1, 8-naphthyridine copper complexes
by Eric Lee Enwall
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 Eric Lee Enwall (1968)
Abstract:
Copper complexes of 1,8-naphthyridine were prepared and the structure of
Bis-(1,8-naphthyridine)-copper (II) chloride determined. Procedures were developed to prepare
1,8-naphthyridine in amounts suitable for use as a ligand for the preparation of coordination
compounds. A new preparation of 4-methyl-1,8-naphthyridine was developed. I, 8-NAPHTHYRIDINE COPPER COMPLEXES
by
ERIC LEE ENWALL
A th esis submitted to the Graduate Faculty in partial
fulfillm ent of the requirem ents for the degree
of
DOCTOR OF PHILOSOPHY
in
CHEMISTRY
Head, Major Department
Chairman, Examining Committee
Graduate Dean
7/
MONTANA STATE UNIVERSITY
Bozeman, Montana
D ecem ber, 1968
iii
•ACKNOWLEDGEMENT
I w is h to e x p r e s s my a p p r e c ia tio n .to .th e fa c u lty o f.th e Departm ent o f
■ C hem istry, for th eir fa ith in me a s a. stu d en t and.for th eir fin a n c ia l support
:• through te a c h in g and r ese a rc h a s s is t a n t s h ip s „ A ppreciation i s a ls o e x ­
p r e ss e d to th e D epartm ent o f Health. E ducation and W elfare for a n .N .D .E .A .
fe llo w s h ip o
To ;the unnamed m ultitude o f graduate stu d en ts and frien d s who h elp ed
• me in e v er y w a y , I w is h .to e x te n d :th a n k s, e s p e c ia lly to D r..Arthur Howard
w ith ou t w h o se gu id a n ce the s y n th e tic portion o f.th is work, w ould have b een
.. im p o s s ib le .
To D r. K enneth Emerson I extend, my th a n k s fo r,h is g u id a n c e , en cou r­
agem en t and g o o d humor in .tim es o f n e e d .
To my parents who, provided for my ed u ca tio n by th eir s a c r ific e s and
• w ith th eir c o n sta n t encouragem en t and fa it h , and to my w ife for her fa ith in
.: m e, sim p le thanks can n ever exp ress, my in d e b te d n e ss .
TABLE OF CONTENTS
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X,
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Introduction
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Experim ental
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■ Preparation, o f C oordination. Compounds „ . . ,
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X-Ray A n a ly tica l T ech n iq u es . . . . . . . . . .
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Summary
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A ppendix A
- S p e c tr o sc o p ic and M a g n etic D ata . . . . .
0
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.
50
A ppendix B
Computer Programs .....................................................
64
A ppendix C
C rystallograp hic. D ata arid G o n io sta t G eom etry . . .
Literature C ited . . .
69
.83
V
L ist o f T ables
Table N p . . T itle
. Page
I.
.Base ,Strength o f P yrid ines
........................................... ...
34
II.
M eltin g P oin ts o f 1, 8 -N ap h th yrid in e . . . . . . . . . . . . . . . .
35
III.
G as C hrom atographic R etention Tim es . . . . . . . . . . . . . . .
36
.IV.
C oord in ates o f E quivalen t P o s itio n s for the S p ace
Group C 2 /c . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
,V.
C oord in ates o f E quivalen t P o s itio n s in th e S p a ce
Group Ce
VI.
......................................................................................................... 39
D e v ia tio n from th e L e a st Squares .Plane for Square
.Planar G eom etry . . . . . . . . . . . . . . .
VII.
j . . . . . . . . . . . . .
63
S in g le C rystal D ata for B is-(1 ,8 -n a p h th y r id in e )cop p er (II) ch lorid e . . . . . . . . . . . . . . . . . . . . . . . . . . .
XII.
62
Room Temperature M a g n etic S u s c e p tib ilitie s and
. M a g n e tic M om ents . . . . . . . . . . . . . . . . . . . . . . . . . . .
XI.
61
Proton M a g n etic R eson an ce S h ifts and C oupling C on­
s ta n ts o f I , 8-n ap h th yrid in e .. . . . . . . . . . . . . . . . . . . . . .
X.
60
The-. M o st I n te n se Bonds in. th e U ltr a v io le t Spectra
o f N aphthyridine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1IX.
. 43
E xtin ction C o e ffic ie n ts o f B is-(l,.8 -n a p h th y r id in e )copper (II) ch lorid e in W ater ...........................................................
VIII.
39
73
S in g le C rystal D ata for B is-(1 ,8 -n a p h th y r id in e )-
Copper (II) bromide ...................................................................................... .75
XIII.
S in g le C rystal D ata for M ethyl naphthyridine copper
,
• C om plex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
vi
xw ,
F inal Atom P o s itio n s and Standard D e v i a t i o n s ............. ...
.76
XV.
Final A nisbtropic Therm al.Param eters
77
XVI.
Bond A n gles and D is ta n c e s , for B is-(1 ,8 -n a p h th y r id in e )-
XVII.
XVIII.
. . . . . . . . . . . . . . . .
Copper(II) ch lorid e . . . . . . . . . . . . . . . . . . . . . . . . . . . .
79
Atom P o s itio n s for F irst D ata C o lle c tio n . . . . . . . . . . . . . .
80
, M o st.In te n se D iffraction. L in es for B is - ( 1 ,8 n ap h th yrid in e)-c o p p e r (II) ch lo rid e (photographic
ddlt^l) . . . .
XIX.
.. . . . . . . . .
. . . . .
. . . . . . . . ■<.
M ost In te n se D iffraction. L in es for 1, 8 -n a p h th y rid in e)copper. (II) ch lorid e (photographic data) . . . . . . . . . . . . . . .
XX.
80
81
M ost. I n te n s e D iffractio n L in es for 18, -n a p h th y rid in eco p p e f (II) chloride, (d iffractom eter data, p o s itiv e
a n g le s onl y )
XXI.
. . . . . . . . . . . .
. . . . . . . . . . .
.. . . . . . . .
81
B is-(1 ,8 -n a p h th y r id in e )-c o p p e r (II) chloride. . . . . . . . . . . .
82
O b served and C a lc u la te d Structure F actors for
v ii
LIST OF FIGURES
Figure
N o.
T itle
1.
Page
. B is-(p y rid in e-1 -^ o x id e)co p p er(II)..chloride .............................
.2
2.
One Layer o f Copper Formate.
Tetrahydrate Structure . . . . . . .
3.
The Structure o f Copper A ceta te M onohydrate . .....................................
4
4.
C u-C u D elta Bond Form ed'by Overlap, o f d x
5
5.
1 ,8 N aphthyridm e . . . . . o .
. . . . . . .
2
3
_y2 O rb itals . . . . . .
. . . . . . .
. . . . . . . . . .
6
, 6.
• S y n th e sis o f L ,8 -N ap h th yrid in e ..........................
8
. 7.
• A lternate Ring C losu res. . . . . . . . . . . . . . . . . . . . . . . . . . . .
9
' 8.
. 4 - M e t h y i- l, 8-N ap h th yrid in e D e riv a tiv e . . . . . . . . . . . . . . . . .
9
9.
A tm ospheric P ressure H ydrogenator . . . . . . . . . . . . . . . . . . . . .
13
10.
A lternate Ring C losu re Products ..............................................................
30
11.
. . . . . . . . . . . . . . . . . . . . .
36
12.
R eson an ce Structures for 2 ,,6 -d ia m in o -p y r id in e . . . . . . . . . . . .
31
1,3.
Tautom erism in \2 -h y d ro x y p y rid in e
33
14.
.-Binaphtlhyridine
15.
■■TTr-Electron D e n s itie s in Pyridine
..........................................................................................................37
One M o le c u le o f B is - ( 1 ,8 -n a p h th y rid in e)-co p p er (II)
ch lorid e P rojected on the b - c Plane
16.
17.
.................................
One M o le c u le o f B is -(1 , 8 -n a p h th y rid in e)-co p p er (II)
........................................................... 42
P acking Diagram for B is- ( 1 , 8 -n a p h th y rid in e)-c o p p e r (II)
ch lorid e, .................................
19.
41
■G eom etry o f Copper C oordination, ..................................................................... 42
ch lorid e P rojected on. th e a - c P la n e
18.
. . . . . . . . . . . . . . . . . . . .
. I ,S -N a p h th y rid in e Bond Length and.Bond A ngles
44
......................................46
v iii
2,0.
. IR Spectrum of. 2 -H y d ro x y -4 -M eth y l-: 7-A m ino-1, .8■N aphthyridine
21.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
UV Spectrum o f 2 -h y d r o x y -4 -m eth y l - 7 -am ino - 1 ,8 naphthyridine ...............................................................................
-22 „
.51
.51
. IR Spectrum o f 2 , 7 -d ih y d r o x y -4 -m e th y l-l,.8 -n a p h th y r id in e ............. 52
23.
UV Spectrum o f 2 ,7 -d ih y d r o x y -4 -m a th y l- I , 8-n aphthyridin e . . . .
24.
IR.Spectrum o f 2 ,7 -d ic h lo r o -4 -m e .th y l-l./ 8 -n a p h th y r id in e ................ 53
25.
. UV Spectrum o f . 2 , 7 - d ic h lo r o -4 -m e th y l-l,.8 -n a p h t h y r id in e ............. 53
26.
. IR Spectrum o f 2 ,7 -d ih y d r a z in o -4 - m eth y l- 1 ,8 -n a p h th y rid in e
27.
54
UV Spectrum o f 2 , 7 -d ih y d r a z in o -4 -m e th y l-l, 8 naphthyridine
28.
...
52
............. ......................... ...................... 54
..IR Spectrum o f 4 -m e .th y l-l, .8-naphthyridine . ................................. ...
55
29.
UV Spectrum o f 4 -m e th y l- 1 , 8-n ap h th yrid in e .............................
55
30.
IR Spectrum o f 2 - a m in o - 7 - h y d r o x y - l,8 -n a p h th y r id in e .................
56
31.
UV Spectrum o f 2 -a m in o - 7 -h y d r o x y -1 , 8-n aphthyridin e
32.
IR Spectrum o f 2 ,7 -d ih y d r o x y -l, 8-n aphthyridin e . . . . . . . . . . .
57
33.
UV Spectrum o f 2 , 7 -d ih y d r o x y r l, 8-n aphthyridin e . . . . . . . . . . .
57
34.
IR Spectrum o f 2 , 7 - d ic h lo r o - l, 8-n aphthyridin e . ..........................
58
35.
UV Spectrum of. 2 , 7 -d ic h lo r o -l, 8 -n a p h th y r id in e ..........................
58
36.
IR Spectrum o f 1 , 8-n ap h th yrid in e . ..................................................................... 59
37.
38.
■ UV Spectrum o f . l , 8-n aphthyridin e ................................. 1.................
59
V is ib le Spectrum o f B is-(1 ,8 -n a p h th y r id in e )-c o p p e r (II)
ch lorid e in W ater
39.
. . . . . . . . 56
.................................60
Ewald Diagram ..............................................................................
70
; iX
4.0.
A verage S c a le for D iffractom eter D ata
8-
n ap hth yrid ine)-c o p p e r (II) ch lorid e . . . . . . . . . . . . . . . . . . . . . .
' 41.
74
Numbering Diagram .for Bis -(naph thyridin e) -c o p p er (II)
ch lorid e . . . . . . . . . . O . . . . . . .
. . . . . . .
. . . . . . . . . . . . .
78
ABSTRACT
Copper c o m p le x e s o f L, S-naph thyridine w ere prepared an d .th e str u c ­
ture o f B is- ( I 8 -n ap h th yrid in e )-c o p p e r (11) ch lo rid e d eterm in ed . Procedures
w ere d e v e lo p e d .to prepare 1 , 8-n ap h th yrid in e in am ounts su ita b le for use„as
, lig a n d for. th e preparation o f coordination, co m p o u n d s. A n ew preparation o f
4 - m e t h y l- l, 8-n ap h th yrid in e w as d e v e lo p e d .
INTRODUCTION
I.
GENERAL
. All copper (II) com pounds e x h ib it param agnetism b e c a u s e o f the u n 9
paired electron , r e su ltin g from th e e le c tr o n ic con figu ration (3d ) o f copper (II).
If th e o n ly contribu tion to the m agn etic moment for any compound co n ta in in g
an atom w ith unpaired e le c tr o n s cam e from th e e lectro n spin.,, th e m agn etic
mom ent for the atom w ith the unpaired e le c tr o n s w ould be g iv e n by .the e x ­
p ressio n :
, |i = Vn(n+2)
w here n is .t h e number o f unpaired e le c tr o n s on th e atom
. y, i s . the m agn etic moment in Bohr m agnetons
The "spin only" v a lu e .fo r a c o p p e r (II) atom w ould then be 1.73 Bohr m agne­
to n s . The e le c tr o n sp in i s not th e o n ly contribution to th e m a g n etic moment.
In m ost c a s e s th e sp in orbit co u p lin g m ust be c o n sid e r e d . If th e sp in orbit
c o u p lin g in copper (II) com pounds i s e stim a te d frojh th e v a lu e s ob tain ed for
.the free io n , th e m agn etic moment i s e x p e c te d to be about 1 .9 -Bohr m agne­
tons. ( I ) . A third, contribution to th e m a g n etic moment may a r ise from the
orb ital momentum o f th e unpaired e lec tr o n on the copper a to m . The fir st tw o
. con trib u tion s are a lw a y s e x p e c te d for copper (II), but the third contribution
may or may not be p r e se n t depend ing on the symmetry of: th e copper c o ­
ord in ation .. If .the c r y sta l fie ld surrounding the copper (II) atom is octah ed ral
or o f sym m etry low er.th an c u b ic , the orbital contribution to th e m agn etic
moment i s e x p e c te d to -b e qu en ch ed ( I ) . If. th e symmetry i s tetrahedral the
orb ital contribution, is not e n tir e ly q u e n c h e d , and the d eg ree o f quenching
may depend on the-.degree o f d isto rtio n from true tetrahedral sym m etry. In
•2
any c a s e th e m agn etic moment for copper (II) is e x p e c te d to be 1.9 Bohr m ag­
n e to n s or greater.
A-number o f copper (II) com pounds e x h ib it m agn etic m om ents w hich are
b e lo w 1.9 Bohr m a g n eto n s. T h ese com pounds w ith "subnormal" m a g n etic
m om ents may be d iv id ed .into tw o - c la s s e s d ep en d in g on th eir m olecu lar and
c r y s ta l structure. (2 ).. In on e typ e o f subnorm al copper (II) com pounds ,. th e
stru ctu res ty p ic a lly have tw o copper atom s bonded to a common n o n -co p p er
atom., or to a common lig a n d m o lecu le or io n . The n o n -co p p er a to m s , lig a n d
m o le c u le s , or io n s are sa id to "b rid g e" th e copper a to m s. In. many c a s e s
th e s e b rid ges c o n n e c t the copper atom s in to lo n g -ch a in s or p la n e s .
Bis -(p y rid in e - 1 -o x id e ) copper (II) ch lorid e. (F ig . I) and copper formate
tetrahydrate (F ig . 2) are ty p ic a l o f com pounds w ith bridged stru ctu res w h ich
h ave subnorm al m agn etic m om en ts,
B is-(p y r id in e -l-p k id e ) copper (II) ch loride (3)
Figure I
3
One Layer of. Coppdr Formate Tetrahydrate Structure
(W^ter M oljScules Omitted) (4)
Figure 2
C opper a c e ta te m onohydrate (F ig. 3) i s ty p ic a l o f the s e c o n d ty p e o f copper
: (TI) com pounds w ith subnormal- m om ents. In-th is typ e o f structure thd copper
atdins are a ls o b r id g e d , but th ey o ccu r a s is o la t e d , m u ltip ly bridged pairs
. w ith a short cop p er-co p p er d is t a n c e . The number o f com pounds in th is .
s e c o n d c la s s i s very sm a ll,, w ith the b in u clea r structure c le a r ly dem on­
strated in fe w com pounds other- than copper (II) c a rb o x y la te s , and not in a ll
copper (II) c a r b o x y la te s .
4
( C .
The Structure o f Copper A ceta te M onohydrate
F ig u re.3
In-both ty p e s o f stru ctu re, som e form o f sp in co rrela tio n m ust o ccu r to
low er:th e m agn etic m om ent.. In copper formate tetra h y d ra te, M artin (5) has
s u g g e s te d that. the;.iff-system o f the ■form ate io n s can overlap w ith .the d
■
'
'‘v ' . :.
,orb itals o f th e copper atom s providing a pathw ay for sp in c o rrela tio n . This
typ e o f in tera ctio n i s known a s "su p erexch an ge" . In copper a c e ta te mono­
h yd rate, a sim ila r kind o f su p erex ch a n g e co u ld occur,, but th ere is a sec o n d
p athw ay a s well;...,The. co p p er-co p p er d is ta n c e in copper a c e ta te m onohydratg-. i s -.2.64
w h ich i s c lb s e to the;! sep a ra tio n in cop p er m etal (§ ). The
short d is ta n c e cou ld a llo w th e o v erla p o f d o rb ita ls on th e tw o atom s to form
. a p artial c h em ica l bond. Bond form ation is accom p an ied by s p in pairing
• w h ich w ould reduce .the. m agn etic m om ent.. A d irect coppery-copper
5
in te r a c tio n cou ld tak e tw o forms: the d^2 o rb ita ls o f th e capper atom s co u ld
overlap, to form a p artial sigm a b o n d , or th e d^2 _
orbitals cou ld overlap
to form a w eak d e lta b on d .(F ig. 4 ).
C u-C u D elta Bond Formed by O verlap o f d ^ V y .2 O rbitals
Figure 4
■ The sigma, bond p rop osal h a s-b ee n supported by Forster and
B a llh a u sen (7) and th e d e lta bond supported by F ig g is and M artin (8 ), who
p r o p o s e d .it, and more r e c e n tly by K okoszka (9)..
I
'
.
V.
I -
No, d e fin itiv e experim ent has b een prop osed to d e c id e b etw een the
p o s s ib le m odes o f in ter a c tio n in cqpper a c e ta te monohydpate a s co rrect.
One p o s s ib le app roach to. th e so lu tio n o f th e problem is to s y n th e s iz e c o m ■
■
■
pounds, w h ich h ave is o la te d pairs o f copper atom s bridged in a manner s im i­
lar to, the bridging in copper a c e ta te m onohydrate and. w h ich have sim ila r
co p p er-co p p er d is t a n c e s . Study o f th e m a g n etic p roperties o f quch com ­
pounds sh ou ld help to determ ine th e true p a th o f in te r a c tio n . If su ch
6
com pounds are tq be s y n th e s iz e d , lig a n d m o le c u le s or io n s are required
w h ich m eet certain, geom etric requirem ents . The lig a n d m ust be b id en tate
w ith th e coord in atin g atom s app roxim ately 2 .6 $ . apart. Two im m ediate p o s ­
s ib ilit ie s would, be a ceta m id e and a ceta m id in e w h ich m ight form the copper
a c e ta te structure w ith .th e s lig h t m o d ifica tio n that nitrogen atom s w ould
o c c u p y som e or a ll o f th e o x y g en p o s itio n s in copper a c e t a t e . Attempts to
prepare popper a ceta m id e and copper a ceta m id in a te have been, reported (10,
1,1), but no com pounds w ith the d e sir e d geom etry have been, o b ta in e d .
Another lig a n d w h ich m ight form the d e sir e d b in u clea r stru ctjire.is
1 , 8-n ap h th yrid in e (F ig . 5 ).
1, 8 -N aph thyrid ine
F igure;5
The tw o nitrogen atom s in. I , S^naphthyridine w h ich co u ld a c t a s c o ­
ordination s it e s w ould be e stim a te d to be .2 .4 $ , the sep a ra tio n o f the cor­
resp on d in g carbon atom s in n a p h th a len e, apart. If the b in u c le a r .structure
w ere ob tain ed in a copper 1 , 8-n ap h th yrid in e com pound, th e cop p er-co p p er
d is ta n c e m ight a ls o be shorter than 2. 6 4 $ and the co p p er-co p p er bond order
■ :
in c r e a s e d .if su c h a bond, e x i s t s . An in c r e a s e d bond order w ould r e su lt ini an
e v en low er m a g n etic mom ent than th at found in copper a c e tp te m pnohydrate.
7
S in ce I ,S-H aphthyridine-C opper(II) c o m p le x e s m ight h ave a b in u clea r
structure sim ila r to the structure o f copper a c e ta te m on ohydrate, it w as d e ­
c id e d to prepare and determ ine, th e structure o f copper (II) com pounds u sin g
1, 8-n ap h th yrid in e and 4 -m e th y l- 1 , 8-n ap h th yrid in e a s lig a n d s .
II.
HISTORY
■■ The fir s t s y n th e s is -a n d is o la tio n of. a fu lly arom atic I.., 8-n aphthyridin e
d e r iv a tiv e w as.reported, by Koller (12).in 1 9 2 4 . He ob ta in ed th e parent b a s e
by .the reaction, se q u e n c e g iv e n in F ig . 6 .
;.
S y n th e sis o f 1 , 8 -N ap h th yrid in e (Koller)
Figure 6
Earlier-, other authors •had-reported s y n th e s is , o f jf/S -n a p h th y rid in e d e r iv a ■ •
■ .'.v- v
•
’
'
'
... •
f iv e s (13); M ost o f th e s e s y n th e s e s w ere Skraup or D obner-vbn. M iller
s y n th e s e s u sin g 2 -am in op yrid in e and. have b een show n .(13) to be s y n th e s e s
o f 1, 4a-rd lazan ap h th alen es v ia .the a ltern a te ring c lo s u r e (Fig.. 7 ).
_ V'.
9
1, 8-n ap h th yrid in e
+
S H2
C
I
C
1, 4 a -d ia za n a p h th a le n e
Alternate- Ring C lo su r es
Figure 7
S ied e (14) reported th e s y n th e s e s o f 4 - m e t h y l- l, 8-n ap h th yrid in e derivatives^
by th e se q u e n c e given , in F ig . 8 .
I
POCl
N
'
4^-M ethyl-l ,S -N a p h th y rid in e D e riv a tiv es. (S eid e)
Figure. 8
10
In -th is c a s e , th e s te r ic hindrance to c y c liz a tio n a t the ring nitrogen w as
s u ffic ie n t to g iv e p referen ce to th e 1, 8-n ap h th yrid in e produ ct. Brown.(15)
h a s a ls o reported th is sam e sy n th e tic s e q u e n c e w ith a fe w m o d ific a tio n s .
The c o n v e rsio n o f 2 , 7 - d ic h lo r o - 4 - m e t h y l- l, 8-n ap h th yrid in e to 4 -m eth y l1 . 8 - naphthyridine by c a ta ly tic hydrogenation w a s reported by O ch ia i and
M iyak i (16).
. In 1 9 6 6 , C arb on i, S e ttim o , and P irisin o (17) reported th e s y n th e s is o f
2 -a m in o -7-h y d r o x y -1 , 8-n ap h th yrid in e from 2 , 6-d iam in op yrid in e and m alic
a c id . Paudler and Kress (18) reported in 1967, the is o la tio n o f 1 ,8 naphthyridine from a Skraup rea ctio n on 2 -am inopyridine in w h ich th ey u se d
m e ta -n itro b en zen e s u lfo n ic a c id a s th e o x id iz in g a g e n t. They proved .the
1 . 8 - naphthyridine structure by proton m a g n etic r eso n a n ce s p e c tr o s c o p y .
Paudler and Kress (19) a ls o prepared 4^ -m eth yl-l.,8-n aphthyridin e and char­
a c te r iz e d it in. the sam e m anner. •
E xcept for th e gold s a lt o f 1, 8-n ap h th yrid in e u sed by R oller (12) to
c h a r a cter iz e 1 , 8 -n a p h th y rid in e, no other com pounds u sin g 1 ,8-naphthyridine
or 1 , 8-n ap h th yrid in e d e r iv a tiv e s have b een rep o rted .
EXPERIMENTAL
I.
PREPARATION OF ORGANIC BASES
A. Preparation, o f I , 8-N ap h th yrid in e
2 -A m in o -7 -H y d r o x y -l, 8 -N aph thyrid ine
The preparation. 2 -h y d r o x y -7 -a m in o -1 , 8-n aphthyridin e w a s e s s e n t ia lly
th at o f C arb on i, P irisin o and S e ttim o .(17). To a mixture o f 22 g . o f 2 , 6 diam inop.yridine and .30 g . o f m a lic a c id w a s added 100 m l. o f su lfu ric a c id .
The a c id w as added s lo w ly a t fir s t w ith stirrin g un til the s o lid w a s w e t. The
rem ainder o f the su lfu ric a c id w a s added and th e mixture s lo w ly heated, un til
;the co p io u s production o f g a s su b sid e d and .then h ea ted stron gly, for.thirty
m in u te s . The so lu tio n w a s poured o n to ic e and n eu tra lized w ith c o n c e n ­
trated ammonium hydroxide to. th e litm u s end p o in t. The product w as c o l­
le cted . by suction, filtra tio n and. dried, in th e a ir . The e stim a te d y ie ld o f
impure product w a s 90%. The compound w a s purified by r e c r y sta lliz a tio n
from dim ethylform am ide. Spectral data a re;g iv en in A ppendix A, F ig . 3.0, 3 1 .
2 ,.7 -D ih y d r o x y -l, 8-N ap h th yrid in e
A s o lu tio n o f 10 g . o f 2 -h y d r o x y -7 -a m in o -1 , 8-n ap h th yrid in e in 200 m l.
o f 10% su lfu ric a c id w a s c o o le d b e lo w 4 ° C . and a saturated so lu tio n o f
sodium n itrite w as added drop w is e u n til th e so lu tio n g a v e a p o s itiv e
p o ta ssiu m io d id e -sta r c h , t e s t tw o minutes, after-th e la s t addition, o f sodium
n i t r i t e .. More co n cen tra ted a c id s o lu tio n s.r e d u c e d the y ie ld . The slurry w a s
added ca re fu lly but q u ick ly to 400 m l. o f b o ilin g w ater and th e y e llo w pre­
c ip ita te ,c o lle cte d . by su c tio n filtr a tio n . An e stim a te d y ie ld o f 75% o f crude
.12
product w as o b ta in e d . The s o lid w a s dried in. the air and pu rified for s p e c ­
tral d ata by c r y s ta lliz a tio n from g la c ia l a c e t ic a c id . Sp ectral data are g iv e n
..in A ppendix A, F ig . 3 2 , 3 3 .
■2 .,.7 -D ic h lo r o -l, 8 -N aph thyrid ine
A 10 g . portion o f 2 , 7 -d ih y d r o x y -1 , 8-n ap h th yrid in e w a s m ixed w ith
. 10 g . o f phosphorus p en ta ch lo rid e and ,covered w ith phosphorus o x y c h lo r id e .
■ The mixture w a s h eated s lo w ly un til th e in itia l rea ctio n su b sid e d and then
reTliixed for thirty, m in u te s . The slurry w a s th en poured onto ic e and
neutralized, w ith con cen trated ammonium hydroxide to th e litm u s end p o in t.
An e stim a te d y ie ld o f 90% o f impure product w as o b ta in e d .. The tan so lid
w a s r e c r y s ta lliz e d from b e n z e n e . The pu rified 2 , 7 - d ic h lo r o - l,8 naphthyridine w as a m ass o f s ilv e r y p la te s w h ich sublim ed ab ove 175®C.
S p ectral data are g iv e n .in Appendix A, F ig . 3£, 3 5 .
1 , 8 -N aph thyrid ine
The c a ta ly tic red uction o f 2 ,7 -d ic h lo r o -l,8 -n a p h th y r id in e w a s done in
th e atm osp h eric p ressu re hydrogenator d escrib ed , b e lo w . A m ixture o f 2 .0 g .
o f impure 2 , 7 -d ic h lo r o -l,8 -n a p h th y r id in e and 1 . 0 g . o f 5% palladium on
ca lciu m carbonate w as p la c e d in. th e hydrogenator and, th e apparatus purged
.. w ith .h y d r o g e n . A 20 m l. p o rtio n .o f 5% p o ta ssiu m hydroxide in m ethanol w a s
s lo w ly added to th e hydrogenator and .the slurry v ig o r o u sly stirred, un til .the
uptake o f hydrogen, c e a s e d . The slurry w a s su c tio n filter e d tak in g care to
- k e e p .th e c a k e w e t to p reven t the c a t a ly s t from ig n itin g . The s o lv e n t w a s
.then, removed, by s lo w evaporation, and th e r esid u e ex tra cted w ith eth y l
a c e t a t e . The impure 1 , 8-n ap h th yrid in e w a s c r y s ta lliz e d from th e e t h y l '
V-:
13
a c e ta te by s lo w evap oration o f th e s o lv e n t and pu rified by su b lim ation under
va cu u m .. The y ie ld o f impure 1 , 8-n ap h th yrid in e w as e stim a te d to be 90%.
T he.I , B -naphthyridine w as not h y g r o sco p ic and w a s stored in a ir. Spectral
. data are g iv e n in A ppendix A, F ig . 36, 37.
An. atm osp h eric pressure, hydrogenator.w a s b u ilt for th e c a ta ly tic re­
d u ction o f d ich loron ap h th yrid in es; . a.:drawing of. the apparatus i s show n
below :
VAC
A. le v e lin g bulb
F. red uction fla sk
B. g a s buret
G. liq u id reserv o ir
C . bubble-trap
H . sto p co ck
D . . three w ay sto p c o c k . v
I . m agn etic spinbar
E . drying tube (calciu m chloride)
J. sto p co ck
•?
A tm ospheric P ressu re H ydrogenator
Figure" 9
The m aterial to be red u ced (a so lid ) and th e c a ta ly s t (a so lid ) w ere p la ced
.. in th e .f la s k F w ith a spinbar and th e apparatus a s s e m b le d . The sto p c o c k D
w a s op en ed to vacuum to rem ove a ll air from the s y ste m and then, opened to
14
th e hydrogen su p p ly .. A s lig h t p ressu re o f hydrogen w a s produced at the g a s
in le t and;the .stop cock J op en ed to f ill th e buret B (p r e v io u sly fille d w ith d e ­
g a s s e d water) w ith hyd rogen. The stop cock . D w as c lo s e d and th e s o lv e n t
. poured in to the. liq u id reserv o ir G . T he.liquid, le v e l in. th e le v e lin g bulb w a s
a d ju sted to eq u al the le v e l in. th e buret and the sto p c o c k H ca re fu lly ■
o p e n e d . A djustm ent o f th e le v e lin g bulb a llo w e d th e .liq u id to, en ter the
fla s k F and a ll sto p c o c k s w ere c lo s e d . The stirrer w as sta rted and red u c­
t i o n continued, u n til g a s uptake c e a s e d . To quench th e r e a c tio n , sto p c o c k J
w a s c lo s e d , sto p c o c k £) w as op en ed to. vacuum and th e hydrogen rem oved.
S top cock D w a s o p en ed to nitrogen and the flask, rem oved.
B. Preparation o f 4 - M e t h y l- l, 8-N ap h th yrid in e
2 - Hy d roxy- 4 - M eth y l - 7 -Amjijfao-1, 8-N aph thyrid ine
The preparation o f 2 -h y d r o x y -4 -m e th y l-7 -a m in o -l, 8-n aphthyridin e
"w a s e s s e n t ia lly .t h a t o f Brown.(15). To 25 g . o f 2 , 6-d iam in op yrid in e and
30 g . o f e th y l a c e ta te w a s added 100 m l. o f .ortho p h osp h oric acid; the m ix­
tu re w as heated, for on e hour. The r esu ltin g so lu tio n w a s poured onto ic e
and n eu tra lized w ith con cen trated ammonium hydroxide to th e litm us end
.. p o in t.. The p r e cip ita te w a s c o lle c te d by su c tio n .filtr a tio n and. d ried .in air to
g iv e a tan s o lid . The y ie ld of.im pure product w a s e stim a te d to be 80%. The.
compound w as pu rified for s p e c tr a l a n a ly s is by the method, o f S eid e (14); a
slurry o f th e impure compound in. b o ilin g w ater w a s a c id ifie d w ith drop w is e
. ad d ition o f co n cen tra ted hyd rochloric ■acid, until, m ost o f th e s o lid had
'
. d is s o lv e d . The so lu tio n w a s filter e d w ith su c tio n .a n d c o o le d . The
2 -h y d r o x y l-4 -m e th y l- 7 ^ am in o - 1 , 8-n ap h th yrid in e p recip ita ted and w as
15
c o lle c te d , by su c tio n filtra tio n and dried in a ir. Sp ectral data are g iv en in
A ppendix A, F ig . 20,, 2 1 .
2 ,-7-D ih y d r o x y l-4 -M e th y l-1 , 8 -N aph thyrid ine
The preparation o f 2., 7 -d ih y tir d x y -4 -m e th y l-l, 8-n ap h th yrid in e w as
e s s e n t ia ll y th at o f S eid e (14). A 25% or 30% su lfu ric a cid so lu tio n w as u se d
to d is s o lv e 10 g . o f crude 2 -h y d r o x y -4 -m e th y l-7 -a m in o -l, 8 -n a p h th y rid in e.
The so lu tio n w a s c o o le d t o l e s s than 4 ° C . and a (saturated so lu tio n o f 1 '
■■
.
sodium n itrite w as added drop w is e u n til th e so lu tio n rea cted p o s itiv e ly to
p o ta ssiu m io d id e -sta r c h .tw o m inutes after th e la s t sodium n itrite a d d itio n .
The slurry w as then, added c a r e fu lly but q u ic k ly to 400 m l. o f b o ilin g w ater.
T h e,resu ltin g s o lid w a s c o lle c te d , by su c tio n filtra tio n and. dried in a ir . The
y ie ld o f impure product w as estim ated , to be 60%. The compound w as puri­
fie d for sp e c tr a l a n a ly s is by re cry s ta lliz a tio n from g la c ia l a c e t ic a c id .
Sp ectral data are g iv e n in A ppendix A, F ig . 22, 2 3 .
2 . 7 - D ic h lo r o - 4 - M e t h y l- l, 8 -N aph thyrid ine
The preparation o f 2., 7 -d ic h lo r p -4 -m e t h y l-l, 8-n aphthyridin e w as
e s s e n t ia ll y th at o f S eid e (14); a.m ixture o f.lO g . o f 2 , 7 -d ih y d r o x y -4 -m e th y l1 . 8 - naphthyridine and 10 g . o f phosphorus p en ta ch lo rid e w a s co v ered w ith
phosphorus o x y ch lo rid e and reflu xed for 30 m in u te s. The so lu tio n w as
poured onto ic e and kept c o o l w h ile n eu tra lized to. the! litm u s.en d point w ith
con cen trated ammonium h yd roxid e. The r e su ltin g w h ite s o lid w a s c o lle c te d
. by s u c tio n filtra tio n and dried in a ir. The y ie ld o f impure product w as e s t i ­
mated, to. be 90%. One r e c r y sta lliz a tio n from b en zen e afforded silv e r y
16
• c r y s t a ls , m .p . 192.5 to. 1 9 4 .0 ° C . The .literature m eltin g p o in t i s 1 9 3 °C .
S p ectral data are g iy e n in Appendix A, F ig . 24, 2 5 .
2 , 7 -D ih y d r g z in o -4 -M e th y l- l, 8-N aph thyrid ine
A m ixture o f 2 .0 g . o f 2 , 7 -d i^ h lo r o -4 -m e th y l-l, 8-n aphthyridin e and
. enough hyd razine hydrate to co y er the naphthyridin e w a s h ea ted until- the
s o lid d is s o lv e d ,, and allow ed , to stand at room tem perature for two. d a y s .
The r e su ltin g red c r y s ta ls w ere c o lle c te d by filtr a tio n , w a sh ed w ith a m in i­
mum o f c o ld w ater and d ried .in air. No p u rifica tio n w a s a ttem p ted . Spectral
data are g iv e n in A ppendix A, F ig . 26, 27.
4 - M e t h y l- l, 8 -N aph thyrid ine
The preparation o f 4 -m e th y l-1 , 8-n ap h th yrid in e w as sim ila r to the
preparation o f I , 6-n aphthyridin e by Albert. (2 0 ). A b o ilin g so lu tio n o f 7 g . o f
copper s u lfa te penthydrate in 30 m l..o f w ater w a s ad d ed , drop w ise at first
and.-then more rapidly a s the in itia l r ea ctio n s u b s id e d , to a so lu tio n o f I g .
o f 2 , 7 -h y d r a z in o -4 -m e th y l-l, 8-n aphthyridin e in 25 m l. o f b o ilin g w a te r .
The so lu tio n w as.-neutralized, to. the litm u s end p oin t with, SN sodium
hydroxide w h ile hot and reflu xed in a beaker for 15 m in u te s . The slurry w a s ■!.
q u ick ly filter e d w ith su c tio n and w a sh ed w ith 10 m l. o f hot w a ter. The com ­
bin ed filtr a te s w ere c o o le d and ex tra cted s e v e r a l.tim e s w ith chloroform .
The com bined chloroform e x tr a cts w ere dried over sodium s u lfa te and. the
so lu tio n filt e r e d .. Evaporation o f the chloroform g a v e a brown o il w h ic h w a s
d is s o lv e d in. h e x a n e .. The .,yield o f impure product w a s e stim a te d to be 80%..
.. Removal o f th e h exan e w ith a stream o f dry nitrogen c a u s e d c r y s ta lliz a tio n
o f 4 -m e th y l- 1 , 8-n ap h th yrid in e as. w h ite fea th ery c r y s t a ls , m .p . 55 .0 to
17
' 5 6 .5 °C .; th e c r y s ta ls w ere v e r y h y g r o s c o p ic . O ch iai (2 6) reports 4 -m e th y l1, 8-n ap h th yrid in e a s an o il.. Sp ectral data are g iv e n in A ppendix A, F ig . 28,
, 29.
. C a ta ly tic R eduction o f 2 , 7 -D ic h lo r o -4 - M e th y l-l, 8-N aph thyrid ine
Two, procedures w ere used: to red uce the d ich lo ro com pound. The fir st
- procedure .was sim ila r to-.that o f O ch ia i (16). A mixture o f 2 .0 g . o f
2 , 7 -d ic h lo r o -4 -m e th y l-l, 8 - n a p h t h y r id in e .1.0 g . o f a. prepared -5%; palladium
on. Calcium carbonate c a ta ly s t and 20 m l. o f a. 10% so lu tio n o f p otassiu m
hydroxide .in m ethanol w ere put in a Parr hydrogenation apparatus and hydro­
g en a ted at 2 atm . u n til hydrogen uptake c e a s e d . . The slurry w a s.filte r e d w ith
su c tio n and the s o lv e n t removed, by e v a p o r a tio n . A brown o il r esu lted w h ich
w a s d is t ille d in.vacuu m to, g iv e a c o lo r le s s o i l . The s e c o n d procedure u se d
, th e atm osp h eric hyd rogenation apparatus d e scr ib e d ab ove (page 13). A dry
/ m ixture o f ,2.0 g . o f 2 , 7 -d ic h lo r o -4 -m e th y l-I.., 8-n aphthyridin e and 1.0 g . o f
th e prepared c a ta ly s t w ere p la c e d in th e apparatus and. the sy ste m purged
• w ith h yd rogen .. S l o w l y 29 m l. o f 5% p o ta ssiu m h yd roxid e.in m ethanol w as
a llo w e d to, en ter the r ed u c tio n -fla sk an d .th e slurry stirred v ig o r o u s ly un til
hydrogen, uptake sto p p e d . The. slurry w a s ,filter e d and th e filtra te treated a s
a b o v e .. The sam e c o lo r le s s o il r e s u lte d . This o il w as show n by thin la y er
. chrom atography to, be a.m ixture o f se v e r a l com ponents w ith tw o predom inant
fr a c tio n s .
II. . PREPARATION OF COORDINATION COMPOUNDS
A , . B is-1 ,8 -N a p h th y r id in e)-C o p p er :(II) C hloride
A s o lu tio n o f 100 m g. o f 1 , 8-n aphthyridin e and 0.2 g . o f copper ch lorid e
in 25 m l. o f w ater w a s a llo w e d to stand, for s e v e r a l d a y s in a c lo s e d c o n ­
ta in e r . The green p rism a tic c r y s ta ls w h ich sep a ra ted w ere removed, by d e ­
cantation. and w a sh ed w ith a minimum o f w a te r . S in g le c r y s ta ls o f th e com ­
pound w ere m ounted for X -ray determ ination, o f th e str u c tu r e . The cry sta l
d e n s ity w a s '1.68.g . / c c .
B. B is- ( I , 8 -N ap h th yrid in e)-C op p er (IIi) Bromide
A so lu tio n o f 7 6 m g. o f 1 , 8-n ap h th yrid in e and 0.2 g . o f copper bromide
in 5 0 m l. o f w ater w as a llo w e d to, stand for tw o d ays in th e o p e n . The red brown c r y s ta ls 'w h ic h formed w ere rem oved by d eca n ta tio n and w a sh ed w ith
a minimum o f w a te r . The product w a s a n a ly z e d for bromide and prelim inary
c ry sta llo g r a p h ic data o b ta in e d . The c r y s ta l d e n s ity w a s 2 .0 0 g . / c c .
. C.
B i s - ( 2 , 7 - D ic h lo r o - 4 - M e t h y l- lf 8 -N a p h th y rid in e)-C o p p er (II) Chloride
Ethanol s o lu tio n s o f anhydrous cop p er ch lorid e and 2 , 7 -d ic h lo r © -4 -
m e th y l-1 , 8-n ap h th yrid in e w ere m ixed and h ea ted g e n tly . The blu e powder
■which, p recip ita ted w a s c o lle c te d by su c tio n filtra tio n and dried in a vacuum
d e s s ic a t o r . Copper a n a ly s is in d ic a te d tw o m o les o f eth a n o l o f s o lv a tio n .
D . : C opper(I) C om plex o f 2.f 7 -D ic h lo r o -4 - M e th y l-l, 8-N aph thyrid ine
An attem pt w a s made to u s e copper (I) ch lo rid e in th e sam e manner a s
■C a b o v e . An orange product r e s u lte d , but no c o n s is t e n t a n a ly s is cou ld be
19
o b ta in e d .. It is p o s s ib le th at no true copper (I) com p lex w a s formed but that
ring c o u p lin g occurred to produce th e orange c o lo r .
E. ■■M ethyl N aphthyridine Copper C om plex
.A green c r y s ta llin e com p lex w a s o b ta in e d .in a sm a ll y ie ld from an
eth a n o l so lu tio n o f the c a ta ly tic red uction product o f 2 , 7 -d ic h lo r o -4 m e th y l-1 , 8 -n a p h th y r id in e . The green com pound c o - c r y s t a lliz e s w ith a
y e llo w pow der and w as sep a ra ted from it m an u a lly . O nly enough m aterial
w a s c o lle c te d to ob tain cry sta llo g r a p h ic data and a s in g le gravim etric
h a lid e a n a l y s i s .
III. ■ ANALYTICAL TECHNIQUES
A.
Thin Layer Chromatography
All th in .layer chrom atography reported here w a s done on s ilic a g e l
p la te s prepared in the laboratory by standard m e th o d s. A n a ly tica l p la te s
had a la y e r o f s ilic a g e l 0.1 mm. thick; th e s ilic a g e l w a s a c tiv a te d by
baking for one hour in a 120 ° C . o v e n . D eterm ination o f sp o t p o s itio n w as
made by th e flu o r e s c e n c e o f the m a teria ls under u ltra v io let lig h t and the
ab sorption o f io d in e vapor on the s p o t s . Preparative p la te s w ere marked
w ith a s ty lu s under UV lig h t and scrap ed in to .ex tra c tio n f l a s k s . All an a­
ly t ic a l p la te s w ere run for p u rp oses o f purity control and no attem pts w ere
made to id e n tify com pounds accord in g to
v a l u e s . The s o lv e n t sy stem
u s e d w as b u ta n o l-a c e tic a c id -w a te r (12:3:5; V /V ).
B.
G as Chromatography
All g a s chrom atography w as done on colum ns p ack ed w ith Gas Chrom
C a s s o lid support; the liq u id p h a se w a s 30% by w eig h t S E -3 0 . All runs
w ere made in th e F&M (M odel 400) g a s chromatograph at 2 3 0 ° C . w ith helium
a s carrier g a s and. d etectio n ' by flam e io n iz a tio n . The sa m p le s w ere in je c te d
in.chloroform and reten tio n tim es m easured from the tim e o f in je c tio n . No
q u a n tita tiv e data w ere tak en from the g a s chrom atographic data other than
reten tio n t im e s .
X
21
C . . N u clea r M a g n etic R eson an ce
N u clea r m a g n etic r e so n a n c e data w ere ob tain ed in a Varian A -60
S p ectrograp h . S am ples w ere run in m ic r o c e lls in d eu terated chloroform w ith
te tr a m e th y lsila n e a s an in tern al r e fe r e n c e .
D.
U ltr a v io le t-V is ib le Spectra
All UV- v is ib l e sp e ctra w ere determ ined on th e DK-2 Spectrophotom eter
in I cm . quartz c e l l s w ith pure s o lv e n t a s r e fe r e n c e .
E.
Infrared Spectra
All infrared sp e ctra w ere determ ined on th e Beckman IR-4 S p ectro­
photom eter w ith a programmed s l i t and dou ble beam . Spectra were, run in
m ic r o -p o ta ssiu m bromide p e lle t s and in chloroform so lu tio n w ith a b a la n cin g
w ed g e c e ll fille d w ith chloroform .
F.
1
Copper A n a ly se s
C opper a n a ly s e s w ere determ ined by iodom etric titra tio n w ith sodium
th io su lfa te , by th e m ethod ou tlin ed by-K oltoff and S a n d ell (21). In a ll c a s e s
s e v e r e d iffic u lty w a s en cou n tered in determ ining end p o in ts; th e end poin t
w ould be a c h ie v e d ,, but w ould fad e o u t. The naph.thyridine seem ed to in ter ­
fere w ith th e end p o in t. E stim ation o f a c c u r a c y for copper determ ination is
g iv e n w ith the a n a ly tic a l d a ta .
G . . H alid e A n a ly se s
The Fajans titration w as attem pted on sa m p les c o n ta in in g
1, 8-n ap h th yrid in e a s a lig a n d , but w a s u n s u c c e s s f u l. W hen the
d ic h lo r o flu o r o sc e in in d ica to r w as a d d ed , th e so lu tio n im m ed ia tely turned
22
orange; th e orange c o lo r m asked the titra tio n end p o in t. H alid e a n a ly s e s
w ere determ ined by a sim p le s ilv e r h a lid e gravim etric determ ination u sin g a
very sm a ll filter in g c ru cib le and determ ining, w e ig h ts on the. M ettler m icro­
b a la n c e . The gravim etric procedure u se d i s o u tlin ed by W alton (2 2 ).
H.
C rystal DensityC ry sta l d e n s it ie s w ere determ ined by th e flo ta tio n m eth od. A c r y sta l
w a s p la c e d in a beaker p a r tia lly fille d , w ith a s o lv e n t in w h ich th e c r y sta l
,
did not d is s o lv e and in w h ich it sa n k . A h e a v ie r m is c ib le s o lv e n t w as
added u n til th e c r y sta l seem ed to rem ain su sp en d ed in th e s o lu tio n . The
so lu tio n d e n s ity w as determ ined by w eig h in g a liq u o ts o f th e so lu tio n w ith ­
drawn w ith a c la s s A .p ip et. The d e n s it ie s w ere e stim a te d to be in error by
no more than 0.05 g . / c c . T h ese a c c u r a c ie s are s u ffic ie n t to determ ine the
number o f m o le c u le s, per unit c e ll in the c r y s t a l.I.
I.
M a g n etic S u s c e p tib ilitie s M easurem en ts
M a g n etic m om ents w ere determ ined by th e Gpuy m ethod on a Gouy
b a la n ce b u ilt at M ontana State U n iv e r sity and p r e v io u sly d e sc r ib e d by
Houk (IO),. All m easurem ents d e scr ib e d here Were made a t room tem perature.
M easu rem en ts w ere made in tr ip lic a te and-the average v a lu e o f the b a la n ce
d e fle c tio n s u se d to c a lc u la te the m a ss s u s c e p t ib ilit ie s a cco rd in g to the
equation;
23
. V = (2a) (Aw) (I)
■
w here
9
(H2) (m)
.1.= sam ple len g th
m = sam p le w e ig h t
g = a c c e le r a tio n o f gravity
Aw = w eig h t ch an ge
H = m agn etic fie ld
The m agn etic fie ld w as determ ined by th e Gouy m ethod u s in g a standard o f
known s u s c e p t ib ilit y o. The standard u se d w a s fr e sh ly prepared c o b a lt mer­
cury th iocyan ate> w h ich o b e y s th e Curie W e is s la w (I);
X g = C /T + 0
0 = 10
X g ( 2 0 ° C . ) = 16,44 x . 10~6 e . s . u . M easu rem en ts w ere made at s e v e r a l v a lu e s o f m agn etic fie ld to prevent
errors due -to,ferrom agn etic im p u r itie s.
IV. . X-RAY ANALYTICAL TECHNIQUES
A . . Powder D iffraction
Two d ifferen t te c h n iq u e s w ere u se d to obtain pow der d iffraction d a ta .
The fir s t tech n iq u e u se d standard photographic te c h n iq u e s w ith a P h illip s
pow der cam era o f radius 57.3 mm. No attem pt w as made to correct for film
sh rin k age in any m easurem ents reported. All m easurem ents o f 2 @ a n g le s
w ere made on a vern ier s c a le film m easuring lig h t b o x , and w ere made from
arc to arc a c r o s s th e c en ter o f th e d iffra ctio n c o n e . The se c o n d .te c h n iq u e ■
u se d th e G eneral E lectric G o n io sta t (b elo n g in g to M ontana State U n iv ersity
C hem istry D epartm ent). In th is te c h n iq u e , 2© d iffraction a n g le s w ere read
d ir e c tly from the p o s itio n o f peak c en te rs on a strip chart record er. T hese
p e a k s w ere gen erated a s the s c in tilla tio n counter m oved in a normal 2 © sc a n
m o d e , and a pow der sam p le o f the m aterial w a s le ft sta tio n a ry a t the fo cu s
o f th e beam . In a ll c a s e s w here o n ly p o s itiv e v a lu e s w ere ta k en th ey ,w ere
ju dged in error by a s much a s 0.2 d e g r e e s due to. m ech a n ica l m isa lig n m en t.
. Error in determ ining th e cen ter o f p ea k s on th e chart paper w a s l e s s than
0.01 d e g r e e s .
B.
S in g le C rystal D iffraction
All c r y s ta ls w ere in it ia lly exam ined under the p o la rizin g m icroscop e
for s ig n s o f tw in n in g . If th e c r y sta l appeared to be s in g le , it w a s o p tic a lly
a lig n e d and m ounted for o s c illa t io n lin e -u p photographs on a W e isse n b e r g
cam era. O s c illa tio n and rotation photographs w ere tak en to a lig n the
cry sta l; fir s t and s e c o n d le v e l W e isse n b e r g photographs w ere tak en i f no
' in d ic a tio n o f tw in ning had ap p eared . If th e c r y sta l w as found to be s in g le ,
a secon d , la y e r photograph w as taken to determ ine the cry sta llo g ra p h ic'
s p a c e group. If th e c r y sta l w as v ery thin in one d im en sio n , p r e c e s s io n
photographs w ere u se d to determ ine th e sp a c e group. For a ll W e isse n b e r g
in v e s t ig a t io n s , copper Ka radiation w a s u sed ; for p r e c e s s io n p h o to g ra p h s,
molybdenum Ka rad iation w as u s e d .
C e ll d im en sio n s w ere determ ined by the m ethods o u tlin e d by Buerger
(23) from film m easurem ents made on a vern ier m easuring lig h t box ca p a b le
o f an a c cu ra c y o f + .0 1 cm . . C a lc u la tio n o f th e |S a n g le for m o n o clin ic c r y s ­
t a ls m ounted on the a or c. a x e s w as done by th e m ethod o f angular lag!.
P r e c e s s io n .photographs w ere a ls o u se d to m easure t h e ,3 a n g le d ir e c tly .
C.
S in gle C rystal D iffraction S tu d ies on B is-(1 ,8 -N a p h th y r id in e )C opper(II) C hloride
All prelim inary work w as done by standard W e isse n b e r g and p r e c e s ­
s io n te c h n iq u e s u sin g cam eras and equipm ent a v a ila b le a t M ontana State
U n iv e r sity . Prelim inary exam in ation o f a c r y sta l o f B is-(1 ,8 -n a p h th y r id in e)cep p er (II) ch lorid e sh ow ed sy ste m a tic a b s e n c e s c o n s iste n t, w ith eith er o f
th e sp a c e groups C /2 c or C e . The c r y sta l w a s mounted a lo n g the a a x is .
The goniom eter head and c r y sta l w ere transferred from th e W e isse n b e r g
cam era to a G eneral E lectric X -R D -5 G o n io sta t w ith a copper tube and
n ic k e l filte r . The c r y s ta l w as a lig n ed by th e " b asal plane" (Appendix C)
align m ent te c h n iq u e . A ccurate c e ll c o n s ta n ts w ere determ ined by averagin g
th e v a lu e s determ ined from high a n g le a x ia l r e f le c t io n s . :
26
The c e ll c o n sta n ts ob tain ed from the g o n io s ta t w ere u se d a s input
data for the com puter program DIFFSET w h ich c a lc u la te d m achin e s e ttin g s
for the c o lle c tio n o f in te n s ity d a ta . G o n io sta t geom etry and a ll programs
u se d are d is c u s s e d in A p p en d ices C and B r e s p e c tiv e ly . One r e fle c tio n w a s
■c h o s e n a s a standard to-p reven t any a c c id e n ta l lo s s o f alignm ent; the in ­
te n s it y o f th is r e fle c tio n w a s tak en at th e b egin n in g and end o f e a ch data
c o lle c tio n s h ift . All in t e n s it y data w ere tak en by te c h n ic ia n s em ployed for
th e p u r p o se . The data w ere tak en by the standard 0 - 28 s c a n te c h n iq u e .
Background in te n s ity w as cou n ted on both th e upper and. lo w er s id e s o f the
p e a k . . The peak w as sca n n e d for 100 s e c o n d s a t a 20 s c a n rate o f 2 d eg rees
per m inute and backgrounds counted for 50 s e c o n d s w ith ou t sc a n n in g . The
in te n s ity o f a peak w a s c o n sid e re d to be th e d ifferen ce b e tw e en the count
for the peak sc a n and th e sum o f the background c o u n t s . All in t e n s it ie s
v w ith a n et count o f l e s s than 30 w ere c o n sid e r e d u n o b ser v e d . In te n sity data
for a ll unique r e fle c tio n s w ith a v a lu e l e s s than 120 d e g r e e s w ere c o lle c t e d .
B ec a u se o f th e nature of th e program DIFFSET, in te n s ity data w ere
c o lle c te d on a ll r e fle c tio n s h , k , l and th en on r e f le c tio n s - ;-h ,k ,I .. When
a lm o st a ll o f th e in te n s ity data for r e fle c tio n fj|, k / 1 had b een c o lle c t e d , th e
in te n s ity for the standard r e fle c tio n su d d en ly dropped a lm o st to z e r o .
O p tica l e x a m in a tio n .o f th e align m ent sh o w ed th at the c r y s ta l had moved
’
’
tr a n s la tio n a lly out o f the X -ray beam . T h e.cry sta l w a s m oved la t e r a lly .
back, in to the beam and the in te n s ity o f th e standard returned to normal . It
w a s a ssu m ed th at the c r y sta l w as s t ill in align m ent and data c o lle c tio n r e ­
su m ed . W hen a ll th e data w ere c o lle c te d structure fa cto rs w ere ^calculated
from th e in t e n s it ie s by the program LI. The structure fa cto rs w ere u se d in a
27
P atterson s y n th e s is (program FOURIER) in w h ich th e s p a c e group am biguity
i s not im portant s in c e a P atterson map i s n e c e s s a r ily c e n tr ic „
The c r y sta l d e n s ity in d ic a te d that there w ere four cop p er a to m s.in the
un it c e ll w h ich m eant that th e-cop p er atom s w ere in s p e c ia l p o s itio n s i f th e
s p a c e group w ere C 2 /c „ The tw o -fo ld a x is seem ed the m ost prom ising p o s i­
tio n and the rem aining c o -o r d in a te o f th e p o s itio n w as determ ined from the
P atterson map . U sin g, th e com puter program MAIR the structure factors for
th is, p o s itio n w ere c a lc u la te d and r efin e d . The- R f or th e copper o n ly w as
52%. . A Fourier s y n th e s is w a s th en c a lc u la te d w ith the programs TCR6 and
ICRl u sin g th e o b se rv e d structure fa cto rs and th e s ig n s o f th e structure
fa cto rs from th e c a lc u la te d p o s itio n for th e copper atom . .The Fourier map
in d ic a te d a p o s itio n for th e ch lorin e atom w h ich w a s th en u se d in a stru c­
ture. factor c a lc u la tio n and refin em en t. The copper and ch lo rin e p o s itio n s
w ere refin ed to an R o f 29%. The c a lc u la tio n o f a n ew Fourier s y n th e s is in ­
d ic a te d th e p o s itio n s o f so m e .o f the lig h t a to m s. S u c c e s s iv e structure f a c ­
tor c a lc u la tio n s and Fourier s y n th e s e s g a v e p o s itio n s for a ll th e atom s
e x p e c te d in .th e stru ctu re. R efinem ent o f th e s e p o s itio n s w ould not p roceed
b e lo w a R o f 16% by eith e r b lock d ia g o n a l or fu ll matrix (program ORFLS)
te c h n iq u e . C h o ice o f C e a s .th e sp a c e group w ould not im prove th e !refine­
m ent. It w ps e v id e n t th at th e data w ere in som e w ay g r o s s ly in error.
■S in ce th e c r y sta l had m oved su d d en ly at about the end o f the h , k , l
data c o lle c t io n , sep a ra te refin em en ts w ere m ad e. The h , k , l data refined in
fiv e c y c le s o f b lock d ia g o n a l refinem ent to a R o f 6%. The - h , k , l data
w ould not refin e b e lo w 14%. The data w ere r e c o lle c te d .
28
The s e c o n d data c o lle c tio n u se d zirconium filter e d molybdenum rad i­
ation , to m in im ize.th e e ffe c t s o f ab sorp tion in th e c r y s ta l. The sa m e .c r y sta l
w a s u se d for the s e c o n d data c o lle c tio n e x c e p t th at a sm a ll fragment w as
lo s t in rem ounting. ^The computer? program DSET w a s w ritten to c a lc u la te
m achin e s e ttin g s for a "chi ninety" a lign m en t p ro ced u re. The c r y sta l w as
a lig n e d on the W e isse n b e r g cam era and transferred to th e g o n io s ta t. C a l­
c u la tio n s determ ined th at th e r e fle c tio n - 2 , 0 , 4 w a s v ery n early perpen­
d icu la r to th e b* - c * plan e; th is r e fle c tio n w a s c h o se n a s th e alignm ent
r e fle c tio n . Ju d iciou s m ovem ent o f th e gon iom eter a rcs and c o n sta n t fo llo w ­
in g w ith th e d e te c to r a llo w e d th e align m en t r e fle c tio n to be m oved to "chi
nin ety". The c r y sta l w a s then a lig n ed by a procedure ob ta in ed from W a ten paugh (24) and very sim ila r to th at o u tlin ed by Jen sen (2 5 ). W hen the c r y s ­
ta l w a s a lig n e d , n ew c e ll c o n sta n ts w ere determ ined by charting the
d iffra ctio n in te n s ity for a number o f r e fle c tio n s for both p o s it iv e and n e g a . tiy e v a lu e s, o f 2 0 . The true v a lu e o f the 2 0 a n g le w a s c o n sid e re d to be the
a v era g e o f th e p o s itiv e and n e g a tiv e v a lu e s . The 20 v a lu e s for 12 r e f le c ­
tio n s w ere entered, in to th e program PARAM w h ich :g a v e the b e s t c e ll
param eters by a le a s t square refin em en t. T h ese c e ll param eters and the
" G on iostat sp ace" c o -o r d in a te s o f th e "ch i ninety" and on e other r e fle c tio n
w ere en tered in to th e program DSET to o b ta in m achine s e t tin g s for data
c o lle c t io n . Three w id e ly s p a c e d r e fle c tio n s w ere c h o se n to u s e a s s ta n ­
dards for s c a lin g data and to prevent a c c id e n ta l lo s s o f a lig n m en t. The
c r y s ta l align m en t w as c h e ck ed e a ch day and the standard r e fle c tio n in ­
t e n s it ie s w ere tak en ev ery four hours and at the b egin n in g and end o f e a c h
data c o lle c tin g d a y . A grap h ical d is p la y o f th e s c a le s ob ta in ed from the.
\
29
standard r e fle c tio n s w as u se d t©. determ ine th e diffractom eter s ta b ility and
i s g iv e n in A ppendix C ,. F ig . 4 0 . The raw in te n s ity data w ere c o lle c te d in a
sim ila r manner to th at u se d before e x c e p t th at 6 0 -s e c o n d s c a n s w ere u se d
and backgrounds cou n ted for 30 s e c o n d s . All data for 2®
l e s s than 60 d e ­
g r e e s w ere'o b ta in ed for h , k , l r e fle c tio n s and a ll data for 2© l e s s than 45
d e g r e e s for - h , k , l .
T h ese data w ere red u ced w ith program RDN to structure
fa c to r s . R efinem ent o f a ll data for 2 © le s s than 45 d e g r ee s w ith th e program
DLS red u ced th e R to 6.8% for is o tr o p ic tem perature f a c to r s . A nisotropic
refin em en t reduced, the R to 6.1%. Bond a n g le s , d is ta n c e s and estim a ted
standard d e v ia tio n s w ere c a lc u la te d w ith the program BAD and are g iv en
to g e th er w ith ta b le s o f structure fa cto rs in A ppendix C .
DISCUSSION
A lthough both 1, 8-n ap h th yrid in e and 4 -m e th y l-l, 8-n aphthyridin e
w ere rep orted .in .th e literatu re (12,. 1$), it w as n e c e s s a r y to d e v e lo p a new
s y n th e s is for e a c h o f th e s e com pou nds. Skraup s y n th e s e s o f .1 ,8 nap h th yrid in es from 2 -am in op yrid in e have b een rep orted .to y ie ld .1 ,4 a .
d ia z a n a p h th a le n e s ,(F ig. 10) rather.than .1 ,8-n a p h th y rid in es (1 3 ). In p y r id in e ,
th e m ost e le c tr o n e g a tiv e p osition , is .the nitrogen ato m .(F ig . 1 1 ).
1, 8-n aphthyridin e
. 1 ,4 a -d ia za n a p h th a le n e
A lternate Ring C lo su re Products
Figure 10
0,822
0.947
0.849
1.586
Tf-Electron. D e n s itie s .in Pyridine .(26)
■ Figure 11
31
Ring, c o n d e n s a tio n , su ch a s o ccu rs in th e Skraup. r e a c tio n , w ould therefore
be lik e ly to o ccu r at th e.rin g nitrogen a s w e ll a s a t th e 3 - p o s it io n in .th e
ring and p o s s ib ly p r e fe re n tia lly a t the ring n itro g en . A r ec e n t report o f th e
s y n th e s is o f 1 , 8-n ap h th yrid in e v ia th e Skraup sy n th e s is , in d ic a te s that som e
. ring c lo su r e c a n .o c c u r in th e 3 - p o s it io n . The 1, 4 a -d ia z a n a p h th a le n e s are
e a s i l y c le a v e d to regen erate 2 -am in o p y rid in es (13); th e 1 , 8-n a p h th y rid in es
are not e a s il y c le a v e d . Proper c h o ic e o f r ea ctio n co n d itio n s co u ld produce
1 , 8 -n a p h th y r id in e . A ttem pts to reproduce the s y n th e s is o f Paudler and Kress
(19) h ave shown, th at th e y ie ld s are in g en era l lo w so th at th e rea c tio n may
not be./of great sy n th e tic u t ility .
S u b stitu en ts in th e 6 -p o s it io n .o f 2 -am in op yrid in e ca n im prove the
y ie ld o f I , 8 -n ap h th yrid in es (13), ■W hen the 6 -s u b stitu e n t is an amino group,
th e y ie ld s are g rea tly en h a n ce d . Figyre 12 sh o w s th at th e 6-am ino group
can contribu te e lec tr o n d e n s ity to th e 3 - p o s it io n .
R eson an ce Structures for 2 -6 -d ia m in o Pyridine
Figure 12
S teric hin drance to ring c lo su r e at the n itrogen i s su rely in v o lv e d a s w e ll,
s in c e a m ethyl group in th e 6 -p o s itio n w ill fncrea'se the y ie ld . The
6-m eth y l group d o e s not promote th e form ation o f 1 , 8-n a p h th y rid in es to the
e x te n t th at the 6-am in o group, d o e s , but th is e ffe c t may b e .a c co u n te d for in
\
I
32
tw o w a y s; th e a b ility o f th e 6 - a m in o - l, 8 -n a p h th y rid in es to form intra­
m o lecu lar hydrogen bonds to th e nitrogen w ould mean greater s te r ic
■hin drance by the am ino group and the a c tiv a tio n o f the 3 -p o s it io n to
e le c tr o p h ilic su b stitu tio n co u ld in c r e a s e th e rate o f ring c lo su r e in the
3 - p o s it io n .
The in c r e a s e d y ie ld o f 1 , 8-n a p h th y rid in es from' 2 , 6 -d ia m in o p y rid in es
g iv e s a n .e x c e lle n t route to su b stitu ted . I , 8 -n a p h th y rid in es w h ich in turn
p ro v id es an e x c e lle n t route to the parent com pound. C a rb o n i, S ettim o , and
. P irisin o (17) reported th e s y n th e s is o f 2 -a m in o -7 -h y d r o x y -l, 8-n aphthyridin e
from w h ich rem oval o f the amino and hydroxy groups w ould y ie ld th e parent
b a s e . The amino group on a b e n z e n e ring can be rem oved by d ia z o tiz a tio n
and treatm en t w ith hypophosphorus a c id . The hydroxy group co u ld be r e i
m oved by d is tilla tio n from z in c , a v ery d e str u c tiv e p r o c e s s , In pyridine
c h e m istr y , it i s d iffic u lt to rep la ce the 2 -am in o group w ith hydrogen by
d ia z o tiz a tio n . in hypophosphorus a cid s in c e it i s d iffic u lt to ob tain s ta b le
■diazonium s a lt s from 2 -a m in o -p y r id in e s e v e n in strong a c id s . In w ea k ly •
a c id ic so lu tio n th e diazonium s a l t d e c o m p o se s im m ed iately to g iv e the
p h en o l. The compound r e su ltin g from the treatm ent o f 2 - amino - 7 - hydroxy1 , 8-n ap h th yrid in e w ith nitrou s a c id i s th en a d ih y d ro x y -1 , 8 -n a p h th y r id in e .
The problem i s to rem ove t w o .2-h yd roxy groups from th e pyridine r in g s. The
■ application o f b e n zen e ch em istry is o n c e more m isle a d in g b e c a u s e the com ­
pound w h ich may b'e c a lle d 2 -h y d ro x y -p y rid in e d o es not e x i s t in the
■p h e n o lic form, but rather in th e keto form a s show n in F ig . 13.
33
A
B
2 -H yd roxyp yridine
: 2 -P yridone
Tautom erism in 2-H ydroxypyridine, (27)
Figure 13
The 2-p yrid on e. typ e o f compound m ay, h o w ev er, he con verted to a
2 -ch lo ro p y rid in e by th e r ea ctio n w ith a m ixture o f phosphorous p en ta ch lo rid e and phosphorous oxytrfch lorid e „ The 2 , 7 -d ic h lo r o -l, 8-n aphthyridin e
ob tain ed in th is se q u e n c e may be hydrogenated to g iv e I , 8 -n a p h th y rid in e.
H ydrogenation o f 2 , 7 - d ic h lo r o -4 -m e th y l-l, 8-n aphthyridin e ob tain ed in th is
sam e manner d o e s not g iv e 4 -m e th y l-1 ,8 -n a p h th y r id in e . The product m ix­
ture c o n ta in s two. predom inant co m p o n en ts. ,I t w as first b e lie v e d that one o f
th e s e com ponents w as the 4 -m e th y l-l, 8-n aphthyridin e a n d ,th a t the sec o n d
com ponent w as a dihydro or tetr a h y d ro -4 -m e th y l- 1 , 8 -n a p h th y r id in e . Gas
■ S.
chrom atography w ith an SE -30 liq u id p h a se r e so lv e d the two, com p on en ts.
S in ce th e SE -30 se p a r a te s com pounds prim arily on a m o lecu la r w eigh t
b a s i s , 4 -m e th y l-l,8 -n a p h th y r id in e and a dihydro or te tr a h y d ro -4 -m e th y l1 , 8-n ap h th yrid in e sh ou ld have sim ila r reten tio n tim e s . The reten tion tim es
d iffered by about ten p ercen t , w h ich is rea so n a b le for the d iffe re n c e p o stu ­
la te d . Thin la y e r chrom atography o f the red u ction product on s ilic a g e l
34
p la te s a g a in sh ow ed tw o predom inant com pounds w ith w id e ly d ifferen t R,
t
v a lu e s . For the products p o s tu la te d , a m aterial w hich se p a r a te s on b a se
stren gth (su c h a s .silic a , g el) sh ou ld g iv e v ery d ifferen t
v a lu e s (compare
th e b a s e stren gth o f pyridine and pip erid in e in Table. I ) .
Table I
BASE STRENGTHS. OF .PYRIDINES (10)
Compound
. pyridine
p ip erid in e
pKa
1 .7 x 1 0 ^
1 .6 x 1 0
“3
Although the. two. predom inant red uction products could be sep a ra ted on a
g la s s a n a ly tic a l g a s chrom atography co lu m n , no sep a ra tio n w a s a c h ie v e d
w ith th e m etal preparative colum ns u s e d . S evere d e c o m p o sitio n occurred
and no product w as r ec o v e re d . D eco m p o sitio n o f th e p a rtia lly hydrogenated
I , 8-n ap h th yrid in e w ould not be u n u su a l, but th e fu lly arom atic b a se sh ou ld
be s t a b le . Preparative th in la y e r chrom atography w as a ls o attem pted to
sep a ra te the tw o predom inant fr a c tio n s , but w as o n ly s u c c e s s f u l in en rich ­
in g the d ifferen t fr a c tio n s .. The PMR sp ectra of. the en rich ed fra ctio n s did
not in d ic a te th at eith e r fraction w as c le a r ly the d esired 4 - m e t h y l- 1 ,8 n ap h th yrid in e.
C a ta ly tic hydrogenation is not the o n ly method o f rem oving a 2 -c h lo r o
group from a. pyridine rin g . T hielepapp e (28) reported th at m etal io n o x id a . tion. o f 2 -h yd rp zin op yrid in es g iv e s .t h e free p y rid in e. Albert (20) has u se d ,
.th is tech n iq u e in th e preparation o f I, 6 -n a p h th y r id in e s. The 2 , 7 -d ic h lo r d 4 -m e th y l- 1 , 8-n ap h th yrid in e w as con verted to the
35
2 , 7 -d ih y d r a z in o -4 -m e th y l-l, 8-n ap h th yrid in e w h ich w a s. then o x id iz e d w ith
copper s u lf a t e „ The in itia l tw o attem p ts to produce 4 -m eth y lT -l,8 naphthyridine by th is m ethod g a v e no product a t a ll and th e sta rtin g m aterial
w a s not r e c o v e r e d . The product may have com p lexed w ith th e e x c e s s copper
io n in so lu tio n and not h ave b een e x tra cted in .th e procedure u s e d . The third
attem pt to prepare.,the compound by th is tech n iq u e produced an estim a ted
90% y ie ld o f c r y s ta llin e 1 , 8-n ap h th yrid in e w h ich w as c h a ra cterized by it s
PMR spectrum and sh ow ed to be pure b y .g a s chrom atography. The product
w a s first ob tain ed a s an o il w h ich is the reported p h y s ic a l form for
4 -m e th y l, I ,.8 -n a p h th y rid in e.. Exam ination o f Table . II w ould in d ic a te that
4 -m e th y l- 1 , 8-n ap h th yrid in e sh ou ld be a s o lid a t room tem perature .
Table. II
MELTING POINTS OF I , 8-NAPHTHYRIDINE , (.13)
Compound
1, 8-n aphthyridin e
4 - m e t h y l- l, 8-n aphthyridin e
2 ,4 -d im e th y l- I , 8-n aphthyridin e
L it. m .p .
99
. (oil)
63
Obs . m . p .
. 9 8 -9 9
56
—
On c o n sid e r a tio n s o f m olecu lar w eig h t a lo n e , 4 -m eth y l and. 2 ,4 -d im e th y l-;
1 , 8-n ap h th yrid in e w ould be e x p e c te d to m elt at a higher tem perature than
.1., 8 -n a p h th y r id in e .. ,H ow ever, th e higher sym m etry o f 1, 8-n aphthyridin e
.probably allow s; b etter p a c k in g in. the c r y sta l and th is co n sid era tio n , cou ld
e a s il y o v e r -r id e the e ffe c t s o f m o le c u le w e ig h t. It i s , h ow ever,, d iffic u lt to
s e e h o w :2 .,4 -d im e th y l-l,8 -n a p h th y r id in e co u ld p a ck .m u ch ,b etter than
4 -m e th y l-l,8 -n a p h th y r id in e . If th e p a c k in g c h a r a c te r is tic s are sim ila r , or
-
36
if. 4 -m e th y l-1 ,8 -n a p h th y r id in e .h as .the .b etter packing- c h a r a c te r is tic s o f the
tw o ■com p ou n d s, it sh ou ld su rely -b e a s o lid a t room tem p erature. The- m elt­
ing; p oin t m ight be lo w enough-to make, c ry sta lliz a tio n , d i f f i c u l t .. Rapid
evap oration o f th e h exan e (w ith a stream o f dry nitrogen) from a. so lu tio n o f
4 - m e t h y l- l, 8-n ap h th yrid in e in. h exan e c a u s e d p recip ita tio n , o f w h ite c r y s t.ta ls .. T h ese c r y s ta ls proved to be 4 -m e th y l-l., 8 -n a p h th y r id in e . Com parison
o f th e g a s chrom atographic c h a r a c te r is tic s o f the pure 4 - m e t h y l- l, 8 naphthyridine w ith those, of:th e o il o b tain ed from c a ta ly tic red u ction o f
2 , 7 -d ic h lo r o -4 -m e th y l- I , 8-n ap h th yrid in e (Table III) c le a r ly sh o w s that
n eith er o f th e predom inant fractio n s in ..the o il is 4 - m e t h y l- l, 8-.
n ap h th yrid in e. T he com pounds rem ain u n id en tified ; th ey both may be
hydrogenated, d eriv a tiv es, o f 4 -m e th y l-l, 8 -n a p h th y rid in e.
. T able III
. GAS CHROMATOGRAPHIC RETENTION TIMES
M aterial
; R etention -time ;(min..)
< 1 , 8-n ap h th yrid in e
2 .0
. 4 -m eth y l-l-,8 -n a p h th y r id in e
2 .0 8
. C a ta ly tic R eduction Product (oil)
• 3 .4 5 , 4 .0
. The fir st cop p er-n ap h th yrid in e co m p lex prepared was: B is - ( 2 , 7 d ic h lo r o -4 -m e th y l-l., 8 -n a p h th y rid in e)-co p p er (II) ch loride e th a n o la te . This
com pound w a s ob tain ed a s a .b lu e pow der w hich, d id not d is s o lv e a s a c o i
ordination com pound in any of-th e ordinary s o lv e n t s . Treatm ent w ith hot
w ater d e str o y s th e c o m p le x , d is s o lv in g copper ch lo rid e and le a v in g the in ­
s o lu b le nap h th yrid in e. The naphthyridine is not a very strong com p lexin g
37
a g e n t. Long ex p o su re, to .the air app arently c a u s e s a lo ss, o f s o lv e n t or a
s o lv e n t ex ch a n g e; th e com pound turns- p in k . The pink m aterial has not b een
in v e s tig a te d . Attem pts to prepare a sim ila r compound w ith copper.(I)
c h lo r id e fa ile d to g iv e any copper (I) c o m p le x . An orange m aterial w a s pro­
d u ced w h ich see m e d to be a mixture, o f th e lig h t blu e B is- ( 2 , 7 -d ic h lo r o -4 m e th y l-1 , 8-n aphthyridin e) -c o p p er (II) ch lo rid e and bright orange organ ic
product.- W hat h as app arently occurred i s a r ea ctio n a n a lo g o u s to .th e
U llm ann c o u p lin g o f aryl h a lid e s. (2 9 ). The product w ould be a
binaphthyridine (F ig . 14) .which, cou ld be h ig h ly c o lo re d . The orange organ ic
product i s s lig h tly s o lu b le in, eth an ol but h a s not been.fu rther in v e s tig a te d .
Binaphthyridine
Figure 14
The sm a ll A m ount.(about 150 m g .) o f 4 - m e t h y l- l, 8-n aphthyridin e
prepared h as p reven ted -the preparation o f any copper c o m p le x e s w ith th is
lig a n d , but. tw o copper c o n ta in in g products w ere prepared from fra ctio n s o f
.the o il ob tain ed by c a ta ly tic .r e d u c tio n o f 2 „ 7 -d ic h lo r o -4 -m e th y l-l/ 8 ■n ap h th yrid in e.. The tw o products p r ecip ita te^ togeth er, from eth an ol s o lu ,t io n s .. One com pound i s a. y e llo w pow der which, probably is a . m ixtu re. The
oth er is a. dark green c r y s ta llin e com pound for w h ic h X -ray data are g iv e n
■(Table XIII). Sam ples o f both com pounds w ere d is s o lv e d in aqu eou s
. ammonia and th e s o lu tio n s ex tra cted and chrom atographed. The green
. 38
c r y s ta ls g a v e a pure m aterial w hich, is one o f the tw o o rg a n ic com ponents o f
the. o il,: but too- l i t t l e w a s a v a ila b le to c le a r ly a s s ig n th e structure o f the
lig a n d other than th at it i s c le a r ly not 4 - m e t h y l- l, 8 -n a p h th y rid in e. The e x ­
tr a c t from the y e llo w pow der w as not much, d ifferen t from:the o il u se d to
give, both th e green and y e llo w p r o d u cts.
. A copper (II) ch lorid e com plex, o f 1, 8-n ap h th yrid in e w a s prepared, by
p recip itation , from a . w ater so lu tio n o f:th e tw o r e a c ta n ts . . No w ater o f hydra-tion i s found in .th e c o m p le x , in d ic a tin g th e strong coord in ation strength, o f
.the com pound„ A nalysis, o f naphthyridine c o m p le x e s w a s d iffic u lt due to :th e
in ter fe r en ce o f nap hth yrid ines. in copper and ch lorid e v o lu m etric .titr a tio n s .
A stu d y o f :the so lu tio n sp ectra .b y -J o b 's m eth o d !in d ica ted th a t th e com plex
formed in. so lu tio n con tain ed , tw o m o les o f I , 8-n ap h th yrid in e per m ole o f
cop p er (II) c h lo r id e .
The s in g le c r y sta l o f B is- ( 1 , 8 -n a p h th y rid in e)-co p p er (II) ch loride '
w as m ounted for s in g le c r y sta l s tu d ie s „ The exp erim en tal procedure fo l­
lo w ed in data c o lle c tio n has b een d e scr ib e d on. p age 2 5 . The fir s t s e t o f
data w ere in error, but th ey w ere s u ffic ie n t for the g en era l so lu tio n o f.th e
c r y sta l and m o lecu lar str u c tu r e . C ry sta llo g ra p h ic data for th is compound
are g iv e n in Table XI. The gen era l p o s itio n in sp a c e ,group C 2/d' i s e ig h t
fo ld b u t.th e m o lecu lar form u la.in d ica ted for the co m p lex .in so lu tio n would
. g iv e o n ly four m o le c u le s in .th e unit c e l l . Other p o s s ib le m o lecu la r formulae
w ould not g iv e a s good agreem ent w ith th e exp erim en tal d e n s ity .. This
m olecular, formula w as a ssu m ed to b e the. true formula for.th e in itia l s ta g e s
o f the structure determ ination and. w a s confirm ed by th e fin a l r e s u lt s ., If
o n ly four copper atom s are to be lo c a te d in a sp a c e group which-, has. an
39
e ig h t.fo ld g en era l p o s itio n ,..th e copper atom s m ust lie on s p e c ia l p o s itio n s .
The s p e c ia l p o s itio n s , for.the sp a c e group C 2 /c are given, im Table JV .
T able IV
COORDINATES' OF EQUIVALENT POSITIONS FOR THE SPACE GROUP C 2 /c . (30)
N o . o f P o s itio n s
; 8 (f)
4 (e )
. 4 (d )
4 (c)
4 (b )
4 (a )
C oordinates
, .( 0 ,0 ,0 ; VzrVZi.O) + x ,y ,z ; x , y, z; x , y , ^ - z ; x , y , l / 2 + z
(0 ,0 ,,0 ; l/2 ,l/2 /0 )+ |0 ,y ,l/4 ,|3 ',y ,.3 /4
I (o ,o ,o ; ¥z tVz >0) +. V4-,V4, Vz; 3A z1A , o
/ (o.,o, 0 ; yz.Vz,®)* Vai Vai Q', 3A-Vai Vz
. ( 0 , 0 , 0 ; Vz,Vz,0) + o rV2 ^ , o , V z , V z
( 0 , 0 , 0 ; VZtVz / 0 ) + 0 , 0 , 0 ; 0 , 0 , 1/2
The sp a c e group i s not u n iq u ely determ ined by the s y s te m a tic ab|- •
s e n c e s . The sp a c e group cou ld also, be C e . In C e , th e g e n e ra l p o s itio n is
four, fold, (Table V ).
Table V
-■ COORDINATES: OF EQUIVALENT POSITIONS IN THE. SPACE GROUP C e (30)
N o . o f P o sitio n s
4 (a )
C oordinates
( 0 ,0 ,0 ; V l . V z . Q ) + x ,y ,z ; x , y , ^ + z
A n a ly sis of-th e P atterson map, g en era ted from .the exp erim en tal data
.in d ic a te d •th a t.th e copper atom s la y on th e tw o fold a x e s or th at the sp a c e
group w a s in fa c t C e . .. (L ocating the copper atom s in th e s p a c e group C e is
no d ifferen t from lo c a tin g th e copper atom s in th e sp a c e group; C 2 /c .if;th e
atom s lie on the tw o fold a x e s .) The g en era l featu res o f .th e P atterson map
w ere a ls o .ta k e n a s .in d ic a tiv e .that the c r y sta l w a s c e n tr o sy m e tr ic . The
40
• cop p er atom w as-.given th e p ositio n . 0.,
The v a lu e o f y w a s determ ined
from .the P atterson m ap.. This p o s itio n w a s refin ed and a Fourier s y n th e s is
. c a lc u la te d .to determ ine ;the p o s itio n s o f ch lo rin e atom s . The Fourier map
in d ic a te d s e v e r a l p o s s ib le lo c a tio n s .for;the ch lorin e a to m s. The ch lorine i s
a. large atom and would, normally, be e x p e c te d to be c le a r ly lo c a te d ; the poor
q u a lity of:th e Fourier map m ay-be due to th e errors known to, be p r e se n t in
• th e data c o l l e c t i o n O n e -p o ssib le lo c a tio n o f.th e ch lo rin e w a s c h o se n and
refin ed .. The refin em en t.w a s co n sid e re d ad eq u ate for the in itia l s ta g e s
(R?-40% ).. S everal Fourier s y n th e s e s w ere c a lc u la te d w ith no s u c c e s s , in
\ lo c a tin g th e atom s .
A n a ly sis o f .the P atterson map> in d ic a te d .that an in co rrect p o s it io n w a s
.ch osen for. the ch lorin e atom; a p o s itio n for.th e ch lorin e in d icated , by the
- P atterson map w as. then, refin ed alo n g w ith th e copper p o s itio n .. This p o s i­
t io n refined, to a lo w er v a lu e .(R —.29%). S u c c e s s iv e c y c le s o f Fourier s y n ­
t h e s is and. refinem ent r e v e a le d the g r o ss c r y sta l stru ctu re.
. The g r o ss structure did not refin e to th e d egree e x p e c te d , and the
p o s s ib ilit y th at .the c r y s ta l w as not cen tre sym m etric w a s in v e s tig a te d . Re­
fin em en t o f.th e structure u s in g .the sp a c e group C e g a v e a. sm a ll im prove­
m ent in R but did not im prove the. e stim a te d standard d e v ia tio n s in .th e bond
le n g th s .■ A n o n -c e n tr ic c a lc u la tio n o f structure factors can improve the R for
a p roposed structure b y m asking som e of. the d isa g reem en t in structure, f a c ­
tors sin ce.-th e p h a se a n g le can absorb so m e o f.th e d isa g r ee m e n t. N o-a lte r ­
n a tiv e rem ained e x c e p t.th a t th e data w ere som ehow in error.
The data w ere r e c o lle c te d w ith more care than had., been, u se d in. the
fir s t c a s e . T h ese data im m ed iately a llo w ed .refin em en t o f th e stru ctu re to- a
41
r e a so n a b le v a lu e o f R (6%)
The fin a l cry sta llo g r a p h ic data are g iv e n in
' T ab les XIV, XV, XVI.. The data for the. in itia l c o lle c tio n procedure, are g iy e n .
■in Table .VII a n d ,it .is clear, th at there i s lit t le d ifferen ce b etw een -th e tw o
s e t s . This agreem ent p o in ts out how n ea rly correct stru ctu res can be w ith
poor d a ta , but at th e sa m e.tim e how v a lu a b le good data, i s in the determ ina
,tion. o f e x a c t c r y sta llo g r a p h ic s tr u c tu r e s .
A p r o je c tio n o f ;the B is -1 , 8 -n a p h th y rid in e)-c o p p er (II) ch lorid e m o le ­
c u le i s g iv e n in"Fig, 15.
C
N
Cu
Cl
One M o lec u le o f Bi$,t(1 >8-n aphthyridin e) -copper, (II) ch lorid e
•
^
.
P rojected on the b -c .P la n e
Figure 15
This p ro jectio n d o e s not c le a r ly sh o w .th e square planar coord in ation o f th e
copper atom . The c lo s e approxim ation to true square planar coordination, is
b etter show n by F ig . 16 and Table VI.
42
N
14
■N
Q M
... 92. 27
' (.3917)
: 9 0.63
. (.3 5 3 0 )
9 0 .6 3
(.3 5 3 0 )
94'. 59
G eom etry o f C opper C oordination
Figure .16
The coord in ation around :the copper m ust a ls o be .view ed from another pro
j e c t io n , ^given in F ig . 17.
One M o le c u le o f B is -(1 , 8-n aphthyridin e) -c o p p er (H) ch lorid e
r
. P rojected on th e a - c Plane
Figure 17
43
■ Table VI
DEVIATIONS FROM THE lLEAST SQUARES PLANE FOR COPPER. COORDINATION
Atom
D e v ia tio n . (&)
Cl 02
-0.4,174
Cl 12
-. 0 .4 1 7 4
: N 04
0.3 3 4 3
■N
14
-0 .3 3 4 3
The s e c o n d nitrogen, atom in the m o le c u le i s lo c a te d in a p o s itio n near-the
cop p er atom and .could be co n sid e re d to be w e a k ly co o rd in a ted . The
geom etry then w ould b e th at o f a d isto rted octa h ed ro n . This co p p ernitrogen d is ta n c e i s lon g but m ust be c o n s id e r e d . The c r y s ta l fie ld sur­
rounding the copper i s d e fin ite ly th at o f a d isto r te d o c ta h e d r o n . Such a
sym m etry sh ou ld destroy- any orb ital contribu tion to th e m a g n etic moment o f
.the. m o le c u le , and a. .vhlue o f .1.9 Bohr m agn etons w ould be e x p e c te d if ;the
orb ital contribu tion i s c o m p le te ly q u en ch ed . The spin o n ly value, o f the
m agn etic moment w ould by 1.73' Bohr m a g n e t o n s b u t th e sp in -o r b it co u p lin g
i n copper com pounds, (a s estim ated.from v a lu e s m easured for.th e free ion)
in c r e a s e s ;the exp ected , v a lu e to 1.9 Bohr m a g n eto n s. A v a lu e o f the m ag­
n etic-m om en t ,le s s th a n 1.9 Bohr m agn etons w ould im ply som e sort o f e x ­
ch an ge, in ter a c tio n in th e cry sta l; but no ex ch a n g e sh ou ld be p o s s ib le . F i g . '
18 g iv e s a-projection, o f :the c r y sta l structure onto th e a - c p la n e o f th e unit
c e l l . The copper atom s are much to far apart for any d ir e ct in tera ctio n .a n d
are not bridged in any w a y by other a to m s . A v a lu e greater than, 1.9 Bohr
m agn etons for th e m a g n etic moment is p o s s ib le if.th e o rb ita l contribution i s
Packing Diagram for B is -(1 , 8 -n a p h th y rid in e)-co p p er (II) chloride
Figure 18
45
not q u en ch ed . O ctahedral geom etry sh ou ld q u en ch .th e orb ital contribution
' Cl) and g eo m etries o f l e s s symmetry, (su ch a s th e square p la n e or d isto rted
octahedron) sh ou ld a ls o quench the orbital co n trib u tio n .
The structure, of. the 1, 8-naphthyridine. (Fig„.19) m o le c u le is a ls o
- a v a ila b le from th e to ta l structure, alth ough it may be d isto r te d s lig h tly by
th e coord in ation „ The a c cu ra c y o f th e b o n d .len g th s i s a ffe c te d by the
p r e se n c e o f;th e h ea v y atom s in the str u c tu r e .
The fin a l refinem ent o f.th e structure w a s done g iv in g a ll the atom s
a n iso tr o p ic therm al p a ra m eters. Two o f .the c r o s s terms in .the a n iso tro p ic
;;therm al param eters for:the copper atom were, not v a r ied . T h ese tw o term s
are in varian t under.the space, group o p era tio n s and m u st.th erefore be held
:
c o n sta n t (3 1 ). N o .large param eter s h ifts w ere o b serv ed and. the structure
' m ay be co n sid e re d to sh o w lit t le a n iso tr o p y .
The c i s - square plan ar coord in ation at the copper atom is :- u n u su a l.
. The structure, o f .B is-p y r id in e-co p p e r (II) chloride. (32) i s ty p ic a l o f th e
geom etry e x p e c te d in nitrogen coord inating copper,( l l ) 'h a li d e s . This stru c­
ture h as a trans sq u are planar geom etry w ith Aong in te r a c tio n s to two
ch lorin e atom s to form an e lo n g a te d o c ta h e d r o n .. T h ese lo n g er in tera ctio n s
are not u n usual and may- c o n s titu te a bridging pathw ay for e x ch a n g e and
sp in c o rr e la tio n . The is o la tio n o f the copper atom s in B i.s-(1 ,8 n ap hth yrid ine)-c o p p er (II) ch lorid e p ro v id es an e x c e lle n t t e s t c a s e for
m easurem ent o f in ter a c tio n b etw een m o le c u le s- in the c r y s ta l.
S in g le c r y sta l s tu d ie s w ere also- begun on B is- ( I 78 -n a p h th y r id in e)-.,
copper;(II) brom ide. The prelim inary photographs sh o w th at an unusual.form
o f d isorder m ust e x is t in .th e c r y s ta l. R otation photographs w ith CuKa
C9
C7
C I0
Ol
1,40 (03)
SS
o
W
4x
CD
CU
1, 8 -N aphthyridine Bond Lengths and Bond A ngles (Standard D ev ia tio n s)
F igure 19
47
rad iation sh o w fiv e layer, lin e s „ The W e isse n b e r g photograph o f:th e fir st i s
ex trem ely w eak and th e s p o ts are s e v e r e ly jalongated a lo n g the trace o f :the
f e s t o o n s . The z e r o , s e c o n d and fourth le v e l s are normal and:the third so
w eak th at it w as o n ly dark enough th e sh o w th e sam e str e a k in g . B eindexing
th e photograph.to make th e normal la y e r s z e r o , one and tw o g iv e s ;th e c r y s ­
ta llo g ra p h ic d a ta .g iv e n in T able XII. The c e ll resu ltin g ,fr o m :th is.in d ex in g
req u ires .that th e copper atom s be d iso r d e r e d . The nature o f f h e streak ing
ind icates:, th a t.th e d isord er i s one d im en sio n a l but no further work has. b een
done to determ ine fh e . e x a c t nature o f th e d iso rd er.
SUMMARY
• S in c e it was- b e lie v e d , that 1 , 8-n ap h th yrid in e m ight form b in u clear
c o m p le x e s w ith, copper (II) h a lid e s , and s in c e su ch b in u clea r co m p lex es
- c o u ld p rovid e inform ation about the nature o f:th e co p p er-co p p er in ter a c tio n s
in copper (II) com pounds w ith subnormal m a g n etic m o m en ts, it w as d e c id e d .
to prepare and determ ine the c r y sta l and m o lecu la r structure o f som e
copper (II) h a lid e c o m p le x e s w ith L78 -n a p h th y r id in e s. Attem pts w ere made
. to prepare both 4 - m e t h y l- l, 8-n ap h th yrid in e and 1 , 8-n ap h th yrid in e for u s e a s
: lig a n d s s in c e no su p p lie rs o f I , 8-n a p h th y rid in es e x i s t .
The preparations o f .1 , 8-n ap h th yrid in e and 4 -m e th y lr l,,8-n aphthyridin e
: g iv e n ,im th e literatu re are'n ot s a tis fa c to r y for;the preparation o f .t h e s e com ­
pounds in the am ounts n e c e s s a r y for u s e a s a .lig a n d in .th e.p rep a ra tio n o f
in organ ic coord in ation com p ou n d s. The preparation o f 4 - m e t h y l- l, 8 naphthyridine d o e s not y ie ld th e fu lly a ro m a tic.b a se in any q u a n tity . The
major products are not:the reported 4 -m e th y l-l,8 -n a p h th y r id in e but probably
. hyd rogenated d e r iv a t iv e s .. A n ew preparation o f 4 -m e th y l-^l, 8-n aphthyridin e
h a s been, d e v e lo p e d w h ich ,g iv e s 4 - m e t h y l- l, 8-n ap h th yrid in e a s a c r y s ta l­
lin e product .for;th e.fir s t.tim e .. The structure o f 4 - m e t h y l- l, 8-n aphthyridin e
i s c le a r ly show n by PMR s p e c tr o s c o p y . A n ew preparation o f .', .
.: 1 , 8-n ap h th yrid in e from r e a d ily a v a ila b le sta rtin g m aterials h as b e e n d e ­
v e lo p e d ., This preparation, g iv e s y ie ld s o f 1 , 8-n ap h th yrid in e in adequate
q u a n titie s ,fo r u s e a s a .ligan d , in th e preparation o f coord in ation com pou nds.
S everal copper (II) c o m p le x e s o f 1 , 8-naphthyridine; h a v e been.prepared
. and c h a r a c te r ise d . The c r y sta l and m o lecu la r structure o f on e o f t h e s e
49
C o m p lex e s, B is- ( 1 , 8 -n a p h th y rid in e)-co p p er (II) c h lo r id e , h as b een d eter­
m ined . The compound .does, not have th e hoped for b in u clea r stru ctu re, but
: the str u c tu r e.is v e r y u n u su al and p ro v id es a. compound w ith is o la te d square
=planar coord in ation w h ich m ay prove u s e fu l a s a, t e s t in s tu d ie s o f lig a n d
field , th eo ry . The square ..planar coord in ation i s a ls o u n u su a l in th a t.it forms
a .c is - s q u a r e p lan e in co n tra st to the tr a n s-sq u a r e p la n e u s u a lly found, in
'. cop p er (II) com p ou n d s.
.
APPENDIX’. A
S p e c tr o sc o p ic and M agnetic. Data
51
40 00
2000
1800
1200
1000
Figure 2 0 . IR Spectrum o f 2 - h yd roxy-4 -m eth y l - 7 - a m in o - l,8 -naphthyridine
F igure 2 1 .
UV Spectrum o f 2 - h y d r o x y - 4 - m e t h y l- 7 - a m in o - l,8 - n a p h t h y r id in e
52
4000
3000
1600
2000
1400
Figure 2 2 . IR Spectrum o f 2 , 7 -d ih y d r o x y -4 -m e th y l-l, 8-n ap h th yrid in e (KBr)
240
260
280
30 0
mu
320
340
F igure 2 3 . UV Spectrum o f 2 , 7 - d ih y d r o x y - 4 - m e t h y l- 1 , 8 -n a p h th y r id in e
360
53
4000
3000
2000
1800
1600
1400
1200
1000
Figure 2 4 . IR Spectrum o f 2 , 7 -d ic h lo r o -4 -m e th y l-1 , 8-n ap h th yrid in e (KBr)
Figure 2 5 . UV Spectrum o f 2 , 7 - d ic h lo r o - 4 - m e t h y l- 1 , 8 -n a p h th y r id in e
54
4000
3000
2000
1800
1200
1000
Figure 2 6 . IR Spectrum o f 2 , 7 -d ih y d r a z in o -4 -m e th y l-l, 8-n ap h th yrid in e (KBr)
Figure 2 7 .
UV Spectrum o f 2 , 7 - d ih y d r a z in o - 4 - m e t h y l- l, 8 -n a p h th y r id in e
55
4000
Figure 2 8 .
24 0
Figure 2 9 .
3000
2000
1800
1600
1400
1200
IR Spectrum o f 4 - m e t h y l- l, 8-n aphthyridin e
300
UV Spectrum o f 4 - m e t h y l - l , 8 -n a p h th y r id in e
IOOO
56
4000
3000
2000
1800
1600
1400
1200
1000
Figure 3 0 .
IR Spectrum o f 2 -a m in o -7 -h y d r o x y -1 , 8-n ap h th yrid in e (KBr)
Figure 3 1 .
UV Spectrum o f 2 -a m in o -7 -h y d r o x y -1 , 8-n aphthyridin e
800
.5 7
4000
Figure 3 2 .
240
3000
2000
1800
1200
1000
IR Spectrum o f 2 , 7 -d ih y d r o x y -1 , 8-n ap h th yrid in e (KBr)
26 0
280
300
mu
320
Figure 3 3 . UV Spectrum o f 2 , 7 -d ih y d r o x y -1 , 8-n aphthyridin e
340
3 60
58
3000
2000
1800
1600
1400
1200
1000
Figure 3 4 .
IR Spectrum o f 2 , 7 - d ic h lo r o - l, 8-n ap h th yrid in e (KBr)
Figure 3 5 .
UV Spectrum o f 2 , 7 - d i c h l o r o - l , 8-n aphthyridin e
„
T ransm ittance
59
2000
1600
IR Spectrum o f 1, 8-n ap h th yrid in e ( C H C lg )
A bsorbance
2
gure 3 6 .
3000
Figure 37.
UV Spectrum o f 1, 8-n aphthyridin e
60
600
Figure 3 8 .
V isib le Spectrum o f B is -(1 , 8 -n a p h th y rid in e)-co p p er (II) ch loride
in w ater.
Table VII
EXTINCTION COEFFICIENTS OF
BIS-(1,8-NAPHTHYRIDINE)-COPPER (II) CHLORIDE IN WATER
6max|mu)
e
368
26 (±1)
700
15 (+1)
61
T able .VIII
THE MOST.INTENSE:BANDS
IN THE! ULTRAVIOLET SPECTRA OF NAPHTHYRIDINES
. (a ll sp ectra .in 9 5% e th a n o l)' ^
'. Compound
Xmax
U l
2 -h y d r o x y -4 -m e th y l - 7 -a m in o -1 , .8-naphthyri din e
333
(
x 10.®)
2 , 7 -d ih y d ro x y -r4 -m eth y l-1 , 8-n aphthridin e
3.39
(
>-10®)
2 /.7 -d ic h lo r o -4 ^ m e th y l-l/.8-naphthyridine
311
(
>10®)
2 , 7 -d ih y d r a z in o -4 -m e th y l-l, .8-naphthyridine
356
( . >10®)
4 -m e th y l- 1 , 8-n ap h th yrid in e
. 255
2 - amino - 7 -h y d r o x y -l, 8-n aphthyridin e
353
(
>10®)
2 ,.7 -d ih y d r a z in o -l, 8-n aphthyridin e
325
(
rO
—
I
A
2 , 7 -d ic h lo r o -l , 8-n ap h th yrid in e
378
(1.3x10® + . I)
1 , 8-n aphthyridin e
307
( 5 .7 x l 0 ' ® i .l )
( a ) ' In a ll c a s e s u l t r a v i o l e t sp ectra w ere determ ined by w eig h in g 2 mg. .
. sa m p les o f th e com pound in. 100 m l. o f 95% e th a n o l. W here e x tin c tio n
c o e f fic ie n ts are reported a s greater than 10®, .the sam p le w a s in co m , p le te ly d is s o lv e d and. i f .it had d is s o lv e d c o m p le te ly , th e e x tin c tio n
c o e f fic ie n t would, have been, greater than 10®.
6 2
. T ab le IX
PROTON MAGNETIC -RESONANCE SHIFTS AND COUPLING CONSTANTS OF
1, 8-NAPHTHYRIDINES
Shift
(ppm)
: Proton
C oupling
cp s
;
I , .8-N ap h th yrid in e
.(DC
„9
a -6
4.5 i . 5
'P
. 2 .6
’■P-Y
8.5 + .5
■Y
L9
■• a - Y
2.2 i .5
2 , 7 -D ic h lo r o -4 - M e th y l-l , 8 -N aph thyrid ine
CH3
Y
6.70
(B-CH3
.9 + . I
.. 1.4
■P
.. 2.32
.C H 3
• . 6.70
a
1.00
P- Y
9 .0 ±. 1.1
4 -M e th y l-1 , 8 -N ap h th yrid in e
•Y
. 1.40
P-Y
9 .0 ±. I .
P.
. 2.33
a -Y
2 .0 ±. ..E
63
. Table X
ROOM TEMPERATURE: MAGNETIC SUSCEPTIBILITIES
. AND MAGNETIC MOMENTS : (a)
Compound
■ XM
(e„ s „.u.„)
2 ,7 -d ic h lo r o - 4 -m e th y l I ,.8-n aphthyridin e (b)
150 (±.100.) x lO " 6
B i s - ( 2 , 7 -d ic h lo r o -.4-m e th y l1 , 8-n aphthyridin e) -c o p p er (II)
ch lorid e eth a n o la te (c)
1505 (±.50) x IO- 6
'-Jjeff
..(Bohr m agnetons)
2.12
• (a)
Ligand corrections, in th e c a lc u la tio n o f.(J eff w ere obtained
. from r eferen ce I .
(b)
. The ex trem ely sm a ll d e fle c tio n s produced, by th is compound
in th e Gouy b a la n c e c a u se d large, estim a ted , e rro rs.
(c)
The v a lu e o f Xg for 2 .,8 -d ic h lo r o -4 -m e th y l-l, 8-n aphthyridin e
c a lc u la te d , from P a s c a ls c o n s ta n ts w as used, in the c a lc u la tio n
o f Ueff for th is com pound.
APPENDIX'. B
. Computer Programs
COMPUTER. PROGRAMS
DIFPSET
This program w a s w ritten in FORTRAN by Dr. Robert W itters at H arvey
: M udd C o lle g e .. This program i s d e sig n e d to c a lc u la te G o n io sta t s e ttin g s .for
th e " b a sa l plane" align m en t o f a c r y s t a l. A ll s e ttin g s fo r r e fle c tio n s a b ove
:the b a s a l p lan e are c a lc u la te d for v a lu e s o f 2 0: le s s .th a n som e input v a lu e .
, The program w ill not om it r e fle c tio n s a b s e n t due to e x tin c tio n .
>
. LI
A data red u ctio n program written, in SP S .for .the 1620 com pu ter, by
- D r s . C harles Caughlanl and. Chi Tang L i, th is program w a s d e s ig n e d for
photographic W e iss e n b e fg d a ta .. The. program c a lc u la te s th e Lorentz and
p o la r iz a tio n co rrectio n .for data on. th e b a s is o f e g u i-in c lin a tio n a n g le
(w h ic h .is zero for a ll d iffractom eter d a ta ). R e fle ctio n s w ith a n .in te n s ity
l e s s than som e input v a lu e are g iv e n .a n .u n o b se rv e d in d ic a to r . ■All other r e ­
fle c tio n s are co n sid e re d o b se r v e d . The program has a p rovision , for c a lc u ­
la tin g , the param eters for a W ilso n , p lo t for o v e ra ll s c a le and tem perature
fa cto r and a. subroutine for.m aking ab sorp tion co rrectio n s .
■ FOURIER
■.This Fourier s y n th e s is program w a s w ritten by D r s . C h arles C aughlan
: and. G eorge S v e tic h in SPS for.th e 1620 com puter. The program w ill a c c e p t
o b se rv e d structure fa cto rs for th e c a lc u la tio n o f a .P a tterso n s y n th e s is or
observed, and c a lc u la te d , structure fa cto rs for th e c a lc u la tio n o f a Fourier
s y n t h e s i s . The program w ill c a lc u la te both Fourier and P atterson s y n th e s e s
66
for a ll space, g r o u p s. The program i s v ery f a s t , but it i s lim ite d in the
a v a ila b le output fo rm a ts.
MAIR
The program w as w ritten, by Dr. G . A. M air and r e v is e d a t th e U niver­
s it y o f Canterbury., Programs P 4, P.5, and P6 w ere ob ta in ed from Dr. Bruce
P en fo ld . The program c a lc u la te d .th e structure fa cto rs for a ll s p a c e groups
and c a lc u la te s s h ifts :to refin e th e input p a ra m eters.. The program m in im izes
th e fu n ction
M = w (kF^)2 - .( F c ) 2 )^2
In a ll c a s e s w - I .
This program w ill refin e p o s itio n s a n d .iso tr o p ic or a n isotrop ic.tem p eratu re
fa cto rs a s w e ll a s t h e o v e r a ll s c a l e .
ICR6
. This program w as. w ritten by Dr. R. van der Helm in SPS a t th e I n s ti­
tu te, for C ancer R esea rch , and is part o f a g e n e ra l Fourier s y n th e s is pro­
gram. The program prepares .structure fa cto r output for.th e sum m ation
portion, o f th e Fourier sy n th esis, program ,(ICR6). The program w a s r e v ise d at
th e U n iv e r sity o f Canterbury for card input and o u tp u t.
ICRl
A lso w ritten, b y /Dr.. R. van der Helm in SP S, th is i s th e summation
portion o f th e Fourier s y n t h e s i s . All sp a c e , group s p e c if ic it y h as b een d e a lt
w ith in ICR6 so :th is, program i s a g en era l o n e . The. program w ill c a lc u la te
67
b oth Fourier and P atterson s y n th e s e s ; output i s on cards in. alphanum eric
.form at.
ORELS
; This program is a. FORTRAN fu ll m atrix le a s t sq u ares refinem ent pro­
gram for c ry sta llo g r a p h ic data w ritten by D r s „ B u sin g, L evy and M artin at
: th e Oak Ridge N a tio n a l L a b o ra to ries. This i s a w id e ly used, refinem ent
: program; th e v e r sio n .u se d , here w as ob ta in ed from W ashington State; U n iver­
s ity .- AU c a lc u la tio n s w ere done by te le ty p e control at th e W estern'.D ata
P r o c e s s in g C enter at ..the U n iv e r sity o f C aliforn ia at Los A n g e le s.
- DSET
. This program w a s 1w ritten by E . L. Enw all to c a lc u la te ;the G o n io sta t
s e ttin g s for th e "chi ninety" align m ent te c h n iq u e . M ach ine s e ttin g s are
c a lc u la te d for in d ic e s in. b lo c k s accord in g to the s ig n s o f.th e various
■in d ic e s and p rovision , is.m a d e,fo r-th e..o m issio n , o f s y s te m a tic a lly a b sen t
.. r e f le c t io n s . The program .g iv e s :the m achine s e ttin g s .for the F r ie d e l1s la w
r e la te d .r e fle c tio n if:th e v a lu e o f.th e o rig in a l r e fle c tio n i s n e g a tiv e .
. .PARAM
This program i s a m od ification , o f th e PARAM from the-X-RAY-65 s y s ­
tem s tap e w ritten, by Dr. James S tew a rt.. The program g iv e s th e b e s t le a s t
sq u ares c e ll param eters o n th e b a s is o f m easured v a lu e s o f 2 0 for any s e t
o f r e f le c t io n s . The program r efin e s o n ly th e param eters v a r ia b le under the
s p a c e group in q u e stio n and w ill .r e c y c le .to con tin u e refin in g u n til th e s h ifts
68
in param eters are very s m a ll. The program w a s m o d ified .a t M ontana State
■U n iv e r sity b y E. L. Enw all „
RDN
This program and DLS w ere w ritten b y Dr. F . Ahmed and. m odified, at
Ohio U n iv e r sity by Dr. G. D . Sm ith. RDN i s a g en era l data,reduction, pro­
gram .for a ll norm ally u s e d data c o lle c tio n g e o m e tr ie s .. The. portion, o f the
• program d e a lin g w ith G o n io sta t geom etry w a s m odified by E . L. Enwall at
M ontan a.State U n iv e r sity .. The G o n io sta t portion has p r o v isio n for Lorentz
a n d .p o la r iz a tio n co rrectio n s and for the. s c a lin g o f data before red u ction .
■E stim ated standard, d e v ia tio n s are c a lc u la te d .fo r a ll r e fle c tio n s by the te c h ­
n iq u e s s u g g e ste d , by Jensen, (2 5 ). No. absorption, correction w a s a p p lied .
DLS
A lso written..in. FORTRAN by Dr. Ahmed and m odified, by Dr. Sm ith, th is
i s a structure fa cto r c a lc u la tio n and. block, d ia g o n a l l e a s t sq u ares, refinem ent
p ro g ra m .. This program m in im iz e s.th e sam e fu n ction a s d o e s MAIR, but the
v a lu e o f W w as determ ined from the e x p r e ssio n ;
W = I / (sig )^ 2
w here s i g .i s :the e stim a te d standard d e v ia tio n in F0 .
BAD
A FORTRAN program w ritten, by Dr.. K. W atenpaugh and m odified by
.■■■E . L. E nw all,. th is program c a lc u la te s bond le n g th s and.bond a n g le s for atom
p o s itio n s entered, a s .in p u t d a ta . Standard, d e v ia tio n s may be c a lc u la te d .if
,the standard, d e v ia tio n s .in p o s itio n s are a lso , g iv e n .a s input d a ta .
APPENDIX C
C ry sta llo g ra p h ic Data. and. G o n io sta t Geom etry
70
G o n io sta t G eom etry
■ The G o n io sta t geom etry c o n s is t s 'df four c ir c le s w hich, d efin e m otions
o f th e in stru m en t.. Two o f.t h e s e c ir c le s , the @circle, an d .th e o j c i r c l e , . l i e
in the: b a s a l p lan e o f.th e in stru m en t. The b a s a l plane, of.the. instrum ent i s
d e fin ed b y .th e lo c i o f the X -ray so u r c e , th e cen ter o f th e c r y sta l and.the
p o sitio n , o f th e d e te c to r . This b a s a l p la n e i s app roxim ately h o r iz o n ta l. All
th e c ir c le s o f th e G o n io sta t have th eir c en te rs a t th e cen ter o f th e c r y s t a l.
The X .circle h a s it s a x is in .the b a s a l p la n e and b is e c t s th e a n g le cen tered
a t th e c r y s ta l c en te r and. d efin ed by the X -ray so u rce and. d e te c to r . The @
c ir c le a x is , lies; in the X c i r c l e .
. In p r a c tic e , the
c ir c le o f :the G o n io sta t i s u s e d o n ly to co m p en sa te
for m e ch a n ica l m is a lig n m e n t.. M otion, in th e other .three c ir c le s, i s u se d to
b rin g.th e rec ip r o c a l la ttice , o f th e c r y sta l in to a p o sitio n , s o th at r e fle c tio n
o c c u r s . The proper c o n d itio n for r e fle c tio n i s b e s t d is c u s s e d .in terms o f th e
Ewald diagram , F ig . 3 9 .
X -ray
Ewald Diagram
Figure .39
71
I f th e recip ro ca l la tt ic e v e c to r R is in .the p la n e o f the c ir c le o f .reflec tio n
■. and. tan gen t to th e .c ircle a. rotation o f th e c r y sta l perpendicular .to .the c ir c le
: o f an am ount 0: w ill c a u s e .th e recip ro ca l la t t ic e v e cto r R to in te r s e c t.th e
c ir c le of. r e fle c tio n . The con stru ctio n , o f .the Ewald diagram .(F ig. 39,) im p lie s
:that a .r e fle c tio n w ill th en .o cc u r at an. a n g le 2 0 to the X -ray beam and in. the
■plane, o f .the c ir c le s o f r e fle c tio n . ■In .terms o f G o n io sta t g eo m etry , a. r e c ip ­
r o c a l, la tt ic e v e c to r m ust li e in the b a s a l p lan e and perpendicular t o the
-. Xrray beam w hen th e v a lu e o f © i s z e r o . The rotation o f 0 w ill bring, the
v e c to r in to r e fle c tin g p o s itio n and- th e d e te c to r , w h ich m o v es at tw ic e -the
. angular r a te , w ill be in p o sitio n . (2 0) to m easure the in t e n s it y o f The d iff­
racted beam . The- $ and X m odes o f m otion, s u ffic e to bring any recip rocal
. la t t ic e p o in t.in to th e proper p o s itio n . The $ m otion (a ll oth er s e ttin g s zero)
c a n bring any r e fle c tio n .into- the. plane, o f th e X c ir c le „ and X m otion can..'
. th en bring th e r e fle c tio n in to the b a s a l p la n e .
The c a lc u la tio n o f s e ttin g s for the. 0, X, and § c ir c le s for co n d itio n s
o f r eflec tio n , dem and:that th e e x a c t real o r ien ta tio n of;th e c r y s ta l be k n ow n.
. The p r o c e s s o f determining, the. e x a c t o rien ta tio n i s e a s i e s t if;the. c ry sta l is
. in one o f tw o p articular o r ie n ta tio n s .. The name "alignm ent" is. g iv en , to .th e
- p r o c e s s o f bringing th e c r y sta l in to one o f .these, o r ie n ta tio n s . T h e.first
a lign m en t p osition , i s th e "basal" p o s itio n . This p o s itio n req uires that tw o
a x ia l row s o.f;the r e c ip r o c a l.la ttic e lie in th e b a sa l p lan e o f the G o n io sta t.
. If th is requirem ent is m et and th e $ v a lu e for proper r e fle c tio n o f one a x ia l
. row i s know n, th e e x a c t o rien ta tio n o f.th e c r y s ta l.is d eterm in ed .. The
. s e c o n d and p referred .a lig n m en t.(b eca u se i t is e a s ie r to attain ) i s the "chi
. ninety" p o s itio n . In th is o r ien ta tio n , one .recip ro ca l la tt ic e v e c to r i s . made
.72
c o in c id e n t with-.the $ a x is and th e proper reflection - § i s determ ined for som e
oth er r e fle c tio n . This d eterm in es th e e x a c t c ry sta l o rien ta tio n . It is not
n e c e s s a r y .to . "align" a c r y sta l a t a l l , but determ ination o f th e e x a ct
o r ien ta tio n .b e co m es more d iffic u lt i f no a lig n m en t i s u s e d . M o st o f the
com puter programs written.:for the c a lc u la tio n o f m achine s e ttin g s for data
c o lle c tio n a ssu m e one, o f th e-tw o align m ent p o s itio n s d e sc r ib e d alth ough a t
l e a s t on e program h as been, w ritten ,for g en era l p o s itio n in g .
. O n cejth e p o sitio n , o f any tw o n o n -o o -lin e a r r ecip ro ca l la tt ic e v e c to r s
i s e x a c tly determ ined (a lig n m en t), a ll ^ ther p o s itio n s c a n .b e .c a lc u la te d .
This i s done by c a lc u la tin g th e p o sitio n s, o f the known v e c to r s in som e
a r tific ia l o rien ta tio n and determining, th e .transform ation from;the a r itific ia l
o r ie n ta tio n .to .th e .r e a l o r ien ta tio n . This transform ation w ill th en convert any
v e c to r in th e a r tific ia l o r ien ta tio n to th e v e c to r in the rea l o r ien ta tio n . The
r e a l o rien ta tio n o f a v e c to r a llo w s th e c a lc u la tio n o f.th e $ and X m otions
n e c e s s a r y to bring :the v e c to r .in to a. p o sitio n , (at .9»’= zero) where., i t is ta n g en t
to .the circle, o f d iffr a c tio n . The 2 0 value, i s c a lc u la te d from the. len g th o f
the. recip ro ca l, la t t ic e v e c to r s o th at a short s c a n m a y b e u s e d to obtain, the
d iffr a cted in t e n s it y .
.73
T a b le XI
SINGLE CRYSTAL. DATA FOR
B IS -Q , 8-NAEHTHYRIDINE) -COPPER (II) CHLORIDE
C ry sta l D im ension:
C ry sta l D e n sity :
,30mm x. ,17mm x .IOmm
■ found
I „68.g„/cc.
c a lc .
U nit C e ll C on stan ts:
a .=
13.745 + .029
b- =
8.192 + .010
. c =
16.382 ±. .013
' ; 6 = 122.32
+ .0 9
■ Vol = 1558.6 R3
C on d ition s for S y s te m a tic a lly A bsent R e fle ctio n s:
h k l; h + k = 2n
hOl; h + I = 2n
. 0k0; (k = 2n)
S p ace Group from S y ste m a tic A b sen ces:
C 2 /c or Ce
M o le c u le s C a lc u la te d per U nit C ell:
4.003
1.68 g . / c c .
S c a le
S c a le Group
A verage S c a le for D iffractom eter D ata Bis -(1 , 8-naphthyridine) -co p p er (II) ch loride
Figure 40
75
T ab le XII
SINGLE CRYSTAL DATA FOR
B I S -U , 8-NAPHTHYRIDINE)-COPPER (II) BROMIDE
C rystal D im en sio n s:
. Imm x .Imm x .4mm
C rystal D e n sity
found
U nit C e ll C o n sta n ts:
a =
4.28
b =
14.66
c =
13.30
8 =
8 5 .6 °
2 .0 0 g . / c c .
c a lc .
2 .0 6 g . / c c .
Vol = 832.0 ft3
C on d ition s for S y s te m a tic a lly A bsent R eflectio n s:
k h l; h + k = 2n
hOl; h + I = 2n
OkO; (k = 2n)
S p ace Group from S y ste m a tic A b sen ces:
C 2 /c or C c
M o le c u le s C a lc u la te d per U nit C ell:
2 .0 6 5
Table XIII
SINGLE CRYSTAL DATA FOR
METHYL NAPHTHYRIDINE COPPER COMPLEX
C rystal D im en sion s:
C rystal D en sity :
C ry sta llo g ra p h ic System :
U nit C e ll C on stan ts:
found
1 .72 g . / c c .
orthorhombic
a =
b =
c =
Vol =
14.7
19.5
20 .4
5840 %.3
M o le c u le s per unit c e ll on b a s is o f m o lecu la r formula Cu(C 9 HgN 2 )C l2: 14.5
76
T ab le XIV
FINAL ATOM POSITIONS AND STANDARD DEVIATIONS
X
y
Z
<yx
cry
az
Cu
I
.5 0 0 0
.3 1 6 0 5
.2 5 0 0 0
.0 0 0 0 0
.0 0 0 2 3
.0 0 0 0 0
Cl
2
.4 3 2 2 4
.1 2 9 6 6
.3 0 8 4 4
.0 0 0 2 2
.0 0 0 3 3
.0 0 0 2 0
N
3
.6 6 7 6 4
.4 4 2 2 6
.4 2 5 6 8
.0 0 0 6 9
.0 0 1 0 8
.0 0 0 6 5
N
4
.4 7 7 5 6
.4 9 4 8 9
.3 2 3 0 8
.0 0 0 6 6
.0 0 1 0 6
.0 0 0 5 8
C
5
.7 6 4 1 0
.4 6 3 7 7
.5 1 0 2 5
.0 0 0 8 6
.0 0 1 4 1
.0 0 0 7 8
C
6
.7 7 6 5 5
.5 7 4 9 9
.5 8 0 3 5
.0 0 0 8 9
.0 0 1 4 2
.0 0 0 7 6
C
7
.6 8 4 7 6
.6 6 6 8 1
.5 6 3 4 9
.0 0 0 8 4
.0 0 1 0 5
.0 0 0 7 3
C
8
.5 7 9 0 7
.6 4 4 4 9
.4 7 1 8 2
.0 0 0 8 7
.0 0 1 1 8
.0 0 0 7 5
C
9
.4 7 7 7 7
.7 3 2 3 2
.4 4 6 2 8
.0 0 0 9 2
.0 0 1 3 5
.0 0 0 8 3
C
10
.3 7 8 9 7
.6 9 8 9 5
.3 5 8 9 3
.0 0 0 9 2
.0 0 1 4 6
.0 0 0 8 4
C
11
.3 8 0 0 0
.5 7 6 8 8
.3 0 0 2 9
.0 0 0 9 3
.0 0 1 3 4
.0 0 0 7 9
C
12
.5 7 5 2 9
.5 2 8 9 2
.8 0 9 8 2
.0 0 0 7 8
.0 0 1 2 2
.0 0 0 7 0
77
T a b le XV
FINAL ANISOTROPIC THERMAL PARAMETERS
BH
B22
B33
B23
B13
B12
Cu I
.0 0 4 4 7
.0 1 0 9 1
.0 0 3 0 4
.0 0 0 0 0
.0 0 3 4 0
.0 0 0 0 0
Cl 2
.0 0 6 7 1
.0 1 3 1 0
.0 0 4 2 5
.0 0 0 2 8
.0 0 5 6 5
.0 0 2 0 9
N
3
.0 0 5 8 2
.0 1 2 9 4
.0 0 4 7 9
.0 0 1 0 2
.0 0 6 3 3
.0 0 3 3 5
N
4
.0 0 6 6 7
.0 1 0 5 3
.0 0 3 5 6
- .0 0 0 2 8
.0 0 4 7 4
.0 0 1 1 1
C
5
.0 0 5 5 3
.0 1 5 0 1
.0 0 3 7 7
.0 0 2 5 3
.0 0 3 6 4
.0 0 1 2 7
C
6
.0 0 6 2 1
.0 1 5 3 7
.0 0 4 0 4
.0 0 2 8 9
.0 0 5 1 5
- .0 0 1 9 7
C
7
.0 0 6 3 0
.0 1 6 5 5
.0 0 3 9 2
- .0 0 1 0 4
.0 0 5 7 8
- .0 0 4 4 9
C
8
.0 0 6 9 9
.0 0 9 2 4
.0 0 4 6 1
.0 0 1 4 2
.0 0 7 3 1
.0 0 0 9 1
C
9
.0 0 7 4 7
.0 1 3 3 4
.0 0 5 0 1
- .0 0 1 3 7
.0 0 7 1 2
- .0 0 1 3 3
C 10
.0 0 7 3 6
.0 1 1 2 3
.0 0 6 1 0
.0 0 1 9 0
.0 0 5 7 0
.0 0 3 5 0
C 11
.0 0 7 4 2
.0 1 2 5 2
.0 0 4 3 3
.0 0 2 1 1
.0 0 6 6 6
-.0 0 0 8 1
C 12
.0 0 5 3 0
.0 1 0 2 6
.0 0 3 3 0
.0 0 1 6 0
.0 0 4 3 8
.0 0 0 2 6
78
Numbering Diagram for B is- ( 1 , 8 -n a p h th y rid in e)-co p p er (II) chloride
Figure 41
79
. T a b le XVI
! BOND DISTANCES AND BOND ANGLES FOR
BIS- ( 1 , 8-NAPHTHYRIDINE)-COPPER (II) CHLORIDE.
•: Bond
•
■:
•
:
.
Cu 1-C102
Cu I -N 03
N Q3-C .05
C 0.5-C 06
C 0 6 -C 07
C 0.7-C 08
C 0.8-C .09
C .09-C 10
C IO-C 11
C I l - N 04
C 12 -N 04
C 1 2 -N 03
C enter Atom a t V ertex
C 102-C u-C 112
- C 102-C u -N 04
- N 0 4 -C u -N 14
■ N ;04-C u -N 03
. C 12 -N 0,3-C .05
- N -03-C 0 5 -C 06
. C 0 5 -C 0 6 -C 07
. C 0 6 -C 0 7 -C .0 8
C .0 7 -C 0 8 -C 09
C 0.8-C:09-C 10
- C .0 9 -C IO-C 11
. C 1.0-C I l - N 04
C I l - N 0 4 -C 12
^..N 0 4 -C 12-C 08
CD
P
0
1
CO.
O
0
1
CM
r—
I
O
. C 1 2 -C 0 8 -C 07
, N 0 3 -C 1 2 -C 08
Length
!Standard D ev ia tio n
2 .2 5 1 4
, 2 .7 5 1 4
; 1 .3 2 0 7
,1 .4 0 2 9
1 .3 6 4 3
1 .4 3 7 4
,1 .4 1 7 2
. 1 .3 7 4 3
.1 ,3 9 2 0
: I . .3614
.1 ,3 6 .3 9
. 1 ,3 5 2 8
.0 0 4 7
.0.224
.0 3 4 6
.0 2 7 3
.0.284
.0 3 6 7
.03.00
.0411
.0 2 4 9
,0 2 6 7
.0321
.0 2 3 4
Angle
. 9 4 ,5 4
9 0 .6 3
.9 2 .2 7
,5 4 .1 7
,11.6.37
; 1 2 4 .0 6
1 1 9 ,8 3
. 1 1 6 .7 5
1 2 1 ,9 0
,1 1 8 .3 2
1 1 9 .5 1
. 1 2 2 .4 9
. 1 1 7 .5 1
. 1 2 2 .6 7
1 1 9 .3 7
1 1.8.64
1 2 4 .1 2
Standard D ev ia tio n
.0 8 1 5
.2 7 5 9
.3 9 1 7
.2 8 1 8
.9 7 1 6
. .9 7 9 8
.9 6 5 7
1 .0 3 3 4
. 1 .0 4 8 6
1 .0 7 5 1
1 .0 6 7 7
1 .0 8 8 4
. .9 9 4 6
. .9 9 6 3
1 .0 7 4 7
1 .0 6 4 2
.1 .0 1 3 9
so
T a b le XVII
: ATOMIC POSITIONS FOR FIRST DATA COLLECTION
X
Atom
Z
Z
Cu
..50.00
. .3 1 5 7
.2 5 0 0
2 .6 3 6
' Cl
.4 3 2 2 ,
.1,293
...3084
2 .4 1 5
. N 03
. .6 6 8 5
.4 4 0 3
.4 2 5 4
3 .0 0 9
N 04
..-4782
.4 9 4 2
.3 2 5 0
, 2 .-234
C .05
..7 6 5 9
.4 6 6 9
...5 1 1 2
2 .9 9 5
■ C 06
. . 78.07
. 5.775
.5 8 1 2
3 .0 9 9
C 07
. .6 8 3 0
.6 6 8 4
.5 6 1 4
. 3 .0 6 6
.. C 08
.5 7 9 7
.6 4 6 8
.4753
■2 .5 8 1
C:09
.4 7 3 7
.7 2 9 4
.4 4 5 7
3 .0 7 3
.' C 10
..3 7 8 6
.6 9 6 6
. .3 6 1 9
.. 3.432
C 11
.3 7 7 9
.5 7 4 1
.2970
2.8.09
C 12
.5 7 3 6
. ..5276
.4 0 7 4
2 .6 9 0
.
.
. Table. XVIII
MOST INTENSE, DIFFRACTION LINES FOR
B IS-(1, 8-NAPHTHYRIDLNE)-COPPER CHLORIDE
(photographic data)
d ( &)
. In te n sity Order
6.8
. 3
5 .4
2
. 4 .5
• I
-3.6
.4
3 .2
5
.
• 81
TabLe.- XDC
MOST JN tEN SE DIFFRACTION LINES FOR
I , 8-NAPHTHYRIDINE COFPER(Ii ) CHLORIDE
(p hotographic data)
. In te n sity Order
) cj (&)
7.6
2
. 6 .4
I
3 .7
3
. 3 .3
. 4
3 .1
5
■ T able XX
MOST. INTENSE DIFFRACTION LINES. FOR
.1 ,8-NAPHTHYRIDINE; COPPER (II) CHLORIDE
: (d iffractom eter data p o s it iv e a n g le s only)
d .( i )
■In te n sity Order
7 .6
I
6 .4
.
2
. 3 .2
3
2 .5
4
3 .7
5
82
T able XXI
TABLE OF OBSERVED AND CALCULATED STRUCTURE FACTORS
OL26
-2
226
0
15
7
46
16
42
I8
-9
51
36
152
9
22
21
K-
I 3L-
63
40
0
2 L47
6
48
KI
94
87
3
-1 0
-1 2
K=
0
-2
4
-4
-6
8
-8
IC
-1 0
K2
-2
4
6
-6
-1 0
-1 2
K0
2
-2
4
6
-6
8
-8
-1 3
-1 2
K=
0
-2
24
17
32
45
0 L64
159
99
38
50
42
48
35
31
29
”
17
29
43
2
58
152
106
51
50
46
51
34
34
27
1 0 -'" 90
21 0 218
101
111
154 161
59
57
13
14
?o
21
97
93
70
69
84
81
0 L- 6
57
53
49
57
53
49
89
89
86
27
26
75
47
23
0 L54
18
-1 1
K-3
I
-7
-1 1
K-
-I
-3
5
-5
-S
-1 1
-1 3
K-1
3
-3
-5
-I
9
K1
86
28
28
74
45
26
8
54
20
3
-3
5
-5
7
-7
9
-1 1
-9
59
I L112
100
38
82
72
34
49
I L144
174
141
147
28
ll
48
39
I L17
56
13
25
28
I L=
57
7«
99
33
53
80
20
79
70
54
2
123
89
40
77
34
46
3
141
174
136
139
85
23
29
61
48
40
12
53
5
26
28
73
89
75
33
55
74
16
75
68
51
29
74
144
69
K1
-I
3
-3
I L53
64
29
36
-1 4
K=
2
-2
-1 3
K=
I
-I
3
-3
59
17
I L81
19
59
69
54
19
-8
21
22
0 L - 10
23
20
56
56
119 122
160
169
82
82
K=
0
-2
-4
-6
0 L - 12
53
49
37
37
136 107
66
72
70
63
-1 4
3
K-2
-4
K1
17
32
120
15
27
117
0 L - 16
38
35
47
45
IL -O
137 135
5
-5
33
35
35
35
-7
9
-9
81
23
18
82
16
16
-I!
-i
.I
5
,3L F
151
99
116
81
152
96
116
89
-1 1
K-1
3
-3
-1 3
3
5
-5
-7
-9
107
%
50
25
44
75
18
59
67
no
93
52
I L=
40
8
%
21
73
13
34
41
34
-I
-5
-5
7
34
9
-5
-7
-9
-1 3
K=
-3
-9
K-1
-3
57
58
55
49
21
29
37
8
14
I L34
35
30
34
I L - 15
40
38
29
26
-4
-6
-1 4
K-
69
13
44
2 L61
50
46
K-
I L - 16
27
29
29
17
19
30
33
17
l 34*
34
2 L- 0
16
22
94
92
94
96
27
24
24
:S
-7
-9
K-
K0
2
-2
4
8
-8
-IS
K0
Z
4
-4
-S
:
SI
31
30
30
31
33
33
34
33
2 LI
53
48
46
39
90
95
107
98
113
46
Al
0 1S
46
-I
104
-4
6
-3
70
17
43
-1 2
K0
2
-2
111
49
46
60
48
90
32
69
17
41
36
33
2 L= 3
27
22
13
249
239
-4
6
-6
8
"8
0
4
-1 2
-1 4
0
2
-2
4
K0
-2
-6
-1 0
-1 2
-1 4
K-
-1 2
-I
-1 0
-1 2
K-6
-8
-1 2
K-6
20
2 L60
92
14
39
30
l::i!
Il “i
I
i
.
■;
I
-I
76
21
28
30
34
2 L91
15
15
39
63
32
2 L29
24
31
35
16
I
U
J
X
1
1
' h
:
,? -I
1
•
30
26
39
34
36
2 L26
:
15
31
31
47
45
32
1
-3
5
-9
-1 3
K=
I
41.
39
5
2 L105
108
K-
3 L-
I3
23
34
-9
,SI
44
106
18
129
30
84
19
18
132
30
82
20
22
j
4T1
*
-7
21
38
3 L35
12
Il
21
3 L-
21
5
12
77
80
71
69
38
20
34
45
3
Ii80
80
69
69
-1 1
-1 3
K3
-5
I
-1 1
W 4;
30
32
40
3 L25
34
43
4 L36
14
14
26
42
39
0
36
11
11
41
39
4 L57
-H
K-7
-1 1
35
21
4 L=
49
-10
25
22
-2
-1 0
K-6
-8
KI
-I
.‘Z.
HO
68
47
66
37
59
19
4 L35
61
30
8
-1 0
K0
2
-2
4
24
22
23
20
3 L - 10
68
65
100
98
44
43
37
36
27
30
41
41
3 L - 11
23
24
15
10
28
31
23
20
35
36
3 L - 12
46
42
48
49
36
33
73
41
65
51
32
10
22
33
29
19
25
11
21
33
50
29
25
22
53
36
12
36
29
13
27
45
28
21
4 L21
24
4 L29
23
5 L115
114
47
29
31
14
19
23
15
32
30
0
116
116
43
61
17
17
32
4 L69
56
55
55
14
28
5
62
56
59
57
28
53
37
4 L16
58
31
31
24
27
52
37
6
15
54
32
23
27
6
-6
-IS
21
» L■
57
90
47
102
19
31
21
4 L29
27
Il
-8
-10
29
43
41
30
-I
3
-9
5 L112
36
45
19
6 L27
19
31
49
52
—
6
-Io'
-11 ,3ZI
20
-I
-3
-5
-7
KI
:i
-5
-7
-9
K-3
5
-9
K-I
-3
16
15
21
25
47
89
88
5 L - 10
18
21
Il I?
47
44
81
81
49
48
5 L - 11
24
22
37
35
23
24
5 L - 12
29
27
34
33
27
27
5 L - 13
41
42
31
32
5 L - 14
40
0
-2
-6
-8
-1 0
K-2
-4
-6
-8
K-
%
39
6 L39
52
35
30
34
48
5 L=
79
83
-8
K1
-I
K-I
5
-5
-7
K-
55
55
33
33
19
I
58
41
51
3
-5
37
32
K-
71
30
53
18
26
37
6 L37
17
21
5 L35
19
66
-2
4
29
55
6
-8
32
25
27
66
30
34
20
29
56
24
5
24
-7
10211
21
5 L=
47
18
57
46
30
23
8
28
25
55
49
5 L29
17
45
6 L16
26
23
16
35
6 L16
66
-9
-1 1
KI
3
-5
49
42
5 L16
32
38
22
24
22
24
24
41
41
28
27
18
19
6 L - 11
20
20
50
52
46
47
23
21
6 L= 12
30
7 L28
29
7 L26
33
16
38
47
40
33
7 L-
H
31
32
0
29
29
I
27
35
18
41
46
41
31
2
42
54
21
33
7 L22
22
7 L29
52
36
58
30
7 L=
57
20
33
4
20
22
5
29
54
38
60
28
31
12
23
25
22
21
:5
l\
-6
28
.'Z.
50
I,
5
29
19
9
27
22
30
23
55
54
33
35
21
6 L57
72
43
43
15
17
-3
5
-5
66
Il Il
L - 13
31
* 2042
199
42
3 L - 14
31
35
40
41
53
50
29
31
4 L=
23
33
27
19
26
4 L24
34
48
31
23
21
46
37
4 L=
37
30
4 L29
-10
101
Il
19
K=
0
2
-4
-6
-1 0
K0
2
-2
-4
-6
-8
-1 0
-1 2
K-
35
10
6
55
117 115
28
26
169
167
22
23
144
138
37
37
32
32
16
15
3 L- 7
43
40
60
57
36
34
37
29
22
20
97
103
14
13
3 L= 8
104
97
96
57
59
69
23
21
I
54
98
49
41
21
337*
28
39
-H
-1 3
2IlmZ
-9
K0
2
-2
33
52
23
3 L-
S i
H U A 81
55
»
1
65
23
63
39
26
-1 0
:
66
22
59
40
39
44
32
30
I L - 11
20
19
46
46
„s
74
123
71
39
77
3 L40
141
142
19
20
146
153
25
21
118
116
83
37
36
-9
11
8
—8
4 L43
66
106
37
23
-6
-8
-10
-1 2
K0
2
-2
1 1
29
172
48
23
K-
2
-8
-1 0
-1 2
K-8
K-1
5
-5
7
-7
6
4
85
23
132
50
32
2 L=
133
42
j
76
19
123
K0
41
44
85
84
76
59
62
I L - 10
27
-1 1
-1 3
K-
6
8
I L - 13
25
46
41
-I I? IS
25
40
-\
-6
49
28
79
145
74
-j
-I!
58
-4
6
-6
-8
-1 0
-I
j
2
12
5^L "
-2
1*2
-6
8
3 L14
50
40
7
13
30
39
-8
-10
K=
0
2
-2
61
39
6 L29
18
23
37
8
27
17
20
7 L=
34
-3
5
-7
K-5
-7
K-I
-3
-5
K-5
K2
K-2
-4
K-2
-4
-6
K-6
K-
33
34
21 22
25
22
7 L= 8
17
17
24
20
7 L- 9
38
40
26
28
17
19
7 L= 10
28
28
8 LI
18
18
8 L- 2
29
30
29
30
8 L= 4
34
35
60
61
40
41
8 L5
18
20
8 L- 6
LITERATURE. CITED
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M agnetoChem istry
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(1965).
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6 . J. N . Van Niekirk and F. R. L. S ch oen in g, Acta C ryst.
227 (1953).
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3-696 (19:62).
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15. E llis ,V. Brown, J. Org. Chem . 3j0, 1607 (1965).
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Chim . (Rome) 5 4 , (8-9) 883-890 (19.64).
84
1 8 . W . W . Pau.dler and T. J.-K r e ss, C hem . and In d . 1557 (1 9 6 6 ).
1 9 . W . W . Paudler and T. J. Kress , J. O rg„ C hem . 32_(3), 832-833', (1 9 6 7 ).
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-21.. I . M . K olthoff and E . B. S a n d e ll, T extbook o f Q u an titative Inorganic
A n a ly sis , .3rd. Ed.,■ .M acm illan C o ., N ew York (1 9 5 2 ).
2 2 .. H . F. W a lto n , E lem entary Q u a n tita tiv e A n a ly s is / P rentice H a ll,
• E nglew ood C lif f s , N ew J e r s e y .(195:8).
2.3. M . J-. B uerger, X -R ay C ry sta llo g ra p h y , John Wiley- and S o n s.I n c ., N ew
York, (1 9 4 2 ).
2 4 .. . K. D . W aten p au gh , p rivate com m u nication.
25 . . G eorge Stout and L yle J e n s e n , X-Ray Structure D eterm in a tio n , The
. M acm illan. Co . , N ew York (19 68).
2 6., R. M. A c h e so n , An In trodu ction.to the C hem istry o f H e te r o c y c lic Com. pounds , .In ters.cien ce P u b lish e r s, N ew York ( i 9 6 0 ) .
27. . A. R. Katritzky and, J. N . G ardner, J. C hem „ S o c . 1461 ( 1952) .
2 8 . E. T h ielep ap p e and. O . S p r e k e ls e n , Ber.. 5_5, 2929 ( 1922) .
2 9 . R oberts, A dvanced O rganic C h em istry , P rentice H a ll, Englew ood
C l i f f s , N ew Jersey . ( 1954) .
3 0 . Norman F . M . Henry and K athleen L o n s d a le , Internation al T ables for
X -ray C r y sta llo g r a p h ic , V o l. I . KYNOCH P r e s s , Birmingham, England
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I STlTE UNIVERSITY LIBRARIES
3 1762 10005448 3
♦
I
D378
En91 Enwall, Eric Lee
cop.2
I, 8-naphthyridine
copper complexes
m AMV a Ki o
A boncsa
JMCWr
D a>7%
E n cU
Oog a