethod of
refinem ent (9)-w ith the R -index equal to 0.25 fo r the non-hydrogen s tru c tu re
along w ith iso tro p ic te m p e ra tu re fa c to rs and a unit w eighting schem e.
th re e cycles of re fin em en t, the R -index dropped to 0.10.
A fter
The te m p e ra tu re
fa c to rs w ere then converted to an iso tro p ic and the w eighting schem e to th a t of
Stout and Je n se n (21).
In two cycles the R -in d ex dropped to 0.065 w ith a
w eighted R -index (Rw^d)> ° f 0.071, w here
I
^w td
D (T w IF o- F g I)2
2 (V w F o l)2 _
and the function m inim ized during le a s t sq u a re s refin em en t was
D w ( |F 0 | - l / k | F c .|)2.
A difference F o u rie r m ap (2) was then calcu lated to lo cate hydrogen
positions.
The tw elve rin g hydrogens w ere lo cated and re fin em en t of th e ir
positions along w ith the o th e r atom s re s u lte d in an R - 0.048 and Rwtc^ ~ 0.050.
A second d ifferen ce m ap w as calcu lated in o rd e r to locate m ethyl hydrogens.
The e le c tro n density around the m ethyl carb o n atom s w as a doughnut-shaped
band, suggesting a lm o st fre e rot".lion of the m ethyl groups around the C-M e
bond.
An attem pt to re fin e hydrogen atom s in a re a s of slig h tly hig h er e le c tro n
12
density w ithin the doughnut, re s u lte d in te m p e ra tu re fa c to rs of approxim ately
tw enty and hydrogen positions m aking no chem ical sen se and hence, w ere not
included in the final s tru c tu re .
R efinem ent of the s tru c tu re w as continued including only those hydrogens
on the phenyl rin g s until the sh ifts in the p a ra m e te rs w ere le s s than one half of
th e ir stan d a rd deviations.
The R -index re m a in ed at 0.048 and an RwtcJ of 0.050
during the final refin em en t.
lis te d in T able 2.
The o b serv ed and calcu lated s tru c tu re fa c to rs a re
The positio n al p a ra m e te rs of the non-hydrogen atom s are
lis te d in T able 3, th e th e rm a l p a ra m e te rs fo r the non-hydrogen atom s are
lis te d in T able 4, and the hydrogen atom p a ra m e te rs a re lis te d in T able 5.
D iscu ssio n of the s tru c tu re *S
,
A draw ing illu s tra tin g th e th e rm a l ellip so id s (13) fo r the m olecule of
S, S, S -tri-p -to ly l p h o sp h o ro trith io ate is shown in F ig u re 2.
a re lis te d in Table
6
and bond angles in T able 7.
The bond lengths
The bond lengths and angles
a re also illu s tra te d in F ig u re 3.
All atom s in the m olecule lie in g e n e ra l p o sitio n s.
The coordination
around the phosphorus is a d isto rte d te tra h e d ro n with th e th re e su lfu rs bent
away fro m the oxygen at angles of 116.7, 116.9, and 116.2° fo r S (I), 8(2), and
8(3) re sp e c tiv e ly .
The angles S(l)-P -S(3), S(2J-P-S(S), and S (l)-P -S (2 ) a re
100.7, 101.4, and 102.3° re sp e c tiv e ly .
The m olecule has n e arly Cg sy m m etry
13
* 2 2 « " Z 2 2 : " , 2 2 we -STle-= ^STle I S -
22 ^ —-«**22
j-*—"♦•‘■•'■•SS >
WV--O2 .
o v j..-..
5Si-:*
:::
0.0
*s: :z':" ’iris
;s:
*;ii
I" i" '" I
'iiii-'-i *:•
=Siiii--: =s-
-ST= - -
%5:»= “ P225 **2="
:: V1" - "-:i""
2=2 !-""2 Ti
2=
r-
• 2 - O - ^ m 2 O.; ; 5 O• <r . • « mm* • m 5o
*?:':*
■iiis:-:'*:
'H
—
; =2** 222
; *" 22 *- °2?
=22- 12-2 *22=2=-=*= 22-*2="*
"==2«2
Siiii- -i-iisi*-:
=*2*22-2 ^21=2=-22= i°»»22*" -2-- *T22*2""* T*2222=*= “f22* *f22-*
=Siii::=Siii
'
II
I----I-"'
—m
—imm «. « —-m*
u~«e**e>«
•■ » o m
mm < - ■ -
—f« m e « »
-« «x m
jm m «
O bserved and calculated s tru c tu re fa c to rs.
Si- -ZZSiSiii-I- SSIZi-- I- IZSii- IZi-I- IZI-Ii- IZI-S IZIi IZii -Z-JiI-Zi -ZiZi-IiI-I-I=SIii- =SiSI- -Si-Si—
Si- =SiSiiiii-I- =SIgi-*
SI! SI' =SSZI SI -SISIiSII-I-I-
j ----Z
-31 i.—
'
Ij......
2" =iK22"-'2 25;;22=22*** 2="222~ 3 SZI--Ii I Z ^ ^ Z ^ ^ Z i S i f s ^ Z ? 1 f « S ^ i i S S ^ ^ ^ I 7 i Z IiiIi^
2» *% »Z S» ~ 2 * ^ 3 2 2 2 2 2 2 2 " *
- =Si--Ii = s - =z- =ZiiSSIS =Zi s s s s s i -Ii z s s * =s i i s ;:s s :;:-s -;
T
T T T
T
f
■omc U-Nm**.
, ■** , - " » ♦ • 2 2 2 p
m♦ m.O•-«» o —22 tl <
m« z>«».* e o —mm<
22
>......... =2 I
2* 2i*
-ZiSSiIiISiI---- 'isiisssisi*;-! -z:;is-s-;iiis-ii -z -s i -i i i s i -i - -zisiu:
=- =z-
= Z -S S J-:--
fssss-s-ii-i” -- = S 3 S i S S S : i i S Z - i = s s t z i - i - l i i i i * : s
= S -Z i-IS isi-I-
% :IS :II:
* V . M . « . . . . O W —. . .
j —
I -------
j —————————S H S — j — — — —
-S IIIIi
—-iilil
"
... -O2 2 2 -O22252- -ZStz-IZ-IZzz: -ziiiiszi-ii 'Z--SIZii--I--S -z-il-sis:i-i-i -zisssssi-iiii
i-i =2 :1 1 -1 1 1 1 1 1 ' =SiSSiiJiii::: =Iisiiist-:! =2 --si:ii--iii; -s -h - s i s i i -i -i ==s«:;si**::i:
7
7
7 -'-'■♦mo-c-c - ->» r
-Smr- Iu-ummmmeeo-.*- T
-'O-Z--S S' u 7
^ *2=:222*222 ^:;2:; 2-2:2 ' 2=222222"22 '=:222":2=%"^2= 2J=2’2?i' =^2%2 2e;==2' 2j 22:'
*s::2: 22* *2*:==222'"2"22 *:::::"2: 22' 2:2 *e;i"22^" '=I::*=*;:;:' -Z==I1=bS^
- ‘ " o m . O --Jm
" -i*;: "22" *2=*"2
-
*22= *22*
x
~
2222 c22^ -22'-
' 22' "2'-*- *2=* ' 2*-' *22=' ' 2* -22- -22***=" *22: 22;;= *
*£=— = “222
*22-
*22—
“ 22*
*22-*-
*52*
*2
;
;
;
i
i
s
s
;
* *22 "
;
*S * * 5 2 *
*£=*— ="
* 2 tlS 2 ;2 2
;
;
;
;
5
—;
*2=- *2222* “22=2-222 *2222*2 *22"=22=*2= B222*2222 *=:2*:-*: *22%2-: 2: *2-222**2 *2222*:*- “
I
I
"2232: -22*-==2"**-: -2=
*=“ *2-: =22x 22222=2;"* =2‘'*- =* 22*22" IZiI-
IZ-=ZIIi =Z--
*2" * 2 " 2 :t 2 " * 2 2 2 = 5 2 ;-" “ 2*2*2" *2*22"
«»rg ^uOmm ♦ON ^ J - i>i • mO«0 C — UO-m O»
J m
________________________________
IZISHSI- IZiiI-S=Zs i i s s s - =ZIiI-S-
=Z-S
= Z iS II
- —~
JU- OXf V
:
;
~
-I
=ZI:
-ZS-
= Z i-S IIS I
_,C —m o m o f - e e 3 -n
=ZS-
- i O —IN-r s- r- d o —
'
"
-I —r.
=
.VA--JVV ZZi22-: IZI- Z-ZI =ZIIZ-II -ZIIIi =-IlS-II 'ZS--SJ-Ii-S' -ZZi
=Z-S-H- =ZiIi-I =Zi- =ri -zSij'ii =ziis:*-i:s*i: =zs-ss;--i-i- =z::
- s i s - i I Z i- - i z i i - i - i z - - Z I i i S I i - - Z iS - S i S i I i- " z s z s s i i i i : : : " z i s i i - m s i i * z t i t - s : : i - - i : -z
- i i i - s =Z--- = Z ii-I- =z- = Z i i i H i i = S i i - I S S i i : : - z i s s s i i i i i i : = z i f i : - : i : s s i - f s i s - s s i i i i : : =z
-IiIl
5
js
-
-2:=22=B
'2::;*:2 -2j:i::;==22=2i-J -2;:S52=2-2-=2 *2JJ:2:=*i*:2 *2;s;=i"2*2s:**
; " 2e:
*2::22e:22
*2 * 2 : = : 2 : " = : : = 2 2 :
* 5 5 :2 2 :;;:? = 2 s:* "
'==;:*
5
* 2 = 2 ss;2 2 * :-;=
*2=222
*= c5 i* 2 = * 5 * = i
* 2 2 ;= 2 i= * 2 -= = s-2
f= ;* ;* * ;* ;
X
* - " 2 : 2:
2-=2-
* 2 2 2 :2 2 2 2 -= -:= ;-
"2 S 5 :::-2 2 2 2 * ";*
* 2 S 2 3 = ::"2 * 2 -
-2 ;-:;= ;:;:2
* 22*= *= :;2-*2
* 2 :s* 2 :;"2 =
2 "::-
% 5 ;::2 = -:::2 * ";-=
* 2 2 ::;= 2 * * 2 :-
^ 2 2 *2:222= = :
* 5 = "= "S :2 :* * *
_ O N - o m o ~ _ r. m
* 5 ;;* 2 2 t-= 2
* 2= ::
* 2 3 := ;= 3 2 "2 ":2 2 "
., * - - - *
2=2 :2 *
2 :5 :2
- 2 " ;j ': 2 ; 2 2 -
•2 2 ;:::*
*2-2*2:22222
22;**2: 2:":2
=2:"*2*22-
22";:*= : 2222*22* 22=-2"*=*
*2:22
“2 * 2 3 * 2 :2 2 ;"
*2=2222-*
* 2 * * * := 2 ;:2 :
* f ; B* 2 = 2 : 2 2 =
*f2 2 * = * ;2 -
*5 = 2 * 2
,-fO -N m ^m om .,OmNmo
^jo -m o m .o i-N -m
_
- N m, o « , o m
_JOmNmmo.,O
* 5 = 2 2 2 :::
*2="2*2=*
2= 22:
=22=2-2*
2 5 2 ;-? :2 * ;:
= ::= 2*2*
* 5 :;-2 2 :-;:
: 2
:3 = :-:2
:52**2*2
25-
=5*22 =53:;j2?=* -J=;=2J22JJiJ-c- 1JJ=I=S
*£ --2 "S -
* 2 2 2 "i2
^552-2*2
*5*
*5*=:
5
* 5 2 :3 ;= = :=
* 5 s= = :;:;3 ?T i* -**22:2
*553253
. JO-Nmo
;J"'5J2==;3:;
— :
5 ;2 jj:;= s:2 * 2 2
“*
*5=2::?:22 *5::=;3:; 2i: 2-: *5?2:*=:;2z:=:2- ^£=s:;s:2=*;2:- %5::2==3:2;:;; *5;:;;:j=;:2*:2
=s:= 32;= ;= 2
- d s ; : ; = ; ; : : 2 2 * 2 N5 ; : 5 ‘' 2 ? ; = 2 : 2 2 = *
- 5 : 5 = ; = J 2 2 * ;2
:* e '5 j2 = = = 3 2 ;;= 2 2 '
14
«22222*
*2*222«
-2 :2 * 2 2
« 2 * '" = :* * =
*2='*= « 2 : » =
* 2 :2 "
-2=2
«2*222-
«22 =222
« 2 2 2 - 2 2 ,*22
^u- »- r < r - c o -
«2 = - 2
«22222
«222
T -I » v~
'mU »< I, * ►-
«22-=
I jfa- *
'2 2 ';::*
"2::%
2*
2 : = '2 « 2
-22 -2 = » :
'2 2 -2 = 2 2
* 2 :';:" :
2?=~*
=2222-
2^*2=
=2
-22-2= 2*
;= :2 S « :2
«f= 2= s-=
“2 2 -2 2 « :
« := « = = ::
-s:*==*=
«==•*
22=2
= 2
«?
' _i - -i vv
;
-IN « e > 3 - V
1
:*2=*2«2:
"g :-2 "::« « :* = -
U %->*- n y 0 1 _i -I » e I- e -
< IN
I
X
1 -I —IN » T <* 1
- :
J 'I I- I' « r O' - I - VI - T
:
J - ♦ y- <j
~
«222222-=
-% =«;«?*
•-= “ «
• 2 = = '",= « = = “ 2 2 " 2 * 2 2 * “' 2 = 2*
«S = 2 = 2« = * 2 2 2 = « r 2 S 2 2 2 « 2 2 *
«22 = 2 = 2 - 1
»2 = - = « : *
«2*2-
^ u -iN -,« ^ T ,-2 1 1
I - - * " «'■«-• * 2 = = | J - - « - * 2 = 21
| J “,P,' * * * 2
| - " >|", ««,B2
| J -«*
' ' ^ 3 1 i ? u'^ 2 *
*‘2 5 2 t 2 2 = >2-r 2 2
* 2*'-p2 - ^ 2 « 2 * -
«•, 2 2 2 5 5 2 2 ” « 2 - - = 2 5 5 2 « »
«fS<==«==s
■=22^2^2S2«22
«2 " 2 * 52«2*-
«2=2252=*
« = -‘ =5552--
“2 2-= = = = --
«2 =1
IJ ' " , « :2= i
|
I - ***' «- - 2==:
I jaaj- - ^ r =
I j - ' .............2=
l j ""«*2==i
I j -*
2 ' 2 5 = 5 22 = 1 5 = = 2 -
' 2 ^ 2 ” 5 5 £ ; = 222
2 5 = 5 2 5 = *=
: ^ :3 :5 := = :::= *
52 * s-s;:s2 2 2 2
«2-5«=525===
2 Ij-^jj --j O==== ^
: ; = 5 - - - 5-
- 2 2 « £ = =1 « « ” 22 =
« 2 ' - 5 5 *3 2 2 * = 2 - J : = ' = = 1 2 = " j * * = =
^ e *==*==:*==
5=1== j : * - = =
J-«Jr22 I-,-*,"*x2=22= IJ—*'«-**222 lJ-«,«-*=2= IJ-"""-
«2=21552=2-
-2**= 2= = ”-« 2
; : : 5 - - *5: « 2 2 := 5 5 :::'
* - * ' ‘= = 2 = 2 I J - - * J
:=
=2=
• 2 = 5 7 5 '* : i5 5 1 *
*252555==:*«=
» > - n , £ ,«
* 2 « s i 5 J 5 * * : : : = i " «15=555=="*-= « « 2 : 2 "
I J - - N - * «« « f - » » 0 ^ 1 - I J - M - ^ O - * » O - - I J - M - O H O Z O 11*1=12
: = = 5 5 * l - 5 = = «=
«=32&===552 N
« = 2 S «M5 5
M
=
V.
-- I
J —M —O f O - - O - —
J
(Continued)
'
* ^ * := 2 = « 2 * -
• + *<,*■* 0 - * .
'^ s s s s 'i s s * = =
=1*52
-=
J —N —O - M f - —
I-
J-MTfO
I / ' = == - =
• « ! " : = ' - - = " * f *==2*2
2 T„ J - M - - O M O M _7 J - O f O M =
« ® 2 ? = : 2 2 ' = = « 2 = = = 1 =N2 -
-- :
J - M —O f M f O M
= J = - = 2 1 = 2=
«52-=
7, J - - O 7
«222= «=, J M7f M _7J f
«N 2 - 2 = 2N 2
' I
J —N O A O = N -
=1-
*5:25-2
11
«f
I
J M« O A M
. NOMO
=
J
ttI S = = - = 15 = : 5 5 ; = 5 = = «1
*f:
= 5 5 : l 5 : 2 « l * 5 % ' : : : ; « 2 : =- 7_ J - N - O A - M i c = N _ J - M - A J M s a - N7O A
, UOONOO
-1S?5==«25SS*
- I S J j S=S==-?=*
‘ S2S?S=-=2S2«
’ ..............................
«5S2*S==2="S ** f 5 2 25= 22= 22= 52= « 5 * * = : ;= 2 1 = 2 2 « 5 = = - « =S*S215* «
’
...........................
............ O f O M . , O - M f
' j .............................. 2 = 2 j — M - O f O . O O - M = ‘
*=22 =
¥ 22 = - * » !2 22 «=
«522=* -SS=:*
5 « = 2 2 = 25«
5*222=
"52*2=2*=222222
=I*-==
: =M- “ =2
«5
J 1 '2 S Z 3=2152=
' 5 = 2 - ' * ? - ===5*
- ! S * * e = ' * ' ! - = S = * ' “ 5 2 * 2 * = * 5 * 2 = 2« * ! * « 2 = '
, « . mm. »
I = j O--OO I oom, , ,
Jcm, , - .
«
«122
l o o o o - f
So-o
__________ i___________i__________ I__________ £___________£______
5:2= 2-
*!2S2-
5=2 «555:*
-OO*==
= *!*= 722= 2-=
* ! = m= 2 2 * *
-52==-
*!2**2=* * ! « = =
25*22-
2!"
= «5*:S51==-1
«5=:==22"
«522=«
J o - O mmmm « 5 * 2 =
«5**2"
“ 5*
,-M
.-CM-M
,JO-M -
S'*2=2*2 =
2 *2 2 2 - ==
1=2=515=2*2-='
'I= JV = = -* -= = = =
O - M - O , OM, O - M
j
:5SS5:-:;-- *;5i;*s*5“:*:
;:i5 ;s * ? i"
2:'
'25:
*!”
" 5-2
jO -M -f«M *,C M -#
=5 '
« !2 = = --*2-” -!5 5 * 5 :5 = * = ';:
5222: 252=«:*=J OMO
"S-=St?*:'*::: ' 5: 2 = =::***
; 2 J 2 S * : * 5 ,- S 2 5
j ;= '5 ':':::::
* e -::t5 '= 2 2 5 ::
* = 5 i* :* i:< * * '
*2*5:
'2*:5:':5's *2::::-2'5'
' 2 5 = S < 3 ' = 5 2 * 2 2 2 5 : = ~ 5 5 = 2 5 5 5 ' = 5 5 5 = S 5 2 52 =5
iS*{5 • 2 5 * 5 * 2 5 3 « : * 2 ' 5 ' * " 'E52:;;*=::* «s25S2-=5 -si:?- i;::::5: *S55
=::
-I
:5 :::::2 5 "
:5 :5 2 = '=
2 ::::5 ::
;2 5 5 ::':
"::S5::5
'
-s ::-:-
5 2 2 :2 ::':
22 * * :'
5 2 * '= *
:2 :
°2?s
* 2 :;;::':
* 2 ":*
* :-':*
* ;:
*2 ::
J,
= 5 2 :"2 :
5 2 * : :: ' = 2 S 5 :sss:-5
- 2 :'::::5 ::::* ::'
:
* : * 5 :: ' » 2 :1 5 :4 5 :':
* 2 :::::* :::::-::'
, J M—, O M ^ J O M O O O C M O O
^ j O - M - O f O M « , o - M- O
,
J O M, M 0
:::2 ::2 '2 "
I : : : ; : ! : * : *"-
-2 i:5 t2 -:i5 2 :::--
'2 i:;5 ::i:::::::*
** 0 f
- s z ::::::;::::::-
'2 i:< = :::5 5 :"
i2 5 :::::::5
5 s ::s 'ii:':::':
-2 * = i5 ::s:;* 5
* * 2 '::::::5 :
j j “- ~ * '" '5 :5 5
—
- 2 ::::'* ':
- 2 ;? : ;'; ':
_ j O - M - O l f O M e , MO,
^ J O - M - O , M,
'2 :::::::::* 5 :':'
-2 :;::::
2 :::
::
:*555= -
- 2 :'5 '= 2 2 ':- 5
:2 ::'::s :5 :s ::
5 'f s * '* : ': : :: *
* 2 : ': " :: : ': * :
;2 ::* :5 ::::::5
*2
JJ" " " '= : 5 5
.- " " I '''* '= = :
t -
" '2 :5 :5
-2 :—
* 2 : :::::':'::':
,' " " '' " " I "
=2
' ! - , =I I =C i S i T
15
TABLE 3Positional param eters of non-hydrogen atoms
in S1S, S -tri-p -to ly l phosphorotrithioate.
Atom
x /a
y /b
8(1)
8(2)
8(3)
P
O
0.0323(2)
0.1606(2)
-0.0916(1)
0.1018(1)
0.2059(3)
0.4718(1)
0.4600(1)
0.3282(1)
0.3792(1)
0.3135(2)
-0.3000(1)
-0.0890(1)
-0.1714(1)
-0.2007 (I)
-0.2228(2)
C(I)
C(2)
C(3)
C (4)
C (5)
0.0372(6)
0.1480(6)
0.1465(6)
0.0376(5)
-0.0698(6)
0.4093(3)
0.4224(4)
0.3819(4)
0.3271(3)
0.3144(4)
-0.4007(3)
-0.4506(4)
-0.5334(4)
-0.5699(3)
-0.5177(4)
C (6)
C(?)
C (8)
C (9)
C(IO)
-0.0722(6)
0.0359(5)
0.3259(6)
0.3358(7)
0.4652(7)
0.3543(4)
0.2843(3)
0.5010(4)
0.5868(4)
0.6217(4)
-0.4342(4)
-0.6632(3)
-0.1164(3)
-0.1486(4)
-0,1636(3)
C (Il)
C (12)
C (13)
C (14)
C(IS)
0.5878(7)
0.5757(7)
0.4468(7)
0.7325(6)
-0.0394(5)
0.5712(4)
0.4845(4)
0.4508(4)
0.6105(4)
0.2582(3)
-0.1486(3)
-0.1171(3)
-0.1012(4)
-0.1657(4)
-0.0762(3)
C (16)
C (17)
C (18)
C(19)
C (20)
0.0277(6)
0.0576(6)
0 . 0 2 0 1 (6 )
-0.0478(7)
-0.0766(7)
0.1782(4)
0.1249(4)
0.1483(4)
0.2285(4)
0.2839(4)
-0.0843(4)
-0.0082(4)
0.0756(3)
0.0811(4)
0.0059(4)
C (21)
0.0521(6)
0.0876(4)
0.1590(3)
.
z /c .
aThe number in parentheses is the standard deviation
and refers to the least significant digits.
16
TABLE 4
T h e rm a l p a ra m e te rs of non-hydrogen atom s
in S, S, S -tri-p -to ly l pho sp h o ro trith io a te .
Atom
8 n a ’b
#22
#33
S(I)
8(2)
8(3)
P
O
216 (S)C
180(2)
135(2)
141(2)
144(5)
45(1)
69(1)
60(1)
45(1)
56(2)
47(1)
46(7)
58(1)
42(1)
56(2)
14(1) .
-18(1)
- 1 (1 )
3(1)
19(3)
7(1)
20(1)
3(1)
4(1)
8(2)
4(1)
-18(1)
1 1 ( 1)
0 ( 1)
0 (2 )
C(I)
C(2)
C(3)
C (4)
C (5)
131(8)
118(9)
125(9)
117(7)
129(9)
42(3)
62(4)
70(4)
40(3)
63(4)
45(3)
57(3)
57(3)
57(3)
66(4)
5(4)
-25(5)
-8(5)
5(4)
-30(5)
-1(4)
-1(5)
33(5)
15#)
13(5)
8 (2 )
3(3)
0(3)
8 (2 )
-10(3)
C (6)
C(7)
C (8)
C (9)
C(IO)
140(9)
206 (9)
146(9)
171(10)
2 0 0 (1 1 )
66(4)
60(3)
47(3)
58(4)
58(4)
56(3)
46(3)
36(2)
52(3)
53(3)
-9(5)
-1(5)
-2(4)
18(6)
-14(6)
30(5)
23(4)
5(4)
2(5)
16(5)
C (H )
C (12)
C(IS)
C (14)
C(IS)
203(11)
141(10)
205(12)
155(9)
129(8)
64(4)
63(4)
40(3)
110(5)
49(3)
37(3)
47(3)
45(3)
.88(4)
46(3)
1 (6 )
13(6)
. -5(6)
-43(7)
-5 # )
7(4)
10#)
7(5)
35(5)
12#)
'
#12
#13
£23
T 3 (3 )
-16(2)
- 6 # )
3(3)
9(3)
-7(3)
-10(3)
-4(3)
5(4)
0 (2 )
17
TABLE 4(Continued)
Atom
jSll
C (16)
C (17)
C (18)
C(19)
C (20)
159(9)
160(9)
157(9)
290(13)
249(12)
C(21)
256(11)
033
012
013
023
56(3)'
54(3)
57(3)
61(4)
52(4) '
47(3)
62(4)
54(3)
45(3)
61(4)
9(4)
20(5)
-14(4)
7(6)
9(5)
19(4)
14(4)
-1(4)
17(5)
19(5)
1(3)
1(3)
-6(3)
-7(3)
-7(3)
74(4)
47(3)
-4(5)
-13.(4)
22(3)
022
aThe /Sjjis have been m u ltiplied by 10^.
^The fo rm of the an iso tro p ic th e rm a l e llip so id s is,
exp (-£ H h 2 - S 2 2 k 2 ~ /S3
3
“ SlS h -6 " S23k -6).
cThe num ber in p a re n th e se s is th e stan d a rd deviation and r e f e r s to the
le a s t significant d ig its.
18
TABLE 5
' H ydrogen atom p a ra m e te rs in
S, S, S -tri-p -to ly l p h o sp h o rp h o ro trith io ate.
Atom
x /a
y /b
z /c
B iso
H(I)
0.222(4)%
0.455(2)
-0.433(2)
2
H(2)
0.219(4)
0.394(3)
-0.564(3)
4.2 (1.1)
H(S)
-0.139(4)
0.285(3)
-0.535(3)
4.0(1.3)
H (4)
-0.143(5)
0,347(3)
-0.395(3)
5.4 (1.2)
H(5)
0.255(4)
0.622(2)
-0.163(2)
5.0(1.3)
H(6)
0.460(4)
0.687(3)
-0.194(2)
6.9 (1,3)
H(7)
0.657(4)
0.448(2)
-0.109(2)
4.8(1.3)
H(8)
0.442(3)
0.403(2)
-0.078(2)
3.1(1.2)
H(9)
0.49(4)
0.160(3)
-0.147(3)
4.5 (1.0)
H(IO)
0.103(4)
0.072(3) .
-0.015(3)
4.7 (1.2)
H (Il)
-0.076(5)
0.250(3)
' 0.142(3)
6 . 6 (1 .3)
H (12)
-0.123(6)
0.342(4)
0.007(3)
9.4(1.8)
.5(1.0)
a The num ber in p a re n th e se s is the stan d a rd deviation and
re f e r s to the le a s t significant d ig its.
19
C7
F ig u re 2.
M olecular s tru c tu re of
S ,S , S -tri-p -to ly l p h o sp h o ro trith io ate
illu s tra tin g the th e rm a l ellip so id s.
20
TABLE
6
Bond d ista n ce s in
S, S, S -tri-p -to ly l p h o sphoro trith io ate
Bond
distance
Bond
d istan ce
S (I)-P
2.072(2)*
C (12)-C (13)
1.371(10)
S(I)-C (I)
1.774(5)
C (IS)-C (16)
1.366(7)
S(2)-P
2.075(2)
C (IS)-C (20)
1.373(8)
S(2)-C(8)
1.779(5)
C(16)-C(17)
1.386(8)
S(S)-P
2.084(2)
C (17)-C (18)
1.387(8)
S(S)-C(IS)
1.781(5)
C (IS)-C (19)
1.369(8)
P -O
1.459(3)
C (IS)-C (21)
1.537(7)
C(I)-C(Z)
1.379(8)
C (19)-C (20)
1.382(8)
C(I)-C(G)
1.367(8)
C(Z)-H(I)
0.87(4)
C(Z)-C(S)
1.374(8)
C(S)-H(Z)
0.89(4)
C (S)-C (4)
1.375(8)
C(S)-H(S)
0.81(4)
C(4)-C(5)
1.372(8)
C(6)-H(4)
0.94(4)
C(4)-C(7)
1.529(7)
C (9)-H(5)
0.93(3)
C(S)-C(G)
1.385(8)
C(IO)-H(G)
1.08(4)
C (8)-C (9)
1.376(8)
C (12)-H(7)
0.94(4)
C(S)-C(IS) ■ ■
1.365(9)
C(IS)-H(S)
0.80(3)
C(S)-C(IO)
1.378(10)
C (16)-H(9)
1.02(4)
C(IO)-C (11)
1.381(9)
C(17)-H(10)
0.92(4)
C (Il)-C (12)
1.387(9)
C (19)-H (H )
1.03(4)
.. 1.544(8)
C(20)-H(12)
0.92(4)
G (H )-C (14)
.
aThe num ber in p a re n th e s is is th e stan d a rd deviation and re f e r s
to the le a s t sig nificant dig its.
TABLE 7
Bond angles fo r S, S, S - tri-p - to ly l p h o sp h o ro trith io ate.
A tom s'
P -S (I)-C (I)
P-S(2)-C (8) .
P-S(S)-C (15)
S(I)-P-S(Z)
S (I)-P -S(S)
S (I)-P -O
S(Z)-P-S(S)
S(Z)-P-O
S(S)-P-O
S(I)-C(I)-C(Z)
S(I)-C (I)-C (6)
C(Z)-C(I)-C(G)
C(I)-C(Z)-C(S)
C (Z)-C (S)-C (4)
C(3)-C(4)-C(5)
C(S)-C (4)-C (7)
C(S)-C (4)-C (7)
C(4)-C(5)-C(6)
C (5)-C (6)-C (l)
S(Z)-C(S)-C (9)
S(Z)-C(S)-C(IS)
D eg rees
10Z.3 (Z)a
98.8 (Z)
10Z.7 (Z)
10Z.3(1)
100.7(1)
116.7(1)
101.4(1)
116.9(1) ■
116.Z (I)
119.1(4)
1Z1.7 (4)
119.0(5)
1Z0.Z(5)
1ZZ.6(5)
115.7(5)
1Z1.9(4)
1ZZ.5 (5)
1Z3.4(5)
119.Z (5)
1Z0.Z(4) ■
1Z1.4(4)
A tom s
C (9)-C (S)-C(IS)
C(S)-C (O)-C(IO)
C(9)-C (IO)-C (11)
C (IO )-C (Il)-C (IZ )
C(IO)-C (H )-C (14)
C (IZ )-C ( l l ) - c (14)
C (Il)-C (IZ)-C (13)
C (IZ)-C (IS)-C (14)
S(S)-C (IS)-C (16)
S(S)-C(IS)-C(ZO)
C(IG)-C (LS)-C(ZO)
C (IS)-C (IG)-C (17)
C(IG)-C (17)-C (18)
C (17)-C (18)-C (19)
C(17)-C (IS)-C (Zl)
C(19)-C (IS)-C (Zl)
C (IS)-C (19)-C (ZO)
C(19)-C (ZO)-C(IS)
C (I)-C (Z)-H (I)
C(S)-C(Z)-H(I)
C(Z)-C(S)-H(Z) '
D egrees
118.4(5)
1Z0.8(5)
.IZLl(G )' .
117.4(5)
1Z0.9(5)
1Z1.7 (5)
1Z1.0(6)
I Z l 1S(G)
1Z1.9(4)
118.1(4)
119.9(5)
118.7(5)
1Z3.0(5)
116.8(5)
1ZZ.3 (5) ■
1Z0.9(5)
IZl.Z(G)
1Z0.4(6)
!24.(2)
116. (Z)
117.(3)
Atoms
C (4)-C(3)-H(Z)
C (4)-C (S)-H(S)
C(G)-C(S)-H(S)
C(5)-C(6)-H(4)
C (l)-C (6)-H (4)
C(8)-C(9)-H(5)
C(IO)-C (9)-H(5)
C (9)-C (IO)-H(G)
C(H)-C(IO)-H(G)
C (Il)-C (IZ)-H (7)
C(IS)-C (IZ)-H(V)
■C(IZ)-C(IS)-H(S)
C(S)-C (IS)-H(S)
C (IS)-C (16)-H (9)
■ C (17)-C (16)-H(9)
C (IG)-C (17)-H(10)
C(IS)-C (17)-H(10)
C(IS)-C (19)-H(11)
C(BO)-C (IS )-H (Il)
C(19)-C(Z0)-H(1Z)
C(IS)-C(BO)-H(IZ)
D egrees
IZL(S)
1ZZ. (3)
115.(3)
1Z7. (3)
114.(3)
IZl-(Z)
1 19.(Z)
115.(2)
1Z4. (Z)
119. (Z)
1Z0.(Z)
1Z0.(Z)
118.(2)
118.(2)
123.(2)
117.(3)
120.(3)
120.(3)
. 1!9.(3)
124.(3)
115.(3)
a The num ber in p a re n th e se s is the stan d a rd d eviation and re f e r s to the le a s t significant digits.
F ig u re 3.
Bond d ista n ce s and angles fo r S, S, S -tri-p -to ly l p h o sp h o ro trith io ate
23
w ith the C 3 axis p a ssin g through the P -O bond.
An explanation fo r the su lfu rs being bent away fro m the oxygen atom m ay
be th a t the tolyl g ro u p s , being d ire c te d upw ard tow ard the oxygen atom , re s u lts
in s te r ic re p u lsio n betw een the tolyl groups and the oxygen atom .
The s te r ic
s tra in can be re lie v e d by in c re a sin g the O -P -S angles.
The P - S (I), P -S (2), and P-S(S) bond d ista n ce s a re 2.072, 2.075, and
2.084 A re sp ec tiv e ly .
The P-S(S) bond length is 4-6 stan d ard deviations longer
than the P -S (I) and P-S(2) bond lengths, a d ifferen ce which m ay be significant.
The P -S (I) and P-S(2) bonds a re not significantly d ifferen t.
lengths may be c o n sid ered n orm al.
All th re e P-S bond
The P=O bond length of 1.459 A is w ithin
the norm al ran g e, (1.42-1.52 A).
Bond angles P - S (I) -C (I), P-S(2)-C (8), and P-S(S)-C (IS) a re 102.3, 99.8,
and 102.7° re sp e c tiv e ly .
T hese a re n o rm al P -S -C angles except when one con­
s id e r s th a t th e re a re two bulky groups on e ith e r end of the bond.
The oxygen
atom is s e p a ra te d fro m the a ro m a tic rin g s by only the sum of th e van d e r W aals
ra d ii, approxim ately 3.27 A.
One m ight expect th at the s te r ic rep u lsio n m ay be
re lie v e d by in c re a sin g the P -S -C angles which m ay have happened fo r the O -P -S
angles.
T hese seem ingly sm a ll angles m ay re s u lt from o v e rla p of o rb itals
betw een the phosphorus atom and the C (I), C (8 ), and C (15) ato m s.
The s tr u c ­
tu re shows th at th ese phosphorus to carbon atom d istan ces a re 2.954, 3.024, and
3.001 A re sp e c tiv e ly , which a re close enough to produce som e o v erlap of o rb ita ls
24
fro m phosphorus and the o rb ita ls of the a ro m a tic carbon atom s; how ever, the
s tru c tu re also shows th a t the phosphorus atom does not lie w ithin the in n er c i r ­
cum ference of the a ro m a tic rin g as was suggested by R. A. Shaw (17) fo r th is
compound as in shown in figure 4.
TMs a rra n g e m e n t may allow som e type of
bonding in te ra c tio n betw een the phosphorus and carbon atom s to take place; how­
e v e r, the ov erlap m odel fo r the bonding pro p o sed by G riffin and G ordon (11) does
not see m to adequately d e sc rib e the bonding.
In th e ir o v erlap m odel they a t t r i ­
bute the o b serv ed lo n g -ran g e coupling betw een the phosphorus nucleus and the
m ethyl pro to n s to o v erlap betw een the v acant d -o rb ita ls of the phosphorus and
the a ro m a tic
77-s y s te m .
• H ow ever, it is believed th a t th e F e rm i contact te rm
(23) is the dom inant te rm in determ in in g coupling in a liquid o r g a s, and is a
m e a su re of the pro b ab ility of the bonding p a ir of e le c tro n s ex istin g at both
nuclei.
Since d -o rb ita ls have z ero p ro b ab ility fo r e le c tro n s at the nucleus, they
cannot contribute to the coupling; w h e rea s, s -o rb ita ls do have a finite p ro b ab il­
ity at the nucleus and can contribute to coupling.
T h e re fo re , if som e type of
bonding does e x ist betw een the phosphorus and the a ro m a tic
77-s y s te m
which
enhances long-range coupling, then it should involve som e s - o r b ita l c h a ra c te r.
The tolyl groups w e re found to be approxim ately p e rp e n d icu la r to the
p lanes of the P -S -C bonds.
The d ih e d ra l.an g les fo r the p lan es P ,S (1), C(I) and
C (2), C (I), C (6 ); P, S(2), C (8 ) and C (9), C (8 ), C (13); and P,S (3), C (15) and
C (16), C (15), C (20) a re 80.5, 78.5, and 70.4° re sp ectiv ely and a re shown in
25
F ig u re 4.
G eo m etrical rela tio n sh ip of the P-S -C bonds
showing the overlap of the van d e r W aals ra d ii fo r
the phosphorus and carbon atom s.
26
F ig u re 5.
The tolyl groups a re p la n a r w ithin ex p erim en tal e r r o r w ith the
la rg e s t deviation 0.02 A fro m p la n arity .
The le a s t sq u ares equations fo r the
planes of the tolyl groups a re given in T able
8.
The su lfu rs a re 0.10, 0.11, and
0.15 A fro m the planes of the tolyl g ro u p s, indicating a bend in the C-S bond.
The su lfu rs a re bent out of the plane 3.8, 4.2, and 5.8° fo r 8(1), 8(2), and 8(3)
re sp e c tiv e ly .
F ig u re
6
shows the d ire c tio n of d isto rtio n in the C-S bond.
This
d isto rtio n of the bond would indicate th at the sp 2 h y b rid izatio n of the carbon atom
m ay have been slightly a lte re d and the s -c h a ra c te r of the bonding o rb ita ls in ­
c re a s e d .
The a ro m a tic C-C bonds a re probably equivalent w ithin ex p erim en tal
e r r o r and range fro m 1.365-1.392 A and av erag e 1.377 A w hich a re n orm al bond
lengths fo r an a ro m a tic rin g .
The bond angles fo r the to ly l groups range fro m
115.7-123.4° and average 120.0°.
d ifferen t ov er th is ran g e.
The bond angles a re probably significantly
The C (S)-C (4)-C (5), C (IO)-C ( I l) - C (12), and C (17)-
C (IS )-C (19) bonds ap p ear to be the s m a lle s t angles in the rin g s and a re located
on the m ethyl end of the a ro m a tic ring.
The C-M e bonds a re 1.529, 1.544, and
1.537 A fo r C(4)-C(7), C (Il)-C (14), and C (IS)-C (21) re sp e c tiv e ly and are not
significantly differen t.
A s te re o g ra p h ic packing diagram (13) fo r the c ry s ta l is shown in F ig u re
7.
It is unlikbly th a t packing is re sp o n sib le fo r the effects d isc u sse d h e re , sin ce
th e re a re no in te rm o le c u la r d ista n ce s le s s than the sum of the van d e r W aals
27
C (13)
C(20)
C(16)
(c )
F ig u re 5.
a) D ihedral angles betw een planes 0(2), 0(1), 0(6) and P , 8(1), 0(1) loolung down
the C (I)-S (I) bond,
b) p lanes 0(9), 0(8), 0(13) and P, 8(2), 0(8) lo o tin g down the C (S)-S(2) bond, and
c) planes 0(16), 0(15), 0(20) and P , 8(3), 0(15) looting down the C(15)-S(3) bond.
28
'
TABLE
8
Equations of L e a st S quares P lanes R e fe rre d to
O rthogonal Axes fo r P(O) (S C g H q -p -M e)^
A tom s in the plane
A
m
n
P(A)
S(A2 )X lO 4
C (l), 0(2), 0(3), 0(4),
C(5), 0(6)
-0.4489
0.8237
-0.3463
7.267
1.48
0 (1 ), 0(2), 0(3), 0(4),
0(5), 0(6), 0(7)
-0.4496
0.8268
-0.3380
7.23
9.33
0(8), 0(9), 0(10), 0(11),
0(12), 0(13)
. 0.0362
0.3399
0.9397
1.026
1.07
0(8), 0(9), 0(10), 0(11),
0(12), 0(13), 0(14)
0.0344
0.3391
0.9401
1 .0 1 2
1.45
0(15), 0(16), 0(17), 0(18),
0(19), 0(20)
0.8856
0.4644
0.0023
1.329
1.60
0(15), 0(16), 0(17), 0(18),
0(19), 0(20), 0(21)
0.8861
0.4635
0.0036
1.326
1.96
P -S (I)-C (I)
0.9559
0.2921
-0.03031
4.254
—
P-S(2)-C(8)
-0.4124
0.7744
-0.4798
5.254
——
P-S(S)-C (15)
-0.1713
0.7725
0.6114
2.329
—
a X ^ x + z» cos j8 ;
Y - y;
Z = x* sin
{$
L 1 S 0 plane: j&X + mY + nZ - P - O
S = sum of sq u a re s of deviations of atom s fro m the plane.
29
p la n e o f th e t o l y l r i n g
F ig u re
6.
D isto rtio n of the th re e P -S bonds in
PO(SCGll4--p-M e )3 w h ere,
X = I, Y = I;
e = 3.8°
X = 2, Y = 8;
e = 4.2°
X = 3, Y = 15;
e = 5.8«.
30
I
F ig u re 7.
StereograpM c packing d iag ram of
S, S, S -lri-p -to ly l phosphorotritM oate.
31
ra d ii.
The p e rtin e n t van d e r W aals ra d ii used a re given by Bondi (8 ): P , 1.80;
S, 1.80; double bonded O, 1.50; a ro m a tic C, 1.77; alip h atic C, 1.70; and
a ro m a tic H, 1.0 A.
SUMMARY AND CONCLUSIONS
The s tru c tu re of
8,8,
S -tri-p -to ly l p h o sp h o ro trith io ate p ro v id es facts
w hich lead to a b e tte r understanding of the m ech an ism fo r long ran g e p h o sp h o ru shydrogen coupling in a ro m a tic e s te r s and th io e s te rs of phosphorus (V).
The d e ta ils of the s tru c tu re a p p ea r to support, in g e n e ra l, the idea of a
p o ssib le o v erlap betw een the phosphorus atom and the a ro m a tic rin g as proposed
by G riffin and G ordon fo r the benzyl phosphorus compound (11); how ever, the
s tru c tu re shows th a t the phosphorus does not lie over the in n e r c ircu m feren ce
of the a ro m a tic ring as w as proposed by G riffin and Gordon fo r the benzyl com ­
pound and by R„ A. Shaw fo r the
8,8
, S -tri-p -to ly l p h o sp h o ro trith io ate compound
(17).
A ccording to the p ro p o sed o v erlap m odel, the angle betw een p h o sp h o ru s,
the linldng atom , and the plane of the rr-elec tro n sy stem (P -X -C ), m ay w ell be
c ritic a l to the value of
With oxygen being the linldng h etero ato m , as in
P(O) (O CgH ^-p-M e)^, the P -X -C angles a re approxim ately 120° and ^Jp_H is
0.7 Hz in CCI4 (17). The P -S -C angles in S» S, S -tri-p -to ly l p h o sp h o ro trith io ate,
P(O) (SCgH ^-p-M e)^, a re 102.3, 98.8, and 102.7° which m ay fa c ilita te a g r e a te r
overlap of the o rb ita ls involved and, in consequence, the la r g e s t values to d ate,
7 J p _ H,
2.0 Hz fo r P(O) (SCgHq-P-Me)S in CCU, a re obtained fo r compounds
containing the P -S -C sy stem .
PART II
I , 3, 2-D ioxaphosphorin an es
INTRODUCTION
The 2-oxo o r th io -1 , 3 , 2-dioxaphosphorinanes, having lone sub stitu en ts
on the rin g carbon atom s as shown in F ig u re
8
(b) and (c), a re of im portance in
co nsidering the effects of su b stitu en ts on the conform ation of the rin g , and
those w ith a single su b stitu en t on the C (5). p o sitio n a re of in te r e s t in providing
inform ation about the p re fe rre d o rien tatio n of the groups on the rin g .
S teric
effects of the C (5) su b stitu en t can be com pared w ith those on the phosphorus
atom .
U nsubstituted o r ''5 ,5 - d isu b stitu ted 2-o x o -1 , 3 , 2-dioxaphosphorinanes,
such as shown in F ig u re
8
(a), have been studied by n .m .r. (10), dipole m om ent
(14), and in a few c a se s X -ra y cry stallo g rap h y (5).
H ow ever, m olecules
having lone su b stitu en ts on the rin g carbon atom s have only re c e n tly been
investig ated (15).
The use of n. m . r . spectro sco p y has been the m o st ex ten siv ely used
technique fo r th ese stu d ies; how ever, n .m .r. does not p e rm it an unambiguous
assig n m en t of the s te re o c h e m istry at phosphorus.
X -ra y cry stallo g rap h y does
lend its e lf to unam biguously d eterm in in g the s te re o c h e m istry .
The 2-oxo d r th io -1 , 3 , 2-dioxaphosphorinanes p re s e n t a unique oppor­
tunity fo r stu d ies of six -m e m b e re d rin g sy ste m s since, unlike m any other
com pounds containing six -m e m b e re d rin g s, they tend to be c ry s ta llin e solids
35
lending th e m selv e s to X -ra y c ry sta llo g ra p h ic stu d ies.
P reviously only one 2 -o x o -l, 3 , 2-dioxaphosphorinane w ith a lone s u b sti­
tuent on the rin g carbon atom s has been in v estig ated using X -ra y c ry s ta llo ­
graphy (15), which is shown in F ig u re
8 (b).
T his in v estig atio n continues that
study and co n trib u tes th re e additional c ry s ta l s tru c tu re s : I) 5 -t~ b u ty l-2 m ethoxy- 2 -o x o - 1 , 3 , 2 -dioxaphosphorinane,
2)
5- t -b u ty l- 2 -phenyI- 2 -th io -
I , 3, 2-dioxaphosphorinane, and 3) 2, 5 -t- b u ty l-2 -th io -l, 3 , 2-dioxaphosphor­
inane, which a re shown in F igure
8 (c),
F ig u re 8.
(a)
Y = O, R ' = H, R2 = H, X = OH
Y = O, R ' = H, R2 = H, X = OPh
Y = O, R ' = Me, R2 = CH gBr, X = B r
(b) Y = O,
R 1 = t -b u ty l, R2 = H, X = Me
(c) Y = O, R ' = H, R2 = t -b u ty l, X = OMe
Y = S, R ' = t -b u ty l, R 2 = H, X = Ph
Y = t - butyl, R ' = H , R2 = t -butyl, X = S
THE CRYSTAL AND MOLECULAR STRUCTURE OF
5-t-B U T Y L -2-M E T H O X Y -2-O X O -l, 3, 2-DIOXAPHOSPHORINANE (CgPO^Hiy)
P re p a ra tio n
The c ry s ta ls w ere supplied by W esley G. B entrude and w ere p re p a re d
as d e sc rib e d in the lite ra tu re (15).
The c ry s ta l used fo r X -ra y an aly sis w as a c o lo rle s s , tra n s p a re n t,
p a ra llelep ip e d w ith approxim ate dim ensions 0.3 x 0.5 x 1.0 m m .
This was
sea le d in a Lindem an g la ss cap illary to p re v e n t lo ss by sublim ation.
D ensity
The density of the c ry s ta ls w as m e a su re d by the flo tatio n m ethod, as
d e sc rib e d in P a rt I, page 5.
The calcu lated density w as b ased on four m o le ­
cules p e r unit cell; De xp = 1.25 g /c m 3 and DCalc = 1.277 g /c m 3 .
D eterm ination of ten ta tiv e c ell dim ensions and space group
W eissenberg photographs of the X -ra y d iffractio n p a tte rn fo r the c r y s ­
ta l C 8 P Q jiiiy , indicated orthorhom bic sy m m etry .
c ry s ta l was m ounted was designated as a.
The axis along which the
The ten tativ e unit c ell dim ensions
w ere found.to be a = 6.13, b = 10.3, and c = 17.6 A in acco rd an ce w ith the con­
vention a > .b > c.
A unit cell of th e se dim ensions would re q u ire four m o lecules
to ag ree w ith its m e a su re d density.
The extinctions b ased on th is cell w ere:
37
hkA:
McO:
0k4:
hOi.:
IiO0:
OkO:
004:
no conditions
h ^ 2n
k + i 7^ 2 n
no conditions
Ii 7^ 2n
k 2n
Sb £ 2n.
T hese extinctions co rre sp o n d e d to e ith e r sp ace group P n 2 ia o r Pnm a w here
the fo rm e r is a n o n -c e n tro sy n n n e tric space group and the la tte r is c e n tro sy m m e tric .
Solution of the s tru c tu re showed the c o rre c t space group to be Pnm a.
D eterm ination of a cc u ra te unit cell dim ensions
The d e term in a tio n of a cc u ra te cell p a ra m e te rs w as obtained by the sam e
p ro ced u re d e sc rib e d in P a rt I, page
6
. Twelve th re e -d im e n sio n a l reflectio n s
w ere sele c ted fo r which p re c is e m e a su re m e n ts of th e +29 and -29 angles w ere
m ade.
The c ry s ta l data a re lis te d in Table 9.
. D ata collection
D ata w ere co llected on the G eneral E le c tric XRD-5 D iffracto m eter,
equipped w ith a sc in tilla tio n coun ter, p u lse-h eig h t d is c rim in a to r, and a G. E 0
single c ry s ta l o rie n te r, using 9-29 scan technique and zirco n iu m filte re d
m olybdenum K0, rad iatio n .
to the spindle axis.
The c ry s ta l w as m ounted w ith the a axis p a ra lle l
E ach peak was scanned fo r 100 seconds and the back­
grounds on each side of the peak w ere counted fo r 50 seconds.
was 2° p e r m inute w ith a takeoff angle of 4°.
The scan ra te
38
TABLE 9
C ry sta l D ata
5 -t-B u ty l-2 -M e th o x y -2 -O x o -l, 3, 2-D ioxaphqsphorinane
C 8 P 04H i7
F .W . 208.19
F(OOO) 448
O rthorhom bic, space group Pnm a
a = 6.123(4)
QL =
b = 10.02(1)
P = 90°
c = 17.65(1)
y
Volume of the unit cell =
1083. A 3
Dexp 1.25 g /c m 3
M olecules /u n it c e ll =
4
D calc =
1.277 g /c m d
90°
= 90°
39
In te n sitie s of 1008 unique re fle c tio n s w ere m e a su re d of which 585 w ere
co n sid ered o bserved, using the c rite rio n 1 ^ 2 a (I). T h ree stan d a rd re fle c tio n s
(114, 121, and 131 re fle c tio n s) w ere checked approxim ately ev ery four hours
during data co llectio n and rem ain ed constant w ith an av erag e deviation of 1.4%,
indicating no d e te rio ra tio n of the c ry s ta l.
S tru ctu re fa c to rs (F0 ) w ere calcu lated fro m the in te n sitie s by applying
the usual L o re n tz -p o la riz a tio n c o rre c tio n , w eights w ere calcu lated fro m stan d ­
a rd deviations as w as d e sc rib e d in P a rt I, page 7.
No ab so rp tio n o r extinction c o rre c tio n s w ere m ade.
The lin e a r a b so rp ­
tio n coefficient of CgPC^H 1 7 fo r MoK0, ra d ia tio n (X = 0.71069 A) is jLt = 2.41 cm - "1The tra n s m is s io n fa c to rs fo r X -ra y s p a ssin g through th e m axim um and m in i­
mum dim ensions of the c ry s ta l a re approxim ately 0.73 and 0.93 resp ectiv ely ;
th is range co rre sp o n d s to approxim ately
value.
12%
v a ria tio n about a m ean in ten sity
S cattering fa c to rs fo r the non-hydrogen atom s and anom alous s c a tte rin g
c o rre c tio n s (&P and A f"), fo r phosphorus w ere taken fro m the In tern atio n al
T ables (12).
S catterin g fa c to rs fo r hydrogen w ere taken fro m Stew ard, et. a l.
pox
S tru ctu re d e term in atio n
The space group w as initially thought to be the n o n -c e n tro sy m m etric
space group Pn2pa, since th e re w ere fo u r m olecules p e r unit cell and Pn2%a
40
has four g e n e ra l p o sitio n s, which would in d icate th a t each m olecule would have
to contain a sy m m etry elem ent.
Since th e re w as no ap p aren t sy m m etry e le ­
m ent contained in th e m olecule, the c en tre sy m m e tric t-pace group Pn2pa was
used to solve the s tru c tu re ;
The positio n s of the phosphorus atom s w ere found fro m the P a tte rso n
sy n th esis (2 ) 0 U sing the phosphorus atom p o s itio n s , the s tru c tu re facto r calc u ­
lation (I) gave an R -in d ex of 0.55, (R =23 IF 0 - F c |/2 3 | F 0 | )„ A F o u rie r m a p '(2)
re v e ale d the positio n of an oxygen and a s tru c tu re fa c to r c alcu latio n gave an
R -index of 0.50.
A subsequent F o u rie r sy n th esis re v e ale d p eak s fo r the r e ­
m aining non-hydrogen atom s, plu s, an additional peak.
T h e re w ere two peaks
of equal in tensity at the rig h t d istan ce fro m the m ethoxy oxygen to be bonded to
it.
The in te n sitie s w ere about one half th a t of the oth er carb o n s.
T his su g ­
g ested th a t the m ethoxy carbon atom was d is o rd e re d and to be found in one
position or the o th er about 50% of the tim e.
R efinem ent
R efinem ent w as begun using th e block diagonal approxim ation to th e le a s t
squares, m ethod (I) and phasing one half a m ethoxy carbon in each of the p o s­
sible positions suggested by the F o u rie r m ap.
C alculation of bond lengths
re v e ale d th a t the bonds w ere long on one side of the rin g and sh o rt on the o th er. .
The atom s on a line through the c e n te r of th e m olecule, including th e P (2),
41
0(13), 0(14), 0(5), 0 (7 ), and C (10), ap p eared to be s M fted along th e b axis.
TM s w as suggestive of som e re s tric tio n im posed by the sp ace group wMch
proh ib it atom s being located along the line bisecting the rin g .
Upon ex am in a­
tio n of the m o lecule, it w as evident th at the m olecule could be p laced on a m i r ­
r o r plane w ith the m ethoxy carbon atom located on e ith e r side of the m ir r o r
50% of the tim e .
P lacing the m olecule on the m ir r o r plane allow s it to be
placed in a unit c e ll of sy m m etry Pnm a ra th e r than the n o n -c e n tro sy m m etric
space group P n 2 ia .
F u rth e r refin em en t of the non-hydrogen atom s in sp ace group Pnm a
along w ith a n iso tro p ic te m p e ra tu re fa c to rs was c a rrie d out using the full m a trix
le a s t sq u a re s (9). An R of 0.086 and Rwtd °£ 0.083 w ere obtained, w here
Rwtd - [Z](Jw|F o - F c D^/Z) (Vw !f 0 |)2 ] 2 and the function m im m ized during le a s t
sq u a re s refin em en t w as Z /w ( |F 0 | - l / k |F c | )2 .
A differen ce F o u rie r m ap was th en calcu lated to lo catio n hydrogen atom
p o sitio n s, in which the q u an tities | F 0- F c | w e re used as co efficien ts of F o u rie r
te r m s .
The m ap showed th a t many of the hydrogens w ere ap p aren tly d is ­
o rd e re d and could not be unam biguously reso lv ed .
TMs is probably the re s u lt
of the d is o rd e re d m ethoxy group p re sen tin g a num ber of d ifferen t p o ssib le
environm ents and s te r ic re q u ire m e n ts about any p a rtic u la r m olecule.
One hydrogen on each m ethyl carb o n w as found to re fin e w ith reaso n ab le
bond length, te m p e ra tu re fa c to r, and bond angle w ith re fe re n c e to the carbon
42
skeleton.
Using the re fin a b le hydrogen fo r a re fe re n c e , p o sitio n s of the r e ­
m aining m ethyl hydrogens w ere calculated.
gens w ere also calcu lated .
P ositions fo r the m ethylene hy d ro ­
Iso tro p ic te m p e ra tu re fa c to rs assig n ed to the
hydrogens w ere th o se of the carbon atom to w hich they w ere bonded, plus 0.5;
bond lengths w ere assig n ed as 1.00 A. R efinem ent w as then continued including
the calcu lated hydrogen p o sitions and assig n ed te m p e ra tu re fa c to rs , which w ere
not allow ed to v ary .
R efinem ent was" continued until the p a ra m e te r sh ifts fo r the non-hydrogen
atom s w e re le s s than half th e ir calcu lated stan d a rd dev iatio n s.
index is 0.059 and RwtfJ.equals 0,060.
fa c to rs a re lis te d in T able 10.
The final R -
The o bserved and c alcu lated s tru c tu re
The p o sitio n al p a ra m e te rs of the non-hydrogen
atom s a re lis te d in T able 11, the th e rm a l p a ra m e te rs fo r the non-hydrogen
atom s a re lis te d in Table 12, and the calcu lated hydrogen atom p a ra m e te rs a re
lis te d in T able 13.
D iscu ssio n of the s tru c tu re
The m olecule of 5- t -b u ty l-2 -m e th o x y -2 -o x o -l, 3 , 2-dioxaphosphorinane
w ith its th e rm a l ellip so id s is shown in F ig u re 9. The bond lengths a re liste d
in T able 14 and the bond angles in Table 15.
D iagram s of th e bond lengths and
bond angles a re shown in F ig u re 10.
The m olecules lie on a c ry sta llo g ra p h ic m ir r o r plane w ith the P (2),
43
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Wo V-
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* £ 2 : 2 : 2 5 2 2 = 3 = 2 2 »»
* £ » 2 2 *2 =: = » '
" " » " * 2 == 2 2 =
» ”
*£5 2 2 =='"=
'" *£=2==:'"=
2= 222=
Zej ^£::25:2=»"»="» -£:z«':z2«=2=32» ~£=;:??==:»2i="2' "
*£i:2::;22«"5*»
£»•
•"*”*"*" * *==—
2=2
............
2££'1 4
'S:-?ji££2'2
i
S:s=::s=== «=:i£i£
;
«z:==="::£:
' ; ’ sj£sj?£
.-'"■'2£i:s , ----- '===-; _^o-...O2.. , ^— ' =:=£
44
TABLE 11
P ositio n al p a ra m e te rs , of non-hydrogen atom s in
_5~t~butyl-2-m ethoxy-2-oxo-l, 3 , 2-dioxaphosphorinane.
Atom
x /a •
y /b
z /c
P(2)
O(I)
0(3)
0(13)
0(14)
0.0333 (4)a
-0.0519(7)
-0.0519(7)
. -0.1027(10)
0.2676(10)
0.2500(0)
0.3744(4)
0.1256(4)
0.2500(0)
0.2500(0)
0.0925(1)
0.0474(2)
0.0474(2)
0.1676(3)
0.1010(4)
0(4)
0(5)
0(6)
0(7)
0(8)
-0.2771(10)
' -0.3285(14)
■ -0.2771(10)
-0.2444(15)
-0.3308(13)
0.1268(6)
0.2500(0)
0.3732(6)
0.2500(0)
0.3738(7)
0.0207(4)
-0.0253(5)
0.0207(4)
-0.1076(6)
-0.1513(4)
0.1262(7)
0.2500(0)
0.3519(14)
0.1481(14)
-0.1513(4)
-0.1143 (5)
0.2234(7)
0.2234(7)
0(9)
0(10)
C (H )
0(12)
-0.3308(13)
0.0040(17)
-0.0850(30)
-0.0850(30)
aThe num ber in p a re n th e se s is the stan d ard deviation and
r e f e r s to the le a s t significant d ig its.
45
TABLE 12
T h e rm a l p a ra m e te rs of non-hydrogen, atom s in
5 - t - butyl -2 -m ethqxy -2 -oxo - 1, 3 ,2 -dioxaphosphorinane.
Atom
P(2)
O(I)
0(3)
0(13)
0(14)
$ l i a ’k
022
225 (7)c
94(3)
280(11)
51(3)
280(11)
51(3)
280(19) ■ ■ 124(7)
' 208(17)
185(8)
033
012
013
023
23(1)
29(1)
29(1).
25(2)
37(2)
0(0)
-2(5)
2(5)
0(0)
0(0)
10(2)
-3(3)
-3(3)
27(5)
-12(5)
0(0)
1(1)
-1(1)
0(0)
0(0)
12(3)
0(0)
. -12(3)
'
0(0)
14(4)
0(4)
0(5)
0(6)
C(7)
0(8)
262(19)
144(21)
262(19)
245(25)
501(25)
. 83(7)
. 114(10)
83(7)
99(10)
117(8)
32(2)
31(3)
32(2)
37(4)
42(2)
-38(9)
0(0)
38(9)
0(0)
-3(13)
-5(5)
11(7)
-5(5)
-19(8)
-28(7)
0(9)
0(10)
0(11)
0(12)
501(25)
369(36)
749(64)
749(64)
117(8)
209(14)
127(15)
127(15)
42(2)
28(3)
31(4)
31(4)
3(13)
0(0)
15(29)
-15(29)
-28(7)
46(9)
61(15)
61(15)
-14(4)
0(0)
-21(7)
21(7)
aThe jSjjtg have been m ultiplied by 10^.
^The e x p re ssio n fo r the an iso tro p ic th e rm a l p a ra m e te rs is of the form :
cThe num ber in p a re n th e se s is th e sta n d a rd deviation and r e f e r s to the
le a s t significant d ig its.
46
TABLE 13
C alculated hydrogen positional p a ra m e te rs and
assig n ed th e rm a l p a ra m e te rs in
5 - t -b u ty l- 2 -m ethoxy- 2 -oxo- 1 , 3, 2-dioxaphosphorinane.
z /c
Atom
x/a'
H(I)
-0.268
0.468
H (2)
.-0 .3 9 1
0.406
H (3)
-0.503
0.250
-0.030
4.0
H (4)
-0^266
0.380
-0.207
6.4
H (5)
-0.292
0.457
-0.121
6.4 ■
H (6)
-0.496
0.368
-0.153
6.4
H(7)
0.065
0.349 .
-0.094
5 .8 .
H (8)
0.050
. 0.250
-0.168
5.8
H(9)
-0.099
0.306
0.267
5.6
H(IO)
-0.193
0.424.
0.216
5.6
H (Il)
0.069
0.394
0.220
5.6
. y /b
-0.009
0.057 '
B iso
'
4.3
4.3
47
Disordered
methoxy group
F ig u re 9.
M olecular s tru c tu re of
5 -t-b u ty l- 2 -m e th o x y -2 -o x o -l, 3 , 2-dioxaphosphorinane
illu stra tin g the th e rm a l e llip so id s.
48
TABLE 14
Bond d istan ces in
5 -t-b u ty l-2 -m e th o x y -2 -o x o -l, 3 , 2-dioxaphosphorinane.
Bond
d is ta n c e , A
Bond
d ista n ce , A
C(4)-C(5)
1.510(8)
' 1.568(4)
C(S)-C(G)
1.510(8)
P (2)-O (13)
1.567(6)
C(5)-C(7)
1.542(13)
P(2)-0(14)
1.443(6)
C(?)-C (8)
1.553(9)
O(I)-C(G)
1.457(7)
C (T)-C (9)
1.553(9)
O(S)-C (4)
1.457(7)
C (7)-C (10)
1.525(14)
O(IS)-C (11)
1.422(14)
P(Z)-O(I)
P(Z)-O(S)
1.568(4)a
a The num ber in p a re n th e se s is the stan d a rd deviation and re fe rs ,
to the le a s t significant digits.
49
TABLE 15
Bond angles in
5-t-butyl-2-methoxy-2-TOxo-l, 3 ,2-dioxaphosphorinane.
A tom s
angle, d e g re es
Atoms
angle, d e g re es
0 (l)-P (2 )-0 (3 )
105.3 (2)a
C (4)-C(5)-C(6)
109.6(6)
0 (1 )-P (2 )-0 (1 3 )
104.6(3) '
C(4)-C(5)-C(7)
115.9(6)
0 (1 )-P (2 )-0 (1 4 )
.112.6(3)
C(6)-C(5)-C(7)
115.9(6)
0 (3 )-P (2 )-0 (1 3 )
104.6(3)
O(I)-C(G)-C(S)
112.2(5)
0 (3 )-P (2 )-0 (1 4 )
112.6(3)
C (S)-C(Z)-C (8)
H O .Z (6)
O (IS )-P (2)-O (14)
116.1(3)
C (S)-C (Z)-C (9)
H O .Z (6)
P (2 )-0 (l)-C (6 )
118.2(4)
C(S)-C (Z)-C(IO)
114.0(6)
P (2 )-0 (3 )-C (4)
118.2(4)
C(S)-C(Z)-C (9)
106.0(6)
P (2)-0(13)-C (H)
123.1(7)
C(S)-C(Z)-C(IO)
10Z.5 (6)
0(3)-C(4)-C(5).
112.2(5)
C (9)-C (Z)-C (10)
10Z.5(6)
a The num ber in p a re n th e se s is the stan d a rd deviation and r e f e r s to the le a s t
significant d igits.
50
1.457(7)
1T
1.510181
^
1.5251181^
1.582(131^
0 -----(a)—- ( o f
/
V
1.553191
1.368(81
] 5)0(81
1.457(7)
(6
^
0 1-P 2-018 112,6(31
02 -P2 - 013 108.6(31
_(M^
i»-«
1.883(61
%
O -C7-C10 118.0161
C8-C7-C9 106.0(61
F ig u re 10.
Bond d istan ces and bond angles of
5 -t-b u ty l-2 -m c th o x y -2 -o x o -l, 3 , 2-dioxaphosphorinane.
51
0(13), 0(14), 0(5), 0(7), and 0(8) atom s located on the m ir r o r in the sp ecial
positions y = 1 /4 and 3 /4 .
The m ethoxy carb o n 0(11), is found on e ith e r side
of the m ir r o r 50% of the tim e .
The m ir r o r re q u ire s th at th e bond lengths and
bond angles a re equal a c ro s s the m ir r o r plane.
The rin g is a d is to rte d c h a ir w ith th e t -butyl and m ethoxy groups tra n s
to each other in axial p o sitio n s.
D ihedral angles betw een the rin g plane 0(1),
0(3), 0(4), 0(6), and planes 0(1), P (2), 0(3), and 0(4), 0(5), 0(6), a re 37.9
and 49.9° re sp ec tiv e ly .' The angles show a flattening of the rin g as co m p ared
w ith 60° fo r an ideal c h a ir.
The equations of the planes a re liste d in Table 16.
The to rsio n a l angles around the bonds of th e rin g a re given in T able 17.
The
to rsio n a l angle about a bond is the d ih ed ral angle betw een th e plan es defined by
the two atom s involved in the bond plus the adjacent atom bonded on e ith e r end
of the bond; e .g . , the to rs io n a l angle about the P (2 )-0 (l) bond is the d ih ed ral
angle betw een the plan es 0(3), P (2), 0(1) and P(2), 0(1), 0 (6).
T hese valu es
show th a t the flattening of the rin g is m ostly on th e phosphate end, w ith all
other to rs io n a l angles n e a r those expected fo r an ideal c h a ir.
M ore is said
about the rin g conform ation la te r in th e sectio n com paring th e I , 3 , 2 -d io x aphosphorinanes on page 100.
P -O bond d ista n ce s a re 1.568 fo r the rin g bonds.
P (2 )-0 (l) o r P(2)-
0(3), and 1.567 A fo r the phosphorus to m ethoxy bond, P (2 )-0 (1 3 ), and m u st be
co n sid ered equal.
The P=O bond of 1.44 A is norm al fo r te r tia r y o rgano-
52
TABLE 16
• Equations o f.p la n e s fo r
5 -t-butyl-^2 -m ethoxy-2 -o x o -1 ,3 , 2 -dioxaphospIiorinanea
A tom s in plane
I
m
n
d
0(1), 0 (3 ), 0(4), 0(6)
-0.323 .
0.000
0.946
0.894
P(2), 0 (1 ), 0(3)
-0.836
0.000
0.548
0.725
0(4), 0(5), 0(6)
-0.932
0.000
0.362
1.714
a Equations of the plane:
hi +
m y + nz - d - 0„0
53
TABLE 17
T o rsio n a l angles in the rin g fo r
5 - t -b u ty l- 2 -m ethoxy-2 -oxo- 1 , 3 ,2 -clioxaphosphorinane „
Bond
T o rsio n a l angle, d e g re es
P (2 )-0 (l)
44.1
O(I)-C(G)
53.4
C(G)-C(S)
55.7
C (S)-C (4)
55.7
C (4)-0(3)
53.4
0(3)-P (2)
44.1
54
phosphate e s te r s .
Bonding around the phosphorus fo rm s a slig h tly d isto rte d
te tra h e d ro n w ith angles ranging fro m 104.6 to 116.1°.
The sum of the P-O
bonds and the P=rO bond is 6.15; m o st o rgano-phosphate e s te r s have sum s
betw een 6.13 and 6.23 A.
C -O bond d ista n c e s in the rin g of 1.46 a re n o rm al values fo r phosphate
e s te r s .
The C-O bond of the m ethoxy group is som ew hat s h o rte r, 1,42 A, th an
th o se in the rin g .
m ay be significant.
T his d istan ce is of the o rd e r of 3 -4 stan d a rd deviations and
P -O -C bonds in the rin g a re 118°.
The P -O -C bond angle
fo r the m ethoxy group is 123° w hich is la r g e r th an th e usual 120°, probably
becau se of s te r ic re p u lsio n s betw een the m ethyl and 0(14) and 0(1) or 0(3).
C-C bonds in the rin g a re 1.51 A and the C-C bonds in the t-b u ty l group
ran g e fro m 1.53 to 1.55 A.
The C (4)-C(5)-C(6) bond angle in the rin g is 109.6°,
a n early p e rfe c t te tra h e d r a l angle.
The C -C -C bond angles of th e t-b u ty l group
ran g e fro m 106.0 to 114.0°; the la rg e s t angle C(5)-C(7)-C (10) is probably due
to s te r ic re p u lsio n s of the C(IO) m ethyl w ith 0(1), 0(3), and 0(14).
The d is o rd e re d m ethoxy group, C (Il) o r C (12), is shown in a Newman
p ro je c tio n along the P (2)-O (14) bond in F ig u re I l (a) and (b).
The m ethyl is
sta g g e re d and 6.7° c lo s e r to the 0(14) atom th an the rin g oxygen.
This a g re e s
c lo sely w ith the values found fo r the 2 -o x o -2 -p h en o x y -l, 3 , 2-d io x ap h o sp h o rinane s tru c tu re shown in F ig u re 11(c).
The packing d ia g ra m for the c ry s ta l is shown in the ste re o g ra p h ic
55
0(3)
0 (3)
c(12)
110.6
110.6
124.7
0 ( 13)
124.7
0 ( 14)
0 ( 14)
C (Il)
0(13)
F ig u re 11.
Newman p ro je c tio n s looking down the P(2)-0(13) bond for;
(a) and (b) the two p o ssib le configurations fo r
5 -t-b u ty l-2 -m e th o x y -2 -o x o -l, 3 , 2-dioxaphosphorinane and
(c) 2 -o x o -2 -p h en o x y -l, 3 , 2-dioxaphosphorinane.
56
diagram , in F ig u re 12.
Packing conditions a re not likely to be an im portant
fa c to r in th e conform ation of the m olecule sin ce th e re a re no in te rm o le c u la r
d ista n ce s le s s than the sum of the van d e r W aals ra d ii.
V alues of the van d e r
W aals ra d ii w e re obtained fro m Bondi (8 ), and the p e rtin e n t ra d ii used w e r e :
P , 1.80; 0 , 1.52; C j 1.70; and Hj . 1.20 A 0
57
F ig u re 12.
S tereograp h ic packing d iag ram of
5 -t-b u ty l-2 -m e th o x y -2 -o x o -l, 3, 2-dioxaphosphorinane
with both the d iso rd e re d methoxy carbon atom s draw n.
THE CRYSTAL AND MOLECULAR STRUCTURE OF
5 -t-B U T Y L -2 -P H E N Y L -2 -T H IO -l, 3, 2-DIOXAPHOSPHORINANE (C1 3 PSO 2 H ig)
P re p a ra tio n
The c ry s ta ls w ere supplied by W esley G. B entrude and w ere la rg e ,
c o lo rle s s , tra n s p a re n t, and need le-sh ap ed in ap p earan ce.
The dim ensions of the c ry s ta l used fo r X -ra y a n aly sis w ere ap p ro x im at­
ely 0.2 x 0.3 x 0.4 m m .
D ensity
The density of the c ry s ta ls w as m e a su re d by the flo tatio n method as
d e sc rib e d in P a r t I, page 5.
The calcu lated density w as b ased on four m o le ­
c u les p e r unit c ell: Dexp = 1.277 g /c m 3 and Dca^c = 1.275 g /c m 3.
D e term in atio n of ten tativ e c ell dim ensions and space group
W eissen b erg photographs of th e X -ra y d iffractio n p a tte rn fo r the c ry s ta l
C i 3 PSO 2 H13, indicated m onoclinic sy m m e try .
ta l w as m ounted w as designated as a.
The axis along which the c r y s ­
The ten tativ e unit c e ll dim ensions w ere
found to be a = 11.30, b = 6.17, and c = 21.17 A. A unit c e ll of th e se dim ensions
would re q u ire fo u r m olecules to ag ree w ith its m e asu re d d en sity .
tio n s based on th is cell w ere:
The ex tin c ­
. 59
hie A: no conditions
IiOi.: i ^ 2n
OkO: k ^ 2n.
T hese extinctions c o rre sp o n d to the sp ace group P2]_/c w ith the b axis unique.
H ow ever, P 2 i/ n w as found to be the space group.w ith the s m a lle s t
angle.
D eterm in atio n of a c c u ra te unit cell dim ensions
The d e term in a tio n of a cc u ra te c e ll p a ra m e te rs w as obtained by the sam e
p ro c e d u re used in P a rt I, page
6,
T w enty-one th re e -d im e n sio n a l re fle c tio n s
w ere se le c te d fo r w hich p re c is e m e a su re m e n ts of the +29 and
m ade.
-2 0
angles w ere
The c ry s ta l d ata a re liste d in Table 18.
D ata collection
D ata w e re co llected on the G eneral E le c tric XRD-5 D iffrac to m e te r
equipped w ith a scin tilla tio n coun ter, p u lse-h eig h t d is c rim in a to r, and G. E.
single c ry s ta l o rie n te r, using 9-29 scan technique and zirco n iu m filte re d m o ly ­
bdenum Kq/ ra d ia tio n .
spindle ax is.
The c ry s ta l w as m ounted w ith th e a axis p a ra lle l to the
E ach peak w as scanned fo r 60 seconds and the backgrounds on
each side of the peak w e re counted fo r
to speed d ata collection.
10
seconds and la te r m u ltip lied by th re e
A c h a rt re c o rd in g of peak in ten sity vs_. 29 was
m on ito red during the data collectio n as a check on the c en te rin g of the peak in
th e sca n ran g e and fo r g e n e ra l ap p earan ce of the peak and backgrounds.
sc a n ra te w as 2° p e r m inute w ith a takeoff angle of 4°.
The
60
Table 18
C ry sta l D ata
5 -t-b u ty l-2 -p h e n y l-2 -th io -l, 3, 2 -d ioxaphosphorinane
C 1 3 PSOBHig-
F „ W„ 270.31
F(OOO) = 572
M onoclinic, Space Group P g l/n
a = - 6.150(2)
c = 20.823(5)
Volume of th e unit c e ll = 1408.
M o lecu les/u n it c e ll = 4
. Dexp = 1.277 g /c m 3
• D calc = 1-275 g /c m 3
■
= 95.17(2)
X
Il
to
O
O
b = 11.036(3)
Cf. = 90°
61
In te n sitie s of 1842 unique re fle c tio n s w ere m e a su re d of which 1259 w ere
c o n sid e re d o b serv ed , using th e c rite rio n 15=2 0 (1). T h re e stan d a rd re fle c tio n s
(the 116, 132, and 115 re fle c tio n s) w ere checked approxim ately ev ery hour
during data co llectio n and re m a in ed constant w ith an av erag e deviation of
1 . 6 %,
indicating no d e te rio ra tio n of the c ry s ta l.
S tru ctu re fa c to rs , (F0), w ere calcu lated fro m the in te n sitie s by applying
the u sual L o re n tz -p o la riz a tio n c o rre c tio n , w eights w ere c alcu lated from sta n ­
d a rd deviations as was d e sc rib e d in P a r t I, page 7.
No ab so rp tio n o r extinction c o rre c tio n s w ere m ade.
The lin e a r a b so rp ­
tio n coefficient of C^gPSC^H ig fo r MoKa ra d ia tio n (X = 0.71069 A) is jU= 3.29
Cm- "*". The tra n s m is s io n fa c to rs fo r X -ra y s p assin g th ro u g h th e m axim um and
m inim um .dim ensions of the c ry s ta l a re approxim ately 0.83' and 0.93 re s p e c ti­
vely; th is ran g e c o rre sp o n d s to approxim ately 6 % v a ria tio n about a m ean in te n ­
sity value.
S catterin g fa c to rs fo r the non-hydrogen atom s and anom alous
s c a tte rin g c o rre c tio n s (A f and A f") fo r phosphorus and su lfu r w e re taken fro m
th e In tern atio n al T ab les (12).
S catterin g fa c to rs fo r hydrogen w ere tak en fro m
Stew ard, e t. a l. (20).
S tru ctu re d e term in a tio n
The s tru c tu re w as solved in th e sp ace group P2]_/n.
The positio n s of
th e phosphorus and su lfu r atom s w ere found using the P a tte rs o n sy n th esis (2).
62
U sing the phosphorus and su lfu r atom p o sitio n s, the s tru c tu re fa c to r calcu latio n
(9) gave an R -index of 0.45.
A F o u rie r m ap (2) re v e ale d the positions of the
rem ain in g non-hydrogen atom s.
R efinem ent
R efinem ent w as begun using th e full m a trix le a s t s q u a re s m ethod of
re fin e m e n t (9) w ith the R -in d ex equal to 0.26 fo r the non-hydrogen s tru c tu re
along w ith iso tro p ic te m p e ra tu re fa c to rs and a unit w eighting schem e.
th re e cy cles of refin em en t, the R -in d ex dropped to 0.098.
A fter
The te m p e ra tu re
fa c to rs w ere then converted to an iso tro p ic and the w eighting schem e to th a t of
Stout and Jen se n .
In th re e cy cles the R -in d ex dropped to 0.081 w ith a w eighted
R -in d ex , (Rw^d), of 0.089.
A d ifferen ce F o u rie r m ap (2) w as th en calcu lated to lo cate hydrogen
atom p o sitio n s.
T h irte e n of the n in eteen hydrogens w e re lo cated fro m the m ap
and the s tru c tu re re fin e d to an R - 0.039 and Rwt^ = 0-034.
A subsequent d if­
fe re n c e F o u rie r m ap w as calcu lated and the rem ain in g hydrogens w ere lo cated .
R efinem ent of the com plete s tru c tu re w as then continued until the sh ifts
in the p a ra m e te rs w ere le s s than one half of th e ir stan d a rd deviations.
fin al re fin e m e n t gave an R of 0.036 and Rw^ °£ 0.031.
la te d s tru c tu re fa c to rs a re lis te d in T able 19.
The
The o b serv ed and c a lc u ­
The p o sitio n al p a ra m e te rs of th e
non-hydrogen atom s a re lis te d in T able 20, the th e rm a l p a ra m e te rs fo r the
63
.2 2
<V*2222~ ''Si-*" °?22C%2 -%2S222"2
o«.
" U* - * -
"2"
.2 2
“ £ ’■’2 2 2 2 “ * 2 Z » »
J
22222'*
___ _____________
“ £22222
s
f
*£«2*'25*22 »£""212222" "£
____________
'£ ='
2" “£22222'""'** «£"=':Z222 “£**22"222* “£
22 I-"4*'"*""*222 ‘
2*2' -£2122-2222
2*2" “£2222"22*2
Or--TO^ )
-0 -2 - 2 '"
°£52"222
• = '22 ""
—;
______________
i
"£22"Z2: -£=2"S:2S "£""22'2Z2"»2 “£222*
“ £2S":22
“£22"52S2
“ £*
] -I —r.
‘
I -> —
" £ 22 " 22* " 2 *2?2 2
22*
“ £
22" 2: 2""2
“ £
222*
"2222
" £ " 2 2 2 =S *22
'£ £ " 2=222222
“£"322=2*22
“£5-2=22=222
'3 -2 3 2 2
" £ 2 2 2 '" ''3 * 2 2 2 5 2 - 2 2 2
-£ 3 3 :2 '2 3 2 " % := '* " = '"
'£ 2 ;* 3 2 := '2 "
- £ 5 5 2 2 2 * 5 2 " '= ;" '
* £ :* = 3 '2 " '
"£52-22
^ £52=2"*2-22222"222
“£ 3 2 3 5 '2 3 2 " 5 :'2 -
“ £ 2 .7 " 2____
* 2 5 '-' " "
“£ 2 5 S S ;* 5 :""2 2 "'
“ £ 7 * 2 3 2 2 '-
“ £ = 2 '2 2
I •" ‘" - ' - * " • • ' = 2 2 * 2 2 2 5
j - J- - * - * " - ' 2 2 2 2 2 2 2 2 2 5
i"
! J -""*-*222222
I - ' - " - * • ' " • • ‘2 2 2 2 2 2
i
;! J - * - * " ' 2 2
' J-
*2*"
"£ '= "2 2 = 2 5 2
2"-
w£'2-==225222I-'-"-*-*"-'222
2222
O b served and c a lc u la ted str u c tu r e fa c t o r s .
2£2~
'" “£=- “£Z2"2Z2 “£22'2-2222 I-*-- ijN**-22
>
-22 .^-"*-22222
2= ‘-•-"*‘•‘»•••832
TA BL E 19
“ £ 2 S 1 2 2 e 2 “ £ H2 <,r*2 “ £ 22 '* '-
- ;
-£2*= 22232"'
' £ 5 2 ” ' 2 2 2 Z2 ° £ " Z 2 '
=£"2"
0£ '= = '5 $ = -
“£:-222222":
7 O-
“252"
22222 “£"=:'
“£"2-
“ £ ' 3 S ' 3 ; =2 “ £ 2 2 " =; " ; - 2 2 * 3 2 5 * ; ^ 2 '
h
I-
"22222
i
5 ? 3 '5 5 * 2 2 2 '2 '
"£ 2 ;"2 5 * 2 2 2 S 5 ;2 "
- £ "2 2 ;2 2 2 5 5222;*-*»2
* £ 2 2 5 2 2 " '2 '2 "
5 5 5 '5 5 e222-2-
“ £ 2 '* 2 2 " 5 2 2 2 3 2 2 "
7 O-
“£ " 2 2 ;:2 5 3 5 2 2 2 2 * " - '2
: £ S 2 2 2 2 * 2 2 '2 "
'5 2 2 2 2 3 2 2 2 5 =
-£ 2 K -2 % :* :* Z 5 * g ;S « ;-
• '2 2 2 2 ; 2 2 2 2 2 5
*£ = = ■_2 2 2 = 2 ; ' 2
“ £23232=2
“£=5 : 2 2 2 5 ; ; ' ;
• ' 222; 2222=
= :5 2 :::-:2 :* 2
" £ 2 S = 2 3 2 2 '~ * 2 -
-£S -= "= -= ;*=
'£ = = 2 " -2 * -2 2
2 £ * = 2 Z ::"
=£22=2
0£S = -:-3 = 5
:': 3 2 ; ;
= 2 £ '2 2 2 '2 2 2 " 2
“ £22 = 2 3 2 = 2 "";"
“ £ = * 2 'S " = ;* 2
“£222*"*""22
“£ * 2 2 2 2 '- -
“£2222
“ £22“ 3-252
»£“ : : a ; *
"Z2;Z222
-S3*"
'22222
£5 = 3 7 = ' 3 ' 5 ' 5
=*-
“£ :2 3 2 2 " :* 5 - 5 -'2 '" 2 '
22252
!■ " * - '- * " - '2 2 2 2 2 2 2 2 2 5 =
*5
I-
" : " ' 2 “ ' ' £ 2 5 5 5 5 ; ; L -' 5 2 2 - 5 = 2 “ £5S = ? 5 2 2 2 e 5 2 2 - =S 2 -
‘•
-£*=2=2*"'=Z=23-;-*"
“£ -;:= :-2 = 3 = 2 * 2 = 5 "
“ £ -= 2 2 S ;*
• '2 2 ; 2 2 2 2 5 =
“£ 2 -'-;-2 "
“£"**2"2
“£Z*Z2;"
“£"22'
“£""'
“£'
i-
'Z Z = ;2 2 2 2 5
*2 '£22'*;'2* -£"*22"2 *£2-222" "£"2" °£"-- "£"
'2
22*22
'£ -2 3 3 5 * 2 2 3 2 2 * 2 5 2 "
-£53:;3:2==5:;£
“£"2
“ 2222
“£=-
“£2=55=5-"
-£2=25=55=22225
i
,
*£2*2*2
- £ " " 22"*2
* £2 * " 2 »"
"£'"**"=""
*£2222"
' £ =' 2
°£222
-£ " =' 5 " 2 '-
" £ .2 2 * * 5 2 '-
"£2"2*2*
“£2*2"2
«
“£ ""* 2 '-2
«
<
loo.P.MN..
<
,
=
1=2 0 ,
,
:=«:«
<X
1£- =' 5 - 2 2 *
,
“£22""52'*
“£'"2*2*
<r
"222
"£"2222*22""
"£ "* = -:=
'£ 5 * 2 * 2 2
2£2"""*
°£?*7S*2
"‘£ 3 2 3 2 ' 2 3 2 '
"£22= ;222= = "2
" £=5e2 " * 2 '2 * 2
"2 :2
“£"2222*22**
“£ ""= * = :
“£222*22
“£ 2 " " '*
“£ :"::* 2
“ £ 3 2 5 2 '2 3 2 2
“£2233222=="2
“£=3"2""2"2"2
i
22*2
;
;:2':;z*: -£==25";2-»;2 *£=*:'*
; '= 2
-£ = " 2 2 :2 2 '5 = 2 2 2 2
"£ 2 5 = 2 “= 2 '2 "
-£ 2 " 2 5 " = 2 3 '5 :* '2
*£;"= "
72=2
“£2225232-5=222'
“ £ 3 3 5 2 " = 2 '2 "
“ £ 2 2 ? 2 '3 2 2 -S 2 2 2 2
“ £2-=* ■222*222-2
2222
. --e - Nm< » , » » 0 - 2 2 2
-*"2222
. -,° - " ' ,- * ' 2 2 2 2 2 2 2
“£5225"22*-22
“ £3*22"
=
I
-£3225333*2*22"
*£;==5S52222=2='
"£ 3 3 = 2 * = 5 ;;2 2 -2 :
-£ -:"Z ""
'£ '2 -- 2 2 2 2
2 £ * 2 '" 2
Z £ '* '
*£225
“ £ S 2 2 5 5 5 5 " 2 " ;'*
“ £ ;= = = = 2 '2 2 2 3 2 = "
“ £ = = = 2 = = ';2 2 2 " :
“£"2-2"-
“£ " 2 " -:2 z ;
“£ " 2 '* 2
“£ '" 2
f £525
I
i
I
i
£2*
° £ = ' 5 £ 2 2 * =2 '
" £ 2 7* 5 5 S 2 " ' 2 2 * 2 = 3 ' 5 2
" £ 2 2 3 = 7 2 2 ; =22* =2 =2 " £2 = 5 2 = ' 2 2 5 2 " - = 2 2 '
' £ 2 ' 5 ? 5 22 2 2 5 12"*
£2"
“£-'=?22"22"
“£25":232"-22-2=2'S2
“£3:327:=2322'=222
“£2=522"22=2*-=22-
“£2'5552=;2322"-
,-=**-222225
.-,0-" * -* " '2 2 2 2 2 2 2 2 :S
, -O-*--** - - » 2 2 2 2 2 2 '
. •'°-"-*--'2222222'
I.
'
222222
53:22"
-£ "5 2 =:3 :;::2 2 2 :
*£S = 2 ; " 2 2 5 S 2 2 n "
" £ 2 = ' : 2 : 2 = ' ’" * "
"£*"223222'223
'£"2*2:":2"
=-*•==* :
5 3 :22"
^£ * 2 2 3 :3 2 5 7 2 :2 :
“£ 3 2 2 2 "3 2 2 ;2 5 3 -=
“ £2= "= 2;= 2*
“£"-225222-2;3
“£'2*:2":2*
“£"32'" “
'22225
I
"*•'222
22 ."*""22 .
'2"**" ®£2?5322::S= -£2-2S5 =2 ' =22-22252 "£255325*222 2222 2-22" -£555"535 ="5 ="22e «* *£223":: =:
2-"2"- “£2;S552:: =5 “£2*2S' =='222*2f252 “£75:Z:=*2222222 2-22" “£555*5255 *53"22""" “£'Z3'=:35
-"*-*" , - - - - '2 2 2 :2 = . -,0-"--*"-222;2222S . -JO- " - * - * " -'22222222= . " * " * ' 2 2 2 2 2 2 5 = :
"22*"
-£525=222=25=2
"£2"2=222;22"2"2*2
"£'""225;*=;*2*
*£3*-S-2S222"
'£22=23*
2£2=*Z222
Z£
"22*'
“ £525 =25 ==SS=2
“£2"2=2'272-*2"2"2
“£*2'*2222-=;==-
“£="-5*23222*
“£'==2S*
“£5="2222
“£
"2=222:2:2
*£2,222522
-£ 3 2 -522
' 222 =; " "
" £ ; =53 = ' ' 3 5 : - 3 2 * ; ; = ; = 2 -
“£5:22222*
“£ 5 2 "2 2 2 3 2 ";= = 2 ;-"
“£ o 2 |= = '3 5 ;-22-225222*
'
22
: : ; 2: : 5=
''£ 2 2 5 5 g 3 S 2 2 25 2 " = 2 ' " "
* £ ' * 2 = 52 = « ' 2 2 7 =
“£ :5 = :? 2 :5 :2 ::" = 2 '" * ;
“£ 2 ':= 2 2 = = * 2 ::5
'2=2:2:2225=
64
TABLE 20
P o sitio n al p a ra m e te rs of non-hydrogen atom s in
5 -t- b u ty l-2 -p h e n y l-2 -th io -l, 3, 2-dioxaphosphorinane.
Atom
x /a
.y /b
z /c
S (17)
P(2)
O(I)
0(3)
0(4)
0.1624(2)a
-0.0519(2)
-0.2672(3)
0.0341(3)
-0.1275(6)
0.0733(1)
0.1819(1)
0.1156(2)
0.2511(2)
0.3098(4)
0.1378(1)
0.0984(1)
0.0707(1)
0.0388(1)
-0.0059(2)
0(5)
0(6)
0(7)
0(8)
0(9)
-0.3012(6)
-0.4193(6)
-0.4550(6)
-0.6460(8)
-0.5479(10)
0.2222(3)
0.1751(4)
0.2758(3)
0.1883(2)
0.3990(4)
-0.0325(2)
0.0227(2)
-0.0883(2)
-0.1051(2)
-0.0708(3)
0(10)
C (Il)
0(12)
0(13)
0(14)
-0.3285(9)
-0.1353(5)
-0.3329(6)
-0.3868(7)
-0.2452(9)
0.2894(5)
0.2979(3)
0.2896(4)
0.3752(4)
0.4666(5)
-0.1480(2)
0.1518(2)
0.1788(2)
0.2235(2)
0.2412(2)
0(15)
0(16)
-0.0482(8)
' 0.0035(7)
0.4760(4)
0.3917(4)
0.2149(2)
0.1701(2)
;
a The num ber in p a re n th e se s is the stan d ard d eviation and
r e f e r s to the le a s t significant d ig its.
65
non-hydrogen atom s a re lis te d in T able 21, and the hydrogen atom p a ra m e te rs
a re lis te d in T able 22.
D iscu ssio n of the s tru c tu re
The m olecule of 5 -t-b u ty l-2 -p h e n y l-2 ~ th io -l, 3 , 2-dioxaphosphorinane
w ith its th e rm a l ellip so id s (13) is shown in F ig u re 13.
lis te d in T able 23 and bond angles in T able 24.
The bond lengths a re .
D iagram s of the m olecule
showing bond lengths and angles a re shown in F ig u re 14.
All atom s in the m olecule lie in g e n e ra l p o sitio n s.
The rin g is a d is ­
to rte d c h a ir w ith the t-b u ty l and phenyl groups cis to each o th e r on the rin g .
The t-b u ty l is e q u a to ria l and the phenyl axial.
The d ih e d ra l angles betw een the
b e st le a s t sq u a re s plane through th e 0(1), 0(3), C (4), 0(6) plane and the plan es
0(1), P (2), 0(3) and 0 (4 ), 0(5), 0(6) a re 49.5 and 30.5° re sp e c tiv e ly , as com ­
p a re d to 60° fo r an ideal c h a ir.
25.
The equations of the p lan es a re liste d in T able
The to rs io n a l angles fo r the rin g bonds a re given in T able 26.
Both the d i­
h e d ra l and to rs io n a l angles show th a t m o st of the rin g d is to rtio n is on the p h o s­
phate end of the rin g .
The aliph atic end of the rin g has to rs io n a l angles n ear
th o se n orm ally o c cu rrin g in six -m e m b e re d rin g s.
M ore is said about the con­
fo rm atio n la te r in the sectio n com paring th e 1 , 3 , 2-dioxaphosphorinanes on
page
100.
The m ir r o r sy m m etry of the m olecule is broken by th e phenyl ring. The
66
TABLE 21
T h e rm a l p a ra m e te rs of non-hydrogen atom s in
5 - t -butyl -2 -phe nyI -2 -th io -1 , 3 , 2-dioxaphosphorinane.
Atom
jSna ’ b
022
033
012
013
023
S (17)
P(2)
O(I)
0(3)
0(4)
■291(4)°
208(3)
237 (8)
198(7)
240(13)
97(1)
73(1)
70(2)
90(3)
78(4)
31(1)
20(1)
22(1)
20(1)
22(1)
51(2)
8(2)
-15(3)
2(3)
-1(7)
2(1)
9(1)
5(2)
13(2)
19(3)
1 1 (1 )
0(5)
0(6)
0(7)
0(8)
0(9)
255(12)
222(12)
290(13)
396(19)
409(20)
56(4)
80(4)
73(4)
119(6)
87(5)
19(1)
24(1)
17(1)
24(1)
26(2)
13(6)
-15(7) .
22(6)
.
-4(9)
53(9)
18(3)
4(3)
6(3)
-29(4)
-13(5)
-2(2)
4(2)
-2(2)
-9(3)
-1(2)
131(7)
76(4)
89(5)
130(5)
113 (6 )
23(1)
17(1)
21(1)
20(1)
15(1)
13(6)
. -8(7)
28(8)
59(9)
96(5)
97(5)
24(1)
23(1)
-28(8)
-6(7)
0 (1 0 )
0(11)
0(12)
0(13)
0(14)
485(23)
198(12)
' 244(14)
301(16)
498(21)
0(15)
0(16)
452(19)
247 (15)
.
1 1 (1 1 )
.
14(4)
2(3)
6(3)
18(4)
5(4) .
1(4)
9(4)
5(1)
7(1)
8(1)
9(2)
8(3)
8(2)
3(2)
3(2)
-3(2)
-7(2)
5(2)
a The /3pjts have been m ultiplied by IO^.
^The e x p re ssio n fo r the an iso tro p ic .th erm al p a ra m e te rs is of the fo rm
exp (-/Siih2-/S22k2 -633 -&2-jSl2hk-Sl3h£-/S23lc^)„
c The. num ber in p a re n th e se s is the stan d a rd deviation and r e f e r s to the
le a s t sig nificant d ig its.
67
, TABLE 22
H ydrogen atom p a ra m e te rs in
5 -t- b u ty l-2 -p h e n y l-l-th io -l, 3 , 2-dioxaphosphorinane.
Atom
x /a
y /b
z /c
Biso
H(I)
H (2)
H (3)
H (4)
H (5)
-0.192 (4)a '
-0.047(4)
-0.228(3)
-0.498(4)
-0.517(4)
0;377(2)
0.344(2)
0.153(2)
0.241(2)
0.107(3)
0.016(1)
-0.036(1)
-0.048(1)
0.042(1)
0 . 1 1 2 (1 )
2.6(6)
3.0(6)
1.9(5)
3.6(7)
5.0(7)
H(6)
H(7)
H(8)
H(9)
H(IO)
-0.719(4)
-0.589(5)
-0.749(5)
-0.644(5)
-0.433(5)
0.215(3)
0.104(3)
0.180(3)
0.425(3)
0.456(3)
-0.142(1)
-0.116(2)
-0.067(2)
-0.103 0
-0.069(1)
4.8(7)
8.4(1.0)
8.3 (1.0)
6.2(8)
5.3(8)
H (Il)
H (12)
H (IS)'
H (14)
H (15)
-0.622(4)
-0.418(5)
-0.217(5)
-0.283(5)
-0.420(4)
0.394(3)
0.330(3)
0.346(3)
0.202(3)
0.224(2)
-0.032(1)
-0.184(2)
-0.139(1)
-0.163(2)
0.168(1)
4.8(7)
7.0(9)
5.0(7)
8.4(1.0)
1.9(5)
H (16)
H (17)
H (18)
H(19)
-0.531(4)
-0.275(4)
0.048(5)
0.136(4)
0.371(3)
0.529(2)
0.543(3)
0.394(2)
0.243 (I)
0.272(1)
0.227 (2)
0.155(1)
.
5.9(8)
5.2(8)
7.7(9)
3.5(6)
aThe num ber in p a re n th e se s is th e stan d a rd d eviation and
r e f e r s to the le a s t significant d ig its.
6 8
F ig u re 13.
M olecular s tru c tu re of
5 -t-b u ty l-2 -p h e n y l-2 -th io -l, 3 , 2-dioxaphosphorinane
illu s tra tin g the th e rm a l e llip so id s.
69
TABLE 23
Bond d ista n ce s fo r
5- t -b u ty l- 2 -p h e n y l- 2 - th io - l, 3 , 2 -dioxaphosphorinane.
A tom s
d ista n c e , A
A tom s
d ista n ce , A
P(2)-S (17)
P(Z)-O(I)
P(Z)-O(S)
P (Z )-C (Il)
O(I)-C(G)
O(S)-C (4)
L 9 1 1 (l)a
1.576(2)
1.587(2)
1.801(3)
1.462(4)
1.452(4)
C(4)-H(2)
C(5)-H(3)
C (6 )-H (4)
C(G)-H(S)
C(S)-H(G)
C (8)-H(7)
0.92(2)
0.96(2)
0.97(3)
0.98(3)
0.91(3)
1.03(4)
C(4)-C(5)
C(S)-C(G)
C (S)-C (7)
C(F)-C(G)
C(T)-C (9)
C(T)-C (10)
1.508(5)
1.507(5)
1.547 (5)
1.537(6)
1.531(6)
1.532(6)
C (8 )-H (8 )
C(9)-H(9)
C (9)-H(10)
C(O )-H (Il)
C (10)-H(12)
C(IO)-H(IS)
1.07(3)
0.91(3)
0.94(3)
0.96(3)
1.00(3)
0.93(3)
C (Il)-C (12)
C(Il)-C (IG )
C (12)-C (13)
C (13)-C (14)
C(14)-C(15)
C (4)-H (l)
1.386(5).
1.374(5)
1.386(6)
1.362(7)
1.374(6)
0.98(2)
C(IO)-H(M)
C(12)-H(15)
C (13)-H (16)
C (M )-H(IT)
C (15)-H(18)
C(IG)-H (19)
1.06(4)
0.92(2)
1.01(3)
0.96(3)
0.97(3)
0.90(2)
.
a The num ber in p a re n th e se s is th e stan d a rd deviation and re f e r s
to the le a s t significant d ig its.
TABLE 24
Bond angles of 5 -t-b u ty l-2 -p h e n y l-2 -tM o -l,3 , 2-dioxaphosphorinane 0
A tom s
S (1 7 )-P (2 )-0 (l)
S(17)-P(2)-0(3)
S(17)-P(2)-C (11)
0 (l)-P (2 )-0 (3 )
0(1)-P(2)~C (11)
0 (3 )-P (2 )-C (ll)
P (2 )-0 (l)-C (6 )
P (2)-0(3)-C (4)
O(S)-C (4)-C (5)
C(4)-C(5)-C(6)
C(4)-C(5)-C(7)
C(S)-C (B)-C (7)
O(I)-C(S)-C(B)
C (S)-C(7)-C (8.)
C(S)-C(Z)-C(S)
C(S)-C(Z)-C (10)
P(2)-C (Il)-C (12)
P(2)-C (Il)-C (16)
C (12)-C (Il)-C (IS )
C (H )-C (12)-C (13)
C (12)-C (IS)-C (14)
C(IS)-C (M )-C (IS)
a n g le s , 0
113„0(l)a
1 1 1 . 8 (1 )
113.8(1)
105.5(1)
106.2(1)
105.9(1)
120.4(2)
117.3(2)
111.8(3)
108.2(3)
113.3(3)
113.6(3)
110.8(3)
109.5(3)
112.1(3)
109.0(3)
120.8(3)
120.2(3)
118.9(3)
119.9(4)
120.1(4)
120.7(4)
A tom s
C (M)-C (IS)-C (16)
C (IS)-C (16)-C (11)
O(S)-C (4)-H (l)
O(S)-C (4)-H (2)
C (5)-C (4)-H (l)
C(5)-C(4)-H(2)
H (I)-C (4)-H (2)
C (4)-C (S)-H(S)
C(S)-C(S)-H(S)
C (7)-C (S)-H(S)
O (I)-C (S)-H (4)
O(I)-C(S)-H(S)
C (S)-C(G)-H (4)
C(S)-C(S)-H(S)
H (4)-C (S)-H(S)
C (7)-C (8 )-H ( 6 )
C(Z)-C (8)-H(7)
C (7)-C (8 )-H ( 8 )
H(S)-C (8)-H(7)
H(S)-C (8 )-H ( 8 )
H(Z)-C(S)-H (8 )
C (Z)-C (9)-H(9)
a n g les ,
0
119.0(4)
121.5(4)
108.(1)
104.(2)
115.(2)
1 1 1 .( 1 )
106.(2)
107.(1)
104.(1)
109.(1)
1 1 2 .( 2 )
99.(2)
1 1 0 .( 2 )
114.(2)
1 1 1 .( 2 )
108.(2)
1 1 1 .( 2 )
1 1 2 .( 2 )
105.(3)
113.(3)
109.(3)
1 1 0 .( 2 )
A tom s
C (Z)-C (9 )-H (10)
C (Z)-C (9)-H (ll)
H(9)-C(9)-H(10)
H(9)-C (9 )-H (ll)
H(IO)-C (9)-H (H )
C(Z)-C (10)-H(12)
C(Z)-C(IO)-H(IS)
C (7)-C (10)-H(14)
H(12)-C (IO)-H(IS)
H(12)-C (IO)-H(M)
H(IS)-C(IO)-H(M )
• C (Il)-C (12)-H(15)
C(IS)-C (12)-H(15)
'
C (12)-C (IS)-H(IS)
C (M )-C (IS)-H (IS)
C(IS)-C (M)-H(IZ)
C (IS)-C (M)-H(IZ)
C(M )-C (15)-H(18)
C (16)-C(15)-H(18)
C (IS)-C (16)-H(19)
C (Il)-C (16)-H(19)
an g les,
0
107,(2)
1 1 1 .( 2 )
104.(2)
109.(3)
115.(2)
1 1 2 .( 2 )
109.(2)
108.(2)
102.(3)
109.(3)
117.(3)
.118.1(1)
122.(1)
1 2 1 .( 2 ) '
119.(2)
123.(2)
116.(2)
119.(2)
1 2 1 .( 2 )
119.(2)
1 1 9 .# )
a The num ber in p a re n th e se s is the stan d a rd deviation and re f e r s to th e le a s t significant
d igits.
71
H16
S17-P2-01
03 -P2-CU
03 -C4-HZ
CS -C4-Hl
C6 -CS-H3
C4 -CS-C7
Ol -C6-H4
C2 -C6-HS
113.0(11
105.9(1)
104.(2)
11S.12)
104.(1)
113.3(3)
112.(2)
114.(2)
CS -C7 -CIO
CS -C7 -C9
C7 -CS -H7
H6 -CS -HS
C7 -C9 -HlO
H9 -C9 -Hll
C7 -C10-H13
H12 -CIO -H14
109.013)
108.6(3)
111.(2)
113.(3)
107.(2)
109.(31
109.(21
109J3)
F ig u re 14.
Bond d istan ces and bond angles of
5 -t-b u ty l-2 -p h e n y l-2 -th io -l, 3 , 2-dioxaphosphorinane.
72
TABLE 25
L east sq u a re s planes r e f e r r e d to orthogonal axes in
5 -t-b u ty l- 2 -phenyI- 2 -th io -1 , 3 , 2 “dioxaphosph.orinanea .
A tom s in plane
4
0(1), 0 (3), 0(4), 0(6)
-0.273
0(1), P(2), 0(3)
0(4), 0 (5), 0(6)
m
n
d(A)
S(A2)
0.630
0.726
2.27
0.0084
-0.556
0.804
0.209
2.32
—
-0.646
' 0.753
-0.126
3.09
———
0(11), 0(12), 0(13),
C (14), 0(15), 0(16)
0.385
-0.596
0.704
0.04
0.0007
0(11), P (2),'8(17)
0.722
0.511
-0.391
0.25
———
aX = x + z* cos jS; Y - y; Z = Z - sin
6
L 0 So p la n e : f X + mY + nZ - d = 0.0S: sum of sq u a re s of deviations of atom s fro m plane.
S
73
TABLE 26
T o rsio n a l angles fo r
5- t -b u ty l-2 -p h e n y l-2 -th io -l, 3 ,2 -diox ap h o sp h o rin an e.
Bond
to rs io n a l an g le, d e g re e s
P(Z)-O(I)
. 38.8°
O(I)-C(G)
51.00
C(G)-C (5)
58.60
C(G)-C (4)
62.2°
C (4)-0(3)
55.60
O(S)-P(Z)
40.2°
74
d ih e d ra l angle betw een the b e st le a s t sq u a re s plane th ro u g h th e phenyl rin g and
th e plane C (Il), P (2), S(17) is 70.2° tw isted around the P (2 )-C (ll) bond tow ard
th e O(I) side of the rin g as shown in F ig u re 15.
S teric re p u lsio n s a re re lie v e d
betw een C (16) and H (19) and the lone p a ir of e le c tro n s on 0(3) by the tw ist, and
s ta g g e rs C (16) and H (19) betw een 0(3) and S (17).
The bonding around the phosphorus form's a slightly d is to rte d te tra h e ­
d ra l w ith bond angles ranging fro m 105.5 to 113.8°.
The P-O(S) bond distance
is 5-6 sta n d a rd deviations lo n g er th an th e P -O (I) bond w hich m ay be a sig n ifi­
can t differen ce.
The P - C ( I l) bond d istan ce is 1.801 A w hich is the sam e as
found in 2, 5 -t~ b u ty l-2 -th io -l, 3 , 2-dioxaphosphorinane.
The P=S bond is
1.-911 A and can be co n sid e re d a n o rm al bond length.
The O(I)-C(S) bond distan ce is 2-3 stan d a rd deviations lo n g er than the
O (S)-C (4) d istan ce w hich m ay be a significant d ifferen ce.
The C-C bonds in
th e rin g a re 1.507 and 1.508 A.
The phenyl rin g is p la n a r w ith an av erag e d isp lacem en t fro m th e b e st
le a s t sq u a re s plane of 0.003 A, and the m axim um d isp lacem en t is 0.006 A at
th e C (16) p osition.
The equation of th e plane is lis te d in T able 25. The C-C
bond d ista n ce s fo r the phenyl rin g ran g e fro m 1.362 to 1.386 A and average
1.377 A.
The C -C -C bond angles ran g e fro m 118.9 to 121.5°.
T hese a re n o r-
m a l values fo r a benzene ring.
The C-C bond d ista n ce s in the t -b u ty l group ran g e fro m 1.531 to 1.547 A
75
S(17)
C ( l6 )
F ig u re 15.
Newman p ro je c tio n looking down the C (11)-P(2) bond.
76
and av erag e 1.537 A„ The bond angles ran g e fro m 108.1 to 112,1°.
The la rg e s t
angle C (5)-C(7)-C(9) is probably th e re s u lt of s te r ic re p u lsio n s betw een C (9)
and the axial hydrogens on the rin g , H (2) and 11(5).
The s te re o g ra p h ic pack in g .d iag ram of the m o lecu les in the unit cell is
shown in F ig u re 16.
Packing conditions a re not lik ely to be an im p o rtan t fa c to r
in the conform ation of the m olecule sin ce th e re a re no in te rm o le c u la r d istan ces
le s s than the sum of the van d e r W aals ra d ii of the atom s in neighboring m o le ­
c u le s.
V alues of the van d e r W aals ra d ii w ere obtained fro m Bondi (8), and
p e rtin e n t ra d ii w e re: P , 1.80; 0 , 1.52; aliphatic C, 1.70; a ro m a tic C 5 1.77;
double bonded S5 1.74; aliphatic H, 1.20; and aro m a tic H, 1.00 A.
77
F ig u re 16.
S tereograph ic packing d iag ram for
5 - t- b u ty l- l- p h e n y l- l- th io - l, 3 ,2 -d ioxaphosphorinane.
THE CRYSTAL AND MOLECULAR STRUCTURE OF
2, 5, -t-B U T Y L -2 -T H IO -l, 3 , 2-DIOXAPHOSPHORINANE (CnPSOgHgg)
P re p a ra tio n
The c ry s ta ls w ere supplied by W esley G. B entrude and w ere la rg e ,
c o lo rle s s , tra n s p a re n t, and n eed le-sh ap ed in ap p earan ce.
The dim ensions of
the c ry s ta l u sed fo r X -ra y an aly sis w ere approxim ately 0.16 x 0.26 x 0.58 m m .
T he c ry s ta l w as sea le d in a L indem an c a p illa ry to p rev en t lo s s by sublim ation.
D ensity
;
The density of the c ry s ta ls w as m e a su re d by the flo tatio n m ethod as
d e sc rib e d in P a rt I, page 5.
The calcu lated density was b a se d on four m o le­
c u le s p e r unit- cell; Dexp - 1.210 g /c m ^ and DcaJ c = 1.218 g /c rn ^ .
D eterm in atio n of c e ll dim ensions and space group
The c ry s ta l was p laced on O regon State U n iv e rsity ’s Syntex P 2 j Auto­
m ated D iffrac to m e te r equipped w ith a PD P -8 com puter and p o la ro id c a s s e tte .
A ro ta tio n a l photograph of the X -ra y d iffra ctio n p a tte rn fo r th e c ry s ta l w as m ade
w ith the P o laro id c a s s e tte , and provided the Auto cen terin g P ro g ra m (22) w ith
c o o rd in a tes.o f fifteen re fle c tio n s.
The p ro g ra m refined the an g u lar positions
fo r the fifteen re fle c tio n s by determ in in g p o sitio n s of the h alf-h eig h t peak in ­
te n sity .
The Autoindexing p ro g ra m (22) com piled a. lis t of p o ssib le axial
79
v e c to rs and the angles betw een th e se v e c to rs.
c e ll w as chosen.
F ro m th is lis t an orth o ro m b ic
The L e a st Squares O rientation M atrix P ro g ra m (22) then
calc u la te d the o rien tatio n m a trix and unit c ell p a ra m e te rs .
obtained w ere a = 10.135, b - 10.716, and c = 12.765 A.
T he cell dim ensions
No stan d a rd deviations
w ere given by the p ro g ra m .
The space group was d eterm in ed by the extinctions in the in ten sity d ata,
and w as found to be Pm cn w ith extinctions:
hk4
h04
hkO
OM
hOO
OkO
004
no conditions
4 ^ 2n
h + k ^ 2n
no conditions
h £ 2n
k^2n
4 f 2n.
Unit c e ll dim ensions w ere again d eterm in ed on o u r XRD-5 G eneral E le c ­
t r i c D iffrac to m e te r by the m ethod d e sc rib e d in P a rt I, page 6.
F ifteen th r e e -
d im ensional and th re e tw o-dim en sio n al re fle c tio n s w ere s e le c te d fo r which
p re c is e m e a su re m e n ts of the +20 and -29 angles w ere m ade.
The re s u lts w ere
a = 10.077(3), b = 10.662(3), and c = 12.703(3) A, which a re significantly d iffe r­
ent than those d e term in e d on the Syntex D iffrac to m e te r.
The cell dim ensions
d e term in e d by the G .E . d iffra c to m e te r w ere u sed fo r re p o rtin g since our p r o ­
g ra m gives, sta n d a rd d eviations, and I have m o re confidence in them .
c ry s ta l d ata a re liste d in T able 27.
The
80
TABLE- 27
C ry sta l D ata fo r
2, 5 -t-b u ty l-2 ~ th io -l, 3 , 2-dioxaphosphorinane.
C H P S O 2 H2 3
F„W„ 250.32
F (000) = 544
O rthorhom bic, Space Group Pm cn
a = 10.077(3)
01 =
90°
b = 10.662(3)
'
j8 = 90°
c = 12.703(3)
.‘
y=90°
Volume of the unit c ell = 1364,8
M olecules p e r unit c ell = 4
Dexp = 1.210 g /c m 3
D calc = 1.218 g /c m 3
81
D ata collection
Two s e ts of d ata w ere tak en fro m the c ry s ta l on two d ifferen t d iffra c to ­
m e te rs .
The f ir s t s e t of d ata w as co llected on the Syntex P 2 i D iffracto m eter
equipped w ith a PD P -8 com puter, telety p e, fo u r-c irc le g o n io m eter, s c in tilla ­
tio n co u n ter, and a p u lse-h eig h t d is c rim in a to r.
In te n sitie s of 1303 unique
re fle c tio n s w ere m e a su re d of w hich 818 w ere co n sid ered o b serv ed , using the
c r ite r io n ISs2 a (I).
Standard re fle c tio n s w e re checked a fte r e v e ry 60 re fle c tio n s
during d ata collectio n and had an av erag e deviation of 6.6%, w hich indicated a
p ro b lem .
The g rap h in F ig u re 17 shows th a t sca le #3 s ta r ts to r is e a fte r
approxim ately 18 h o u rs and r is e s rap id ly a fte r 35 h o u rs, indicating a rap id
drop in in ten sity .
d ata collection.
S cales I and 2 re m a in ed re la tiv e ly co n stan t throughout the
The p ro b lem could be explained by e ith e r c ry s ta l d e te rio ra tio n
o r by c ry s ta l slippage.
In o rd e r to d e term in e which case applied, the c ry s ta l
w as m ounted on our G eneral E le c tric XRD-5 d iffra c to m e te r.
In te n sitie s of the
th re e sta n d a rd re fle c tio n s w e re co llected and th e ir r a tio 's to th o se collected on
th e Syntex d iffra c to m e te r w ere n early equal.
T his su g g ested th a t the c ry s ta l
had probably m oved during d ata co llectio n on the Syntex.
The 818 o b serv ed re fle c tio n s w e re re -c o lle c te d on the G .E . d iffra c to ­
m e te r.
E ach peak w as scanned fo r 60 seconds and the backgrounds on each
side of the peak w ere counted fo r 10 seconds and m ultiplied by 3.
A c h a rt
re c o rd in g of peak in ten sity vs_. 29 w as m o n ito red during th e d ata co llectio n as
h
k
I
sc a le I
I
-I
I
8
sca le 2
I
0
2
0
sca le 3
4
2
-I
1 .4 -
nitial in te n s ity / Intensity of re flectio n
t—
1 I Q
0
0
1 .2—
00
0 0
1 . 1“
© 00
a
B
CO
to-
a
i . o ^ | I®
| |
© a 57 „ B
a e a g g
b
a Hg B
b
a B
_
6>
0 .9 -
®0
0
©
©0
0
0 0
B
0 B
®
T im e, h r.
0
I
I
I
I
I
I
5
10
15
20
25
30
I---------- 1---------- 1
35
F igure 17.
Scale fa c to rs fo r d ata collected on the Syntex D iffracto m eter.
40
45
83
a check on the cen terin g of the peak in the sca n .ra n g e and fo r g en eral a p p e a r­
ance of the peak and backgrounds.
off angle of 4 °.
The sca n ra te w as 2° p e r m inute with a ta k e ­
■
■
Of the 818 o b serv ed re fle c tio n s co llected on the Syntex in stru m e n t, 763
w e re c o n sid ered o b serv ed by the G.E„ in stru m e n t.
T h ree sta n d a rd re fle c tio n s
(the 014, 330, and 421 re fle c tio n s) w ere checked approxim ately ev ery hour
during data collection and re m a in e d constant w ith an average deviation of 1.1%,
indicating no d e te rio ra tio n of the c ry s ta l.
S tru ctu re fa c to rs , (F0), w ere calcu lated fro m the in te n sitie s by applying
th e u su al L o re n tz -p o la riz a tio n c o rre c tio n , and w eights w ere calcu lated from
stan d a rd .d e v ia tio n s as w as d e sc rib e d in P a r t I, page 7.
No ab so rp tio n o r extinction c o rre c tio n s w ere m ade.
The lin e a r a b so rp ­
tio n coefficient of C nPSO gH gg fo r MoK0/ ra d ia tio n (X = 0.71069
c m -1 .
A) is
3.33
The tra n s m is s io n fa c to rs fo r X -ra y s p a ssin g th ro u g h the m axim um and
m inim um dim ensions of the c ry s ta l a re approxim ately 0.80 and 0.95 re s p e c ti­
vely; th is ran g e c o rre sp o n d s to approxim ately 8% v a ria tio n about a m ean in te n ­
sity value.
S catterin g fa c to rs fo r the non-hydrogen atom s and anom alous
s c a tte rin g c o rre c tio n s, (Af' and A f”), fo r phosphorus and su lfu r w ere tak en
fro m the In tern atio n al T ables (12).
fro m Stew ard, e t, a l. (20).
S catterin g fa c to rs fo r hydrogen w ere tak en
84
S tru ctu re d e term in a tio n
The s tru c tu re w as solved using the d ata co llected on th e Syntex d iffra c to ­
m e te r.
The positions of the phosphorus and su lfu r atom s w e re found fro m the
P a tte rs o n sy n th esis (2)0 U sing the phosphorus and su lfu r atom p o sitio n s, the
s tru c tu re fa c to r calcu latio n (9) gave an R -in d ex of 0.46.
A F o u rie r m ap (2)
re v e a le d positio n s of two oxygen atom s and th re e ring carb o n a to m s , giving an
R -in d ex of 0.31.
A subsequent F o u rie r m ap showed the rem ain in g non-hydrogen
atom po sitio n s.
R efinem ent
'
R efinem ent w as begun using the full m a trix le a s t s q u a re s m ethod (9) of
re fin e m e n t w ith the R -index equal to 0.18 fo r the non-hydrogen s tru c tu re along
w ith iso tro p ic te m p e ra tu re fa c to rs and a unit w eighting sch em e.
cy cles of re fin em en t, the R -index dropped to 0.11.
A fter th re e
The te m p e ra tu re fa c to rs
w e re th en converted to a n iso tro p ic and the'w eighting schem e to th a t of Stout and
Jen se n .
In th re e cy cles the R -in d ex dropped to 0.087 w ith a w eighted R -index,
(Rwtd)>
0.11.
A differen ce m ap w as calcu lated to locate hydrogen atom p o sitio n s, and
a ll of the hydrogen atom p o sition s w ere located fro m the m ap.
R efinem ent of the com plete s tru c tu re was then continued until the sh ifts
in the p a ra m e te rs w e re le s s than one half of th e ir stan d a rd dev iatio n s.
The
85
final re fin em en t of the Syntex data gave an R of-0.057 and an RwtcJ of 0.066.
A fter the d ata w ere re c o lle c te d on the G0E. d iffra c to m e te r, the s tr u c ­
tu re re fin e d to an R of 0.048 and an RwtcJ of 0.038.
The o b serv ed and calcu lated
s tru c tu re fa c to rs a re lis te d in T able 28. The positional p a ra m e te rs of th e non­
hydrogen atom s a re lis te d in T able 29, the th e rm a l p a ra m e te rs fo r the non­
hydrogen atom s a re lis te d in T able 30, and the hydrogen atom p a ra m e te rs a re
lis te d in T able 31.
-D iscu ssio n of the s tru c tu re
The m olecule of 2, 5 —t- b u ty l- 2 - th io - l, 3 , 2-dioxaphosphorinane w ith its
T h erm al ellip so id s is shown in F ig u re 18.
32 and bond angles in T able 33.
F ig u re 19.
The bond lengths a re liste d in Table
Bond lengths and angles a re diag ram m ed in
'
The m olecule lie s on a c ry sta llo g ra p h ic m ir r o r plane on which the
atom s P (2), S(15), C (5), C (7), C(10), C ( I l ) 5 and C (14) lie on the sp ecial p o s i­
tio n s x = 1 /4 and 3 /4 .
The rin g is a d is to rte d c h air w ith the t -butyl groups cis
to each o th er w ith the t -butyl group on th e C (5) position axial and eq u ato rial on
th e P (2) position.
B entrude had p re d ic te d th a t the thio group would be axial,
but had also p re d ic te d a boat conform ation fo r the rin g (6).
The rin g is flatten ed as shown by th e d ih ed ral angles betw een the plane
0(1), 0(3), C (4), C (6) and the planes 0(1), P(2), 0(3) and C (4), C (5), C (6); the
8G
" 'oS'-*"*
<0. 02''
"
2
"S"2"Z"
-0 S
: 2
i o
2
2
w
SaS"' -Sf-rSt«°2Z»2 «2°-,. <2"2« iSr- “222 “2"
2
2
2":"
2
:
I
2 «2 2 * 2 ; 2 a * 2 : »
..................r "
“ 22«
2
3
*zs:
; 2 := :*= *2 “
i
«2%S*32
-SS2132222
“22223222»
“ 22"
2*
-% :--2S 2*
" S - == : 2 2 2 2 2 3
"S S S -22*2*"»
*Z"2S3*
"'S
3»
“ 2 : t' - 2 S 2 »
“ 2 =2 : 2 2 2 2 2 2 2
“223"23"2""2
“2*22»"
“2
«2223»
“S222--
“2=22* “22»2*» *2222 “2
- i m * <r O ►
-»
^ -I # n - - O
H
:
»S
"2:*=
i
2=22 2 = 2
S i -
222» “2*22'"»* jg: - -sf
*2322
2*2
22*2«
-O --J2 -O
-Z2«S"»
S -S
S " “ 2 * 2 t'
000- - 2-
O-O1 - -O
Nf--O
222
I
Zr-1Z
e-s
______________ x__________________
“ S'" 2 2 2 S » 2 »
S"’3 “' e YS"6 * 2 = '
O b served and c a lc u la ted s tr u c tu r e f a c to r s .
=
e S-r S *2%»s - z s * = 2 » ~ z : = z » : " 2
s"
0 0 2 « “ 2««
2
_ N —f f —
£"""**" f " "
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~ s s : : s - 2 i-*
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-■-22
:S: "2:22222- 'sisiss-s:* -z::-::: -s2:i:J'2::- -s:::::-:- -3*2
222 -221:222- •2 s:2 :s -2 2 - j s s ; - : : : j 2 : 2 i ; : - " : f '2:3322«=»
: 5«S
o —-« f' » r- i O- —
3 *&; = » » S 3 3 » = = = ~ s = s : s = " 2 :
t j o n « m « ■ O O-J 2
, J i JJ2J NN
0 Ju= » 2 3 2
......................... 2 =
»
"Sf = = S =
* “Z"22 “:»"»=« “£=»=22
2 “S="»222»:2:
2
"S « « * * 2 S =23"*
'*s;22t' S 2 2 2 2 » * * - »
" Z : : 3 : S S " = « »S!22 = : S 2 3 = = 2 »Sf SSSS23
“ = « « » » 2 3 2 2 = '»
“ £33**i223**»*
“ 52t==2S*=*
“223=23:32=2
“ 2233323
......=2 ........ '‘*2=22 . .......=22 ........»2=2
.
« S f * S 3 2 3 = « 3 = '‘ s;3 = 2 3 2 2
*Z2 = S * » 2 »
»Z3»
,=N
-E -SSSS=-S=
“E=S2»«3"
“:3«
i2* “:»» ’=
“ S3222==
CJ U- O
,N,
%
2 =222
“ 222
2ST
*222232
“ 2*
“ 223232
-
2
$
Z 3S:3«322
~23»==2=22»
"’2 S « 3 * « 2 2 2 2 = » »
' 2 =3 =2225«
22SS3«3=2
“ 22*2=S222*
“23"3«*'33=2«2= “2:3S=:23»
i u o - N m♦ . , - N «o -.in
uuN -m -N -m
I
22
» % * s » ; 2 »=* * 2 S : « a » 2 2
*2 * 2 * 2 = 2 2
22
- -
i o . o . - n j - n .
ig - o o n - n j -
I ON N o o » N
i o o r - N N - n
= 2 **«»
= %*««
222=22S3==3»2
U 0-N n-^-»0-nj«
222 °222SS=2 "
2= “ 2 3 2 3 5 2 2
522
' ' 2 ; : = 2 3 == » =2 = * *'22"3 =3 » * : * 2
' 2 2 = = = 5» = S » 2 * : ? S
52=
“2;2=32=3*222»
“ 22=2=2222
“222S=2*«:*2
“2«*52
»NN
-S2«S-*2"= =
»23=222
22=22*2
=23=2«»
22»»
*22=32»
»»=2
*»22
“22*3*22*2=
“ 23=3=2
“2:2=2=
“22:=»»
“ 2«*
“22=322
u —n - - - n , » o
. UO--NO
, u m —N I
J
I
i
» 2 * 2 * « 2 * ” ="=
-S ::::::-" ::::-:
......................2 = 2
=222»*
22=*
“222*=2"2" “22=*=
, u c _ - f . - . ,
, U ..............
*2= 5»
» 2 2 5 5 2 2 3 2
s i::"
“s s : s - s s i
»*2 = 2
, U -N m --N ,
-Unoom N2 N
"2=33222=
“2=5=2232
"
I
* 2 5 " = = * 3 » *»
»2**33=
- S i'::::" " '
^ u o - N m - n - N ,-O -N 2
* 2 2 = 3 « 2 = '= -
“
=*» “2«=S2»=2
» --2
' ,2 2 2 2 * : 5 , " = = S 3 ' = ' 2 2 2 = S » 5 » * » «»
’• 2
2=2=22S3223»2
. ..................... =23
°2:=33=2
$ ......................"
-2 2 S 3 I '= * 3 2 * '* "223==2=3=222
“ 22=5=23
“ 2S55?*2=?2»»»
“2:3 = 3 3 3 5 :2 3 3
U N--ON-
e UO-Nm < n - N e « # 2
u-Nm-m-NO-OJS
* 2 * = * 2 5 2 * * » 2 * 2
u o —N m f ^ N - O - N -
" 2 = '2 * * * » =
" 2 2 * « 2 = 2 " 2
* 2 : » 2 2 » 2 2 2
js :-s :---:
-s ::" * -:-:
js :-::" ii:
^ U N m - n - o o Jj
^u N m « - e » o - j
^ u N mf n « N o »
I
i
°2=3252:
" 2 3 - = 2 S 2 J n»»=2
'12 3 3 = 5 S S = 2 » 5 2 2 «
"2=25525S=»»2
'2 5 2 3 2 2 =
“ 2322=22
“2 = ::2 = 3:3»«= 2
“2 :3 5 5 33:2*522»
“2=3:S3=32»»:
“ 25= := "=
i un-
t u ...................2 = 2 = 3
..............................2 3 2 2
. -'- ", " ' » « » » 2 2 2
. ...................
- on-
87
TABLE 29
P ositio n al p a ra m e te rs of non-hydrogen atom s in
2,
5- t -b u ty l- 2 -th io - 1 , 3 , 2-dioxaphosphorinane.
Atom
x /a
y /b
8(15)
P(2)
O(I)
0(3)
0(4)
0.2500(0)a
0.2500(0)
0.3724(2)
0.1276(2)
0.1260(5)
0.1104(2)
0.0193 (I)
-0.0730(2)
-0.0730.(2)
-0.1789(4)
0.2943 (I)
0.1633(1)
0.1490(2)
0.1490(2)
0.2230(4)
0.2500(0)
. 0.3740(5)
0.2500(0.)
0.3706(7)
0.1294(7)
-0.2607 (6)
-0.1789(4)
-0.3604(5)
-0.4449(6)
-0.4449(6)
0.2155(5)
0.2230(4)
0.1275(4)
0.1381(5)
0.1381(5)
0.2500(0)
0.2500(0)
■ ■ 0.3742(6)
0.1258(6)
0.2500(0)
-0.3039(7)
0.1144(6)
0.1961(6)
0.1961(6)
0.0329(8)
0.0176(6)
0.0456(5)
0.0485(5)
0.0485(5)
-0.0540(6)
0(5)
0(6)
0(7)
(3(8)
0(9)
C<10)
C (Il)
0(12)
C (13)
0(14)
z /c
a The num ber in p a re n th e se s is the standard, d ev iatio n and
r e f e r s to the le a s t significant d ig its.
\
88
TABLE 30
T h e rm a l p a ra m e te rs of non-hydrogen atom s in
2, 5- t -b u ty l- 2 -th io -1 , 3, 2-dioxaphosphorinane..
Atom
/3 iia ’b
#22
#33
#12
#13
#23
8(15)
P(2)
O (I)
0(3)
0(4)
131(2)0
74(2)
68(3)
68(3)
86(6)
101(2)
61(2)
63(2)
63(2)
85(5)
58(1)
47(1)
56(2)
56(2)
57(3)
0(0)
0(0)
7(2)
-7(2)
-7(5)
0(0)
0(0)
1(2)
-1(2)
11(4)
29(1)
C(5)
0(6)
0(7)
0(8)
0(9)
88(7)
86(6)
85(7)
143 (8)
143 (8)
79(6)
85(5)
56(6)
104(6)
104(6)
41(4)
57(3)
61(5)
112(6)
112(6)
0(0)
' 7(5)
0(0)
28(6)
-28(6)
0(0)
-11(4)
0(0)
-4(6)
. 4(6)
16(5)
1(3)
2(4)
10(5)
10(5)
0(10)
C (H )
0(12)
0(13)
0(14)
162(12)
,92(7) .
131(8)
131(8)
197 (14)
80(8)
74(6)
. 99(6)
99(6)
107 (9)
58(5)
57(5)
104(5)
104(5)
50(5)
0(0)
0(0)
. -35(6)
35(6)
0(0)
0(0)
0(0)
8(5)
-8(5)
0(0)
-8(5)
7(5)
23(5)
23(5)
5(6)
a The j8ij!s have been m u ltip lied by IO^1
'-’The e x p re ssio n fo r the an iso tro p ic th e rm a l p a ra m e te rs is of the form :
exp (-jSiih 2 - 6 2 2 k 2 - 8 3 3 ^ - ^ h k - ^ i g M - ^ s k A ) ,
c The num ber in p a re n th e s e s is the sta n d a rd deviation and r e f e r s to the
le a s t significant d ig its.
6 (1 )
3 (2 )
3(2)
1(3)
89
TABLE 31
■Hydrogen atom p a ra m e te rs in
2, 5 - t- b u ty l-2 -th io -l, 3 , 2-dioxaphosphorinane.
Atom
x /a
y /b
z /c
Biso
H(I)
H (2)
H(3)
H(4)
H (5)
0.047 (3 )a
0.116(3)
0.250(0)
0.384(3)
0.453(3)
-0.227(3)
-0.150(3)
-0.312(5)
-0.150(3)
-0.227(3)
0.201(3)
0.298(3)
0.285(4)
0.298(3)
0.201(3)
3.8(8)
3.7(8)
4.8 (1.3)
3.7(8)
3.8(8)
H (6)
H (7)
H(8)
H(9)
H(IO)
0.374(4)
0.448(5)
0.375(5)
0.125(5)
0.052(5)
-0.515(4)
-0.405(4)
-0.477(4)
-0.477(4)
-0.405(4)
0.075(4)
■ 0.117(3)
0.207(4)
0.207(4)
0.117(3)
7.9(1.3)
6.8(1.5)
7.4(1.5)
7.4(1.5)
6.8 (1.5)
H (H )
H (12) ,
H (13) ■
H(M)
H(15)
0.126(4)
0.172(4)
0.2500(0)
0.328(4)
0.446(5)
-0.515(4)
-0.255(3)
-0.382(5)
-0.255(3)
0.140(4)
0.075(4)
0.005(3)
-0.035(4)
0.005(3)
0.047(4)
7.9 (1.3)
5.2 (1.2)
5.8(1.6)
5.2 (1.2)
7.6(1.6)
H (16)
H (17)
H (18)
H (19)
H(20)
0.366(4)
0.372(4)
0.333 (4)
0.250(0)
0.167(4)
0.249(4)
0.251(4)
-0.018(4)
0.080(5)
-0.018(4)
0.122(3)
-0.016(4)
-0.058(4)
-0.114(5)
-0.058(4)
8.3 (1.5)
7.3 (1.4)
7.1(1.4)
5.5 (1.7)
7.1(1.4)
H (21)
H (22)
H (23)
. 0.128(4)
0.134(4)
0.054(5)
0.251(4)
0.249(4)
0.140(4)
-0.016(4)
0.122(3)
0.047(4)
7.3 (1.4)
8.3 (1.5)
7.6(1.6)
■
a The num ber in p a re n th e se s is the stan d a rd deviation and r e f e r s to
the le a s t sig n ifican t dig its.
90
F ig u re 18.
M olecular s tru c tu re of
2, 5 -t- b u ty l- 2 - th io - l, 3, 2-dioxaphosphorinane
illu s tra tin g the th e rm a l e llip so id s.
91
TABLE 32
Bond d ista n ce s fo r
2, 5-t-b u ty I- 2 -th io -1 , 3 , 2-dioxaphosphorinane.
Bond
Bond
d ista n ce , A
S(15)-P(2)
P (2 )-0 (l)
P (2)-0(3)
P (2 )-C (ll)
O(I)-C (6)
1.927 (2)a
1.588(3)
1.588(3)
1.807(6)
1.47 0(5)
0(3)-C (4)
C(4)-C(5)
C(S)-C(G)
C(S)-C(Z)
C(7)-C(8)
d istan ce, A
C(G)-H(S)
C(S)-H(G)
C(8)-H(7)
C(S)-H(B)
C(9)-H(9)
0.98(3)
1.10(5)
0.93(5)
0.94(5)
0.94(5)
1.470(5)
1.526(6)
1.526(6)
1.543 (8)
1.518(7)
C (9)-H(10)
C(O)-H(Il)
C (10)-H(12)
C(IO)-H(IS)
C(IO)-H(M)
0.93(5)
1.10(5)
0.96(4)
1.07(6)
0.96(4)
C(?)-C(9)
C(Z)-C (10)
C (Il)-C (12)
C (Il)-C (13)
C (Il)-C (14)
1.518(7)
1.520(9)
1.525(7)
.1.525(7)
1.535(10)
C (12)-H (15)
C (12)-H(16)
C (12)-H(17)
C(M )-H (IS)
C (M )-H (19)
0.94(5)
1.09(4)
1.01(4)
1.00(4)
0.91(6)
C (4)-H (l)
C(4)-H(2)
C(S)-H(S)
C(6)-H(4)
0.98(3)
1.01(3)
1.04(5)
1.01(3)
C (M )-H (20)
C (IS)-H (21)
C (13)-H (22)
C (IS)-H (23)
1.00(4)
1.01(4)
1.09(4)
0.94(5)
,
aThe num ber in p a re n th e se s is the sta n d a rd deviation and r e f e r s to
the le a s t sig n ifican t d ig its.
92
TABLE 33 '
Bond angles fo r
2, 5 - t -b u ty l- 2 -th io -1 , 3, 2-dioxaphosphorinane.
A tom s
angle, 0
Atoms
a n g le ,°
S(15)-P (2)-0(1)
S(15)-P(2)~0(3).
S(15)-P(2)-C (11)
0 (l)-P (2 )-0 (3 ).
0(1)-P (2)-C (11)
114.3 (I)G114.3(1)
115.6(2)
101.9(1)
104.6(2)
0 (3 )-P (2 )-C (11)
P (2)-Q (l)-C (6)
P (2)-0(3)-C (4)
O(S)-C (4)-C (5)
C(4)-C(5)-C(6)
104.6(2)
114.3(2)
114.3(2)
112.9(3)
109.9(4)
C (4)-C (S)-H(S)
C(G)-C (S)-H(S)
C(Y)-C(S)-H(S)
O (I)-C (6)-H (4)
O(I)-C(G)-H(S)
C(4)-C(5)-C(7)
C(6)-C(5)-C(7)
O(I)-C(G)-C (5)
C(5)-C(7)-C(8)
C (S)-C (Z)-C (9).
116.0(4)
116.0(4)
112.9(3)
110.2(4)
110.2(4)
C(S)-C (G)-H (4)
C(S)-C(G)-H(S)
H(4)-C (G)-H(S)
C(Y)-C(S)-H(G)
C(Y)-C(S)-H(Y)
108. (2)
HO. (2)
HO. (2)
H I . (2)
1 1 2 .(3)
113.1(4)
106.3(4)
108.4(4)
108.4(4)
10Y.5 (4)
C(Y)-C (S)-H(S)
H(G)-C(S)-H(Y)
H(G)-C(S)-H(S)
H(Y)-C(S)-H(S)
C (Y)-C (9)-H(9)
HO.
94.
116.
113.
HO.
(3)
(4)
(4)
(4)
(3)
C(Z)-C (S)-H(IO)
C (Y)-C (9 )-H (ll)
H(S)-C (9)-H(10)
H (9)-C (9)-H (H )
H (IO )-C (S)-H (Il)
112.
H I.
113.
116,
94.
(3)
(2)
(4)
(4)
(4)
,
C(S)-C(Z)-C(IO)
C (S)-C (Y)-C (9)
C(S)-C(Y)-C (10)
C(S)-C(Z)-C(IO)
P(2)-C (Il)-C (12)
P(2)-C (Il)-C (13)
P(2)-C (Il)-C (14)
C (12)-C (Il)-C (13)
C (12)-C (Il)-C (14)
C (IS)-C (Il)-C (14)
C
10Y.5 (4)
111.4(4)
110.3(4)
110.1(4)
. 110.1(4)
.
.
O(S)-C (4)-H (l)
O(S)-C (4)-H(2)
C (5)-C (4)-E (l)
C(5)-C(4)-H(2)
H (I)-C (4)-H(2)
. 103. (2)
.112. (2)
HO. (2)
108.(2)
HO. (3)
.
104.
104.
105.
112.
103.
(2)
(2)
(2)
(2)
(2)
93
TABLE 33'
(Continued)
Atoms
angle, 0
C (7)-C (10)-H(12)
C(T)-C (IO)-H(IS)
C(T)-C (IO)-H(M)
H(IB)-C (IO)-H(IS)
H(IB)-C (IO)-H(M)
11B. (B)
1 0 5 .(B)
112. (2)
109. (3)
HO. (3)
H (13)-C
C (Il)-C
C (Il)-C
C (H )-C
H (IS)-C
109.
106.
105.
10T.
114.
(10)-H (14)
(IB)-H(IS)
(IB)-H(IG)
(IB)-H(IT)
(IB)-H(IG)
H (IS)-C (IB)-H(IT)
H(IG)-C (IB)-H(IT)
(3)
(3)
(2)
(3)
(4)
' 112. (4)
113. (3 )
Atoms
C (Il)-C (M )-H(IS)
C (H )-C (M)-H(19)
C (H )-C (M)-H(BO)
■H (IS)-C (M )-H(19)
H(IS)-C (M)-H(BO)
;
a n g le ,°
'
106.
105.
10T.
114.
112.
(3)
(B)
(3) .
(4) ‘
(4)
H (19)-C (M)-H(BO)
C (H )-C (13)-H(Bl)
C (H )-C (IS)-H(BB)
C (H )-C (13)-H (23)
H(Bl)-C (13 )-H(22)
113. (3)
10T,. (3)
105. (2)
. 106.(3)
113. (3)
H(Bl)-C (IS)-H(BS)
H(BB)-C (13)-H(23)
112. (4)
114. (4)
a The num ber in p a re n th e s e s is th e stan d a rd deviation and re fe rs
to the le a s t sig nificant dig its.
94
H13
H16
R
R
1.09(41
H5
1.10(51
HlS
1.01(41
HlS
1.00(41 09116)
MX
Q
y 6 [,
i SZ(KS) 11.518(71
.518(71 0^°- x ' HS P
' >V- -/ /
H4
v R^ 0.960)
H4 GGv
ossoi
0.94(51
^
OWmT ^ 20I9i
Cf
wiO
HI2
H17
1.525(7)
1.53511» 1.00(41
X ___>"
*»
%H20
H15
y 181,1
OWISIi&C
OW
ISI
&
'D
HlO
H9
V
1.04(5)
c/
V "
1.526(61
.(6)
1.56
1.588(31
M
094(5)
1.927(2)
Cf
R
H23
H3
1.01131
Cf
H2
I
095(31
Hl
Hl 7
*<113.131
U 4.(4IJa2V 107.(3)
HJ 9
HlS
114.(4)
B
106.131'l c H H 113.(3)
V i S o i \ u o . H 4 l / 107.0)
1.09(41
©H20
C7 -CS -HlO 112.(3)
HS -CS -Hll 116.141
Cl -CIO-1113 105,(21
H12 -C10-H14 110(31
PZ -CU -C14 111.4(41
ClZ -C11-CI3 110.314)
CU -C12-H16 105.(21
H15 -ClZ-H17 112.(41
CU -C14-H19 105.12)
HlS -C14 -H20 112.141
CU -C13-HZZ 105.121
HZl -C13-H23 112.(4)
F ig u re 19.
Bond d ista n ce s and bond angles fo r
2 , 5 -t- b u ty l-2 -th io -l, 3 , 2-dioxaphosphorinane
95
d ih ed ral angles a re 50.3 and 46.0° re sp e c tiv e ly as co m p ared to 60° fo r an id eal
c h a ir.
34.
The equations of the plan es and the d ih ed ral angles a re liste d in T able
The to rs io n a l angles about the rin g bonds a re given in T able 35.
F ro m the
to rs io n a l a n g le s, it can be see n th a t m o st of the flattening of the rin g is on the
carb o n end of the rin g , in c o n tra st w ith the o th er I , 3-, 2-dioxaphosphorinanes
th a t have been studied.
M ore is said about the conform ation la te r in the sectio n
com paring the I , 3 , 2-dioxaphosphorinanes on page 100.
The bond angles around the phosphorus fo rm a d is to rte d te tra h e d ra l
w ith bonds ranging from 101.9 to 115.6°.
The P -C (Il) bond is 1.807 A which is
the sam e as th a t found fo r the 5 -t-b u ty l-2 -p h e n y l-2 -th id -l, 3 , 2-d io x ap h o sp h o rihane.
The P=S bond is 1.927 A w hich is slig h tly lo n g er th an the 1.911 A bond
found in the 5 -t-b u ty l-2 -p h e n y l-2 -th io - compound.
The P -O bond d istan ces a re
1.588 A which a re n o rm al bond lengths fo r phosphate e s te r s .
The C-O bonds
a re 1.470 A and the C-C bonds in the rin g a re 1.526 A, w hich a re n orm al bond
lengths.
The C-C bond d ista n ce s of the t-b u ty l group on the phosphorus range
fro m 1.525 to 1.535 A and average 1.528 A.
to 111.4° w hich a re n e arly te tra h e d ra l.
The bond angles range from 107.5
The C-C bond d ista n c e s of the t-b u ty l
group on the C (5) position ran g e fro m 1.518 to 1.543 A and av erag e 1.525 A.
The bond angles range fro m 106.3 to 113.1°.
The angle C(5)-C(7)-C(10) a p p ea rs
to be in c re a s e d by s te r ic rep u lsio n s betw een C(IO) and O(I) and 0(3) on the rin g .
96
TABLE 34
Equations of p lan es fo r
2, 5 -t- b u ty l-2 -th io -1 , 3 ,2 -dioxaphosp h o rin an ea .
A tom s in plane
A
m
n
d(A)
0(1), 0(3), C (4), C (6)
0.000
0.639
0.768
0.96
0(1), P(2), 0(3)
0.000
-0.183
0.983
2.00
0(4), 0 (5), 0 (6 ).
0.000
-0.109
0.994
3.02
a Equation of the p la n e : Ax + my + nz - d = 0„0
97
TABLE 35
T o rsio n a l' angles fo r
i-t-b u ty l-2 -th io --1 ,3 , 2-dioxaphosphorinane,
Bond
a n g le, d e g re es
P(Z)-O(I)
57.6°
C(I)-C(G)
58.80
C(G)-C(S)
51.4°
C (S)-C (4)
51.4°
C (4)-0(3)
58.8°
0(3)-P (2)
57.6°
98
The packing of the m olecu les in the unit cell is shown in the stereo g rap h ic
d ia g ra m in F ig u re 20.
Packing, conditions a re not likely to be an im portant
fa c to r in the conform ation of the m o lecu le, since th e re a re no in te rm o le c u la r
d is ta n c e s le s s th an the sum of the van d e r W aals ra d ii of neighboring m o lecu les.
V alues of the van d e r W aals ra d ii w ere obtained fro m Bondi (8).
The p e rtin ­
e n t ra d ii w e re: P, 1.80; 0 , 1.52; C, 1.77; double bonded S, 1.74; and H,
1.20 A.
99
F ig u re 20.
S tereograp h ic packing d iag ram fo r
2, 5 -t- b u ty l-2 -th io -l, 3 , 2-dioxaphosphorinane.
COMPARISON OF TH F 1 , 3 , 2-DIOXAPHOSPHORINANES
A lis t of the 1 , 3 , 2-dioxaphosphorinanes fo r w hich c ry s ta l s tru c tu re s
h av e been done is given in T able 36.
Points of co m p ariso n fo r the s tru c tu re s a re : I) the conform ation of the
rin g , 2) c o m p ariso n of s iz e effe cts of v a rio u s axial su b stitu en ts bonded to th e
phosphorus atom , and 3) co m p ariso n of the effects of su b stitu en ts bonded on
th e C (5) position.
The bond angles and bond d istan ces in the rin g a re not sig n i­
ficantly d ifferen t fro m th o se expected.
T ab les 37 and 38 show a co m p ariso n of
th e bond d ista n ce s and bond angles of the 1 , 3 , 2-dioxaphosphorinanes.
2, 5 -t- b u ty l-2 -th i6 -l, 3, 2-dioxaphosphorinane is unique in th e s e r ie s b e­
cau se the t -butyl on the phosphorus atom is e q u ato rial r a th e r th an axial as the
su b stitu en ts fo r the r e s t of the s e r ie s a re .
T his m ay be due to the la rg e s te r ic
re p u lsio n s betw een the bulky t-b u ty l and the 1 ,3 - oxygen ato m s and axial m e th y ­
len e hydrogens being g r e a te r than the 1-2 kcal p re fe re n c e fo r th e su b stitu en t to
be axial (7) causing the c h a ir to in v e rt.
All the I , 3, 2-dioxaphosphorinane s tru c tu re s studied to th is point have
been found to be in the c h a ir conform ation.
The d ih ed ral angles betw een the
p la n es O(I)., 0(3), 0(4), C (6) and 0(1), P (2), 0(3) show a g e n e ra l flattening of
the rin g , as com pared to the p e rfe c t c h a ir w ith d ih ed ral angles of 60°.
d ih e d ra l angles fo r the seven s tru c tu re s a re lis te d in T able 36.
The
T h ere a p p ea rs
TABLE 36
Compound
Ref.
R -index
Intensitycollection
D ihedral angle
D ihedral
0(1), 0 (3), C(4), C (6)C(4), C (5), C(G)0 (1), P(2), 0(3)
0(1), 0 (3 ), C(4), C(G)
OH
a)
0.108
Photographic
40.4°
54.2°
0.115
Photographic
36.5°
53.1°
0.045
D iffracto m eter
36.7°
52.5°
0.069
D iffracto m eter
33.5°
54.9°
OPh
Br
CH2 -B r
CH3
t-b u ty l
d)
0<^Q
(15)
10-1
(5b)
TABLE 36
(Continued)
Ref.
Compound
D ihedral angle
D ihedral angle
0(1), 0(3), C (4), C (6)C (4), C (5), C (6)0(1), P(2), 0(3)
0 (1), 0(3), C(4), C(6)
R -in d ex
Intensity
co llectio n
0.059
D iffrac to m e te r
37.9°
49.9°
0.036
D iffrac to m e te r
35.8°
56.0°
0.048
D iffracto m eter
50.3°
46.0°
OCH3
0 ^ /\)
e)
t-b u ty l
102
S
!I
x t-b u ty l
g)
t-b u ty l
TABLE 37
C o m parison of bond d ista n ce s fo r the
1 ,3 ,2 -dioxaphosphorinane s .
A tom s
aa
b
C
d
e
f
g
P(Z)-O(I)
1.56b
1.56(1)
1.57(1)
1.56(1)
1.568(4)
1.576(2)
1.588(3)
P(Z)-O(S)
1.58
1.57(1)
1.54(1)
1.58(1)
1.568(4)
.1.587(2) •
1.588(3)
P(2)=0
1.51.
1.48 (I)
1.44(2)
1.48(1)
1.443 (6)
P(Z)=S
—
P(Z)-X
1.55
1.59(1)
2.171(6)
O(I)-C(G)
1.46
1.45(2)
O(S)-C (4)
1.46
C(4)-C(5)
C(S)-C(G)
—
---- -
1.911(1)
1.927(2)
1.81(3)
1.567(6)
1.801(3)
1.807(6)
1.47 (2)
1.51(2)
1.457(7)
1.462(4)
1.470(5)
1.43(2)
1.49(3)
1.46(3)
1.457(7)
1.452(4)
1.470(5)
1.51
1.49(2)
1.50(3)
1.54(2)
1.510(8)
.1.508(5)
1.526(6)
1.53
1.49(2)
1.59(3)
1.49(2)
1.510(8)
1.507(5)
1.526(6)
—
—
a The le tte r s r e f e r to the compounds shown in T able 36.
^ Standard deviations a re 0.02-0.05 A.
•
103
------
———
TABLE 58
C om parison of bond angles fo r the
1 , 3 , 2-dioxaphosphorinanes.
Itl
JSL
JdL
JSL
JD- '
JSl
Q (l)-P (2 )-0 (3 )
104.6(5)°
106.6(6)° ■ 104.9(7)°
104.4(4)°
105.3(2)°
105.5(1)°
101.9(1) o
0(1 )-P (2 )-Y
110.1(5)
115.3(6)
113.8(8)
113.2(5)
112.6(3)
113.0(1)
114.3(1)
0 (1 )-P (2 )-X
109.5(6)
101.7(6)
104.4(5)
110.0(5)
104.6(3)
106.2(1)
104.6(2)
0(3 )-P (2 )-Y
110.2(6)
111.8(6)
116.1(8)
' 112.9(4)
. 112.6(3)
111.8(1)
114.3(1)
105.1(7)
107.0(6)
105.1(5)
107.5(4)
104.6(3)
105.9(1)
104.6(2)
X -P(2)-Y
116.6(7)
113.7(6)
111.5(7)
108.7(5)
116.1(3)
113.8(1)
115.6(2)
P (2)-Q (l)-C (6)
120.8(9)
117.7(9)
119.9(11)
119.7(7)
118.2(4)
120.4(2)
114.3(2)
O(I)-C(G)-C (5)
105.8(14)
110.5(13)
109.6(15)
. 110.5(10)
112.2(5)
110.8(3)
112.9(3)
C (G)-C(S)-C (4)
113.8(14)
109.9(14)
110.5(16)
107.7(10)
109.6(6)
108.3(3)
109.9(4)
C(S)-C (4)-0(3)
109.4(16)
112.0(13)
108.5(16)
110.7(9)
112.2(5)
111.8(3)
112.9(3)
C (4)-Q (3)-P(2)
116.9(11)
117.5(9)
121.0(12)
120.2(8)
118.2(4)
117.3(2)
114.3(2)
0 (3 )-P (2 )-X
■
aThe le tte r s r e f e r to the compounds shown in Table 36.
LOT
A tom s
105
to be a g e n e ra l c o rre la tio n betw een the d ih ed ral angle on the phosphate end of the
rin g and the size of the axial su b stitu en t w ith the exception of 2, 5- t -b u ty l- 2 th io -1 , 3 ,2 -dioxaphosphorinane fo r w hich th e t -butyl on th e phosphorus atom is
e q u a to ria l r a th e r than axial.
The c o rre la tio n follow s, in g e n e ra l, th at the
g r e a te r the flattening (sm a lle r d ih ed ral angle) the la r g e r th e su b stitu en t in the
ax ial positio n , Me > P h > B r > 0„
It is difficult to com pare th e Me and Ph g ro u p s
as to s iz e as f a r as w hat the 1 , 3-p o sitio n s and axial hydrogens see .
The phenyl
rin g is la r g e r in o v e ra ll d im ensio n s, but th e hydrogen on th e m ethyl probably
ap p ro ach es the axial hydrogens m uch c lo s e r, m aking it a p p ea r la r g e r s te ric a lly
th an the phenyl.
The hydroxy, m ethoxy, and phenoxy g roups a re co n sid ered to
be ju s t an oxygen atom since the hydrogen, m ethyl, and phenyl groups bonded
to the oxygen fo r the v ario u s compounds point away fro m th e axial position.
The siz e c o rre la tio n m ay be explained by s te r ic re p u lsio n s betw een th e axial
p o sitio n of the phosphorus atom and th e oxygen atom s in th e rin g plus the axial
m ethylene hydrogens.
T h ese s te r ic in te ra c tio n s m ay be re lie v e d by flattening
th e phosphorus end of the rin g , th u s, d e c re a sin g the d ih ed ral angle.
phenoxy-2-oxo compound see m s to be out of o rd e r.
The 2 -
T his m ay be because th e
d a ta w ere photographic and refin ed to an R -index of 0.115, m aking the a ccu racy
of the angle som ew hat u n c ertain .
The 2 , 5 -t-b u ty l-2 -th io compound does not
f it into the c o rre la tio n betw een B r and O w here one would expect to find su lfu r.
H ow ever, fo r th is compound, the phosphate end has been in v e rte d com pared to
106
th e o th e rs in the s e r ie s and the bulky t-b u ty l group in th e e q u a to ria l position.
The C (14) m ethyl on th e t-b u ty l is in p o sitio n to have s te r ic in te ra c tio n s w ith
th e oxygens in the rin g and the C(IO) m ethyl on the axial t-b u ty l group bonded to
th e C (5) position.
T hese s te r ic in te ra c tio n s would tend to co u n ter the flattening
e ffect of th e axial su lfu r and in c re a s e the d ih ed ral angle.
A nother way in which the s te r ic s tra in involving the ax ial su b stitu en ts at
phosphorus can be re lie v e d is by bending th e axial su b stitu en t tow ard the equa­
to r ia l su b stitu en t.
T his angle d e c re a s e s in th e o rd e r OH, M eO, P h , PhO , B r,
Me being 116.6, 116.1, 113.8, 113.7, 111.5, and 108.7°, roughly as p re d ic ted
by th e in c re a sin g s iz e of the group w ith the m ain exception of th e phenyl group.
T he o rd e r of the phenyl may be due to th e fa c t th at the la r g e r su lfu r atom is in
th e e q u a to ria l p o sitio n r a th e r than oxygen, m aking the ap p ro ach of the axial
g ro u p m o re difficult.
The m ean value fo r the O (I)-P(B )-X and O(S)-P(B)-X
a n g les v a ry little , (104.4 -1 0 8 .8 °), over the s e r ie s and show no firm size c o r r e ­
la tio n .
The O(I)-P(B)-O(S) angles re m a in alm o st constant, (1 0 4 .4 - 106.6°),
o v e r the s e r ie s .
W ith the exception of th e OH-compound, th e m ean angle of
O (I)-P(B )-Y and O(S)-P(B)-Y re m a in a lm o st constant o v er th e s e r ie s , (112.4 114.9°).
The angles O (I)-P(B )-X , O(S)-P(B)-X, O (I)-P(B )-Y , and O(S)-P(B)-Y
would not be expected to v a ry in any sy ste m a tic m ethod w ith the size of the
ax ial su b stitu en t X.
The d ih e d ra l angles betw een the plan es 0(1), 0(3), C (4), 0(6) and C (4),
107
C (5), C (6) show little differen ce fo r the eq u ato rial su b stitu en t, (5 3 .1 -5 6 .0 °). ■
F o r th e compounds containing axial su b stitu en ts on the C (5) p o sitio n , th e re is
som e flatten in g of the rin g w ith the d isu b stitu te d compound w ith the -C H g-B r.
group having le s s affect th a t the t -butyl g ro u p s.
T ins is p ro b ab ly due to s te r ic
re p u lsio n of the axial group w ith th e 1 , 3-oxygens in the rin g .
In the -C H g -B r
group, the B r points away fro m the rin g m aking co n sid erab ly le s s s te ric s tra in
than the la rg e t-b u ty l g ro u p s.
In the c ase of the 2, 5- t -butyl compound, th e re
is also p o ssib le s te r ic re p u lsio n p o ssib le betw een the two t-b u ty l groups which
could explain why the g re a te s t am ount of flatten in g of the c arb o n end of th e rin g
o c c u rs fo r th is compound.
SUMMARY AND CONCLUSIONS
The th re e 1 , 3 , 2-dioxaphdsphorinahe s tru c tu re s re p o rte d in th is d is s e r ­
ta tio n continues the study of six -m e m b e re d cyclic phosphorus com pounds, and
le ad s to a b e tte r understanding of the effects of su b stitu en ts on the conform ation
of the rin g (chair, boat, skew) as w ell as providing in fo rm atio n about the o r i­
entatio n al p re fe re n c e s of the g ro u p s.
C o m p ariso n w ith oth er s im ila r m o lecu les
is also m ade p o ssib le .
The conform ations fo r the seven I , 3 , 2-dioxaphosphorinanes whose
s tru c tu re s have been in v estig ated have all been the c h a ir.
A lso shown is an
ax ial p re fe re n c e fo r the su b stitu en t on th e phosphorus.
In v e stig ato rs have r e ­
p o rte d th is axial p re fe re n c e to be 1-2 k ilo c a lo rie s (7).
The exception in the
s e r ie s is the 2 , 5 -t- b u ty l-2 -th io -l, 3 , 2-dioxaphosphorinane w hose rin g co n fo r­
m ation is in v e rte d on the phosphate end of the rin g w ith re s p e c t to the r e s t of
th e 1 , 3 , 2-dioxaphosphorinanes and th e t -butyl on the phosphorus is eq u ato rial.
F o r th is compound, it a p p ea rs th a t s te r ic re p u lsio n s betw een th e bulky t -butyl
and the 1 , 3 -oxygens and the axial m ethylene hydrogens a re g r e a te r than the 1-2
k ilo c a lo rie p re fe re n c e fo r the axial conform ation.
A nother fe a tu re of th is s e r ie s of com pounds, is th a t th e re is a g en eral
flatten in g of the rin g , e sp e c ially on th e phosphate end.
T h e re ap p ears to be a
g e n e ra l c o rre la tio n betw een the siz e of the axial su b stitu en t on the phosphorus
109
and the am ount of flattening on the phosphate end of the rin g .
T his effect can be
see n in the d e c re a se of the d ih e d ra l angle (Y shown in F ig u re 21) betw een the
p la n es of the c h a ir as the size of the axial su b stitu en t on the phosphorus is in ­
c re a s e d , M e> Ph > B r > O.
T his sam e effect can a lso be seen with the axial
su b stitu e n ts on the C(5) end of the rin g , t -b u ty l> C H g-B r > H .
C(5)
F ig u re 21.
D ihedral angles between the planes of the c h a ir
fo r the I , 3, 2-dioxaphosphorinanes.
LITERATURE CITED
1.
Ahmed, F . R . , "NRC-10 S tru ctu re •F a c to r L e a st S quares (Block
D iagonal)", N ational R e s e a rc h Council, Ottawa, O ntario, Canada (1966).
2.
Ahmed, .F . R.. ," F o u rie rs fo r D isto rte d and U n d isto rted N ets".
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3.
Ahm ed, F .R . >"Symbolic Addition P ro ce d u re (C en tro sy m m etric)",
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C ouncil, O ttawa, O ntario, Canada (1966).
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B en tru d e , W. G . , p riv a te com m unication (1971).
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B en tru d e , W. G.. and K. C. Y ee, T e tra h e d ro n L e tte r s , 1970, 46_, 3999.
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Bondi, A ., J . P h y s. C hem . , 1964, 68, 441.
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Edm undson, R . S. , T e tra h e d ro n , 1964, 20_, 2781; K. D. B a rtle , R. S.
Edm undson, and D. W. Jo n es, I b id ., 1967, 23^, 1701; R. S. Edm undson
and E . W. M itchell, J . Chem . Soc. (C), 1967, 2091; M. T suboi, F.
K uriyagaw a, K. M atsuo, and Kyogoku, B ull. C hem . Soc. Ja p a n , 1967,
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In te rn a tio n a l T ables fo r X -Ray C ry stallo g ra p h y , Vol. Ill, T ables 3 .3 .1A,
3.3.2C . B irm ingham : Kynoch (1962).
N ational
Ill
13.
Johnson, C0 K . , "O RTEP: A F o rtra n T h e rm a l E llip so id Plot P ro g ra m
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K ainosho, M. and T 0 Shim ozaw a, T e tra h e d ro n L e tte r s , 1969, 865.
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Nixon, J . F 0. and R. S c h m u tz le r, S p ectro ch im . A cta, 1966, 22, 565.
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Shaw, R. A . , to be published.
18.
Shaw, R. A.
19.
S te rn h e ll5 8. , R ev. P u re and Appl0 C h e m . , 1964, 14, 15; Ibid. , Q u a rt.
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20.
S te w a rt5 R 0 F . , E 0 R. DavLdson5 and W. T 0 Sim pson, J . Chem . P h y s. ,
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Stout5 G. H. and L 0 H. J e n s e n 5 "X -R ay S tru ctu re D eterm in atio n ", p. 454,
New Y ork: M acm illan (1968).
22.
Syntex A nalytical In s tru m e n ts 5 p ro g ra m sy ste m fo r the Syntex Pg^ D if­
fra c to m e te r equipped w ith a PD P -8 co m p u ter.
23.
D rag o , R 0 S. , "P h y sical M ethods in Inorganic C h e m istry ", p. 270, New
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337, B oston: A llyn and B acon (1970); J 0 W 0 E m sle y , J . F een ey , and
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and M. Woods, P h o sp h o ru s, 1_, 41.
"LIBRARY
M ontana S ta te UmxroiS^
Bozeman
MONTdMA Cr * i - ____
3 1762 10011658 9
Warrant, Ronald W
Structural studies
of organo-phosphorus (v)
esters and thioesters
DATE
ISSUED TO
C r in
zH r-
7 6 /< JU>
ft1 %
zy/
-L
V /zi
'1
vH
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