Structural studies of organic titanium compounds
by Keith Donald Watenpaugh
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 Keith Donald Watenpaugh (1967)
Abstract:
Using the "Symbolic Addition Procedure" the structures of three organic compounds of titanium are
solved by x-ray diffraction.
Dichlorodiphenoxytitaniurn(IV) crystallizes in space group P21/nwith a = 9. 82A, b= 14. 01A, c =
9.84, B = 94°50'. The compound is dimerically located around the center of symmetry, the two
titaniums being joined with oxygen bridges, each titanium being penta coordinated in the form of a
trigonal bipyramid.
The first hydrolysis product of tetraethoxytitanium (IV) crystal-lizes in space group P21/a with a = 27.
99A, b = 22. 42A, c=23.21A β =117°15'. Chemical analysis and density measurements indicate the
compound to have the empirical formula Ti7024(C2H5)19 with 8 molecules per unit cell. The
compound, is made up of TiO6 octahedra sharing edges. Bonds from oxygen atoms to neighboring.
titanium atoms varies from one to four. Due to the complexity of the compound, all the carbon atoms
could not be located.
μ-oxo-bis [chlorobis(:2, 4-pentandionato)titanium(IV) ] . chloroform crystallizes in space group P21/n,
with a = 1 5. 744, b = 22. 63, c = 8. 89, å β=100°'. The two titanium atoms are six-coordinated in an
octahedral arrangement to oxygen and chlorine atoms with an oxygen bridge between the two
titaniums. The acetylacetonate groups are in the cis arrangement in the octahedra and are distorted, out
of the planar rings due to steric effects. A chloroform molecule appears to be hydrogen bonded to the
molecule.
Large oxygen containing bond angles are found in the compounds due to sp hybridization of the
orbitals. STRUCTURAL s t u d ie s o f o r g a n ic t it a n iu m c o m p o u n d s
by
K EITH DONALD W ATENPAUGH
A th e s i s s u b m it te d to the G ra d u a te F a c u lty in p a r t i a l
f u l f i l l m e n t of t h e r e q u i r e m e n t s f o r t h e d e g r e e
' of
DOCTOR OF PHILOSOPHY
■in
C hem istry
APPROVED:
M ONTANA S TA TE UNIVERSITY
B ozem an, . M ontana
J u n e , ■I 96?
iii
ACKNOWLEDGEMENTS ■
' I w i s h t o t h a n k D r . C. N. C a u g h l a n - for. h i s a d v i c e - a n d g u i d a n c e
a n d the- o t h e r m e m b e r s : of t h e f a c u l t y of M o n t a n a S t a t e U n i v e r s i t y f o r
th e ir help.
, I w f s h t o a c k n o w l e d g e th e N a t i o n a l A e r o n a u t i c s a n d S p a c e
' A d m i n i s t r a t i o n - f o r a f e l l o w s h i p ' w h i l e w o r k i n g . o n t h e -r e s e a r c h a n d
an NSF G r a n t (GP-5474). fo r p a r t i a l su p p o rt.
A ls o I w i s h to thank
H a r v e y M u d d C o l l e g e f o r u s e of -the d i f f r a c t o m e t e r on w h i c h s o m e , of
t h i s d a t a Wa s t a k e n , t h e C o m p u t i n g C e n t e r s of M o n t a n a S t a t e U n i v e r s i t y
a n d U n i v e r s i t y of W a s h i n g t o n ,
a n d W e s t e r n - D a t a P r o c e s s i n g . C e n t e r of
t h e U n i v e r s i t y of C a l i f o r n i a a t Los- A n g e l e s f o r a g r a n t of c o m p u t i n g
■t i m e .
F i n a l l y , . I w i s h to th a n k m y w ife , J o y c e , fo r h e r u n d e r s t a n d i n g
and patience-w hile-the r e s e a r c h w as underw ay.
r
. Lv
TABLE OF CONTENTS
Page
LIST O F TA B LE S
vi
LIST O F FIGU RES
viii
ABSTRACT
ix
INTRODUCTION
I
P A R T I.
4
G e n e r a l Th eo r y-
In tro d u c tio n and the P h a s e P r o b l e m
■4
. I n d i r e c t M e t h o d s : of S o l v i n g C r . y s t a l S t r u c t u r e s
' D i r e c t M e t h o d s of S o l v i n g C r - y s ta l S t r u c t u r e s
P A R T II.
5
.
8
T h e C r y s t a T S t r u c t u r e* of D i c h l o r o d i p h e n o x y t i t a n i u m ( I V ) 19
P r e p a r a t i o n of t h e C r y s t a l s
19
D e n s i t y D e t e r m i n a t i o n ' of T i C l ^ f O C
19
C ©!lection-of D a ta
20
S tructure-D eterm ination
22
R e f i n e m e n t of t h e S t r u c t u r e
28
D i s c u s s i o n - of t h e S t r u c t u r e
30
P A R T HI.
S t r u c t u r e of t h e ’F i r s t H y d r o l y s i s P r o d u c t of
T etraethoxytitanium (IV )
41
P re v io u s S tru c tu ra l Investigations
41
P r e p a r a t i o n of t h e C o m p o u n d
42
D e t e r m i n a t i o n of t h e S p a c e G r o u p a n d C e l l D i m e n s i o n s
42
V
Pcige
C ollection-of the D ata
45
D e t e r m i n a t i o n - of t h e S t r u c t u r e
46
R e f i n e m e n t of t h e S t r u c t u r e
48
D i s c u s s i o n of t h e S t r u c t u r e
'51
P A R T IV.
S t r u c t u r e of | i - o x o - b i s
[chlorobis(2, 4-pentandionato)
Iitanium (IV ) ] • c h lo ro f o r m
,64
Introduction
64
P r e p a r a t i o n - o f the C r y s t a l s
64
C o l l e c t i o n - o f the- D a t a
65
D e t e r m i n a t i o n of t h e . S t r u c t u r e
68
R e f i n e m e n t of t h e S t r u c t u r e
70
• D i s c u s s i o n of t h e S t r u c t u r e
'
.
80
SUMMARY AND CONCLUSIONS
84
LITERATURE CITED '
86
vi
LIST O F T A B L E S
P A R T II.
■T a b l e - I
T a b l e II
Page
S u m m a r y of C r y s t a l D a t a f o r T i C l ^ ( O C
C o o rd in a tes O btained for I n c o r r e c t S tru c tu re
of T i C l ^ O C ^ ) ,
T a b l e III
24
A s s i g n m e n t of V e c t o r s D u e t o I n c o r r e c t
S t r u c t u r e of T i C l ^ ( O C ^ H ^ ) ^
T a b l e IV
I n i t i a l C h o ic e - of S i g n s f o r T i CI ^ ( OC
Table V
A s s i g n m e n t of V e c t o r s D u e t o C o r r e c t
25
g) ^
S t r u c t u r e of T i C l ^ ( O C ^ H g ) ^
T a b l e VI
T a b l e VI I
- A t o m i c C o o r d i n a t e s of T i C l ^ ( O C
27
29
32
A n i s o t r o p i c T e m p e r a t u r e F a c t o r s , of
t ic
TableV III
21
V o c 6h A
’
33
P r i n c i p a l A x e s of t h e T h e r m a l E l l i s p o i d s - of
t ic
V o c 6 hV 2
T a b l e IX
Bond D is ta n c e s in T iC l^fO C ^H ^)^
35
Table X
B o n d A n g le s in T iC l^ (O C ^ H ^ )^
36
T a b l e - XI
.O b s e r v e d and .'C alcu lated -S tru ctu re F a c t o r s
fo r T iC y O C ^
37
P A R T III. .
T a b l e XI I
C h e m i c a l A n a l y s i s of t h e H y d r o l y s i s P r o d u c t
of T i ( O C 2H 5 )4
TT
vii
Page
T a b l e XI II
S u m m a r y of t h e C r y s t a l D a t a f o r
44
T i 7 ° 2 4 ( C 2H 5>l 9
T a b l e XIV
Ti and.O P o sitio n s-in -T i ^ O ^ f C ^ H , . ) ^
T a b l e XV
B o n d D i s t a n c e s B e t w e e n T i a n d . O A t o m s in
49
53
T i 70 2.4<C 2H 5»1 9
T a b l e XV I
B o n d A n g l e s of T 17O 2 4 ( C 2H ^ )19
58
T ab le X V I I ' O b s e r v e d and C alculated: S tr u c tu r e s
F a c to r s for
9
62
P A R T IV.
T a b l e X V I I I ' C h e m i c a l A n a l y s i s of [ T i C H a c a e ) ^ ] ^ G ' C H C l ^
T a b l e XIX
66
S u m m a r y of C r y s t a l D a t a f o r
[ T i C l ( a c a c ) 2 ] 20 - C H C l 3
’ 67
T a b l e XX
A t o m i c C o o r d i n a t e s of [ T i C l ( a c a c ) „ ] „0* C H C l
LL
3
T a b l e XX I
T h e r m a l P a r a m e t e r s a.nd\Mean S q u a r e
D i s p l a c e m e n t of [ T i C l ( a c a c ) 2 ] ^,O' C H C l ^
71
72
T a b l e - XXII
B o n d D i s t a n c e s in [ T i C l ( a c a c ) 2 ] 20* C H C l ^
74
T a b l e XXIII
B o n d A n g l e s in [ T i C I ( a c a c ) 2 ] 20 ' C H C l ^
76
T a b l e XXI V
O b s e rv e d and C alcu lated S tru c tu re F a c t o r s
f o r [ T i C l ( a c a c ) 2 ] 20 ' C H C l 3
T a b l e XXV
78
E q u a t i o n s , of L b a s t S q u a r e s P l a n e s R e f e r r e d
.
t o O r t h o g o n a l A x e s i n [ T i C l ( a c a c ) 2 ]20 ,'C H C l^
TT
82
TT
vlii
LIST O F FIG U R E S
Page
F igure I
A r r a n g e m e n t of O n e D i m e r U n i t of
T iC 1 ^ ( 0 0 P r o j e c t e d . i n t h e U n i t C e l l
F igure 2
31
C o o r d i n a t i o n A r o u n d t h e T i t a n i u m A t o m in
T i C l 2 ( O C 6H 5 )2 D i m e r
F igure 3
38
A r r a n g e m e n t of T i t a n i u m s a n d O x y g e n s .i n
52
T170 24<C 2H 5>,9
F igure 4
[ T i C l ( a c a c ) 2 ] 20* C H C l 5 S t r u c t u r e (ab p r o j e c t i o n )
79
F igure 5
S t r u c t u r e , of [ T i C l ( a c a c ) _ ]
81
O
T
TTTrN r
)
ix
ABSTRACT
U s i n g t h e " S y m b o l i c A d d i t i o n P r o c e d u r e " t h e s t r u c t u r e s of
t h r e e o r g a n i c c o m p o u n d s of t i t a n i u m a r e s o l v e d b y x - r a y d i f f r a c t i o n .
D ic h lo ro d ip h e n o x y tita n iu m (IV ) c r y s t a l l i z e s , in s p a c e group
P 2 ] / n . . w i t h a = 9. 82A, b = 14. Ol A, c = 9.'84, B = 9 4 ° 5 0 ' . T h e c o m p o u n d
i s d i m e r i c a l l y l o c a t e d a r o u n d th e c e n t e r of s y m m e t r y , t h e tw o t i t a n i u m s
being, jo in e d w ith oxygen b r id g e s , e a c h ti ta n i u m being p e n ta c o o r d in a te d
.in t h e f o r m ' of a t r i g o n a l b i p y r a m i d .
o
T h e f i r s t h y d r o l y s i s p r o d u c t of Ltetr.aethQxy'tifanium./- ( I V ) ' , c r y s t a l l i z e s - i n s p a c e g r o u p P 2 ^ / a w i t h a = 27. 99A, b = 22. 42A, c =. 23f 21 A,
P = I l T 0 I S 1. C h e m i c a l a n a l y s i s a n d d e n s i t y m e a s u r e m e n t ' s i n d i c a t e th e
c o m p o u n d t o h a v e thg e m p i r i c a l f o r m u l a T 1-7 0 2 4 ' 2 ^ 5 ) I 9 w i t h 8
m o l e c u l e s p e r u n i t c e l l . T h e c o m p o u n d , i s m a d e u p of T i O ^ o c t a h e d r a
s h a r i n g e d g e s . . B o n d s f r o m o x y g e n a t o m s to n e i g h b o r i n g , t i t a n i u m a t o m s
v a r i e s f r o m o n e t d ' f o u r . D u e to t h e c o m p l e x i t y of t h e c o m p o u n d , a l l
the c a r b o n a t o m s c o u ld n o t be lo c a te d .
p - o x o - b i s [chlorobis(:2, 4-penta ndionat'o)tita nium (IV ) ] - c h l o r o f o r m
c r y s t a l l i z e s in s p a c e g r o u p P 2 ^ / n., w i t h a '= I 5. 744, b = 22. 63, c = 8. 89, A
6 = I 00°1 8 ' . T h e tw o t i t a n i u m a t o m s a r e s i x - c o o r d i n a t e d i n a n o c t a h e d r a l .
' a r r a n g e m e n t to oxygen an d c h l o r i n e a t o m s w ith an o xygen b r id g e b e t w e e n
t h e t w o t i t a n i u m s . T h e a c e t y l a c e t o n a t e g r o u p s a r e in t h e c i s a r r a n g e m e n t
i n t h e - o c t a h e d r a a n d a r e d i s t o r t e d , o u t of t h e p l a n a r r i n g s d u e to s t e r i c
e f f e c t s . A c h l o r o f o r m m o l e c u l e a p p e a r s t o b e h y d r o g e n b o n d e d to t h e
! m olecule.
i
L a r g e oxygen containing-bond an g les a r e found.in the com pounds
d u e -to s p h y b r i d i z a t i o n - o f t h e o r b i t a l s .
INTRODUCTION.
W o r k on t h e c h e m i s t r y of o r g a n i c c o m p o u n d s of t i t a n i u m b e g a n
in t h e m i d d l e : of t h e n i n e t e e n t h c e n t u r y .
H ow ever, d u rin g the la s t
s e v e r a l d e c a d e s , w i t h ' i n c r e a s e d i n t e r e s t in m e t a l o r g a n i c co m p o u n d s
i n g e n e r a l , t h e o r g a n i c c o m p o u n d s of t i t a n i u m h a v e a l s o b e e n th e
s u b j e c t of c o n s i d e r a b l e s t u d y .
T h e s e co m p o u n d s h ave found a num ber,
of i n d u s t r i a l a p p l i c a t i o n s b e c a u s e - of t h e i r i n t e r e s t i n g c h e m i c a l a n d
physical p ro p e rtie s.
S i n c e a c c u r a t e k n o w l e d g e , of t h e i r s t r u c t u r e s
has. b e e n l a c k i n g , p r o b a b l y b e c a u s e - o f c e r t a i n i n h e r e n t d i f f i c u l t i e s i n
studying th e ir s tr u c tu r e s ,
m any w rong conclusions have been made
concerning reactio n m e ch an ism s.
O n e - i m p o r t a n t a n d i n t e n s i v e l y s t u d i e d c l a s s of o r g a n i c c o m ­
poun ds ; of t i t a n i u m is t h e a l k y l a n d a r y l t i t a n a t e s , w i t h t h e g e n e r a l
f o r m u l a Ti(OR)^.
E x t e n s i v e s t u d i e s : of t h e c h e m i c a l p r o p e r t i e s , of
t h e s e c o m p o u n d s h a v e b e e n c a r r i e d o u t by m a n y d i f f e r e n t g r o u p s u s i n g
m o le c u la r w eight d eterm in a tio n s,
a n a ly tic a l data and dipole m o m e n t
V
values.
A s a. r e s u l t , of t h e s e s t u d i e s ,
s tru c tu re s w e re postulated for
the a s s o c i a t e d co m p o u n d s and th e s e p r o p o s e d s t r u c t u r e s w e r e u sed
e x t e n s i v e l y t o e x p l a i n t h e c h e m i s t r y of t h e o r g a n i c t i t a n a t e s .(I, 2, 3),
a l t h o u g h no a c t u a l s t r u c t u r e d e t e r m i n a t i o n s w e r e m a d e u n t i l 1963.
s t r u c t u r e of t e t r a e t h y l t i t a n a t e w a s d e t e r m i n e d i n 1963 b y I b e r s (4),
The
2
a n d t h e s t r u c t u r e of r a o n o m e t h y l t r i e t h y l t i t a n a t e . by W i t t e r s (5) in 1964.
N e i t h e r of t h e s e d e t e r m i n a t i o n s a g r e e d . w i t h th e p r o p o s e d s t r u c t u r e s in
s o l u t i o n a n d t h u s s u g g e s t e d t h a t t h e i n t e r p r e t a t i o n of t h e c h e m i s t r y of
t h i s c l a s s , of c o m p o u n d s , b a s e d . . o n p o s t u l a t e d s t r u c t u r e s w a s p r o b a b l y
incorrect.
F o r t h i s r e a s o n , i t w a s . of i n t e r e s t t o c o n t i n u e t h e s t r u c t u r a l
s t u d i e s of t h i s class-, of c o m p o u n d s .
P a r t i c u l a r i n t e r e s t e x i s t s - in th e
s t r u c t u r e - of t h e h y d r o l y s i s p r o d u c t s of t e t r a e t h y l t i t a n a t e .
M olecular
w e i g h t e v i d e n c e ( I) i n d i c a t e s , t h a t t h e t e t r a e t h y l t i t a n a t e e x i s t s a s a
t r i m e r i n s o l u t i o n , y e t c r y s t a l s t r u c t u r e s s t u d i e s . h a v e s h o w n th e
o r g a n i c t i t a n a t e s to b e t e t r a m e r s .
S i n c e the. h y d r o l y s i s p r o d u c t f o r m s
b y a d d i n g s m a l l a m o u n t s : of w a t e r t o s o l u t i o n s of t h e t e t r a e t h y l t i t a n a t e ,
d e t e r m i n a t i o n of t h e s t r u c t u r e s h o u l d i n d i c a t e w h a t m o l e c u l a r s p e c i e s
e x i s t in s o lu tio n a n d s o m e t h i n g ab o u t the p o l y m e r i z a t i o n p r o c e s s upon
hydrolysis.
A c l a s s , of c o m p o u n d s c l o s e l y r e l a t e d to t h e a l k y l a n d a r y l
t i t a n a t e s is the alkoxy and a r y l o x y t i t a n i u m h a lid e s ,
w h e r e 1X i s a h a l o g e n ,
T 'iX ^O R )^
C e rta in c h e m ic a l and physical c h a r a c te r is tic s ,
su c h a s t h e -i n te n s e c o lo r-o f the phenoxy t i ta n i u m h a l i d e s ,
th a t t h e r e w e r e sig n ific a n t d iffe re n c e s in s t r u c t u r e s .
suggested
, -
No x - r a y c r y s ta l
s t r u c t u r e s , of t h e s e h a l i d e c o m p o u n d s h a d b e e n p r e v i o u s l y r e p o r t e d a n d
t h u s i t a p p e a r e d s i g n i f i c a n t ;to d e t e r m i n e , t h e s t r u c t u r e s .
3
A t h i r d g e n e r a l c l a s s , of t h e o r g a n i c t i t a n i u m c o m p o u n d s a r e
the c h e la te d c o m p o u n d s.
T h e m o s t w i d e l y s t u d i e d c o m p o u n d of t h i s
c l a s s i s d i c h l o r o b i s ( a c e . t y l a c e t o n a t o ) t i t a n i u m (IV), w h i c h e x h i b i t s
interesting spectroscopic features.
A s a r e s u l t of s p e c t r a l s t u d i e s
(6, 7), i t w a s c o n c l u d e d . t h a t t h e a c e t y l a c e t o n a t e g r o u p s w e r e a r r a n g e d
.in a c i s c o n f i g u r a t i o n a r o u n d , t h e t i t a n i u m .
T his is an in t e r e s tin g
c o n c lu sio n sin c e the cis c o n fig u ra tio n s e e m s
able -than the t r a n s c o n f ig u ra tio n . „
less, s t a r i c a l l y f a v o r ­
T h u s , v e r i f i c a t i o n of t h i s a s
w e l l a s s t u d y of t h e b o n d i n g . i n r e l a t i o n t o t h e c o l o r of t h e c o m p o u n d , i s
significant.
A l s o of i n t e r e s t a r e t h e h y d r o l y s i s p r o d u c t s of t h e
ace ty la ceto n ate com plex.
T h e s e h av e b e e n m e n tio n e d .in the lite r a t u r e ,
b u t no d e t a i l e d s t u d i e s h a v e b e e n r e p o r t e d .
R e c o g n i z i n g th i s . T a c k - of s t r u c t u r a l i n f o r m a t i o n ,
a study w as
u n d e r t a k e n of t h r e e , of t h e c o m p o u n d s f r o m t h e a b o v e c l a s s e s w i t h th e
e x p e c t a t i o n , of b e i n g , a b l e t o a n s w e r s o m e - of t h e q u e s t i o n s p r o p o s e d
th ro u g h the s t r u c t u r a l know ledge obtained.
T h is d i s s e r t a t i o n c o n ta in s the stu d y an d d is c u s s ip n - o f the
c r y s t a l a n d m o l e c u l a r s t r u c t u r e s - of d i c h l o r o d i p h e n o x y t i t a n i u m ( I V ), t h e
■first h y d r o l y s i s p r o c t u c t of t e t r a e t h y l t i t a n a t e ,
.V
and a h y d ro ly s is product
of d i c h l o r o b i s ( a c e t y l a c e t o n a t o ) t i t a n i u m ( I V ) .
E a c h of t h e s t r u c t u r e s
w a s s o l v e d by t h e " s y m b o l i c a d d i t i o n p r o c e d u r e , " t h e t h e o r y of w h i c h
is p r e s e n te d .in so m e detail.
TT
:1
PART I
GENERAL THEORY
In tro d u c tio n and the P h a s e P r o b l e m
W h e n x - r a y b e a m im p in g e s , on a s in g le c r y s t a l , th e c r y s t a l
acts as a th r e e - d im e n s io n a l g ratin g diffracting.the beam .
The position
of a d i f f r a c t e d . w a v e f r o m a p l a n e of a t o m s i n t h e c r y s t a l i s g i v e n by
the B r a g g equation,. n \ = 2 d .sin Q .
The w ave w ill have a c e rta in
a m p l i t u d e a n d p h a s e a n g l e r e l a t i v e to t h e i n c i d e n t b e a m .
The am plitude
a n d p h a s e a r e d e p e n d e n t on t h e r e l a t i v e p o s i t i o n s , of a t o m s in t h e u n i t
c e l l a n d m a y be. d e f i n e d a s
.„
2iri(hx, + k y + Iz ) = | E ( h k l ) | ^ ( h k l )
F(hkl)
1 ^ e
1J
..J
J
.
J
j =1
w h e r e f.
=
s c a t t e r i n g f a c t o r of t h e J t h a t o m - f o r ' T h e p a r t i c u l a r
d iffraction angle,
(h, k e I)
= M i l l e r i n d i c e s d e s c r i b i n g a p a r t i c u l a r s e t of
planes,
( x . , y . , z . ) = p o s i t i o n of t h e . j t h a t o m in t h e u n i t c e l l ,
c|)(hkl)
= p h a s e a n g l e of t h e d i f f r a c t e d b e a m r e l a t i v e to
the in c id en t beam .
T h e i n t e n s i t y of a d i f f r a c t e d w a v e i s p r o p o r t i o n a l t o t h e s q u a r e of t h e
a m p l i t u d e - of t h e w a v e , i. e.
,
I( hk l) a | F ( h k l ) | 2 .
©
5
I t is. t h i s t e r m w h i c h i s e x p e r i m e n t a l l y m e a s u r e d b u t t h e p h a s e a n g l e
c a n n o t be m e a s u r e d .
If t h e p h a s e c o u l d b e m e a s u r e d d i r e c t l y , the
e l e c t r o n d e n s i t y of t h e u n i t cell, of a c r y s t a l c o u l d be c a l c u l a t e d w i t h
the F o u r i e r s e r i e s ,
P (xy z)
i. e.
J.
V
I F ( h k l ) I e - +(bkl) ^ i f h x + k y + j z)
h
k
I
w h e r e V = v o l u m e of t h e u n i t c e l l .
I(h, k, I)
■4>(hkl)
= i n d i c e s of a l l r e f l e c t i n g p l a n e s w h i c h r a n g e o v e r a l l
possible in teg ers,
= p h a se angle a s s o c i a t e d w ith F(hkl),
| F (hkl) | = a b s o l u t e v a l u e of t h e s t r u c t u r e f a c t o r .
If s u f f i c i e n t l y s m a l l i n t e r v a l s of x, y, z w e r e t a k e n o v e r th e u n i t
c ell, a contour m a p .o f the e le c tro n d en sity w o u ld .in d ic a te reg io n s
w h e re ato m s w e r e located.
A t o m s w i t h a l a r g e n u m b e r of e l e c t r o n s
w o u l d g i v e r e g i o n s of h i g h e r d e n s i t i e s a n d . t h e i r l o c a t i o n s c o u l d . e a s i l y
be d e t e r m in e d .
However,
since the p h a s e angle can n o t be d ire c tly
m e a s u r e d , o th e r m e th o d s m u s t be d e v i s e d .f o r obtaining.it.
I n d i r e c t M e t h o d s of S o l v i n g C r y s t a l S t r u c t u r e s
I n t h e e a r l y d a y s of x - r a y c r y s t a l l o g r a p h y ,
s o l v e d by t r i a l a n d e r r o r .
structures w ere
F r o m a , t r i a l s t r u c t u r e , the s t r u c t u r e
f a c t o r s w e r e c a lc u la te d and c o m p a r e d w ith the e x p e r im e n ta lly m e a s u r e d
0
J
6
stru ctu re factors.
T h e c o r r e c t n e s s , of t h e p r o p o s e d . s t r u c t u r e c o u l d
be in d i c a te d by the a g r e e m e n t (or d i s a g r e e m e n t ) b e t w e e n c a l c u l a t e d
and o b se rv e d s tru c tu re fa c to rs.
A function u s e d .to m e a s u r e the a g r e e ­
m e n t b e t w e e n c a l c u l a t e d .and. o b s e r v e d s t r u c t u r e f a c t o r s i s t h e r e l i a b i l i t y
index or R - fa c to r defined as
R
w h e r e F -= o b s e r v e d s t r u c t u r e f a c t o r ,
o
F =
c
calculated stru c tu re factor,
T he s u m m a t i o n s a r e o v e r all the s t r u c t u r e f a c t o r s .
M o s t s t r u c t u r e s th a t h ave b een s o lv e d h av e u s e d the "heavy
atom " m ethod.
If a c o m p o u n d . c o n t a i n s a h e a v y a t o m , , t h i s a t o m w i l l
d o m i n a t e t h e p h a s e s , of t h e s t r u c t u r e - f a c t o r s .
T h u s , if t h e c o r r e c t
p o s i t i o n of t h e h e a v y a t o m c a n be f o u n d . i n t h e u n i t c e l l , o n e c a n . u s e
t h e c a l c u l a t e d p h a s e s f r o m the. h e a v y a t o m a n d . o b s e r v e d s t r u c t u r e
f a c t o r s to p ro d u c e a F o u r i e r m a p w h ic h fre q u e n tly show s the positions
. of t h e . l i g h t e r a t o m s .
In- 1934, P a t t e r s o n (8) p u b l i s h e d a p a p e r d e s c r i b i n g , a n e w
m e th o d u s in g w h a t h a s b e c o m e known as the " P a t t e r s o n function. "
TT
T
7
T his function-is
P(uvw) =
\ p ( x y z ) p ( x + u , y + v, z-.-f w ) d V
J y
j.
•
h
’| F ( h k l ) | Z« - 2 T i ( h u + k v ' + lw)
k
I
N ote th a t the p h a se does, not a p p e a r in th is function.
T h e v a l u e - o f th e
f u n c t i o n a t (u, v , w) i s s i m p l y t h e a v e r a g e v a l u e - of t h e p r o d u c t of t h e
e l e c t r o n d e n s i t i e s a t t h e e n d s of a v e c t o r of f u n c t i o n a l l e n g t h (u, v, w)
a ll o rig in a tin g at the o rig in .
If t h e r e a r e n. a t o m s i n t h e u n i t c e l l ,
t h e r e w i l l be. n ( n - l ) . n o n - o r i g i n p e a k s i n t h e P a t t e r s o n m a p .
even w ith a sim ple s tru c tu re ,
T herefore,
a rath e r com plex P a tte rs o n m ap results.
T h i s is c o m p l i c a t e d f u r t h e r by the f a c t th a t th e a t o m s a re . n o t point
p a r tic le s and d ifferen t ato m s w ith s im ila r in te ra to m ic v e c to rs m ay
be s u p e rim p o s e d , in the P a t t e r s o n m ap.
T h e u s e of t h e P a t t e r s o n m a p a n d t h e h e a v y a t o m m e t h o d s o r
a c o m b i n a t i o n * of t h e t w o m e t h o d s i s b y f a r t h e m o s t c o m m o n m e t h o d
of s o l v i n g , c r y s t a l s t r u c t u r e s a t t h e p r e s e n t t i m e .
C om plete discussion
of t h e s e m e t h o d s a p p e a r s : in s t a n d a r d t e x t s on x - r a y c r y s t a l l o g r a p h y
m ethods.
A d e t a i l e d c o n s i d e r a t i o n of t h e u s e of t h e s e t w o m e t h o d s in
s o l v i n g a s p e c i f i c s t r u c t u r e i s g i v e n b y L i (9).
TT
8
D ir e c t M ethods-of Solving C r y s t a l S tr u c t u r e s
R e c e n t l y , a t l e a s t f o r t h e c e n t r © s y m m e t r i c c r y s t a l s , a n ew
m ethod has been u se d w ith -increasing su ccess.
T his m ethod..is f a c i l i ­
t a t e d . i n t h e c e n t r o s y m m e t r i c c a s e b y t h e f a c t t h a t t h e p h a s e a n g l e of a
s t r u c t u r e f a c t o r m u s t b e a m u l t i p l e , of n- a n d t h e c o s i n e of t h e p h a s e
angle, t h e r e f o r e , is 11 .
The m ethod, thus f a r , has not p ro v ed as
u s e f u l i n s o l v i n g n o n - c e n t r i c s t r u c t u r e s , i n w h i c h a n i n f i n i t e n u m b e r of
phase angles a re possible.
T h e " s y m b o l i c a d d i t i o n p r o c e d u r e " u s e d , in s o l v i n g s t r u c t u r e s
involves a re la tio n s h ip betw een s tr u c tu r e fa c to rs.
is u s u a l l y r e f e r r e d to a s the
Y
relationship.
Lj 2
its h i s t o r y and th e o ry follows.
This relationship
A b rief discussion-of
I n 1947, H a r k e r a n d K a s p e r (10) r e p o r t e d t h a t , a l t h o u g h t h e
p h a s e 'o f the s t r u c t u r e f a c t o r s could not be d e t e r m in e d , t h e r e w e r e
s o m e e x p l i c i t r e l a t i o n s h i p s b e t w e e n a m p l i t u d e s , of s t r u c t u r e f a c t o r s
and phases.
U s i n g .c e r ta in a lg e b ra ic in e quality re la tio n s h ip s such as
t h e C a u c h y i n e q u a l i t y , r e s t r i c t i o n s e x i s t on t h e c h o i c e of p h a s e s w h i c h
a re possible.
S in c e the s p e c if ic r e l a t i o n s h i p s w ill d e p e n d on the
s y m m e t r y of t h e c r y s t a l , m a n y r e l a t i o n s h i p s b e t w e e n s t r u c t u r e f a c t o r s
m a y be developed.
T hus, additional re la tio n s h ip s have b een developed
b y O k a y a a n d N i t t a ( 1 1 ) , K a r l e a n d H a u p t m a n (12), a n d H a u p t m a n a n d
K a r l e (13).
9
T h e s e i n e q u a l i t i e s h a v e b e e n u s e d w i t h a c e r t a i n a m o u n t of
s u c c e s s in s o l v i n g . s o m e s t r u c t u r e s .
(1 4,
I n 1952, a s e r i e s of p a p e r s
15, 16) w a s p u b l i s h e d i n w h i c h w a s g i v e n a r e l a t i o n s h i p of p a r ­
tic u la r value fo r phase d e te rm in a tio n s.
B a s ic a lly , the re la tio n s h ip
w a s t h e s a m e in e a c h p a p e r b u t d e r i v e d i n d i f f e r e n t w a y s .
In 1953,
H a u p t m a n a n d K a r l e (17 ) a n d H u g h e s (16) o b t a i n e d t h e s a m e r e l a t i o n ­
sh ip by tw o a d d itio n a l d e r i v a t i o n s .
S a y r e ' s (14) d e r i v a t i o n of t h e r e l a t i o n s h i p i s b a s e d u p o n a n
e x a m i n a t i o n -of t h e e l e c t r o n d e n s i t y w h e n t h e a t o m s w e r e r e p l a c e d by
the " s q u a r e d a to m s . "
T h e e l e c t r o n d e n s i t y a t l o c a t i o n x .i n a u n i t c e l l
i s give n, b y t h e ' F o . u r i e r s e r i e s
P(y,
.= i
y
FHe - - H X
F
=
s t r u c t u r e f a c t o r w i t h i n d i c e s H,
H
=
s e t of i n d i c e s (h, k, I),
H x ;= (hx:+ k y + I z ),
V
= v o l u m e of t h e u n i t c e l l .
T h e s q u a r e d d e n s i t y a t x m a y be r e p r e s e n t e d by t h e F o u r i e r s e r i e s
-ZiriHx
P^(X)
w here
f
,F fi
H 6
=
TTT TT
T rJ
T
10
T h e g.^. t a k e s , i n t o a c c o u n t t h e c h a n g e - i n s h a p e of the. n e w d e n s i t y .
The
s q u a r e d d e n sity m a y a lso be w r itte n
p 2 (x)
= P (x) p (x) =
I V f e ’ -Z1TiHx
V Z
n*
_
H
-I V F
-ZiriHx
-V Z
He '
H
J
A c c o r d i n g t o c o n v o l u t i o n t h e o r y of F o u r i e r s e r i e s , t h i s b e c o m e s
J.
V
P^(X)
v
Zv
F
F
H 1 :■ H 2.
,e - ^ ( H 1H ,)=
H2
w e l e t H 1 + H .= H a n d s i n c e t h e s u m m a t i o n s r u n o v e r a l l i n t e g e r s
v. I
2
qpH
V Yj f H 1 ^H 2
gH F H
giving the S a y re r e la tio n
f H
=
"I
gyV
F „ F.
Zv - H^ H -H g
H2
(I )
Z a c h a r i a s e n (16) a n d H u g h e s (18) d e v e l o p e d a s i m i l a r r e l a t i o n
u sin g n o r m a liz e d u n ita ry s tr u c tu re -factor s r a th e r than the u su al
s t r u c t u r e f a c t o r s.
N o r m a l i z e d u n i t a r y s t r u c t u r e f a c t o r s t a k e int o
a c c o u n t the. f a c t t h a t t h e x - r a y s c a t t e r i n g p o w e r of a t o m s d e c r e a s e ' s
/
/
11
a s t h e s c a t t e r i n g angle- i n c r e a s e s .
The n o rm alize d u n ita ry stru ctu re
f a c t o r is d e f i n e d b y
U
Zj
Z
H ;
e
■2-rriHx.
J
j = I
w h ere Z.
Z
= n u m b e r of e l e c t r o n s o n the. j t h a t o m ,
= t o t a l n u m b e r of e l e c t r o n s in t h e u n i t c e l l .
F o r t h e c e n t r o s . y m m e t r i c c a s e , t h i s m a y b e g i v e n by
N /z
uH=
w h e r e g^
2
g. c o s Ztt H x .
J
J
j = 1
=
T h e H u g h e s d e r iv a tio n -o f th e -s ig n r e l a t i o n s h i p is a s follows:
gi c o s 2-rr H j X i
U
UH
=
2
U
2 X
,
Sj =O= Zt H 2-X.
j
g .g . c o s 2-TTH 1X. c o s 2-rr H 0X.
ij
I i
2 j
12
=-- 2 ^
^
g . g j [ c o s 2 i r ( H j X . + H ^ x j ) +' c o s Z i r f H ^ . - H^Xy)]
i
j
■
=
2y
g . 2 [cos2-rr(H1 +
+
2 2^ 2y Si S j t c o s 2'n-(H 1x i + H 2x j) + c o s 2 tt( H 1x . -
•i
)x. + c o s 2Tr ( H 1 - H ^ x . ]
i
V j
If t h e a v e r a g e . i s t a k e n o v e r a l l p o s s i b l e v a l u e s of
keeping
= H
c o n stan t, then
c o s 2ir(H
since
I
H 2 )xi
c o s 2ir(H - 2 H ^ x i
w ill have all p o s sib le in te g r a l v alu es both p o sitiv e and
negative.
A lso
Si S j t c o s 2'rr(H1x i + H 2Xi ) + c o s
i
= 0
J
w here i /
j
N o w , if a l l the, a t o m s a r e t h e s a m e ,
= ^ . , w h e r e N e q u a ls the n u m b e r
T
13
of a t o m s i n t h e u n i t c e l l a n d . t h e m e a n v a l u e
u
H 1u H 2
I
I
Si COS 2lrfH 1 + H Z)3%
= — U
N
-H + H
I
z
*
T h u s , th e H u g h e s r e l a t i o n s h i p is
Uh T ' N f u H i u H 2 '
(2)
H a u p t m a n a n d . K a r l e ,(17), u s i n g . a s t a t i s t i c a l a p p r o a c h t o th e
p h a s e p r o b l e m , ■i n d e p e n d e n t l y d e r i v e d s e v e r a l e x p r e s s i o n s w h i c h c a n
■
be u s e d to d e t e r m in e the sign-of a re fle c tio n , the m o s t im p o r ta n t being
the
r e l a t i o n s h i p , g ive n by
s •
E H E H-H
: I
I
(3)
is th e n o r m a l i z e d s t r u c t u r e f a c t o r w h ic h is s i m i l a r to th e u n i t a r y
s t r u c t u r e f a c t o r e x c e p t t h a t it r e d u c e s the a t o m s to p o in t a t o m s by
c a n c e l i n g t h e - v i b r a t i o n a l c o n t r i b u ti o n in th e s t r u c t u r e , f a c t o r .
s(E^.)
m e a n s t h e " s i g n - o f E^.. "
T h e t h r e e r e l a t i o n s ( I , 2, 3) a r e e s s e n t i a l l y t h e s a m e s i n c e t h e
s i g n s of t h e s t r u c t u r e f a c t o r s , u n i t a r y s t r u c t u r e f a c t o r s a n d t h e
TT
T T5V
14
n o r m a l i z e d s tru c tu re -.fa c to rs m u s t be the s a m e .
H o w e v er, they all
h a v e t h e c o m m o n l i m i t a t i o n t h a t w i t h o u t k n o w i n g t h e s i g n s of t h e ' E 1^
I
a n d E^. , t h e s i g n of E^. c a n n o t b e d e t e r m i n e d .
K a r l e a n d H a u p t m a n ;(17) h a v e a l s o s h o w e d t h a t c e r t a i n p h a s e s
a r e d e t e r m i n e d o n l y b y the: c h o i c e of t h e o r i g i n a n d n o t b y t h e - s t r u c t u r e .
F o r e x a m p l e , t h e s t r u c t u r e f a c t o r s : of a c e n t r o s y m m e t r i c c r y s t a l a r e
F(hkl)
f . c o s 2-rr(hx. + k y ; + Iz1.)
J
-J
J
-I'
j = I
If t h e o r i g i n w e r e m o v e d t o ( l / 2,
F 1- (Iikl)
.= ^
l / 2,- l / 2), t h e n
F c o s 2-Tr[h(x +
+ k(y^ + ^ ) + l(z^ + -^)]
j
f . [ c o s 2-n-(hx. + k y . +" I z. ) c o s ^ ( h + k +, I)
J
J
J
J
+ sin2 u (h x ^ + ky^ + l z j ) | s i n v ( h + k + I)
=
y
f . [ c o s 2Tr(hx. + k y . + Iz .) c o s Tr(h + k-+,-1)
J
J
J
J
( _ l )h + k-+ l F ( h k l )
15
T h e r e f o r e , w h e n (h + k.+. I) = a n e v e n - i n t e g e r , t h e F ( h k l ) is c a l l e d a
"stru c tu re - invariant. "
H auptm an and K a rle d isc u s s e d th e se s tru c tu re
■i n v a r i a n t s a n d s h o w e d . t h a t t h e s t r u c t u r e , f a c t o r s of t h r e e , l i n e a r l y
i n d e p e n d e n t v e c t o r s (h, k, I), m o d u l o 2, c o u l d be a s s i g n e d a r b i t a r y
phases.
S a y r e (14), Z a c h a r i a s e n (1 6 ) , K a r l e a n d H a u p t m a n (17) a n d
o t h e r s h a v e s h o w n t h a t if t h e v a l u e s : of t h e s t r u c t u r e f a c t o r s w i t h k n o w n
p h a s e s a r e - l a r g e , t h e n u s u a l l y t h e r e l a t i o n s h i p £j
h o l d s f o r e a c h s e t of ( H
H- H^ ) .
=
x-
y
T h e r e f o r e , by k n o w in g th e p h a s e s
of o n l y t w o l a r g e s t r u c t u r e f a c t o r s o r n o r m a l i z e d , s t r u c t u r e f a c t o r s ,
the sign-of a . t h i r d s t r u c t u r e f a c t o r m a y be d e t e r m i n e d .
If the. n e w o n e
i s l a r g e , . it, in t u r n , m a y be. u s e d . t o d e t e r m i n e t h e s i g n s , of a d d i t i o n a l
stru ctu re factors.
G e n e r a l l y , t h r e e known s ig n s a r e n o t enough to d e t e r m i n e the
s i g n s of s u f f i c i e n t s t r u c t u r e . f a c t o r s to s o l v e a s t r u c t u r e .
A dditional
s i g n s c a n be f o u n d u s i n g ( i n e q u a l i t i e s a n d . o t h e r . - l e s s g e n e r a l s i g n
r e l a t i o n s h i p s , b u t t h e s e m a y n o t h e l p m u c h in g i v i n g u s e f u l p h a s e s to
g e n e r a t e a d d itio n a l p h a s e s by the ^
'rela tio n sh ip .
A l s o , a l l too
f r e q u e n t l y , w r o n g p h a s e s a r e i n s e r t e d . i n t o t h i s . c h a i n p r o c e s s e a r l y in
the d e te r m in a tio n w ith d i s a s t e r o u s r e s u l t s .
Z a c h a r i a s e n .(16) s u g g e s t e d
.that a f t e r t h r e e o r ig i n d e t e r m i n i n g s i g n s . o r p h a s e s a r e p ic k e d , a s e t
of s y m b o l i c s i g n s m a y b e a s s i g n e d w h e r e n e c e s s a r y .
T h e s i g n s : of
16
m a n y a d d itio n a l s t r u c t u r e f a c t o r s m a y be d e t e r m i n e d a s co m b in a tio n s
of t h e s e s y m b o l i c s i g n s a l o n g w i t h the* o r i g i n d e t e r m i n i n g s i g n s .
T h i s m e t h o d w a s h a r d l y u s e d u n t i l 1963 w h e n K a . r l e a n d K a r l e
,(19) b e g a n u s i n g i t in t h e i r " s y m b o l i c a d d i t i o n p r o c e d u r e . "
Their
m a i n c o n t r i b u t i o n t o t h e p r o c e d u r e w a s . t h e u s e of t h e H a u p t m a n a n d
K arle probability relationships.
sE
H
F o r the
e
y
relationship
H -H 1
t h e y h a d d e r i v e d t h e p r o b a b i l i t y of t h e s i g n b e i n g p o s i t i v e a s t h e
function
. I
1 f I
t a n h T-T- T
p + (e h > = 2 + 2
2N1' 7
a s s u m i n g t h a t a l l a t o m s : i n the. unit, c e l l w e r e i d e n t i c a l .
'
(4)
By req u irin g
■ <
t h e s i g n - o f a n o r m a l i z e d s t r u c t u r e f a c t o r t o h a v e a h i g h p r o b a b i l i t y of
b e i n g . c o r r e c t b e f o r e i t i s u s e d ,to d e t e r m i n e s i g n s , of o t h e r n o r m a l i z e d
s t r u c t u r e f a c t o r s , t h e a s s i g n m e n t of w r o n g . s i g n s m a y b e n e a r l y
elim inated.
U si n g , t h i s p r o b a b i l i t y e q u a t i o n (4),. i t i s s e e n t h a t one
y
Z-Z2
r e l a t i o n s h i p m a y b e e n o u g h to d e t e r m i n e w i t h h i g h p r o b a b i l i t y t h e s i g n
of a p a r t i c u l a r s t r u c t u r e f a c t o r , w h i l e m o t h e r c a s e s m a n y r e l a t i o n ­
s h ip s w o u ld be n e c e s s a r y .
17
A s the. n u m b e r of s i g n s b e i n g d e t e r m i n e d . i n t e r m s of s y m b o l i c
signs in c re a s e s ,
exam ple,
r e l a t i o n s b e tw e e n the sy m b o lic sig n s a p p e a r .
some
ma y. h a v e r e l a t i o n s w h i c h a s s i g n it s i g n s (ab) , (c),
( ab ), ( ab ) , (c), e t c .
a r e the s a m e .
For
T h i s w o u l d i n d i c a t e t h a t s i g n (ab) a n d s i g n (c)
If t h i s s a m e r e l a t i o n b e t w e e n s y m b o l i c s i g n s a p p e a r s
f o r o t h e r s t r u c t u r e f a c t o r s , t h e n o n e of t h e s y m b o l i c s i g n s m a y b e
elim inated.
T h e i m p o r t a n c e of e l i m i n a t i n g s y m b o l i c s i g n s i s r e a d i l y
u n d e r s t o o d w h e n - o n e c o n s i d e r s t h e n u m b e r of p o s s i b l e s i g n c o m b i n a t i o n s
If t h e r e a r e . n s y m b o l i c s i g n s ; l e f t a t t h e e n d of a s i g n d e t e r m i n a t i o n ,
t h e n t h e r e a r e 2^ p o s s i b l e c o m b i n a t i o n s , f r o m w h i c h t h e c o r r e c t s e t
m u s t be c h o s e n .
U s u a lly , f e w e r . f i n a l s y m b o li c ,signs r e m a i n a f te r a
d e t e r m i n a t i o n of a s e t of s i g n s t h a n w e r e i n i t i a l l y a s s i g n e d .
In s o m e
c a s e s a l l of t h e s y m b o l i c s i g n s c a n b e e l i m i n a t e d .
T o d e t e r m i n e w h i c h c o m b i n a t i o n of s i g n s i s c o r r e c t , a n E - m a p
is u su ally calcu lated .
A n E - m a p i s s i m i l a r to a n e l e c t r o n d e n s i t y m a p
e x c e p t t h a t n o r m a l i z e d s t r u c t u r e f a c t o r s a r e u s e d , in c a l c u l a t i n g ,the
F o u rier series.
T he d iffe re n c e b e tw e e n the E - m a p and the e le c tro n
d e n s i t y m a p is t h a t t h e E - m a p a s s u m e s p o i n t a t o m s w i t h o u t v i b r a t i o n
a n d t h e e l e c t r o n d e n s i t y m a p c o n t a i n s m o r e d i f f u s e p e a k s d u e to th e
v i b r a t i o n of t h e a t o m s a n d t h e i r f o r m f a c t o r s .
Once an E -m a p h as.b e en
c a l c u l a t e d o v e r t h e u n i t c e l l , it m u s t b e e x a m i n e d . f o r a r e a s o n a b l e
chem ical stru ctu re.
T h e v a l i d i t y of m a n y E - m a p s c a n b e a s c e r t a i n e d
18
on c h e m i c a l g r o u n d s .
If s e v e r a l p o s s i b l e s t r u c t u r e s r e m a i n w h i c h
a r e c h e m i c a l l y r e a s o n a b l e , . i n c o r r e c t s t r u c t u r e s m a y b e r u l e d , ou t on
t h e b a s i s , of t h e a g r e e m e n t b e t w e e n the- o b s e r v e d a n d c a l c u l a t e d
s t r u c t u r e f a c t o r s : o r t h e f a i l u r e of a . s t r u c t u r e to r e f i n e b y t h e l e a s t s q u a re s technique.
T h e c o r r e c t E - m a p d o e s n o t a l w a y s .i n d i c a t e th e
p o s i t i o n s , of a l l t h e a t o m s ; i n a s t r u c t u r e .
If, h o w e v e r , a m a j o r i t y of
t h e a t o m s a r e found, o r if t h e h e a v y a t o m s a r e f o u n d , t h e n b y t h e u s e of
p a r t i a l s t r u c t u r e fa c to r c a lc u la tio n s and F o u r i e r m a p s , the re m a in in g
a t o m s m a y be-, l o c a t e d .
T h i s m e t h o d . o f s y m b o l i c s i g n d e t e r m i n a t i o n h a s p r o v e n to be
e x t r e m e l y p o w e r f u l in t h e s t r u c t u r e s t u d i e s r e p o r t e d h e r e ,
since-in
e a c h c a s e a m a j o r p o r t i o n of the- s t r u c t u r e c o u l d be a s c e r t a i n e d , f r o m
the E -m a p .
TV
I
P A R T II
T H E C R Y S T A L S T R U C T U R E O F D I C H L O R O D I P H E N O X Y T I T ANI UM (IV )
■P r e p a r a t i o n - o f t h e C r y s t a l s
C r y s t a l s . o f T i C l ( O C . H ) w e r e p r e p a r e d b y h e a t i n g T i C l ( O C >H_)
Lt
o o ^
3
6 5
i n a c l o s e d c o n t a i n e r a t 120 t o 150 d e g r e s s a n d o n e m m . H g . p r e s s u r e .
T h e T i C l ^ ( O C ^ H g ) d i s p r o p o r t i o n a t e s , l i b e r a t i n g T i C l ^ a n d c r y s t a l s of
T i C l ^ ( O C ^ H ^ ) ^ c o l l e c t On t h e w a l l s , of t h e c o n t a i n e r .
T h e T i C l g ( O C ^ H g ) w a s p r e p a r e d b y a m e t h o d f i r s t d e s c r i b e d by
L u c h i n s k i a n d . A l t m a n n (20), w h i c h w a s u s e d b y C r o w e a n d C a u g h l a n (21)
to o b ta in p u r i f i e d c r y s t a l s .
T h i s m e t h o d c o n s i s t s . of s l o w l y m i x i n g c o l d
d i l u t e s o l u t i o n s of p h e n o l i n p e t r o l e u m e t h e r a n d . c h l o r o f o r m w i t h a
s i m i l a r solution-of tita n iu m t e t r a c h l o r i d e .
Upon d is ti lli n g an d cooling
c r y s t a l s of T i C l g ( O C ^ H g ) a r e o b t a i n e d .
C r y s t a l s of T i C l ^ ( O C ^ H g ) ^ h a v e a d e e p r e d c o l o r a n d a r e u n s t a b l e
in m o i s t a i r a lth o u g h th e y h y d r o l z e m u c h l e s s r e a d i l y th a n e i t h e r T iC l^
o r the s i m p l e t i ta n i u m a lk o x id e s .
C ry sta ls w e re sealed.in P y re x c a p il­
l a r i e s and. o n e w a s s e l e c t e d . f o r t h e x - r a y s t u d y .
Its a p p ro x im a te
dim ensions w e re 0.2 x 0.2 x .l m m .
D ensity D eterm ination-of T iC l^ O C ^ H g )^
T h e d e n s i t y of t h e c r y s t a l s w a s d e t e r m i n e d b y m e a s u r i n g . t h e
d e n s i t y of - a s o l u t i o n of c a r b o n t e t r a c h l o r i d e - in b e n z e n e i n w h i c h t h e
20
c ry sta ls rem a in ed suspended.
T h e d e n s i t y of T i C l ^ ( O C ^ H ^ ) ^ w a s
d e t e r m i n e d t o b e 1 .4,93 g / c m .
C o l l e c t i o n of t h e ‘D a t a
T h e l i n e a r a b s o r p t i o n c o e f f i c i e n t f o r CuKcx
r a d i a t i o n i s 91. 04
c m * a n d .fo r'M o Ka
I 0. 34 c m * .
a b s o r p t i o n - of C u Ka
ra d ia tio n -w o u ld a ffe c t the in te n s ity m e a s u r e m e n t s
F o r t h e s i z e of c r y s t a l u s e d , t h e
e n o u g h t h a t a b s o r p t i o n c o r r e c t i o n s w o u l d h a v e t o be a p p l i e d .
W i t h M o Ka
r a d ia tio n , h o w e v e r , the a b s o r p t i o n is n e g lig ib le .
I n te n s i ty d a ta w a s . o r ig in a lly ta k e n -o n the c r y s t a l u s in g a •
B u e r g e r p r e c e s s io n c a m e r a u sin g Mo Ka
pictures,
radiation.
F r o m these
P 2 / n s y m m e t r y w a s i n d i c a t e d by l a t t i c e p a r a m e t e r s a n d
I
s y s t e m a t i c e x t i n c t i o n s , , i. e. , k / 2n f o r t h e OkO z o n e a n d h+1 /
the hOl zone.
2n f o r
U sin g the c e l l d i m e n s i o n s and a s s u m i n g . f o u r m o l e c u le s
p e r u n i t c e l l , t h e c a l c u l a t e d d e n s i t y i s I . 50 g / c m .
T able I gives a
. . s u m m a r y of th e c e l l d a t a .
T h e in t e n s ity d a ta u s e d .i n the s t r u c t u r e d e t e r m i n a t i o n w as
co llected.on a G e n e ra l E le c tric X RD-5 d iffra c to m e te r w ith a G en eral
E l e c tr i c single c r y s t a l o r ie n te r and scin tillatio n co u n te r for detecto r.
I n d e p e n d e n t r e f l e c t i o n s w e r e c o l l e c t e d by t h e - 2 0 - s c a n t e c h n i q u e
( m o v i n g . c r y s t a l - m o v i n g . c o u n t e r m e t h o d ) u s i n g I 00 s e c o n d s c a n s a n d
r e a d i n g . t h e b a c k g r o u n d f o r 50 s e c o n d s on e a c h s i d e of t h e p e a k .
The
s c a n r a t e in 20 w a s . t w o d e g r e e s p e r m i n u t e , t h e t a k e - off a n g l e f o u r
TI
I C l! "
T
TABLE I
S u m m a r y of C r y s t a l D a t a f o r T i C l ( O C . H L L
2
6 5 2
a = 9. 821(3> A
• b = 14. 006(4) : A
c = 9. 836(3)
A
p = 9 4 ° 50'(1 O')
Space Group
P2 / n
M o lecu les p e r unit cell
4
■ C alculated density = 1 . 5 0 g / cm
M e a s u re d density = 1 .4 9 g / c m ^
22
degrees.
Z irc o n iu m filte re d m olybdenum radiation w as u s e d ” ’ The
d i f f r a c t o m e t e r s e ttin g ;fo r the individual r e fle c tio n s w e r e c a lc u la te d
u s i n g a c o m p u t e r p r o g r a m b y W i t t e r s (22).
2600 r e f l e c t i o n s w e r e
c o l l e c t e d . o f w h i c h 1175 w e r e t r e a t e d a s o b s e r v e d , t h a t i s , a t l e a s t
300 c o u n t s a b o v e b a c k g r o u n d .
T h e . i n t e n s i t y d a t e w a s c o r r e c t e d f o r the- L o r e n t z - p o l a r i z a t i o n
f a c t o r u s i n g a c o m p u t e r p r o g r a m f r o m t h e c r y s t a l l o g r a p h i c l i b r a r y (23).
F o r m f a c t o r s fo r individual re fle c tio n s w e r e a ls o c a l c u la te d by this
program .
T he f o r m f a c t o r ta b le s w e r e ta k e n f r o m the I n te rn a tio n a l
T a b l e s f o r C r y s t a l l o g r a p h y (24).
S tru ctu re D eterm ination
I n i t i a l a t t e m p t s t o s o l v e t h i s s t r u c t u r e w e r e m a d e w i t h th e
s t a n d a r d m e t h o d of i n t e r p r e t i n g . o f a t h r e e - d i m e n s i o n a l P a t t e r s o n m a p .
F o r the c r y s t a l s y m m e t r y P 2 ^ / n , th e r e a r e equivalent a to m s at
coordinates
x , y, z;
-x,
-y,
-z;
l / 2 + x,
1 / 2 - y,
I / 2.+ z;
l / 2 - x,
l / 2 + y,
I / 2 - z.
C o n s i d e r i n g t h e v e c t o r b e t w e e n a n a t o m a t x, y, z a n d a t I / 2 -. x,
l / 2.+ y,
l / 2 - z , w e o b t a i n u = l / 2 - 2x, v = I / 2,- w = 1 / 2 - 2z.
T h i s m e a n s t h a t f o r e v e r y a t o m i n t h e . u n i t c e l l , a p e a k i s o b t a i n e d on
■ 23
the
V =
l / 2 . s e c t i o n - o f t h e P a t t e r s o n m a p d u e to t h e s c r e w s y m m e t r y u p
the y ax is.
T h e o t h e r v e c t o r s w h ic h one c a n w o r k w ith , due to s y m m e t r y
t r a n s f o r m a t i o n s of t h e e q u i v a l e n t a t o m s , a r e t h e c e n t e r of s y m m e t r y
(2x, 2y, 2z) a n d . t h e o n e d u e to t h e d i a g o n a l g l i d e ( 1 / 2 ,
l / 2 - 2y,
l / 2).
T h e s e c t i o n a t v = l / 2, a n d t h e l i n e a t u = l / 2, w = I / 2 a r e c a l l e d t h e
H a r k e r sectio n and.line resp ectiv ely .
T h e m a j o r p e a k . o n -the M a r k e r s e c t i o n w a s a t ..(I / 2,
T h i s i n d i c a t e d a t i t a n i u m a t o m w i t h c o o r d i n a t e s (0, y,
l / 2, 0).
l / 4).
The m a jo r
p e a k on t h e M a r k e r l i n e w a s a t v = . 45 i n d i c a t i n g t h e y c o o r d i n a t e s of
t i t a n i u m w a s . . 025.
T his peak w as also p r e s e n t w ith a p p ro x im a te ly the
ex p ec ted peak height.
A r o u n d e a c h of t h e p e a k s w e r e " s a t e l l i t e " p e a k s
w h ic h one w o u ld e x p e c t to get f r o m t i t a n i u m to c h l o r i n e v e c t o r s , a l s o
w ith the c o r r e c t peak h eig h ts.
Som e r e m a in in g " s a te llite " peaks could
b e a t t r i b u t e d t o t i t a n i u m .t o ■o x y g e n v e c t o r s ; t h u s , e x p l a i n i n g e v e r y
m a j o r peak, in the P a t t e r s o n m a p .
found f r o m the P a t t e r s o n m a p .
T ab le M gives the a to m ic positions
T a b l e IM s h o w s t h e c a l c u l a t e d a n d
a c t u a l p e a k h e i g h t s d u e - t o t h e v e c t o r s b e t w e e n a t o m s g i v e n i n T a b l e II.
U sin g .th e s e tita n iu m and c h lo rin e positions the s t r u c t u r e fa c to r
c a l c u l a t i o n g a v e a n R - i n d e x of 52% w h i c h w a s n o t u n r e a s o n a b l e f o r t h i s
n u m b e r of a t o m s c o n s i d e r i n g t h e p s e u d o - s p e c i a l p o s i t i o n of t h e t i t a n i u m .
A F o u r i e r m a p s h o w e d t h e p o s i t i o n s of t h e o x y g e n s a n d s o m e r a t h e r
d isto rte d phenyl rings.
W i t h t h e s e n e w p o s i t i o n s c a l c u l a t e d f r o m the.
T A B L E II
C o o r d i n a t e s O b t a i n e d f o r I n c o r r e c t S t r u c t u r e - of
T ic y o c ^ );,
A tom
x'
Ti
, . 000
Cl(I) '
-.175
Cl(Z)
O(I)
.200
000 .
■y
”
Z
. . 025
• . 250
-. 025
" . 650
. 025
- . 675
.025
.075
25.
■T A B L E III
A s s i g n m e n t s of V e c t o r s ' D u e t o I n c o r r e c t S t r u c t u r e
.o fT ic y o c ^ ) ,
Peak
No.
P ositions
As signm ent
Peak
H eight
Calc.
H eight
I 62
I 22
--
y
X
T i-T i
I
2
.
■
T i-C l(I)
. 500
. 500
. 700
. 450
.100
35
47
. 325
.
450
. . 075
42
47
. 450
.... 350
36
'22
95
94
. 575
I 08
94
.500
-.1, 75
98
72
000
.400
1 10
94
.000
.425
I 06
94
3
-Ti-Cl(Z)
4
Ti-O (I)
5
T i-C l(I)
. 675
6
T i - C 1(2)
.
7
Ti-O (I)
■
■8
T i-C l(I)
, .
800
9
Ti-C l(2)
•
I 75
■
Z
500
300
.
’
■
„ 500
.
.
500
.
500
,
. .
.
.
00
600
’
050
, .
500
.6 7
61
000
050
- .
325
47
44
■ T i-C l(I)
■. 1 7 5
. 050
.100
35
47
I3
Ti-C l(2)
. 800
, . 050
. . 075
35
47
14
T i-T i
C l(I)-C l(I).
C1(2) -C1(2)
. 500
. . 450
. 500
I 62
1 94
I0
T i-T i
. .
000
11
T i-(I)
' .
,12
- .
TT
T
%6
F o u r i e r m a p , t h e R - i n d e x d r o p p e d t o 42%.
T his can n o t be c o n s id e r e d
g o o d w h e n - a l l t h e a t o m s a r e i n c l u d e d , b u t l e a s t - s q u a r e s ' r e f i n e m e n t of
t h e s t r u c t u r e f a c t o r s w a s u s e d a n y w a y t o s e e if t h e s t r u c t u r e w o u l d
refine.
T h e R - i n d e x d r o p p e d to a b o u t 35% in t h r e e c y c l e s of f u l l
m a t r i x r e f in e m e n t in d ic a tin g that the s t r u c t u r e w a s p r o b a b ly i n c o r r e c t.
A d d i t i o n a l a t t e m p t s t o i n t e r p r e t t h e P a t t e r s o n m a p a l w a y s l e a d to t h e
sam e structure.
A l t h o u g h t h i s s t r u c t u r e e x p l a i n e d a l l t h e - m a j o r p e a k s , tw o p e a k s
w e r e m i s sing, f r o m the v = l / 2 s e c ti o n w h ic h sh o u ld h a v e b e e n p r e s e n t.
T h e s e w e r e t h e d o u b l e w e i g h t C l - C l v e c t o r p e a k s a r i s i n g , f r o m th e
screw sym m etry.
T h u s , a l t h o u g h t h e s t r u c t u r e w a s r u l e d , o u t , no
■o t h e r s t r u c t u r e c o u l d b e p o s t u l a t e d a t t h a t t i m e w h i c h w a s m o r e
satisfactory.
A t t h i s . p o i n t , it w a s d e c i d e d t o t r y t h e s y m b o l i c s i g n d e t e r ­
m ination w hich has been b riefly d escrib e d .
Com puter p ro g ram s w ere
w r i t t e n to c a l c u l a t e th e n o r m a l i z e d s t r u c t u r e f a c t o r s an d fin d the
r e l a t i o n s , a n d to s e a r c h th r o u g h t h e m f o r s y m b o l i c a l l y a s s i g n e d p h a s e s .
T h e - l a r g e s t 242 n o r m a l i z e d s t r u c t u r e f a c t o r s ( > 1 . 4 ) w e r e us.ed.
i n i t i a l c h o i c e of s i g n s a r e s h o w n in T a b l e IV.
relatio n s w e re calculated,
The
M o r e - t h a n 50 00 s i g n
s o m e r e f l e c t i o n s h a v i n g a s m a n y a s 100
r e l a t i o n s c o n t r i b u t i n g to t h e i r s i g n s .
S u b s e q u e n t l y , 230 s i g n s w e r e
a s s i g n e d w ith only one a r b i t r a r y c h o ic e r e m a i n i n g .
U s i n g t h e s e tw o
rr
27
T A B L E IV
I n i t i a l C h o i c e , of S i g n s , f o r T i C l ^ ( O C ^ H g ) ^
h
k
■I
S ig n
E
.0
-5
■2
'-■+
1.83
2
8
I
. 4*
2. 48
-3
I'
6
+
2.99
-3
9
I
a
2.93
2
2
.4
b
2. 27
6
2
2
C
3.86
-3
I
I
d
ZL 86
28
p o s s i b l e s e t s of s i g n s , t w o t h r e e - d i m e n s i o n a l E - m a p s w e r e c o m p u t e d .
T h e c o r r e c t s t r u c t u r e w a s i m m e d i a t e l y a p p a r e n t “i n - o n e of t h e E - m a p s .
U p o n c h e c k i n g t h e s i g n s a f t e r r e f i n e m e n t , a l l 230 s i g n s p r o v e d .to be
correct.
T a b l e V s h o w s t h e n e w v a l u e s of t h e p r i n c i p a l m e a s u r e d a n d
c a l c u l a t e d v e c t o r s a s c o m p a r e d . t o t h o s e in T a b l e III.
T h e s t r u c t u r e f a c t o r c a lc u la tio n w ith new t i t a n i u m , . c h lo rin e
a n d . o x y g e n p o s i t i o n s g a v e a n R - i n d e x of 42%.
U sing th e se s tr u c tu re
f a c t o r s , a F o u r i e r m a p w a s c a l c u l a t e d w h i c h g a v e t h e p o s i t i o n s of t h e
c a r b o n s in t h e p h e n y l r i n g s .
t o 29%.
W ith th e s e p o s itio n s, the R - index d ro p p ed
T h e only d if f e r e n c e b e tw e e n the i n c o r r e c t an d th e c o r r e c t
s t r u c t u r e w as. th a t the two m o l e c u l e s w e r e m o v e d I A c l o s e r to g e th e r
along, the-z a x is.
T h i s , . in e f f e c t , c h a n g e d . t h e z c o o r d i n a t e of t i t a n i u m
t o t h a t of t h e c h l o r i n e s a n d t h o s e of th e c h l o r i n e s to t h e z c o o r d i n a t e
of t h e t i t a n i u m .
T h e p e a k o n th e H a r k e r s e c t i o n w h i c h h a d b e e n
i n t e r p r e t e d a s a 4 w e i g h t e d T i - T i p e a k , w a s n ow i n t e r p r e t e d a s 8
Cl( 1)-C1(2) v e c t o r s w h i c h f e l l in a p p r o x i m a t e l y the. s a m e p l a c e .
The
T i - C l v e c t o r s co u ld be ex p lain ed by e i th e r the c o r r e c t o r i n c o r r e c t
structure.
R e f i n e m e n t of t h e S t r u c t u r e
R e fin e m e n t s t a r t e d w ith the a to m p o sitio n s w h ic h gave an
R - i n d e x of 29%.
T h e f u l l m a t r i x l e a s t - s q u a r e s r e f i n e m e n t p r o g r a m , of
B u s i n g , L e v y a n d M a r t i n w a s u s e d (25).
T h re e cycles vary in g
TT
29
TABLE V
A s s i g n m e n t of V e c t o r s ; D u e t o t h e C o r r e c t S t r u c t u r e
=O f T i c y o c ^ ) ; ,
P e a k No.
A ssignm ent
P e a k H eight
1-62'
14 4
Ti-C l(I)
35
47
3
Ti-Cl(Z)
42
47
4
Ti-O (I)
36
22
.5
Ti-C l(I)
95
94
Ti-Cl(Z)
108
94
, 98
81
I
T i-T i
2
6 ..
7
' T i-T i
.
C alc. Height
8
Ti-C l(I)
1 06
94
9
Ti-Cl(Z)
' MO
.94
1.0
C l(I)-C l(Z)
67
72
11
T i-T i
47
31
I2
T i-C l(I)
35
47
13
Ti-Cl(Z)
35
47
14
T i-T i
C l(I)-C l(I)
Cl(Z)-Cl(Z)
162
194
30
p o s i t i o n a l p a r a m e t e r s d e c r e a s e d t h e R - i n d e x to 19%; t h r e e c y c l e s
v ary in g p ositional p a r a m e te r s and.individual iso tro p ic te m p e r a tu r e
f a c t o r s r e d u c e d . t h e R - i n d e x . t o 11%; a n d t h r e e c y c l e s v a r y i n g p o s i ­
t i o n a l p a r a m e t e r s a n d a n i s o t r o p i c t e m p e r a t u r e f a c t o r s - h r ought the
R - i n d e x t o 6, 1%.
equally.
D uring,this refin em en t, all reflectio n s w e r e w eighted
' -
F i n a l p o s i t i o n a l p a r a m e t e r s a r e . l i s t e d in T a b l e VI.
T a b l e VII
l i s t s t h e a n i s o t r o p i c t e m p e r a t u r e f a c t o r s , a n d T a b l e VI II l i s t s th e
a n i s o t r o p i c t h e r m a l p a r a m e t e r s in t e r m s of t h e m e a n - s q u a r e a m p l i ­
t u d e s of v i b r a t i o n a l o n g t h e p r i n c i p a l a x e s of t h e t h e r m a l e l l i p s o i d s .
The bond.lengths and bond angles w ith s ta n d a rd deviations a r e listed
in T a b l e s IX a n d X.
T a b l e XI c o n t a i n s t h e o b s e r v e d a n d c a l c u l a t e d
stru ctu re factors.
■D i s c u s s i o n of t h e S t r u c t u r e
F i g u r e I s h o w s t h e a r r a n g e m e n t of t h e m o l e c u l e i n t h e u n i t
I
cell.
D i c h l o r o d i p h e n o x y t i t a n i u m (IV) i s a d i m e r - l o c a t e d a r o u n d . t h e
c e n t e r of s y m m e t r y .
The titanium atom s a re each pentacoordinated
and a r e connected by oxygen b rid g e s .
The titanium - oxygen distances
v a r y c o n s i d e r a b l y , t h e s h o r t e s t b e i n g I. 744( 10) A , . t h e n e x t I. 910(9) A,
a n d . t h e - l o n g e s t 2. 122(9) A.
T h e i o n i c T i - O d i s t a n c e i n r u t i l e is I. 9 4 4 A,
w h e r e a s in T i ^ O ^ t h e d i s t a n c e s r a n g e f r o m I. 83 to 2. 7 (26).
31
F IG U R E I.
A r r a n g e m e n t of One D i m e r U n i t of
T i C l 9( O C z H c ) - P r o j e c t e d i n t h e U n i t
C ell
5
T A B L E VI
A t o m i c C o o r d i n a t e s of T i C l A O C .H )
L
X
T i ( I)
Cl(Z)
C l (3)
O (4)
O (5)
C (6)
C (7)
C (8)
C (9)
C (10)
C (11)
C (12)
C (I 3)
C (14)
C (I 5)
C (16)
C (17)
0. 5031 ( 2 ) a
0. 3207 (3)
0. 69 58 (3)
0. 4 9 2 7 (7)
0. 4 9 7 2 (9)
0. 48 07 (I 0)
0. 59 58 (I 3)
0. 5827 (15)
6. 4 5 6 3 - (I 6)
0. 3388 (15)
0. 35 10 (12)
0 . 4 8 1 6 (11).
0 . 4 5 6 4 (12)
0. 4 3 4 9 (I 5)
0. 4 4 4 4 (I 3)
0. 4 7 0 7 (I 3)
0. 4 90 8 (I 3)
b
D Z
Z
y
.
0. 4 7 1 4 (I)
0. 53 53 (3)
0. 5269 (3)
0. 41 66 (5)
0. 3628 (5)
0. 31 67 (7)
0.2656(8)
0 . 1 6 7 5 (8)
0.1256(8)
0 . 1 7 7 9 (9)
0.2769(9)
0.2919(7)
0. 3191 (8)
0.2486(10)
0. 1 5 0 4 (10)
0 . 1 2 8 2 (8)
0. 1 9 8 3 (8)
-
0.3389(2)
0. 2275 (3)
0.2663(3)
0. 51 56 (6)
0. 2518 (7)
0. 5381 (9)
0. 57 36 (11)
0. 5929 (12)
0. 5801 (12)
0. 5510 (12)
0. 5272 (11)
0 . 1 5 7 5 (11)
0. 0218 (11)
- 0 . 0768 (11)
- 0 . 0392 (14)
0. 09 74 (13)
0 . 1 9 9 1 (11)
a T h e n u m b e r in p a r e n t h e s i s i s t h e s t a n d a r d d e v i a t i o n a n d r e f e r s to
th e -le a s t sig n ifican t digits.
T A B L E VII
A n i s o t r o p i c T e m p e r a t u r e F a c t o r s of T i C l ^ ( C ) C j-)^
Ti(I)
Cl(Z)
Cl(3)
0(4)
0(5)
C(6)
0(7)
0(8)
0(9)
0(10)
0(11)
0(12)
C d 3)
0(1.4)
0(15)
0(16)
0(17)
P d , i)*
P ( 2 , 2)
. 0 1 34( 3)b
. 0164(5)
. 0 1 4Z(5)
. 0 11 3( 10 )
. 0Z03(14)
. 0 08 7( 1 5)
. 0 1 4 4( 1 8)
.0183(21)
. 0 21 2( 23 )
. 0174 (2 2)
. 0 11 5( 18)
. 0 10 5( 15)
. 0145.(19)
. . 0 2 0 5( 2 3)
. 0 1 4 6( 2 0)
. 0 14 4( 19 )
. 0 1 5 8( 1 9)
- . 0035(1)
. 00 68(2)
. 00 68(2)
. . 0041(4)
. 0043(4)
. 00 38(5)
. 0045(6).
. 0036(6)
.0033(6)
.0053(8)
. 0060(8)
. . 0046(6)
. 0062(7)
. 0 0 84 (1 0)
.0069(9)
.0041(7)
. 004 2( 6)
.
P U , 2)
P D , 3)
. 0058(1)
' . 0130(4)
. 0136(4)
. 0063(7)
.0082(9)
. 0059 (1 0)
. Oil 3(14)
. 0137 (1 6)
.0111(15)
• . 0 1 24 (1 5)
. 0 1 29 (1 4)
. 0090 (1 2)
. 007.5(1 3)
. 0092(13)
. 0 1 59 ( 1 8 )
. 0170 (1 8)
.0096(13) .
.
.
.
.
.
.
.
.
-.
-.
.
-.
-.
-.
-.
.
.
0005(2)
0016(3)
0003(3)
0002(5)
0007(7)
0006(8)
0 0 21 (1 0)
0 0 07 (1 0)
0 0 06( 11 )
0 0 23 (1 1)
0 0 03( 10 )
0001(8)
0 0 1 2 (1 0 )
0 0 12( 13 )
0014(11)
0007(9)
00 21(9)
a T h e f o r m of t h e a n i s o t r o p i c t h e r m a l e l l i p s o i d . i s
e x p [ - ( P 1 ^ 2 + P2 Zk2 + (3SS ^ 2 + 2PlZh k + 2 P i z M + Zp2 3 W ) ]
b
T h e n u m b e r in p a r e n t h e s i s , is the s t a n d a r d d e v ia tio n and
r e f e r s to th e l e a s t s ig n if i c a n t dig its.
P U , 3)
P(2, 3)
- . 0003(2)
- . 0049(3)
. 0039(3)
.. 0012(6)
. 0000(9)
. 0022(9)
. 0015(12)
. 0020(15)
. 0039(1 5)
. 0047(1 5)
. 0020(12)
. 0030(11)
. 0017(12)
. 0002(1 3)
. 0036(14)
. 0009(1 5)
. 0015(13)
- .. 0 0 0 6 ( 2 )
- . 0009( 3)
- . 0015( 3)
- . 0004(4)
- . 0016( 6)
- . 0005(6)
.0010(8)
- . 0001( 8)
- . 0007(8)
-. 0030( 9)
' - . 0026(8)
0016( 8)
- . 0013(8)
-. 0031( 10)
- . 0051.(11)
- . 0028( 10)
- . 0010 (7 )
34
T A B L E VIII
P r i n c i p a l A x e s of t h e T h e r m a l E l l i p s i o d s
of T i c y o c ^ ) ; ,
M e a n - S q u a r e a m p l i t u d e of v i b r a t i o n ( in A^)
A tom
. Max.
Ti(I)
Cl(Z)
0(3)
0(4)
0(5)
C(6)
0(7)
0(8)
0(9)
0(10)
0(11)
0(12)
0(13)
0(14)
0(15)
0(16)
0,(17)
. 0667
.1088
. .0823
■ 0551 .
..1 0 0 5
. 0459
. 0772
. 0 89 4
■ .1050
: .1,027
. . 07 92
■. 0611
. . 07 62
.1031
..1 1 2 3
:.0917
.0816
.
Med.
. 0362
- . 0637
:.0702
. . 041 6
.. 05 14
, . 03 83
0553
. 06 60
' . . 0506
- .0568 •
..0571
. 0478
..0582
..0 9 0 5
.0654
. 0697
-.0510
Min.
,.0262
. 0427
0484
-.0293
..0299
,.0224
.. 0363
... 0349
.0318
. 0347
. . 0403
. 0300
... 0333
-.0344
.. . 0370
. 0323
.. 0319
■35
T A B L E IX
B o n d D i s t a n c e s in T i C l (OC .H )
Z
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
0(4)
' 0(5)
■0 ( 6 )
0(7)
0(8)
'0 (9 )
0(10)
0(1 U
C(IZ)
0(13)
0(14)
0(15)
■C(1 6)
' C( 17)
-
T i(l')
Cl(Z)
Cl(3 )
0(4)
0(4' )
0(5)
C(6)
C(IZ)
C(7)
0(8)
0(9)
0(10)
C (Il)
0(6)
0(13)
0(1-4)
0(15)
C(1 6)
C(1 7)
O(IZ)
6
5
2
3. Z74(3)A
Z. Z09(3)
2. Zl 9(4)
I . 91 O(Z)
Z . 1ZZ(9)
1 . 7 4 4 ( 1 0)
1 . 4ZZ(11 )
I . 359(19)
I . 35 9(10)
1 . 3 9 5 ( 1 5)
I . 369(Z8)
I .376(1 Z)
I . 413 (1 6)
' I . 386(ZZ)
' I . 390(1 3)
I , 388(Z7)
I , 4Z4(1 4)
I. 382(18)
I . 404(Z6)
1.374(9)
.
-
Tt
T
I
3.6
TABLE X
B ond.A ngles in T iC l^(O C ^H g)^
A tom s
Cl(Z)
Cl(Z)
Cl(Z)
Cl(Z)
C l ( 3)
C 1(3)
Cl(3)
0(4)
0(4)
0 (4 ')
-
Ti(I) Ti(I) T i ( I t) Ti(I) -
D egrees
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
-
0(3)
0(4)
0 (4 ')
0(5)
P(4)
0 (4 ')
0(5)
0 (4 ')
0(5)
0(5)
0(4)
0(4)
0(4)
0(5)
-
T id ')
C(6)
C(6)
C(IZ)
1 0 8 . 5(3)
1 2 3 . 2(4)
128.3(4)
165.9(6) >
.1 1 2 .id )
1Z.0. 7(1)
90. Z(Z)
96.7(3)
12 3. I(Z)
89. 4(2)
98.1(3)
71.5(2)
95.4(3)
16 7. 0(3)
■0 ( 4 )
0(4)
' C (Il)
C (6)
C( 7)
0(8)
0(9)
C(LO)
-
C (6)
G (6)
C(6)
0(7)
C (8)
C(9)
C(IO)
C (Il)
-
0(7)
C (Il)
0(7)
C(8)
0(9)
C(IO)
CdD
C(6)
118.7(7)
118.1(7)
1 2 3 . 2(7)
11 8. 0(8)
12 0. 2(9)
121.9(9)
11 8. 4(9)
118.2(8)
0(5)
0(5)
C(1 3)
C(IZ)
C(1 3)
C(1 4)
C d 5)
C d 6)
-
C(IZ)
C(IZ)
C(IZ)
C (I 3)
C ( 1 4)
C(1 5)
C d 6)
C ( 1 7)
-
C d 3)
C(1 7)
C d 7)
C d 4)
C d 5)
C d 6)
C(1 7)
C(IZ)
117.1(8)
119.6(8)
12 3. 3(8)
118.7(8)
120.2(9)
11 8. 2(10)
122. 6(9)
117. 0(8)
T
37
T A B L E XI
Observed and Calculated Structure Factors for TiCVOC4H1V
P=,?
E E
I »»>' 4,
I l
tn M
a =E
;;i -is
I:'
-i
E IS
1 E-f
*
»»1»2* -»U
M
•*»
IS *
2S1
IS I
2»»
i:
IOO
201
1*2
^
-1*0
l»»
:;,1 in
1*0
2TI
2»*
i.,10
Ml
»11’ »»2
IM
V
I!! ’"!ii
ISS "E
Su“
IM
ItO
I
*1
IOO11 120
111
12T
- 2^ I*
102 -122
r ir
I
♦* Il
2*0
-2*
2*2
M
E
.S-%
' . I 1" M
111
II*
- I
12 I
21*
210
IV*
102
in ;1::
SSi .SE
,ti
E -E
r,, v
%
FJi=
ISO
221
1*1
1»*
20*
-I* *
i;v r
1 SE.;:
I"..-':'
i::
I l l l f -IM
i > 'E
V ’-iii
!.."-ll.
SI: :E
!** ir
I* * * * -!!*
iii
18I
I -
'll
*-»h
Iio i»i
I lO l 1I M I
in *•*
M l
MM
I**
-0*1
♦ IT
- 12*
JiT - ISOII *
111
IT *
-E
I
-1 1 1
100
,
r ,’r
jo* 4*»
»01
- T l*
111
»*T
ISl
-ii:
III
Si; -!Si
jc cr
10*
122
TOO
Iil
.Si;
Jm
Ml
2*2
IS*
I
- ilf .
21«
IS;
|*o
E
21*010
J
ST2 * SW
ii:
- 1*0
=C
120 1 IlT
’ .t.
.t.
.PV1
2 0 » " 20*
IIT1 t
in -in
!Si -E
*1*
-*T 2
2io
2*
0 mi
211
Sii i!H
!m “
-12T
.Tl
11»
-111
Tl
10*
-* l
IlO
y •-,i.
«0«
• Each group of numbers contains I, 10Fo, and IOF..
2TS
* *I
410
I
I**
112
2**
IOS
I
ITT
-IM
-U S
-2 *
IS *
I
IS -JS
- J j 4. * - { j ,
100
IM
- 20*
7 .Ti
i ' ‘.ih
1F -Hi
1*1
IT *
C 'Z
j,J
-
-
j*s * 1*2
E r
E'
Tm*Al
::: ti:
f 22T
-1ST
-S M
E l f TJ
' s
; |m
MO
2*2
2**
-2 * 2
HO
Fio'1?
*2T -12«
2*1
V1
1*2 -I**
SZXE
IMlf iU
sr. rZ
1*T
2*1
21* * 221
IT I
I* *
MO - I S *
1*0 -ITO
?«. ; {,s
SH ES
. 0 IOOT
212
ITO " I S I
E "Si
I" Zr
112
S*
2*.
12*
-* *
2*0
1*2 - I * *
Ml
202
S IO I
E
in: 'Si
Si:
-*»*
-H S
20*
Iii
10*
-* !*
H l
i; it4,
iii
'»• Im
-i*n
MT * A t
,4t 2
t“n T
11*
IS *
2SS
Ml
1*9
-2 0 0
? T * ‘ a ITi *
I M 11- I * *
II*
111
* 1 * 1
101 -**
- r .'7
SH SSi
- 1.L
*22
I* *
20S
-* M
MS
I* *
MS
204
IS *
IS * ' - I I *
|2 S * 2 * |
E" Z
STT
MO
iIT..1
1.i.
* -1 * 4
21*
2*1
M2
‘
"n
M*
» * l 2 *02
'Si "'Si
IS*1IS*
21* -21«
212
- I* * !! 7
12*
III
201
UO
no
i I
fU
i.
IO*
-2 * 7
-T l
I:...,
JS
T2*1
2*4
22T
SZ‘"!Z
“* :Si!
i s ’-!:«
' -I.,
IS#
- 22*
1*2
-U l
IS *
1*0
lie -us
tI *,»
1,U
* -1 * 0
»
M L
IT l
IT l
12$ - I M
to. 11 :»
°-u
? 2
t: “2!
I
122 -1 2 2
S 10 I
22*
21*
-O
O L
SO - I U
20* - 2 * 2
. . T
I l
4
iii
!Ti -I
::s
X !1
I S -I
-ii
E ..I-T
M
T
i:
i1?,0
MO * 12»
T
:« • a.
2**
M
I -Ml
2*4
202
1*2
11»
O
r i 212
12 12
is 1
Ut -7,
=C-=S
=S".Cl
1S IU
21»° 2*1
IS*
HO
*2»»
-IM
p .f
- m 12 lU
7 ' . 'I'
,H
,2V T
1*1
1S Ut
I f i
iii
1SS SSi
21*
JTl
" !TSn ItT*
E
*
2*0
MT
IT S 12- I S I
10*
10*
*
* L
112
I**
ii.
it: s :
220 * 2 M
ii*
*2 -iso
211
MT - IS *
* * l
111
IM
- fZf E
*l M
I* *
F
IlT O
IM * -117
I**” IT*
7 ,
E E
i..'1
22* ii*
. i**,.
l*T
I UI
IZiZZ
Sii Ei
SZ«T
II*
IM
I
T L
20* - 21»
ITS
MO
-112
1*1
2., ’ J,
22
201
I OI
10*
IT2
* 12 I
IS * - I * *
-s»
TO*
- j: ,-T
iii I
s i 1 1S 1SI
-*
2 S*
E ih
22*
=S ■ *
I:
l:
,'T
IS IS
122 ’ -I
E
SiXE
21*2IO-1*L2
2 OI
;%
llf
.
1SS "l02
-IOT
1ST
iti UT
1*2» 0 I S l*
12*'-1*1
SO* * 1*2
E
lie -112
z,
2«* 0 ^ T
5 i
E"-,C
I
Ii"12Iii
E* E
Sm11-E
1 4
E -iii
!'I
IM
,= = ;
E "I
s
E -Ii
Ml
IiS -TO
^
E
iL'.
IM
Z
-D i
- |»"Z
I i
ii
I Si
I
11 T l 1112*
i:S‘"E
I
'I!
" |T T ° p i
:?!i
;;;
120
- r . u.
-H
E ifE
D* Z
EXE
S«“"!s!
iii
OT
E ' -2*2T
21
-Ml
-•«
-S
r,
... " iii
.Ti
I I
•C-2
in
1” / r
- E '. I
ISO
111
111 -M T
ITT
111
- »
* I
2
111
14*
:::
172
I* *
OO
-1 * 0
22*
21*
" E * fTT
-
f -i.
2 1 * * 22*
121 - I S *
no -is*
E 1ST
*X..-T
1X
,-L
•z?
38
F I G U R E 2.
C o o rd in a tio n A ro u n d the T itan iu m A to m
i n T i C l 2 ( O C 6 H 5) 2 D i m e r .
39
T h e tw o t i t a n i u m - c h l o r i n e d i s t a n c e s a r e n e a r l y t h e s a m e ,
2. 219(6) a n d 2. 20 9(6) A,, a n d a r e s l i g h t l y l o n g e r t h a n t h o s e r e p o r t e d
f o r T i C l 4 , i. e. , 2. 185 A (27).
T h e p l a n e f o r m e d b y t h e two . t i t a n i u m s , t h e b r i d g i n g o x y g e n s
0 ( 4 ) a n d 0 ( 4 ' ) , a n d . t h e c a r b o n s C(6) a n d C ( 6 ' ) is p l a n a r to w i t h i n th e
s t a n d a r d e r r o r of t h e d e t e r m i n a t i o n .
of t h e a t o m s , f r o m t h e p l a n e i s 3 x 10
T h e s u m of t h e s q u a r e d e v i a t i o n s
-8
Z
A .
T h e tw o t i t a n i u m s , t h e
t w o b r i d g i n g o x y g e n s , a n d t h e o t h e r tw o n o n b r i d g i n g o x y g e n s a l s o l i e
n e a r l y in a p l a n e .
T h e s q u a r e d e v i a t i o n f r o m t h e p l a n e i n t h i s c a s e is
3 x IO '4 A 2.
T i t a n i u m - i s p e n t a c o o r d i n a t e d , t h e c o o r d i n a t i o n b e i n g : i n th e f o r m
. of a d i s t o r t e d t r i g o n a l b i p y r a m i d .
F i g u r e 2 shows the c o o rd in a tio n
w i t h s o m e of t h e b o n d a n g l e s , t h e o t h e r s b e i n g l i s t e d . i n T a b l e X.
The
e q u a t o r i a l p l a n e i s f o r m e d b y T i , C 1(2), C l ( 3 ) , a n d 0 ( 4 ) a n d . t h e s u m
<of t h e s q u a r e d e v i a t i o n of t h e s e a t o m s , f r o m a p l a n e i s 4 x 10
-2
2
A ,.
T h e a p e x o x y g e n 0 ( 4 ' ) f o r m s the: l o n g e s t T i - O b o n d , w h i l e t h e o t h e r
a p e x o x y g e n 0 ( 5 ) f o r m s , t h e s h o r t e s t , t h e d i f f e r e n c e . b e i n g a l m o s t 0. 4 A.
. A n e s p e c i a l l y n o te w o r th y f e a t u r e is the u n u s u a l l y l a r g e bond
a n g l e f o r C,( 1 2 ) - 0 ( 5 ) - T i .
The angle is 1 6 5 .9 °.
The o th e r oxygen bond
angles a re T i - 0 ( 4 ) - T i' = 108.5°, T i-0 (4 )-C (6 ) = 123.2°, and T i ' -0 (4 )C ( 6) = 128. 3 ° .
T he angle at 0 ( 5 ) is m o s t unusual.
A n-oxygen bond
a n g l e of 18 0 ° h a s b e e n o b s e r v e d . i n t h e p y r o p h o s p h a t e a n i o n b y L e v i
T
s
40
a n d P e y r o n e l (28),. in C l ^ R u - O - R u C l ^ b y M a t h i e s o n , M e l l o r , a n d
S t e p h e n s o n (29), a n d . i n [ T i G l 2 ( C 5H 5 )] 20 b y C o r r a d i n i a n d A l l e g r a (30).
A n o x y g e n b o n d a n g l e of a b o u t 150° h a s b e e n o b s e r v e d . i n H 5S i - O - S i H 5
b y s e v e r a l a u t h o r s (31).
T h e c a s e in T i C l 2 ( O C ^ H 5 )2 i s s o m e w h a t
d i f f e r e n t in t h a t t h e t w o a t o m s a t t a c h e d . t o o x y g e n a r e d i f f e r e n t , w h e r e a s
t h e o t h e r s , i n v o l v e t h e s a m e k i n d of a t o m o n e a c h s i d e of t h e o x y g e n .
It
should, a l s o b e n o t e d . t h a t the. b o n d d i s t a n c e b e t w e e n C( 12) a n d 0 ( 5 ) is
short,
I. 36(2) A ,, s u g g e s t i n g a p a r t i a l d o u b l e - b o n d c h a r a c t e r , a n d
a l s o th e O ( S ) - T i d is ta n c e , is s h o r t ,
I. 7 4 4 A .
T h e T i - O d i s t a n c e in
r u t i l e is 1 .9 8 8 A, a n d th is is a s s u m e d t o b e .io n ic .
In ( T i C l 2C 5H 5 )2O
t h e T i - O d i s t a n c e , i s 1 . 7 8 A , and,.in t h i s C o r r a d i n i a n d A l l e g r a p o s t u l a t e
a p a r t i a l double -bond c h a r a c t e r a r i s i n g ,fro m donation-of e l e c tr o n s f r o m
p
a n d P^ f i l l e d o x y g e n o r b i t a l s t o t h e d : U n f i l l e d t i t a n i u m o r b i t a l s .
The
s a m e s p h y b r i d i z a t i o n i s p o s t u l a t e d . f o r t h i s , o x y g e n in T i C l 2 ( O C ^ H 5)2 .
B e c a u s e , of t h e p l a n a r n a t u r e of t h e 0 ( 4 ) b o n d s a n d t h e f a c t t h a t
t h e s e a r e d i r e c t e d a t n e a r l y 1 2 0 °, w e p o s t u l a t e t h i s o x y g e n i s s p
h y b r i d i z e d a n d h a s t h r e e 0"b o n d s .
2
T h e r e m a i n i n g , l o n e p a i r of e l e c t r o n s
i s a p p a r e n t l y i n v o l v e d . i n a tt b o n d w i t h f h e 3 - d . o r b i t a l s of t i t a n i u m .
Tnr
TT
P A R T III
S T R U C T U R E O F T H E FIR ST HYDROLYSIS P R O D U C T
O F T E T R A E T H O X Y T I T A NI U M (IV )
P rev io u s S tru c tu ra l Investigations
■ I n v e s ti g a ti o n s of t h i s c o m p o u n d w a s b e g u n s e v e r a l y e a r s a g o b y
W i t t e r s , w h o s e p r e l i m i n a r y i n v e s t i g a t i o n i s r e p o r t e d . i n . h i s t h e s i s (5).
W i t t e r s fou nd, f r o m , l a t t i c e p a r a m e t e r s a n d s y s t e m a t i c e x t i n c t i o n s t h a t
t h e s p a c e g r o u p w a s PZ^ / a.
Conditions, f o r re fle c tio n s to e x is t w e r e
k = Zn f o r t h e OkO r e f l e c t i o n s a n d h = Zn f o r th e h O l r e f l e c t i o n s .
T h e d e n s i t y of t h e c r y s t a l s w e r e d e t e r m i n e d by t h e f l o t a t i o n m e t h o d . i n
a b e n z e n e - c a r b o n t e t r a c h l o r i d e s o l u t i o n g i v i n g a d e n s i t y of I . 305 g / c m ^ .
C h e m i c a l a n a l y s i s of t h e c o m p o u n d . i n d i c a t e d t h a t it w a s t h e c o m p o u n d
w h i c h B r a d l e y (Z) h a d . a s s i g n e d t h e f o r m u l a T i ^ O ^ O C ^ H , . ) ^
H owever,
u s i n g , t h e m e a s u r e d d e n s i t y , c e l l v o l u m e a n d . t h e m o l e c u l a r w e i g h t of
B r a d l e y ' s p r o p o s e d c o m p o u n d , W i t t e r s . o b t a i n e d a c a l c u l a t i o n of 9. 5
m o l e c u le s p e r un it c e l l . . F r o m t h i s c a lc u la tio n it w a s ev id en t that
s o m e t h i n g w a s w r o n g i n t h e f o r m u l a a n d s t r u c t u r e p r o p o s e d by
B radley,
b u t h e w a s u n a b l e to s o l v e .the s t r u c t u r e f r o m t h e e x t r e m e l y
c o m p lic a te d P a tt e r son m ap.
w eight peaks.
T h is w a s due m a i n l y to th e m a n y m u l tip l e
A T i - T i v e c t o r w o u l d g i v e a c a l c u l a t e d p e a k h e i g h t of
5. 7 b u t t h e p e a k s i n P a t t e r s o n m a p w e r e a s h i g h a s 310.
W itte rs then
t u r n e d h i s a t t e n t i o n t o t h e s t r u c t u r e of t h e u n h y d r o l y z e d a l k o x y t i t a n i u m ( I V )
I
42
c o m p o u n d s in h o p es th a t th e ir s i m p l e r s t r u c t u r e s m ig h t sh ed a new
l i g h t on t h e h y d r o l y s i s p r o d u c t ,
. P r e p a r a t i o n - o f th e C o m p o u n d
The firs t hydrolysis product w as p re p a re d fro m fresh ly distilled
t e t r aethoxytitanium :(IV).
A s o l u t i o n of r a t i o I m o l e t e t r a e t h o x y t i t a n i u m (I V )
" ■- - :
•
.•
t o I 0 m o l e s of d r y b e n z e n e w a s p l a c e d . i n a n a p p a r a t u s w h i c h a l l o w e d
s lig h t ly m o i s t n i r t o g e n to p a s s o v e r the solution.
D ry nitrogen w as
slo w ly bu b b le d th r o u g h c o n c e n t r a t e d s u lfu ric acid, th r o u g h a tube f ille d
w ith s o d iu m h y d ro x id e pellets and fin ally over the solution.
s e v e r a l d a y s , c r y s t a l s of t h e h y d r o l y s i s p r o d u c t f o r m e d .
A fter
S e v e r a l of
t h e s e c r y s t a l s w e r e s e a l e d in P y r e x c a p i l l a r i e s a n d a d d i t i o n a l c r y s t a l s
w e re analyzed.
T h e s e w e r e s e a l e d . i n a g l a s s t u b e a n d s e n t to H u f f m a n
L a b o r a t o r y of W h e a t r i d g e , C o l o r a d o f o r a n a l y s i s .
T h e r e s u l t s of t h i s
a n a l y s i s a n d . t h o s e of W i t t e r s a n d B r a d l e y a r e g i v e n i n T a b l e XII.
F r o m B r a d l e y ' s a n a l y s i s t h e f o r m u l a w a s c a l c u l a t e d t o be T i ^ O ^ ( C ^ g
and f r o m the H uffm an L a b o r a t o r y a n a ly s is ,
Ti O
I
(C H )
Ct D l O
D e t e r m i n a t i o n of S p a c e G r o u p a n d C e l l D i m e n s i o n s
C o m p a r i s o n of W e i s s e n b e r g p h o t o g r a p h s of t h e s e n ew c r y s t a l s
w i t h t h o s e of W i t t e r ' s s h o w e d t h a t t h e c o m p o u n d s w e r e i d e n t i c a l .
A lso
t h e s p a c e g r o u p w a s c o n f i r m e d a n d c e l l d i m e n s i o n s n e a r l y th e s a m e .
T a b l e X I I I p r e s e n t s t h e c e l l d i m e n s i o n s a s c a l c u l a t e d f r o m the
43
T A B L E X II
C h e m i c a l A n a l y s i s of t h e - H y d r o l y s i s P r o d u c t
of T i ( O C 2H 5 )4
B r a d l e y (2)
Ti
26.1%
, W i t t e r s (5)
25. 9%
Huffman Labs.
27. 2%
C
34. 6% ■
H
7. 2%
OEt
residue
67. 7%
65. 0%
6.2%
7.8%
44
T A B L E X II I
S u m m a r y of t h e C r y s t a l D a t a f o r T i Cl (C H )
7 24 2 5 1 9
a = 27. 99(1 )
b = 22. 42(1)
c = 23. 21.(1)
P = 11 7 ° I 5'
Space Group
P 2^/a
.M olecules p e r unit cell
8
' dm e«.- * 'i; 305
d c a l c . ^ 1 - 3 04 8 / c m 3
M o l e c u l a r w e i g h t b a s e d on d e n s i t y
1272
M o lecu lar w eight b ased.on analysis
1271
45
diffractom eter.
In c lu d e d in the ta b le is th e m e a s u r e d an d c a l c u l a t e d
d e n s i t y u s i n g . t h e r e s u l t s of t h e c h e m i c a l a n a l y s i s a s s u m i n g e i g h t
m o l e c u l e s p e r unit, c e l l a n d s e v e n t i t a n i u m s p e r m o l e c u l e .
C o l l e c t i o n of t h e D a t a
A c r y s t a l w i t h a p p r o x i m a t e d i m e n s i o n s of 0. I x.O. I x 0. 5 m m
w as s e le c te d .fo r intensity m e a s u r e m e n ts .
The lin e a r absorption
c o e f f i c i e n t u s i n g C u K a r a d i a t i o n is 78. 2 c m
r a d i a t i o n i t i s 9. 0 c m
-1
.
-1
, w h i l e w i t h M o Kcx
T o a v o i d t h e n e c e s s i t y of c o r r e c t i n g . f o r
a b s o r p t i o n , ■M o Kot r a d i a t i o n w a s u s e d .
T h e in te n s ity d ata w e r e c o lle c te d .o n a G e n e r a l E l e c t r i c X R D -5
d i f f r a c t o m e t e r in th e s a m e m a n n e r a s f o r . T iC l ( O C . H ) .
2
6 5 2
However,
, 4 0 s e c o n d s c a n s w e r e . n e c e s s a r y b e c a u s e of t h e d a n g e r of o v e r l a p p i n g
peaks.
O v e r 6000 r e f l e c t i o n s w e r e c o l l e c t e d u p to a 29 a n g l e of
40 d e g r e e s .
No re fle c tio n s could be o b s e r v e d above th is angle.
Of
t h e s e 6000 r e f l e c t i o n s only, 919 w e r e e n o u g h a b o v e b a c k g r o u n d t o b e
c o n s i d e r e d . o b s e r v e d ( > 200 c o u n t s ) .
The reaso n for the sm all num ber
of o b s e r v a b l e r e f l e c t i o n s i s t h a t t h e c r y s t a l w a s s m a l l i n o r d e r to be
a b l e t o s e p a r a t e t h e c l o s e l y s p a c e d r e f l e c t i o n s a n d b e c a u s e of m a n y
e x t i n c t i o n s d u e to a d d i t i o n a l p s e u d o - s y m m e t r y a n d a . s u b c e l l in t h e c e l l .
A l s o i n v o l v e d . i s t h e h i g h t h e r m a l v i b r a t i o n s w h i c h h a v e p r o v e d . t o b e so.
c h a r a c t e r i s t i c of t h e s e t i t a n i u m . c o m p o u n d s . (5)(4).
A lth o u g h th is is n o t
en o u g h d a ta to r e s u l t in a h ig h ly a c c u r a t e s t r u c t u r e d e t e r m i n a t i o n , it
____ _______ ___________ — — ?---- 1----------------- n— v 1—r -------------- irm
ru n
ITT
46
is c e r t a i n l y ad e q u a te to d e t e r m in e the s t r u c t u r e u n e q u iv ic a lly as to its
atom arran g em en t.
D e t e r m i n a t i o n of t h e S t r u c t u r e
S in c e a l l p r e v i o u s a t t e m p t s to s o lv e the s t r u c t u r e - f r o m . t h e
P a t t e r s o n m a p h a d f a i l e d , it w a s d e c i d e d to a p p ly th e d i r e c t m e th o d s
of s y m b o l i c s i g n s d e s c r i b e d e a r l i e r .
The stru c tu re facto rs w ere
n o r m a l i z e d u s i n g t h e n u m b e r of e a c h a t o m - t y p e e x p e c t e d , f r o m t h e
c h e m i c a l a n a l y s i s r a t h e r t h a n f r o m the; p r o p o s e d f o r m u l a
T i O (OC H )
.
6 4
Z 3 16
201 n o r m a l i z e d s t r u c t u r e f a c t o r s
g r e a t e r t h a n I. 5- in m a g n i t u d e w e r e u s e d t o c a l c u l a t e t h e
A b o u t 9 0 0 0 r e l a t i o n s w e r e c a l c u l a t e d in t h i s c a s e .
y
relations.
T h re e origin d e t e r ­
m ining signs and four sym bolic signs w e r e assig n ed .
A fter' several
p a s s e s of a s s i g n i n g s y m b o l i c s i g n s t o t h e r e f l e c t i o n s , a l l t h e s y m b o l i c
sig n s e x c e p t one w e r e e lim in a te d .
Then these 2 0 1 reflections w e re u se d
t o d e t e r m i n e t h e s i g n s of 9 4 a d d i t i o n a l n o r m a l i z e d s t r u c t u r e f a c t o r s
b e t w e e n I. 2 a n d . I. 5 i n m a g n i t u d e .
t h e o ne a r b i t r a r y c h o i c e of s i g n .
Two E -m a p s w e r e calculated w ith
B oth E -m a p s gave the s a m e m o l e c u l a r
s t r u c t u r e , b u t o n e of t h e m p l a c e d t h e m o l e c u l e s t o o c l o s e t o g e t h e r . . t o
be c h e m ic a lly r e a s o n a b le .
A l l t i t a n i u m s a n d o x y g e n s c o u l d be l o c a t e d
on t h e E - m a p .
A t th i s point, it w a s fe lt th a t th e h y d r o l y s i s p r o d u c t w a s p r o d u c e d
e i t h e r by tw o t r i m e r s c o n d e n s in g ,to f o r m the f i r s t h y d r o l y s i s p r o d u c t o r
47
b y a d d i t i o n - o f a d i m e r , w i t h a s t r u c t u r e s i m i l a r to t h a t of d i c h l o r o d i p h e n o x y t i t a n i u m ( I V ) , t o a t e t r a m e r , w i t h t h e s t r u c t u r e of th e
tetraethoxytitanium .
titanium s.
B o t h of t h e s e w o u l d g i v e a m o l e c u l e w i t h s i x
O n e a c h - o f t h e t w o m o l e c u l e s in t h e a s y m m e t r i c u n i t t h e r e
w e r e sev en titanium ' peaks.
Two. of t h e s e w e r e s m a l l e r t h a n t h e r e s t
a n d it s e e m e d t h a t e i t h e r t h e E - m a p h a d . n o t b e e n a b l e t o t e l l w h i c h
p la c e to put the .titanium , or th a t th e one t i t a n i u m w a s r a n d o m l y l o c a t e d
in the two p o s itio n s.
F r o m the s t r u c t u r e - o f the s u s p e c t e d com pound,
the la tte r condition w ould not be at all u n re a s o n a b le .
The R -index for
puttin g th e t i t a n i u m in-one o r the o th e r p o sitio n w a s th e s a m e (about
40%).
By p u ttin g h a l f a tita n iu m , in e a c h p la c e th e R - i n d e x w a s d e c r e a s e d
a n d on r e f i n i n g w i t h t h e f u l l - m a t r i x l e a s t s q u a r e s p r o g r a m , t h e R - i n d e x
l o w e r e d t o 28%.
B y p u t t i n g ;in p o s s i b l e c a r b o n a t o m s , t h e R - i n d e x i v a s
further-low ered.
A t t h i s p o i n t , a r e - e x a m i n a t i o n of t h e c h e m i c a l a n a l y s i s i n d i c a t e d
th a t s e v e n t i t a n i u m s f i t the a n a ly s is m u c h b e tte r th a n six.
If t h e c h e m i c a l
a n a l y s i s w e r e c o r r e c t , t h e c o m p o u n d s h o u l d be T i O
C H .
i l*4 oo / o
P utting
in the s e v e n t i t a n i u m atom s- l o w e r e d th e R - in d e x a b o u t tw o p e r c e n t m o r e .
B y t h e u s e of F o u r i e r m a p s a n d d i f f e r e n c e F o u r i e r m a p s , m a n y p o s s i b l e
c a r b o n p o s itio n s w e r e found, alth o u g h not a ll the c a r b o n a to m s co u ld be
located.
T h e l i m i t e d a m o u n t of d a t a d e c r e a s e d t h e r e s o l u t i o n of t h e
i n d i v i d u a l a t o m p o s i t i o n s w h i l e t h e d i s o r d e r m a n i f e s t e d . i t s e l f in h i g h
therm al param eters.
TT
T
4.8.
;
-R e f i n e m e n t of t h e - S t r u c t u r e
T h e h y d r o l y s i s p r o d u c t w a s r e f i n e d on a n I B M 7 0 9 4 c o m p u t e r
u s i n g t h e - O R F L S p r o g r a m a s m o d i f i e d b y S t e w a r t (33).
A ll reflectio n s
w e r e w eig h ed equally.
R e f i n e m e n t w a s s l o w b e c a u s e of t h e l i m i t e d
s i z e of t h e c o m p u t e r .
T h r e e p a s s e s of r e f i n e m e n t v a r y i n g d i f f e r e n t
s e t s of p a r a m e t e r s w e r e r e q u i r e d t o c o m p l e t e o n e c y c l e of r e f i n e m e n t .
T h e f i r s t s e t of r e f i n e m e n t i n v o l v e d 14 . t i t a n i u m , 48- o x y g e n , a n d 45
carbon atom s.
V a r y in g the p o s iti o n a l p a r a m e t e r s and..individual
i s o t r o p i c t e m p e r a t u r e f a c t o r s , t h e r e a r e 428 p a r a m e t e r s t o be v a r i e d .
F i v e t i t a n i u m a t o m s w e r e v a r i e d in e v e r y p a s s to t i e all the r e f i n e m e n t s
together.
titanium s,
A long w ith th e s e five tita n iu m a to m s , t h r e e additional
16 o x y g e n s , a n d 15 c a r b o n s w e r e a l l o w e d t o v a r y in e a c h
p a s s , i. e. , 157 p a r a m e t e r s w e r e a l l o w e d , to v a r y i n e a c h p a s s .
In
o t h e r w o r d s , a. 157 x 157 m a t r i x w a s r e q u i r e d t o b e b u i l t u p a n d s o l v e d
e a c h p a s s , of t h e f u l l m a t r i x r e f i n e m e n t .
18% a f t e r t w o c y c l e s .
T he R - in d e x w a s r e d u c e d to
A new F o u r i e r m a p and d iffe re n c e m a p w as
calcu la ted and additional carb o n ato m s w ere-lo cated .
S e v e ra l oxygen
a t o m s w e r e a d j u s t e d t o the. p o s i t i o n s o n t h e F o u r i e r m a p .
R efinem ent
w i t h t h e s e n e w c a r b o n s a n d a d j u s t e d o x y g e n p o s i t i o n s s t a r t e d . a t R = 22%
w i t h 128 a t o m s .
T w o a d d i t i o n a l c y c l e s of r e f i n e m e n t r e d u c e d . t h e R - i n d e x
t o 13%.
T he R -in d ex w ith ju s t tita n iu m and oxygen a to m s afte r r e f i n e ­
m e n t w a s 20%.
T a b l e XI V g i v e s t h e p o s i t i o n a l a n d t h e r m a l p a r a m e t e r s
I
TT
49
T A B L E XIV
T i a n d .O P o s i t i o n s , in T i ^ iO
X
Ti(I)
Ti(Z)
Ti ( 3 )
T i( 4)
' Ti(S)
' T i( 6)
Ti ( 7 )
Ti(B)
Ti ( 9 )
Ti ( IO )
T i(Il)
Ti(IZ)
Ti(IS)
T i ( l 4)
0(1)
0(2)
0(3)
0(4)
0(5)
0(6)
0(7)
0(8)
Q<9)
0(10)
0(1.1)
0(12)
0(13)
0(14)
0(15)
. 0(16)
0(17)
0.(18)
0(19)
0(20)
0(21)
. 313(1)
■. 1 8 6 ( 1 )
. 683(1)
, 803(1)
. 75 2(1)
. 878(1)
. 621(1)
. 214(1)
.196(1)
. 331(1)
. 336(1)
. 767(1)
. 638(1)
. 890(1)
. 321(6)
.360(3)
. 815(4)
, 679(3)
. 170(5)
. 238(6)
.379(3)
.798(3)
.150(3)
.258(9)
. 625(7)
. 670(5)
. 7 59( 2)
. 885(8)
.137(5)
. 74 1(2)
. 888(7)
.628(3)
.711(5)
. 809(3)
. 584(3)
y
.
. 010(1)
. O08(D
. 030(1)
.017(1)
. 085(1)
. 082(1)
. 098(1)
. 236(1)
. 2 40 (1 )
. 255(1)
.239(2)
. 1 82 (1 )
.174(2)
. 169(1)
. 021(7)
. 069(3)
■ . 01 9(5)
. 029(4)
. 020(5)
. 066(6)
.039(3)
.036(3)
. 051(3)
■ . 058(9)
. 075(7)
. 051(5)
.038(2)
. 069(8)
J 078(6)
. 071(3)
.081(8)
. 099(4)
. 14 7( 6)
• .135(4)
• .151(4)
(Et)
19
Z
94 6(2)
. 88 4(1)
' . 88 1(2)
.935(1)
.010(1)
. 07 2(1)
.945(1)
- . 555(1)
.371(1)
. 43 8(1)
. . 613(2)
. 502(2)
. 43 4(2)
. 555(1)
. 88 4(8)
. 9 84 (4 )
. 03 8(5)
. . 9 81 (4 )
. 81 0(6)
, . 075(7)
.146(4)
. 85 9( 4)
. 039(4)
. 925(11)
.,041(8)
.791(7)
.087(2)
.158(10)
.883(6)
.926(3)
. 982(9)
. 87 4( 5)
. 014(7)
. 04 4(4)
. 9 42 (4 )
B
.
6.96
.86
6.28
2.80
2.92
5.89
5. 05
2.89
3. 52
5. 46
7. 92
3. 11
9. 29
4. 38
10. 60
2. 87
6. 36
5. 21
8. 05
8. 45
2.68
I. 43
1.14
I 0. 27
6.65
9.16
0. 00
11.06
4. 53
. 97
I. 00
5. 67
3.92
I.. 28
6.58
50
T A B L E X IV ( C o n t in u e d )
T i a n d .O P o s i t i o n s in T i ^ O ^ ^ E t )
0(22)
0(23)
0(24)
0.(25)
0(26)
0(27)
0(28)
0(29)
0(30)
0(31)
0(32)
0(33)
0(34)
0(35)
0(36)
0(37)
0(38)
0(39)
0(40)
0(41)
0(42)
0(43)
0(44)
0(45)
0(46)
0(47)
0(48)
x
Y
z
.928(6)
9.42(6)
. 565(8)
. 390(5)
.167(4)
. 269(4)
. 26 5(6)
w379(5)
. 885(4)
. . 885(4)
. 7 72( 5)
.952(5)
. 640(5)
. 644(4)
. 341(6)
. . 845(5)
. 221(3)
. 703(4)
. 831(2)
.193(3)
.719(4)
. 810(5)
.772(4)
. I 63(6)
. 582(3)
. . 596(5)
. 9 29( 4)
. I 32(7)
. . 04 5(7)
. 047(8)
.169(6)
.180(4)
.187(5)
.187(6)
.196(5)
. 17 1( 6)
.187(5)
■. 21 1(6)
. 21 8(5)
.195(5)
' .197(4)
. 23 6( 8)
■ . 2 2 6 (5 )
. 245(5)'
, . 23 4(4)
■ . 23 0(2)
. 2 52 (3 )
. 1 05 (5 )
. . 11 2(6)
. 18 4( 4)
■ .173(7)
. 21 9(3)
■ . 093(5)
. 098(6)
.113(7)
.11,2(8). 902(10)
. 614(7)
; 36 1(5)
. 57 3(5)
■ . 4 2 0 (7 )
. 4 6 0 (6 )
. 4 6 6 ( 6)
. 648(6)
. 58 4(7)
. 603(6)
. 35 2(6)
. 51 2(5)
. 695(8)
■ . 53 3(6)
. 627(4)
.476(5)
. 35 9(3)
. 29 7( 4)
. 4 69 (5 )
. . 500(7)
. 4 3 3 (5 )
. 524(7)
■ . 393(3)
. . 413(6)
.591(6)
.
B
9. 06
I 0. 67
12 . 69
8. 50
3.12
4. 08
11.49
1.75
6.98
5. 08
6. I 5
6. 36
6.99
7.17
14. 56
8.86
6.94
3. 73
1.88
6.27
6.49
9. 65
3. 35
10. 85
2. 10
10. 97
I 0 . 49
51
f o r t h e t i t a n i u m a n d o x y g e n a t o m s .w i th t h e i r ■s t a n d a r d d e v i a t i o n s .
F i g u r e 3 g i v e s t h e s t r u c t u r e of o n e of t h e t w o a s y m m e t r i c m o l e c u l e s
in the u n it c e l l w ith th e a v e r a g e bon d d i s t a n c e s .
T a b l e XV l i s t s t h e
b o n d d i s t a n c e s a n d T a b l e X V I l i s t s t h e b o n d a n g l e s of t h e t i t a n i u m a n d
oxygen ato m s.
T a b l e XVII l i s t s the -o b s e r v e d a n d c a l c u l a t e d s t r u c t u r e
I
factors.
■D i s c u s s i o n of t h e S t r u c t u r e
T h e u n it c e l l c o n ta in s 8 m o l e c u l e s ; thus t h e r e a r e 2 m o l e c u le s
of t h e h y d r o l y s i s p r o d u c t in t h e a s y m m e t r i c u n i t .
T h ese m olecules
a r e r o u g h l y r e l a t e d b y a g l i d e in t h e c d i r e c t i o n l o c a t e d a t y = 1 / 8 a n d
a l s o , t h e r e i s n e a r l y a tw o f o l d a x i s l o c a t e d b e t w e e n t h e c e n t e r s of
s y m m e t r y on t h e a c p l a n e .
T h e s e two f a c t o r s a c c o u n t e d fo r the m a n y
e x t i n c t i o n s s i n c e t h e y c a u s e m a n y r e f l e c t i o n s t o be u n o b s e r v a b l e .
A l t h o u g h th e u n i t c e l l c o n t a i n s a c e n t e r of s y m m e t r y , t h e m o l e c u l e
does not.
I t d o e s c o n t a i n a n a p p r o x i m a t e t w o - f o l d a x i s of r o t a t i o n .
T h e t i t a n i u m a t o m s a r e e a c h s i x - c o o r d i n a t e d to o x y g e n s in d i s t o r t e d
octahedrons.
T h e T i - O bond d i s t a n c e s v a r y c o n s i d e r a b l y , the s h o r t e s t
b e i n g I. 6 A a n d t h e l o n g e s t 2. 9-A .
T h e s t a n d a r d d e v i a t i o n s of t h e s e
a t o m s a r e 0. 3 A , w h i c h a r e l a r g e , t h e r e f o r e t h e a c t u a l b o n d l e n g t h s
a r e quite u n c e r t a in .
In T i ( O C H ^ ) ( O C ^ H ^ ) ^ (5) t h e T i - O b o n d d i s t a n c e s
v a r y f r o m I. 5 A t o 2. 5 A , in T i ( O C H )^ (34) t h e d i s t a n c e s v a r y f r o m .
I. 8 A t o 2. 4 A , a n d in T i ^ O ^ (26) t h e y v a r y f r o m 1. 8 t o 2. 7 A.
The
52
F I G U R E 3.
A r r a n g e m e n t of T i t a n i u m s a n d O x y g e n s
m T i 7 O2 4 ( C 2 H 5) 1 9 .
53
. T A B L E XV
(a)
Bond D is ta n c e s '
Between- T i t a n i u m and O x y g e n A to m s
in T i 7O 2 4 ( C 2H 5 )19
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(L)
Ti(I)
- O(I)
- 0(2)
- 0(4)
- O(IQ)
-0(11 )
-0(13)
Ti(Z)
Ti(Z)
Ti ( Z )
Ti(Z)
Ti(Z)
Ti(Z):
_
. I. 6'A
1.8
I. 8
1.8
2.5
2. I
0(3)
0(5)
0(10)
0(13)
0(14)
0(15)
1.9
I. 6
2. O
1.7
2. 5
2. I
Ti(3) - 0(4)
T i ( 3) - 0 ( 6 )
Ti(3) - 0 .( 7 )
T i(3)\- 6(12)
T i ( 3 ) - 0 ( 1 6)
Ti(3) - 0 (18)
2.4
2. 9
2.2
2. O
1.7
2,1
Ti(4)
Ti(4)
T 1(4)
Ti(4)
Ti(4)
Ti(4)
-
0(3)
0(6)
0.(8)
0(9)
0(16)
0(17)
2.3
2. I
1.8
1.9
2. O
2. 5
Ti(5)
Ti(5)
T i (S )
T i (S )
Ti(S)
Ti(S)
-
0(3)
0(4)
0(13)
0(16)
0(19)
0(20)
■
2.2
2.2
2.0
1.9
1.8
1.8
Ti(6)
Ti(6)
Ti(6)
Ti(6)
Ti(6)
Ti(6)
-
0(3)
0(14)
0.(17
O(20)\
0(22)'
0(23)
2. I
1.9
2. 2
2. I
1.7
1.8
Ti(7)
Ti(7)
Ti(7)
Ti(7)
Ti(7)
Ti(7)
-
0(4)
0(11)
0(18)
O(W)
0(21)
0(24)
2. I
2. 2
1.7
2. 5
1.6
1.8
Ti(8)
Ti(8)
Ti(8)
T i ( 1S)
Ti(8)
Ti(8)
-
0(27)
0(32)
0(35)
0(38)
0(39)
0(45)
1.8
-1.9
2. 3
1.6.
1.8
1.9
Ti(9)
Ti(9)
Ti ( 9 )
Ti(9)
Ti(9)
Ti(9)
-
0(2:$)
0(28)
0(34)
0(39)
0(41)
0(44)
1.6
. 2.1
2. 0
2. 4
1.7
2. 5
Ti ( IO )
Ti ( IO )
Ti(IO)
Ti ( IO )
T i ( l 0)
Ti(IO)
-
0(28)
0(29)
0(30)
0(37)
0(40)
0(44)
2. 3
1.8
2. I
2. I
1.9
2. I
T i(Il)
T i(Il)
T i(Il)
T i(Il)
T i(Il)
T i(Il)
- 0(25)
- 0(27)
- 0(31)
- 0(32)
-,0(36)
- 0(37)
2. 2
2. 0
2. I
2. 0
1.9
2.1
.
W - f .1 “• »■
.:55:fr :
T i ( I Z)
Ti(IZ)
T i ( l 2)
Ti(IZ)
Ti(IZ)
Ti(IZ)
- 0(32)
- 0(37)
- 0(39)
- 0(42)
-0(43)
- 0(44)
2, 0
2. 2
2. 0
'
I
2. 0
1.7
T i ( l 3)
Ti(13)
T i ( l 3)
T i ( l 3)
T i ( l 3)
T i ( l 3)
-0(34)
- 0(35)
- 0(39)
- 0(42)
- 0(46)
- 0(47)
2.. 0
1.8
2. I
2. 5
1.7'
2.1
Ti(l
Ti(l
Ti(l
T,i(l
Ti(l
Ti(l
-
2..0
2. 3
1.9
I .. 7
2.4
1.9
4)
4)
4)
4)
4)
4)
0(30)
0(31)
0(33)
0(37)
0(43)
0(48)
• \'
(a) T h e s t a n d a r d d e v i a t i o n . o f the, b o n d s a r e a p p r o x i m a t e l y . 2A
56
"
'
B o n d A n g l e s , of
■>
T A B L E XVI L -
' -
' . ’
.
. 1
'A round T itanium and Oxygen A tom s
A tom s
A ngle
0 ( I)
OC I )
0 ( I)
0 ( I)
0 ( I)
0 ( 2)
u9( 2)
0 ( 2)
0 ( 2)
0 ( 3)
0 ( 3)
0 ( 3)
0(10)
0.(10)
0.(11)
- Ti(I)
. Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
- Ti(I)
-T i(I)
- Ti(I)
- 0(2)
r 0(2)
- 0.(10)
- 0(11)
- 0(15)
- 0(4)
-0(10)
- 0(11)
- 0(13)
- 0(10)
- 0(11)
- 0(13)
- 0(11)
- 0(13)
- 0(13)
0 ( 3)
0 ( 3)
0 ( 3)
0 ( 3)
0 ( 5)
0 ( 5)
0 ( 5)
0 ( 5)
O lO
0(10)
O(IO)
0(13)
0(13)
0,(14)
-
-
0 ( 4)
° ( 4)
0 ( 4)
O 4)
O 4)
O 6
0 ( 6)
0 ( 6)
0 ( 6)
0 ( 7)
0 ( 7)
0 ( 7)
0(12)
0(12)
0(16)
- T i ( 3)
- Ti(3
- ■Ti( 3)
- T i 3)
- T i 3)
-T i 3
- T i ( 3)
- T i( 3 )
- T i ( 3)
- T i ( 3)
- T i ( 3)
- T i ( 3)
- T i ( 3)
- T i ( 3)
- Ti( 3)
Ti (2 )
Ti(Z)'
Ti (2 )
T i( 2 )
T i( 2 )
Ti (2 )
Ti (2 )
T i( 2 )
Ti 2
T i (2)
Ti (2 )
T i( 2 )
Ti (2 )
Ti (2 )
'
87
I 57
97
81
104
98
92
101
I 58
I 04
76
78
166
68
98
0(5)
0(10)
0(13)
0(14)
0(10)
0(13)
0(14)
0(15)
0.(13)
O(IA)
0(15)
0(14)
0(15)
0(15)
160
1 00
81
77
100
107
84
, 89
71
■169
. 96
98
I 60
95
-0(6)
- 0(7)
- 0(12)
- 0 16) '
- 0 18)
- 0 7)
- 0(12)
-0(16)
- 0(18)
- 0(12)
-0.(16)
-0(18)
-0(16)
- 0(18)
-0(18)
91
83
162
83
74
87
I 06
80
1 65
97
I 61
92
100
88
97
57
0 ( 3) - Ti ( 4 ) - 0 ( 6 )
0 ( 3) - Ti ( 4 ) - 0 ( 8 )
0 ( 3) - T i( 4 ) - 0 ( 9 )
0(
3) - T i ( 4) - 0 ( 1 6 )
0(
3) - T i( 4 ) - 0 ( 1 7 )
0(
6)- T i ( 4 ) - 0 ( 8 )
0(
6)- T i ( 4) - 0 ( 9 )
0(
6) - T i ( 4 ) - 0 ( 1 6 )
0(
6) - T i( 4 ) - 0 ( 1 7 )
0 ( 8) - T i ( 4) ■- 0 ( 9 )
0 ( 8) - T i( 4 ) - 0 ( 1 6 )
0(
8) - T i( 4 ) - 0 ( 1 7 )
0(
9) - T i( 4 ) - 0 ( 1 6)
0 ( 9)) - T i( 4 ) - 0 ( 1 7 )
0 ( 1 6 ) - T i( 4 ) - 0 ( 1 7 )
87
I 64
87
79
84
107
67
96
152
I 04
94
86
.158
87
107
0(
3)0(
3) 0(
3) 0(
3) 0(
3)0 ( 4) Q( 4) 0(
4) 0(
4) 0(13) 0(13) 0(13) 0(16) 0(16) 0(19) -
T i ( 5) - 0 ( 4 )
171(5) - 0 ( 1 3 )
171(5) - 0 ( 1 6)
Ti( S) - 0 ( 1 9 )
Ti(S) - 0 ( 2 0 )
Ti(.5) - 0 ( 1 3 )
171(5) - 0 ( 1 6 )
Ti ( 5 ) - 0 ( 1 9 )
Ti ( 5 ) - 0 ( 2 0 )
Ti(S) - 0 ( 1 6 )
Ti(S) - 0 ( 1 9 )
Ti ( 5 ) - 0 ( 2 0 )
Ti (S) - 0 ( 1 9 )
Ti (S) - 0 ( 2 0 )
Ti(5) - 0 (2 0 )
.1 02
68
85
161
. 82
71
. 85
86
170
13 8
99
I 03
112
104
88
0(
3)0(
3)0(
3)0(
3)0(
3)0(14) 0(14) 0(14) 0(14) 0(17) 0(17) 0(17) 0(20) 0(20) 0(22) -
T i ( 6) - 0 ( 1 4 )
T i ( 6) - 0 ( 1 7 )
Ti ( 6 ) - 0 ( 2 0 )
Ti ( 6 ) - 0 ( 2 2 )
T i ( 6) - 0 ( 2 3 )
T i ( 6) - 0 ( 1 7 )
Ti(6) - 0 ( 2 0 )
T i ( 6) - 0 ( 2 2 )
T i( 6 ) - 0 ( 2 3 )
T i( 6 ) - 0 ( 2 0 )
T i ( 6) - 0 ( 2 2 )
T i ( 6) - 0 ( 2 3 )
T i ( 6) - 0 ( 2 2 )
Ti(6) - 0 ( 2 3 )
T i ( 6) - 0 ( 2 3 )
87
96
77
I 68
111
I 65
92
81
78
1.02
97
87
I 01
167
69
58
0 ( 4)
0 ( 4)
0 ( 4)
0 ( 4)
0 ( 4)
0(11)
0(11)
0(11)
0.(11)
0(18)
0(18)
0(18)
0(19)
0(19)
0(21)
-
Ti(7) - O ( H )
Ti ( 7 ) - 0 ( 1 8 )
Ti(T) - 0 ( 1 9 )
Ti (7 ) - 0 ( 2 1 )
Ti(7) - 0 ( 2 4 )
T i( 7 ) - 0 ( 1 8 )
Ti(7) - 0 ( 1 9 )
Ti(7) - 0 (2 1 )
Ti(7) - 0 ( 2 4 )
Ti(7) - 0 (1 9 )
T i( 7 ) - 0 ( 2 1 )
Ti(7) - 0 ( 2 4 )
Ti (7 ) - 0 ( 2 1 )
T i( 7 ) - 0 ( 2 4 )
Ti (7 ) - 0 ( 2 4 )
0(27)
0(27)
0(27)
0(27)
0(27)
0(32)
0(32)
0(32)
0(32)
0(35)
0(35)
0(35)
0(38)
0(38)
0(39)
- T 1(8) - T i( 8 ) - T i( 8 ) - Ti(8) - Ti (8 ) - Ti(8) - Ti(8) - Ti ( 8 ) - T 1(8) --Ti(S) - T 1(8) - Ti(8) - Ti(8) - Ti(8) - Ti(8) -
0(26)
0(26)
0(26)
0(26)
0(26)
0(28)
0(28)
0(28)
0(28)
0(34)
0(34)
0(34)
0(39)
0(39)
0(41)
- Ti(9) - 0 ( 2 8 )
- Ti(9) - .0 ( 3 4 )
- Ti(9) - 0 ( 3 9 )
- Ti ( 9 ) - 0 ( 4 1 )
- Ti ( 9 ) - 0 ( 4 4 )
- Ti(9) - 0 ( 3 4 )
- T 1(9) - 0 ( 3 9 )
- Ti(9) - 0 (4 1 )
- Ti(9) - 0 (4 4 )
- Ti(9) - 0 ( 3 9 )
- Ti ( 9 ) - 0 ( 4 1 )
- Ti(9) - 0 (4 4 )
- Ti(9) - 0 ( 4 1 )
- T i( 9 ) - 0 ( 4 4 )
- T i( 9 ) - 0 ( 4 4 )
76
90
. 73
I 62
94
1.65
84
87
.
92
■ 95
I 08
86
99
I 66
94
0(32)
0(35)
0(38)
0(39)
0(45)
0(35)
0(38)
0(39)
0(45)
0(38)
0(39)
0(45)
0(39)
0(45)
0(45)
■
.
.
■
‘
77
168
99
I 00
' 93
IQO
82
; 81
1 70
93
67
89
I 51
103
98
83
107
99
102
154
I 61
87
104
76
75
■90
■90
157
67
96
59
0(28)
0(28)
0(28)
0(28)
0(28)
0(29)
0(29)
0(29)
0(29)
0(30)
0(30)
0(30)
0(37)
0(37)
0(40)
-
Ti(IO)
Ti ( IO )
Ti ( IO )
T i ( IO )
Ti ( IO )
Ti(IO)
Ti ( IO )
T i ( IO )
Ti ( IO )
Ti(IO)
Ti ( IO )
Ti ( IO )
Ti ( IO )
T i( IO )
Ti ( IO )
-
0(29)
0(30)
0(37)
0(40)
0(44)
0(30)
0(37)
0(40)
0(44)
0(37)
0(40)
0(44)
0(40)
0(44)
0(44)
90
I 67
94
I 08
82
99
96
. 95
I 64
76
81
87
156
71
101
0(25)
0(25)
0(25)
0(25)
0(25)
0(27)
0(27)
0(27)
0(27)
0(31)
0(31)
0(31)
0(32)
0(32)
0(36)
-
T i(Il)
T i(Il)
T i(Il)
Ti(Tl)
T i(Il)
T i(Il)
T i(Il)
T i(Il)
T i(Il)
Ti(Il)
T i(Il)
T i(Il)
T i(Il)
T i(Il)
T i(Il)
-
0(27)
0(31)
0(32)
0(36)
0(37)
0(31)
0(32)
0(36)
0(37)
0(32)
0(36)
0(37)
0(36)
0(37)
0(37)
96
104
I 61
I 04
86
I 60
. 70
. 94
I 06
. 91
84
74
90
87
I 58
0(32)
0(32)
0(32)
0(32)
0(32)
0(37)
0(37)
0(37)
0(37)
0(39)
0(39)
0(39)
0(42)
0(42)
0(43)
-
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
T i ( l 2)
-
0(37)
0(39)
0(42)
0(43)
0(44)
0(39)
0(42)
0(43)
0(44)
0(42)
0(43)
0(44)
0(43)
0(44)
0(44)
85
75
112
121
157
117
I 50
. 81
79
92
158
98
69
89
72
60
0(34)
0(34)
0(34)
0(34)
0(34)
0(35)
0(35)
0(35)
0(35)
0(39)
0(39)
0(39)
0(42)
0(42)
0(46)
-
0(30)
0(30)
0(30)
0(30)
0(30)
0(31)
0(31)
0(31)
0(31)
0(33)
0(33)
0(33)
0(37)
0(37)
0(43)
- T i ( l 4)
- T i ( l 4)
- Ti(14)
- Ti(14)
- T i(H )
- T i(H )
- T i(H )
- T i(H )
- T i(H )
- T i(H )
-T i(H )
- T i(H )
- T i(H )
- T i(H )
- T i(H )
Ti(2)
Ti(2)
Ti(2)
Ti(4)
Ti(4)
T i (S )
Ti(I)
Ti(I)
Ti(I )
Ti ( 3 )
Ti(3)
Ti (S)
Ti(3)
-
T i ( l 3)
Ti(13)
T i ( l 3)
T i ( l 3)
Ti(13)
T i ( l 3)
Ti(13)
Ti(13)
T i ( l 3)
Ti(IS)
T i ( l 3)
T i ( l 3)
Ti(13)
Ti(13)
Ti(13)
-0 ( 3 )
-0 ( 3 )
-0 ( 3 )
-0 ( 3 )
-0 ( 3 )
-0 ( 3 )
-0 ( 4 )
-0 ( 4 )
-0 ( 4 )
-0 ( 4 )
-0 ( 4 )
-0 ( 4 )
-0 ( 6 )
-
-0(35)
- 0(39)
- 0(42)
- 0(46)
- 0(47)
- 0(39)
- 0(42)
- 0(46)
- 0(47)
- 0(42)
- 0(46)
- 0(47)
- 0(46)
- 0(47)
- 0(47)
1 49
84
93
75
1 05
72
I Ol
91
I 05
78
I 04
1 59
I 67
82
96
-
I 66
I 02
88
82
104
77
77
99
91
95
175
. 93
81
I 64
90
0(31)
0(33)
0(37)
0(43)
0(48)
0(33)
0(37)
0(43)
0(48)
0(37)
0(4-3)
0(47)
0(43)
0(47)
0(47)
Ti ( 4 )
Ti ( 5 )
Ti(6)
Ti(S)
Ti ( 6 )
T i ( 6)
T i ( 3)
Ti ( 5 )
T i( 7 )
Ti(S)
Ti ( 7 )
Ti (7 )
Ti (4 )
•
158
98
105
90
■95
95
151
107
117
80
88
97
72
.61
■Ti(.
Ti(
Ti(
Ti(
Ti(
Ti(
T i(
Ti(
Ti(
Ti(
Ti(
Ti(
I)
I)
I)
I)
2)
3)
3)
4)
4)
3)
5)
5)
-0(10)
-0 ( 1 1 )
-0(13)
-0 ( 1 3 )
-0(14)
-0 ( 1 6 )
-0 ( 1 6 )
-0(16)
-0(17)
-0(18)
-0(19)
-0(20)
-
Ti(Z)
Ti(7)
Ti(Z)
Ti(B)
Ti(B)
Ti(4)
Ti(B)
Ti(B)
Ti(6)
Ti(7)
Ti(7)
T i ( 6)
T i ( 8)
-0(27)
T i ( 9)
-0(28)
Ti(IO)
-0 ( 3 0 )
T i ( l I ) -0 ( 3 1 )
Ti(
8) - 0 ( 3 2 )
T i(
8) - 0 ( 3 2 )
T i( Il) - 0(32)
Ti(
9) - 0 ( 3 4 )
Ti(
8) - 0 ( 3 5 )
Ti(IQ) - 0 ( 3 7 )
T i ( IO )
-0 ( 3 7 )
Ti(IO)
-0 ( 3 7 )
T i( Il) - 0(37)
T i(Il)
-0 ( 3 7 )
-
T i(Il)
T i ( IO )
T i ( l 4)
T i ( l 4)
T i(Il)
T i ( l 2)
T i ( l 2)
T i ( l 3)
Ti(13)
T i(Il)
T i ( l 2)
T i ( l 4)
Ti(12j
T i ( l 4)
I 07
101
93
95
106
102
99
109.
107
14.3
. 94
1 02
88
1 13
T i ( l 2)
-0 ( 3 7 )
T i ( 8)
-0 ( 3 9 )
T i ( 8)
-0 ( 3 9 )
T i ( 8)
-0(39)
T i ( 9)
- 0(39)
T i ( 9)
-0(39)
T i ( l 2) - 0 ( 3 9 )
T i ( l 2) - 0 ( 4 2 )
Ti(IZ) - 0(43)
T i ( 9)
-0(44)
T i ( 9)
-0(44)
T i ( l 0)
-0(44)
- T i ( l 4)
- Ti(9)
- Ti(IZ)
- T i ( l 3)
—T i ( l 2)
- T i ( l 3)
- T i ( l 3)
- T i ( l 3)
- Ti(14)
- T i ( IO )
- Ti(IZ)
- Ti(IZ)
I 05
1 45
I 02
114
95
91
I 03
87
90
9Z
■ 99
1 12
.
109
91
Ill
105
11 2
106
112
1 05
85
108
96
106
62
T A B L E XVI I.
O b s e r v e d a n d C a l c u l a t e d S t r u c t u r e s F a c t o r s f o r Ti
v y w
*
*
6
d
12
I*
1600
86*
528
1296
752
1
336
1280
70*
**8
2
*912
320
368
2192
*16
62*
5**
3
1328
62*
*
2560
560
872
*32
*
6
LO
12
0
1
3
*
6
8
2
2
5
0
**e
2037
-9 2 8
$89
1376
-8 6 7
K
0
306
8*7
-6 8 1
713
H
O
-5 3 1 3
251
-* * *
-2 3 7 7
399
-5 8 7
-6 3 2
K
0
1**0
-5 0 8
K
0
-2 6 9 7
*30
1*00
*61
*03
592
6
1792
*06*
HO*
62*
1664
54*
992
7
336
*16
102*
6*0
1296
6
368
1**0
2768
1376
262*
10*0
*80
9
688
912
10
560
62*
800
13**
528
11
*16
560
I*
78*
752
6*0
6*0
592
16
992
118*
1232
3
*
S
7
8
9
I
3
*
5
8
9
10
5
10
3
*
6
8
9
1
2
0
1
2
3
7
0
1
2
18
656
752
2
5
7
9
I*
16
K
0
1*11
3983
-1 1 1 7
7 36
1323
-5 5 3
916
K
0
- 8 17*
7*
655
-8 9 7
383
1387
K
0
360
-1 2 9 1
-2 9 1 9
1272
-2 * 9 1
1010
673
K
0
631
-7 1 0
K
0
267
685
8*7
138*
-5 2 9
K
0
291
819
K
0
-8 8 1
593
-8 6 3
-7 2 2
-6 9 7
K
0
105*
-1 2 8 0
1222
*75
76
6*16
7060
400
*85
1184
825
38*
569
9*4
1273
560
-5 7 3
I
K
I
2
2*0
—* 2
*
5
6
102*
1293
528
591
*00
55
- I
K
I
1
38*
-8 9 1
2
560
-6 7 2
*
1056 -1 3 * 6
5
480
-33*
8
* 6*
281
I*
-6 2 9
576
2
K
I
272
-491
I
I*
528
2
896
4*32
6*0
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63
n u m b e r of b o n d s t o t h e o x y g e n s i n T i 7O 2 4 ( E t ) ' ^ v a r i e s f r o m tw o to
four.
T h e b o n d a n g l e s a r o u n d o x y g e n r a n g e . f r o m 7 1° t o 1 60 ° w i t h
s t a n d a r d d e v i a t i o n s of 4 ° .
T h e m a j o r i t y of t h e b o n d a n g l e s a r e
e s s e n t i a l l y t h e t e t r a h e d r a l a n g l e of 1 0 9 ° w h i c h w o u l d b e e x p e c t e d f o r
the o x y g e n .c o n ta in in g bonds.
A l t h o u g h m o r e t h a n 60 c a r b o n s w e r e i n c l u d e d d u r i n g t h e - l a s t
c y c l e s of r e f i n e m e n t , t h e i r p o s i t i o n s a r e q u i t e u n c e r t a i n .
Their
s t a n d a r d d ev iatio n s w e r e v e r y high, as w e ll as th e ir t e m p e r a t u r e
factors.
T h i s d i f f i c u l t y in f i n d i n g c a r b o n p o s i t i o n s . w i t h c e r t a i n t y h a s
b e e n a c h a r a c t e r i s t i c of a l l of t h e t i t a n i u m a l k o x i d e c o m p o u n d s s o l v e d
.thus f a r .
E v e n in t h e c a s e of T i ( O C H 2 )4 (34) w h i c h w a s 6 t i m e s o v e r
d e t e r m i n e d , n o t a l l of t h e c a r b o n s c o u l d b e l o c a t e d .
I t w a s h o p e d t h a t b y s o l v i n g t h e s t r u c t u r e of t h i s h y d r o l y s i s
p r o d u c t , t h e n a t u r e of t h e s p e c i e s i n s o l u t i o n a n d t h e m e c h a n i s m of
p o l y m e r i z a t i o n w o u l d be s h o w n ; t h a t i s , w h e t h e r t w o t r i m e r u n i t s
c o m b i n e d u p o n h y d r o l y s i s f o r m i n g c h a i n s of t r i m e r u n i t s l i n k e d
t o g e t h e r o r w h e t h e r d i m e r s o r t e t r a m e r s w e r e t h e b a s i c u n i t of t h e
polm er.
U n f o r t u n a t e l y , as. c a n be s e e n , t h e r e a r e a n o d d n u m b e r of
t i t a n i u m a t o m s , w h i c h m e a n s t h a t a m i x t u r e of v a r i o u s m o l e c u l a r
w e i g h t unit s, p r o b a b l y e x i s t i n t h e s o l u t i o n of t h e u n h y d r o l y s i z e d
te tra e th y l titanate.
P A R T IV
STRUCTURE OF
jjl - O X O - B I S
[ C H L O R O B I S (2, 4 - P E N T A N D I O N A T O ) T I T A N I U M (IV)]
Introduction
R o s e n h e i m a n d c o - w o r k e r s (35) a n d . l a t e r D i l t h e y (36) s t u d i e d
the r e a c tio n b etw ee n tita n iu m t e t r a c h l o r i d e and a c e ty la c e to n e and
..isolated a c o m p o u n d w ith the e m p i r i c a l f o r m u l a T i C l (acac) .
2
2
M ore
r e c e n t l y t h e c o m p o u n d h a s b e e n s t u d i e d b y M e h r o t r a e t . a l . (37, 38, 39),
Y a m a m o t o a n d K a m b a r a (40), F a y e t . a h
(6).
(7), a n d B r a d l e y a n d H o l l o w a y
N M R s t u d i e s b y t h e l a s t t w o g r o u p s of w o r k e r s h a v e - i n d i c a t e d
t h a t t h e a c e t y l a c e t o n a t e g r o u p s a r e i n t h e c i s p o s i t i o n s of t h e t i t a n i u m
. o c t a h e d r o n as. o p p o s e d t o t h e s t e r i c a l l y m o r e s t a b l e t r a n s p o s i t i o n .
W e w e r e i n t e r e s t e d in s t u d y i n g t h e c r y s t a l s t r u c t u r e - o f T i C l ^ ( a c a c ) ^ ,
b u t c r y s t a l s , of t h e h y d r o l y s i s p r o d u c t [ T i C l ( a c a c )
-obtained.
]-Q .
L L
CHGl
3
w ere
In m a n y w a y s this com pound:.is m u c h m o r e i n t e r e s t i n g .
■P r e p a r a t i o n of t h e C r y s t a l s
C r y s t a l s of t h i s c o m p o u n d w e r e p r e p a r e d b y t h e m e t h o d
s u g g e s t e d b y D i l t h e y (36) f o r T i C l ^ a c a c ) ^ .
C h l o r o f o r m s o l u t i o n s of
I'1
a c e t y l a c e t o n e and t i ta n i u m t e t r a c h l o r i d e w e r e m i x e d so th a t the r a t i o
A
of a c e t y l a c e t o n e t o t i t a n i u m t e t r a c h l o r i d e w a s 2:1.
r
The chloroform w as
p r e v i o u s l y d r i e d a n d t h e r e a c t i o n c a r r i e d ou t in a c l o s e d f l a s k a w a y
65
fro m atm ospheric m oisture.
The re s u ltin g deep r e d solution was-
w a r m e d . f o r s e v e r a l h o u r s a n d p a r t of t h e c h l o r o f o r m d i s t i l l e d . o f f .
Upon cooling, yellow c r y s t a l s f o r m e d w h ic h w e r e r e c r y s t a l i z e d . f r om
the c h l o ro f o r m .
Cl.
T h e s e c r y s t a l s w e r e t h e n a n a l y z e d . f o r T i , C, H , a n d
T a b l e XVIII s u m m a r i z e s , the r e s u l t s .
The. o b s e r v e d r e s u l t s fa ll
b e tw e e n t h e - c a l c u l a t e d r e s u l t s f o r the two c o m p o u n d s.
P e r h a p s the
- s u b s t a n c e a n a l y z e d w a s . a m i x t u r e of t h e t w o c o m p o u n d s , b u t t h e one
c r y s t a l u s e d fo r the c r y s t a l study w a s th e .h y d ro ly s is p roduct.
T h e c r y s t a l c h o s e n fo r the x - r a y w o r k w a s e n c lo s e d .in a
P y r e x c a p i l l a r y a n d h a d d i m e n s i o n s , of a p p r o x i m a t e l y 0 . 2 x 0 . 2 x 1 . 0 m m .
C ollection-of the D ata
T h e l i n e a r a b s o r p t i o n c o e f f i c i e n t f o r C u K a r a d i a t i o n i s - 88. 0 c m
a n d f o r M o K a 9. 9 c m ^ .
A g a i n , t h e a b s o r p t i o n - o f C u Kor r a d i a t i o n
w o u l d b e s i g n i f i c a n t e n o u g h to a f f e c t t h e - i n t e n s i t i e s w h i l e t h e - a b s o r p t i o n
of M o K a w o u l d n o t .
S y s t e m a t i c e x t i n c t i o n s o c c u r r e d on t h e OkO z o n e
■when k / 2 n a n d on t h e h O l z o n e w h e n h + £. / 2n.
The c ry sta l was
m o n o c l i n i c w i t h a = I 5. 7 4 4 , b = 22. 6 2 8 , c = 8. 888 A a n d (3 = 1 00. 30°„
T h e r e f o r e , in d icatio n s w e r e th a t the space, group w a s P 2 ^ / n „
The
c a l c u l a t e d d e n s i t y i s 1 . 4 7 0 c o m p a r e d ,to t h e m e a s u r e d d e n s i t y , of
3
1.474 g / cm .
A s u m m a r y of t h e c r y s t a l d a t a a p p e a r s i n T a b l e ' X I X .
T h e c o l l e c t i o n - o f t h e d a t a w a s s i m i l a r t o t h a t of t h e h y d r o l y s i s
p r o d u c t of t e t r a e t h y l t i t a n a t e w i t h 40 s e c o n d s c a n s a n d 40 s e c o n d
-I
T A B L E XVIII
C h e m i c a l A n a l y s i s , of [ T i G l ( a c a c ) ^ ] ^O" C H C l
C alculated
[ T i C l ( U c a c ) ^ ] I2O- C H C l 3
O bserved
T iC l2 (acac)
%
A t o m s ■'
A
■
A tom s
3l
A tom s
2
15.11
2
I 3. 72
23. 4
4. 4
22. 37
4
25.38
5
Oxygen
20. 4
8.6
20.19
8
20. 62
.9
C arbon
37. 3
20. .8
37.89
20
36. 11
21
4. 45
28
4.18
29
T itanium
. 14. 4
C hlorine
H ydrogen
4. 5
30
■
2
67
T A B L E XI X
S u m m a r y ' of t h e C r y s t a l D a t a f o r [ T i C l ( a c a c ) ^ ]
CHCl^
a.= 15. 7 4 4 —. 005
.b-= 22. 628 — . 008
c=
8. 888 — . 0 0 3
(3 = 1 0 0 Ol 8 ' - 15 '
Space Group
PZ^/ n
M olecules per-unit cell
^c a l e
'd
4
= 1.470
m eas = 1.474
'
"
66
background readings.
20 angl e- of 5 0 ° .
A b o u t 4 0 0 0 r e f l e c t i o n s w e r e s c a n n e d to a m a x i m u m
O f t h o s e s c a n n e d . I 272 w e r e e n o u g h a b o v e b a c k g r o u n d
t o b e c o n s i d e r e d . o b s e r v e d ( g r e a t e r t h a n 300 c o u n t s a b o v e b a c k g r o u n d ) .
T h e s e w e r e c o r r e c t e d f o r - L o r e n t z - p o l a r i z a t i o n a n d r e d u c e d to s t r u c t u r e
factors.
D e t e r m i n a t i o n ' of t h e S t r u c t u r e
I n b o t h of t h e p r e v i o u s s t r u c t u r e s , o v e r 200 n o r m a l i z e d s t r u c t u r e
f a c t o r s h a d b e e n u s e d to c a l c u l a t e th e s ig n r e l a t i o n s a n d the s t r u c t u r e .
I t was., of i n t e r e s t t o s e e if f e w e r r e l a t i o n s c o u l d b e . u s e d . i n s o l v i n g a
s t r u c t u r e w i t h a. f a i r Iy l a r g e n u m b e r of a t o m s .
The structu re-facto rs
w e r e .n o rm a liz e d a s s u m in g , the c o m p o u n d w a s TiC l^(C gH ^O ^)^.
117 r e f l e c t i o n s w e r e u s e d t o c a l c u l a t e a b o u t 2 4 0 0 y
Then
relationships.
I n s i x c y c l e s , of t h e s y m b o l i c s i g n p r o c e d u r e , a l l t h e s y m b o l i c s i g n s
e x c e p t one w e r e e l i m i n a t e d and 114 sig n s w e r e d e t e r m i n e d .
U sing the
t w o s e t s of s i g n s . E - m a p s , w e r e c a l c u l a t e d .
B o t h E - m a p s c o n t a i n e d o n l y f o u r l a r g e p e a k s w h i c h c o u l d be
titanium -or chlorine atom s.
Six l a r g e p e a k s w o u ld be e x p e c te d .f o r two
m o l e c u l e s of T i C l ^ ( a c a c ) ^ in t h e a s y m m e t r i c u n i t .
I n t e r p r e t i n g the
two l a r g e s t p e a k s a s t i t a n i u m p e a k s an d a s s u m i n g o c t a h e d r a l c o o r d i n a t i o n
a r o u n d t h e t i t a n i u m m e a n t t h a t o n e of t h e s t r u c t u r e s w a s c h e m i c a l l y
u n r e a s o n a b l e s i n c e ' i t h a d to h a v e o x y g e n - o x y g e n bonds a n d c h l o r i n e oxygen,bonds.
The- o t h e r s t r u c t u r e w a s c h e m i c a l l y r e a s o n a b l e , b u t
69
m e a n t th a t t h e r e w a s a T i - O - T i bond.
A f t e r t r y i n g t o p u t in m o r e t h a n
-o n e c h l o r i n e a r o u n d e a c h t i t a n i u m a t o m , , i t w a s . f e l t t h a t t h e s t r u c t u r e
of t h e o ne E - m a p m u s t b e c o r r e c t a n d th a t, tw o c h l o r i n e s h a d s o m e h o w
been lost.
T h e a c e t y l a c e t o n e r i n g s , c o u l d b e l o c a t e d on a F o u r i e r m a p
c a l c u l a t e d . f r o m a . s e t of s t r u c t u r e , f a c t o r s , o b t a i n e d b y u s i n g two
t i t a n i u m , two c h l o r i n e , and nin e oxygen a t o m p o s i t i o n s .
By putting
i n t h e s e a c e t y l a c e t o n a t e r i n g s , a n B.- i n d e x of 40% w a s . o b t a i n e d .
This
R -in d e x :is quite high a s s u m in g .th a t all the a to m s h a d b een located, but
no o th e r s t r u c t u r e co uld be found.to ex p lain the P a t t e r s o n m a p .
The
d ata w as. then re fin e d .w ith the full m a t r i x r e f in e m e n t p r o g r a m , , Two
c y c l e s of r e f i n i n g p o s i t i o n a l p a r a m e t e r s r e d u c e d . t h e R - i n d e x t o 32%
w h ich m e a n t that the s t r u c t u r e w a s p ro b a b ly w ro n g .
A f t e r th e e x p e r i e n c e
w ith T iC l^(O C ^H ^)^, it s e e m e d p o s s ib le that the s t r u c t u r e w as c o r r e c t
b u t l o c a t e d i n t h e w r o n g p o s i t i o n in t h e u n i t c e l l .
T h e •o n l y o t h e r
a r r a n g e m e n t i n t h e . u n i t c e l l t h a t w a s r e a s o n a b l e w a s i d e n t i c a l to th e
o th e r s t r u c t u r e o b ta in e d f r o m the E - m a p , but f o r m e d by in t e r c h a n g i n g
the ti ta n iu m and c h lo rin e p o sitio n s.
structure.
T h is w o u ld give the s a m e m o l e c u l a r
T h e R - i n d e x :f o r t h i s p o s i t i o n w i t h t w o t i t a n i u m s , , tw o
c h l o r i n e s , a n d n i n e o x y g e n s w a s . s i m i l a r t o t h a t in t h e o r i g i n a l p o s i t i o n ,
but w h e n -a F o u r i e r m a p w a s c a lc u la te d , no a c e ty la c e to n a te rings
could be-located.
If t h i s s t r u c t u r e w e r e c o r r e c t , t h e a c e t y l a c e t o n a t e
r i n g s w o u l d c e r t a i n l y b e v i s i b l e on t h e F o u r i e r m a p .
a s s u m e d to be w r o n g .
It w a s t h e r e f o r e
70
C l o s e r r e - e x a m i n a t i o n of t h e F o u r i e r map. f r o m the- o r i g i n a l
s t r u c t u r e ( w i t h R = 32%) s h o w e d t h r e e - l a r g e p e a k s n o t c h e m i c a l l y
r e l a t e d t o t h e r e s t of t h e m o l e c u l e .
They fo rm e d an e q u ilate ral trian g le
w i t h s i d e s of a p p r o x i m a t e l y 2. 8 A .
T h is T s about the c o r r e c t d ista n ce
f o r C l - C l d i s t a n c e s in c h l o r o f o r m .
Since this w a s c r y s t a l l i z e d f r o m
a c h l o r o f o r m s o l u t i o n , t h e r e w a s a p o s s i b i l i t y of a . c h l o r o f o r m m o l e c u l e
-in t h e u n i t c e l l .
P u t t i n g in t h e t h r e e c h l o r i n e a t o m s a n d a c a r b o n b e t w e e n
t h e m , r e d u c e d t h e R - i n d e x t o 22%, t h u s , c o n f i r m i n g t h e p r e s e n c e of
c h l o r o f o r m in the s t r u c t u r e .
■R e f i n e m e n t of t h e S t r u c t u r e
T w o c y c l e s of r e f i n e m e n t v a r y i n g p o s i t i o n a l and: i s o t r o p i c t e m p e r a
t u r e f a c t o r s r e d u c e d . t h e R - i n d e x t o 13%.
R efinem ent using.anisotropic
t h e r m a l p a r a m e t e r s r e q u i r e d t w o p a s s e s t o c o m p l e t e o n e c y c l e of
refinem ent.
In each" p a s s , of r e f i n e m e n t , t h e - t i t a n i u m a n d c h l o r i n e a t o m s
w e r e u s e d t o c a u s e o v e r l a p of t h e t w o m a t r i c e s .
m e n t r e d u c e d . t h e R - i n d e x t o 7, 4%.
param eters.
T w o c y c l e s of r e f i n e ­
T a b l e XX l i s t s t h e f i n a l p o s i t i o n a l
T a b le XXI lis ts the a n is o tr o p ic t h e r m a l p a r a m e t e r s and
t h e r o o t - m e a n - s q u a r e a m p l i t u d e s of v i b r a t i o n of t h e t h e r m a l e l l i p s o i d s .
The bond-lengths and bond angles w ith s ta n d a rd deviations a r e liste d
in T a b l e s XXlI and.XXIII.
T a b le XXlV c o n ta in s the o b s e r v e d and c a l ­
culated s tru c tu re fa c to rs.
F i g u r e 4 s h o w s t h e a r r a n g e m e n t of t h e
a t o m s in th e u n it c e l l p r o j e c t e d . o n th e ab plane.
■71
T A B L E XX
A t o m i c C o o r d i n a t e s of [ T i C l ( B c a c ) ^ ]
Ti(I)
Ti(Z)
C l(l)
C 1(2.)
Gl( 3)
Cl(4 )
Cl(B)
0(1)
0(2)
0(3)
0(4)
0(5)
0(6)
0(7)
0(8)
0(9)
C(I)
C(2)
0(3)
0(4)
G(B)
0(6)
0(7)
0(8)
0(9)
0(10)
0(11)
0(12)
0(13)
0(14)
0(15)
0(16)
0(17)
0(18)
C.(i9)
0(20)
0(21)
X
y
. 230 3( 4)
.7507(4)
■ . 311 2( 6)
. 828 1( 5)
.8668(7)
. 849 2( 7)
. . 9 9 54 ( 8)
. 2 52 2 ( 1 2 )
■ . 1 653(13)
. 1204(13)
. 3 29 6( 13 )
. 2 00 7( 12 )
■. 6 87 3( 11 )
. 6 38 1( 12 )
. 8 52 4 ( 1 0 )
.7458(14)
. 8 86 3( 2 3)
. 4387(21)
.3501(24)
. 2 8 8 9( 2 7)
, .2031(29)
■ . 1 26 3 ( 2 0 )
■ . 9 88 2 ( 1 9 )
. 0 6 4 1( 1 9)
. . 0705 (2 0)
.1379(18)
. 6344 (2 6)
.9651(18)
. 8 7 4 4( 2 5)
.8051(22)
. . 7 1 9 8( 2 2)
. 6458 (2 0)
. 5 05 8( 18 )
.5926(20)
. 61 34(22)
■ . 691 6(23)
. . 71 30(24)
. 1296(2)
. 0267(2)
.1413(4)
. 0283(4)
.1675(5)
. 1865(5)
.2329(6)
. 0526(8)
. 1336(9)
.1207(9)
■. 1556(9)
. 21 87(8)
. 0352(9)
• , 0304(10)
. . 0395(8)
- .1169(9)
. 2 2 26 (1 5)
.1556(18)
.1478(14)
, . 1303(1 6)
: .1251(16)
. 1 1 53 (1 4)
. 1268 (1 5)
■.1 5 8 8 (1 7 )
■ . 2178 (1 6)
. 2 4 76 (1 4)
.1865(13)
. 0396(15)
. 0327(13)
. 0259(1 5)
: . 0248(13)
. 0199(15)
. 05 42(14)
. 0735(1 6)
.1297(16)
. 1508 (1 6)
. 21 85(14)
-
CHCl^
Z
■ . 91 74(6)
. 0224(5)
. 26 10(7)
. . 26 80(7)
.-4884(9)
.7999(9)
. 6930(14)
. 0001(1 6)
. . 7985(19)
. 0875 (1 9)
. 9 3 37 (1 9)
. 0 2 18 (1 9)
. 8 0 37 (1 7)
. 0850(19)
. . 9 3 69 ( 1 7 )
. 0 3 69 (2 0)
.6419(39)
* . 7808(33)
. 7 9 48 ( 4 0 )
: .6741(37)
■. 6 7 5 3 ( 3 7 )
..5370(28)
■. 1 7 1 0 ( 3 5 )
. 1 2 55 ( 2 9 )
. . .1209(30)
.0666(27)
. 5539(38)
■. 78 1 8 (3 0 )
. 7 9 53 ( 3 4 )
. . 6765 (3 6)
.6759(26)
■. 5413(29)
.1676(32)
.1280(26)
. 1 3 46 ( 3 0 )
.0867(30)
. .0898(42)
TT
T T T
.72
T A B L E XXI
T h e r m a l P a r a m e t e r s and M ean Square D isp la c e m e n t
of [ T i C l f a c a c ) 2 ] 20 * C H C l
( T h e s e a r e g i v e n a s B j j 1s r a t h e r t h a n (Bjj1s)
0( 9)
C(IO)
C(H )
C(IZ)
C d 3)
C d 4)
C(1 5)
B(ZZ)
B(33)
B(IZ)
B(1 3)
B(23)
. 5. I
4. 5
8. 4
6.0
10. 4
13. 0
9. I
7. 9
6. I
4. Z
5. 6
6. 7
5. 5
4. 5
3. 0
7. 0
9.1
4. Z
3. I
3.7
6. 5
■7 . 0
2. 5
1.3
3. 6
1.7
.1 5 .0
Z. 7
7. 8
2. 5
8.6.
4. 3
3. 5'
6. 5
5. 7
I 0. 5
8. 3
11.1
4. 4
6. 2
3. 4
7. 3
6. 0
6. 9
5. 4
6. 5
6. 3
7. 0
.16. 3
6. 3
6. 8
6.0
6. 7
7. 6
6. 7
4. 6
4.8
1.4
10. 8
4. I
.8.6
4. 5
1. 6
I. 5
0. 8
I. 5
2. 9
3. 4
1Z. 4
-0. 5
2. 3
1.9
I. 6
Z. Z
I. Z
3. 0
0. 8
1.4
6.9
Z. 7
6 ,1
3.9
3.9
• 1.5
6.9
2. 4
5.9
2. 6
7. 5
3. 2
2. 4
4. 7
-0. 9
-0 . 3
-9. 3
-0. 8
-0. 7
I. 5
0. 0
-I. 4
1. 6
0. 3
-0. 5
-2. 3
I. 4
0.7
0. 6
-0. 5
I. 3
-3. 4
-2. 2
1.7
•I. 5
1.4
0. 5
-1 .4
I. 6
-I. 8
0. 6
-3. 4
0. I
0.7
-0. 4
-2. 3
1.9
1.7
1.5
1.7
2. 3
3. 3
3. 4
1.1
1.1
0. 5
2. 5
2. 2
-0. I
1.4
1.1
I. 3
5.5
2. 5
-0. 3
-0. 3
-0. 6
“ 2. I
3.0
-1.1
1.4
-0. 4
4. 0
2. 0
-0.1
3. 2
-0. I
-0. I
-0. 5
-0. 4
-0.3
-0. 6
I. 2
-0. 8
I. 4
-0. 2
0. 6
-1.0
. 0. 2
-0. 2
-0.6
0. 5
0. 6
-0.7
-0. 7
1.9
1.5
0.5
0. 2
-1 .6
-0. 9
-2.8
-0. I
-0. 5
1.1
0. 8
-0. 3
0. 4
0. 07
0.06
0.11
0. 08
0. 15
0. 17
0. 17
0.11
0. OS
0. 06
0.11
0. 10
0. 09
0. 07
0.08
0.10
0.17
0. 21
0. 10
0.10
0.10
0.11
0. 12
S
O
T i(l)
Ti(Z)
Cl(I)
Cl(Z)
0(3)
0(4)
0(5)
0(1)
0(2)
0(3)
0(4)
0(5)
0<6)
0(7)
0(8)
0(9)
c(i)
C(Z)
C(3)
C(4)
C(5)
C(6)
C(7)
0(8)
B (Il)
M ean Square
D isplacem ent A 2
MAX
MED
MIN
0.11
0. 06
0. 20
0. 14
0. 11
0. 11
0. 13
0. 05
0. 01
0. 01
0. 04
0. 01
0. 08
0. 01
0. 06
0 .1 1
0. 03
0.1 1
0. 03
0. 10
0. 14
0. 00
0. 05
0. 07 ■ 0. 03
0. 02
0. 04
0. 00
0.06
0. 02
0. 06
0. 01
0. 07
0. 03
0. 06
0. 04
0. 00
0. 01
0. 07
0.08
0.03
0. 01
0. 06
0. 07
0. 02
0.03
0.06
0. 04
0. 07
0. 01
0. 08
0. 07
0. 01
0. 01
0. 03
0. 02
0. 05
0. 02
0. 04
0. 01
0. 08
0. 01
0.05
0. 02
0. 06
0. 00
0. 08
0. 01
0. 04
73
T A B L E X X I ( C o n t in u e d )
( T h e s e a r e g i v e n a s B j V s r a t h e r t h a n Bij’s) ..
M ean-Square
‘J
J
D isplacem ent
B(IZ)
MAX
MED
B (Il)
B(ZZ)
B(1 3) B(23)
MIN
B( 33)
0
3
3
3
6
4
a. 3
7.7
3. 7
3. I
7. 8
2. 6
Z. 7
4. 0
1.1
3. Z
1.0
8. 5
-0. I
.0. 5
0. 6
-I, 7
I. Z
1.4
-1.2
2. 5
0. 7
0.7
1.2
2.8
-0. 4
-I. 5
-0. 3
-1.3
-I. 3
-I. 3
0.11
0.10
0. 06
0. 09
0. 11
0. 16,
0. 09
0. 06
0. 04
0. 05
0. 07
0.11
0.
0.
0.
0.
01
01
02
00
N
O
O
6.
3.
4.
6.
5.
1Z.
CO
O
O
C d 6)
C(IT)
C d 8)
C d 9)
C( 20)
C(Zl)
a.
T h e a n i s o t r o p i c t e m p e r a t u r e f a c t o r s f o r O ( I ) a n d C (I 5) a r e n o n p o sitiv e definite. F o r m e a n s q u a r e d is p la c e m e n t, the p ^ ^'s w e r e
g i v e n v a l u e s of . 0001, w h i c h w a s ; l e s s- t h a n t h e s t a n d a r d d e v i a t i o n .
b.
S t a n d a r d d e v i a t i o n of B j j ' s a r e a p p r o x i m a t e l y 0 . 1 f o r t i t a n i u m a n d
c h l o r i n e a t o m s , " 0. 5 f o r o x y g e n a t o m s , a n d I . 0 f o r c a r b o n a t o m s .
74
T A B L E XXII
B o n d D i s t a n c e s , i n [ T i C l ( a c a c ) ^ ] ^O" C H C l
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
T i(l)
- 0.(1)
-0(2)
- 0(3)
- 0(4)
- 0(5)
- C l(l)
Ti(Z)
Ti(Z)
Ti(Z)
Ti(Z)
Ti(Z)
Ti(Z)
-
0(1)
0(6)
0(7)
0(8)
0(9)
Cl(Z) v
.
.1.79(2)
2. 03(3)
I . 95(3)
1.94(3)
2. 07(3)
2. 32(2)
I . 81(2)
'2. 03(3)
I . 95(2)
I . 91(2)
2. 05(2)
2.30(1)
A c e t y l a c e t o n a t e G r o u p (I)
0 ( 2 ) - C (5)
0 ( 4 ) - C (3)
G(Z) - C (3)
G (3) - C (4)
C (4) --C(B)
C(B) - C ( 6 ) '
I . 35(6)
1.34(5)
1.43(6)
I . 37(9)
1.36(7)
I . 58(8.)
A c e t y l a c e t o n a t e G r o u p (2)
0 ( 3 ) - C (8)
0 ( 5 ) - C(IO)
G (7) - C (8)
C (8) - 0 ( 9 )
C (9) - C(IO)
C(IO) - C ( I l )
I . 32(6)
1.31(5)
I . 51(8)
1 . 34( 6)
1.41(7)
1.49(5)
A c e t y l a c e t o n a t e G r o u p (3)
0 ( 6 ) - C(1 5)
0 ( 8 ) - C(1 3)
C ( I Z ) - C(1 3)
C(1 3) - C(1 4)
C ( 1 4) - C(1 5)
C(1 5) - C(1 6)
1.35(4)
: I . 37(5)
I . 46(6)
1.38(8)
1.34(5)
1.52(6)
T
T T
JL
75
T A B L E XXII (C ontinued)
A c e t y l a c e t o n a t e G r o u p (4)
0 ( 7 ) - C(1 8)
0 ( 9 ) - G 1(ZO)
G ( I S ) - C(1 7)
C ( 1 8) - C ( 1 9)
C ( 1 9) - C(ZO)
C(ZO) - C ( Z l )
I . 31(6)
I . 28( 6)
I . 53(6)
I . 31(6)
1.45(7)
1.57(6)
C h lo ro fo rm G roup
C ( I ) - C 1(3)
C ( I ) - C l(4 )
C ( I ) - C l(5 )
CU) - 0(5)
C(I) - 0(4)
I . 83(6)
I . 81(6)
1.71(5)
3. Z l (6)
3. 35(6)
V
j
Ir T T
T
76
T A B L E X X in
B o n d A n g l e s , in [ T i C l ( a c a c ) ] O ' C H G l
■Z Z
3
0(1)
0(1)
0(1)
0(1)
0(1)
0(5)
0(5)
0(5)
0(5)
0(2)
0(2)
0(2)
0(3)
Ti(I)
-
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
T i(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
Ti(I)
- 0(1)
- Cl(I)
- 0(2)
- 0(3)
- 0(4)
- 0(5)
- Cl(I)
- 0(2)
- 0(3)
- 0(4)
- 0( 4) .
- 0(3)
- Cl(I)
-0(4)
- Ti(2)
96.3(3)
91.9(4)
97. 0(4)
94. 6(4)
17 6. 0(5)
87. 6(4)
84.1(4)
83. 0(4)
84. 9(5)
85. 5(4)
89. 2(4)
17 0. 3(4)
167.3(5)
167.5(11)
0(1)
0(1)
0(1)
0(1)
0(1)
0(9)
0(9)
0(9)
0(9)
0(6)
0(6)
0(6)
0(7)
-
Ti (2 )
T i( 2 )
Ti (2 )
Ti (2 )
Ti (2 )
Ti (2 )
T i( 2 )
T i( 2 )
Ti (2 )
T i( 2 )
T i( 2 )
T i( 2 )
T i( 2 )
- 0(2)
-0(6)
- 0(7)
-0(8)
-0(9)
- 0(2)
- 0(6)
- 0(7)
- 0(8)
-0(7)
- 0(8)
- 0(2)
-0(8)
96.9(3)
89. 4(4)
93. 8(4)
96. 5(4)
17 5. 8(4)
86.8^4)
87. 0(4)
83.9(4)
85. 3(4)
87. 3(4)
84. 8(4)
17 3. 3(4)
166. 9(5)
1A c e t y l a c e t o n a t e G r o u p (I)
T i ( I ) - 0 ( 2 ) - C(5)
T i ( I ) - 0 ( 4 ) - C (3)
0 ( 4 ) - C(3) - C (2)
0 ( 4 ) - C(3) - C(4)
C(2) - C(3) - C(4)
C(3) - C(4) - C( S)
C(4) - C(5) - C(6)
0 ( 2 ) - C(5) - C(6)
0 ( 2 ) - C(5) - C (4)
1 2 3 . 3(13)
1 3 1 . 0(13)
1 1 7 . 5(24)
1 2 0 . 6(26)
121.8(25)
12 3. 5(27)
1 2 9 . 1(28)
I 05. 3(24)
12 5. 3(30)
77
■ T A B L E X X III ( C o n t in u e d )
A c e t y l a c e t o n a t e G r o u p (2)
T i ( I ) - 0 ( 3 ) - C(8)
' T i ( I ) - 0 ( 5 ) - C(IO)
0 ( 3 ) - C(8) - C(7)
0 ( 3 ) r C(8) - C(9)
C(7) - C(8) - 0 ( 9 )
0 ( 9 ) - C(I O) - C ( I l )
0 ( 5 ) - C(IO) - C(9)
0 ( 5 ) - C(IO) - C ( I l )
13 3. 5(13)
I 32'. 8(13)
H O . 8(21)
12 5. 7(24)
I 23. 5(22)
118. 8(19)
I 21.4(21)
11 9. 7(20)
A c e t y l a c e t o n a t e G r o u p . (3)
Ti(Z) - 0 ( 6 ) - C(1 5)
Ti(Z) - 0 ( 8 ) - C(1 3)
0 ( 8 ) - C(1 3) - C ( I Z )
0 ( 8 ) - C(1 3) - C ( 1 4)
C ( I Z ) - C(1 3), - C(1 4)
C (I 3) - C ( l 4) - C ( I S )
C ( 1 4) - C(1 5) - C( 16 )
0 ( 6 ) - C(1 5) - 0 ( 1 4 )
0 ( 6 ) - C(1 5) - C(1 6)
12 6.
13 5.
118.
11 4.
12 6.
131.
12 9.
12 1.
108.
A c et -y la ce t o n a t e ' G r o u p ('4)
Ti(Z) - 0 ( 7 ) - C(1 8) .
; Ti(Z) - 0.(9) - C(IO)
0 ( 7 ) - C(1 8) - C(1 7)
0 ( 7 ) ' - C(1 8) - 0 ( 1 9 )
■ 0 ( 1 7 ) - C(1 8) - C ( l 9)
C(1 8) - C(1 9) - C(ZO)
0 ( 9 ) - C(ZO) - C ( Z l )
■0 ( 9 ) - C(ZO) - C(1 9)
C hloroform
0 ( 3 ) - C(I) - 0 ( 4 )
0(3) -C (I) - 0(5)
0 ( 4 ) - C(I) - 0 ( 5 )
5(12)
6(12)
3(23)
7(23)
7(24)
0(26)
1(21)
6(22)
9(19)
I 33. 5(14)
I 30. 7(14)
1 1 4 , 3(21)
1 2 6 . 3(24)
1 1 9 . 4(22)
121.4(24)
11 5. 9(23)
12 3, 8(25)
I 03. 7(18)
1 0 8 . 5(19)
1 0 7 . 7(19)
IT
TrT
I
78
T A B L E XXIV
O b se rv e d and C alcu lated S tru ctu re F a c t o r s
fo r [T iC l(aca c)^ ] ^O-CHCl^
Il
I ill
S=
Si
P .s
I: Si :L'i
I
r .- i
S i!
I* " 7 »
i
II
I " .
!
Il
II
1 1
" Su .-j
■SSJ^JJ
I
U7
**"**1
I
S=
ii ii* ***
:Z ‘ 2
5 IS
•
S
K SR
I*
I! Z
Z
Z
-RS
-jr.
SR
! I
Z Z
- z -is H
i
Z : = S 2 SK
■ :"! =
I S S
ii S i i
K Z -S
. L '. . i
I S -S
I S SS
JZ -Z
ii S SS
K Z S
UM 'l l
ii
:: si
S
!
.I
i:
S
J S 'T S
Si Z -Z
3S3
I l
I
S IS -Si
! '= SSI
it si -S
ii Es :E
is ' s i
1 1 1
ii Sn i i
I Kl1SS
J S SS
i -is '-Z
i l
Ii =
- '- ! “
! 2
.1 =
l
-Z
. *S
K
3
1 1 1
K S Z
I I I
C -Z
• Sn ii!*
:> > :
• *»»
IS S =
K Z SI
I Eis = ; I:
K Z KI
: E =
r .z
}• »u
ii in in I
J ".is -z I Hi 3
S K SR
i Si =
K 2 21
- U 1V.
I Z SR
2
" r2- .-S
3 KR
i s si: I IR -Z
K JK S
K Z SR
r .* s
K Z -SR S -K 1K
: K SR
.I S -Z
I $ =
K K SR
Jai
.-1 1 1
I... "in!
ill.
S -Z
Z 21
2 3
" r* .—. I ill SR
I Z M K Z SR
J W -US I Z SR
H r .- s
I*
I Z Z
! 1E 1KS I K Z
r .
: hi jx
!I Z SR I Z -K
K S 1SK I Z SK
*
-i* J S SK
I Z KS K K SK
S..*-,J
"-F =
S Si!
I SI 411 i S -Ri
» IS 4m K K Z
I Y sH
i l l
" r .- i
I Z SK
I Z Z
J Z SR
‘• - r . - i
I S SS
Z -Si
S 5
S = Ji
K 2
S
Z Si
IR Z
2 K
- 1-. V J
IK Z
. 2 =Z
.IR -SK
Z -K
8 1.1 -W*
K Z SR
»m !*.!
Z Si
Z -IZ
R .2 =SS
IM Im
ii 2 Z
'Z SSS
SR
ii is
1“ . ”!
to SR
K :K
K SS
to SR
KS SK
r .z
Z Z
-is 2:
2 -to
Z -Z
;; to Z
r .- i
-to KR
to SK
to =
ii Z SR
J Z ":=
I" z ' Z
-I.,
i l l
Ti
K 2 Z
K Z , SI i S 3
i iIm 411
ii K 1IK I -K Z
I z 3
I Ml 1*7 ii
J KR KR
lit 411 K
J 'IR SK 1 1 1
IS IR SR
ii Z =
I .is Lr;
= 5 -3
i l l
I I I
I
to "-Si
to SR
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[TiC l(acac) ]
(ab projection)
80
D isc u ssio n -o f the S tr u c tu r e
F i g u r e 4 s h o w s t h e p r o j e c t i o n of t h e s t r u c t u r e d o w n t h e c a x i s .
S i n c e t h i s : is t h e s h o r t a x i s , m o s t of t h e s t r u c t u r e is e v i d e n t .
F igure 5
s h o w s t h e a r r a n g e m e n t of t h e a t o m s in t h e m o l e c u l e a l o n g . w i t h s e l e c t e d
bond d is ta n c e s .
T h e t i t a n i u m a t o m s a r e . o c t a h e d r a l l y ,c o o r d i n a t e d w i t h
a s m a l l a m o u n t of d i s t o r t i o n .
T h e a c e t y l a c e t o n a t e . g r o u p s : on e a c h
t i t a n i u m a r e c i s t o e a c h o t h e r , a g r e e i n g w i t h t h e s o l u t i o n s t u d i e s .of
T i C l ^ ( a c a c ) ^ (6,7').
T h e m o l e c u l e h a s a n a p p r o x i m a t e c e n t e r of
s y m m e t r y l o c a t e d at th e -o x y g e n jo in in g th e two t i t a n i u m a t o m s .
The
c h l o r o f o r m m o l e c u l e may. b e b o n d e d to t h e m o l e c u l e b y w e a k h y d r o g e n
b o n d i n g t o t h e t w o a t o m s 0 ( 4 ) . a n d 0(5).
T h e T i - C l d i s t a n c e s a r e 2. 32
a n d 2. 30 A, w h i c h a r e l o n g e r t h a n t h e b o n d s in T i C l ^ ( O C
T h e r e T s s o m e d i s t o r t i o n of t h e T i ( a c a c ) r i n g s w h i c h a r e
p a r a l l e l to th e ac plane.
T h i s c o u l d be e x p e c t e d s i n c e t h e r e is s t e r i c
i n t e r a c t i o n b e t w e e n t h e s e a c e t y l a c e t o n a t e g r o u p s a n d t h e a t o m s on t h e
o t h e r t i t a n i u m a t o m in t h e m o l e c u l e .
T h e d e v i a t i o n of t h e a c e t y l a c e t o n e
g r o u p s f r o m t h e i r l e a s t s q u a r e s p l a n e s a r e l i s t e d . i n T a b l e XX V .. It'c a n a l s o b e s e e n t h a t t h e t i t a n i u r n at o m , i s th e a t o m m o s t d i s p l a c e d f r o m
t h e p l a n e of t h e r i n g s , w h i l e t h e a c e t y l a c e t o n e .g r o u p i s s t i l l q u i t e p l a n a r .
A g a i n , a s i s t h e c a s e i n the. o t h e r c o m p o u n d s s t u d i e d , a . l a r g e
oxygen bond angle e x ists.
T h e a n g l e T i ( l )-0(T))-Ti(2) i s 1 6 7 . 5 ° .
The
. bond d i s t a n c e s to th is o xygen a r e a l s o s h o r t e r th a n the o t h e r T i - O bon d s
81
on
ACETYLACETONATE
ACETYLACETONATE
GROUP 4
F I G U R E 5.
S tr u c t u r e of [T iC l(B cac)^ ]-, O
82
T A B L E XXV
E q u a t i o n s ;of L e a s t S q u a r e s - P l a n e s R e f e r r e d t o O r t h o g o n a l A x e s
in [ T iC l(a c a c ) ] O - CHCl
UU
3
X = x.+ z c o s (3; Z = z s i n (3; Y = y
a X + b ' Y_ + c Z = D;-S - s u m of s q u a r e s , of d e v i a t i o n of a t o m s f r o m p l a n e ;
D = o r i g i n to p l a n e d i s t a n c e in A n g s t o m s .
T i(l)acac(l)
acac(l)
T i(l )acac(2)
acac(2)
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acac(3)
Ti(2)acac(4)
acac(4)
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A ll a to m s given equal w eight.
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T
83
i n t h i s m o l e c u l e a n d c o m p a r a b l e t o t h e b o n d s i n T i G l 2 ( O C ^ H 5 )2 w h i c h
a r e . f e l t to be p a r tia lly double-bonded.
the c a s e in this m o l e c u l e , a lso .
T h e s a m e , t h i n g is m o s t l i k e l y
This, oxygen-is p r o b a b l y
sp h y b r id i z e d
a n d d o n a t i n g e l e c t r o n s t o f o r m tt b o n d s w i t h t h e e m p t y 3- d . o r b i t a l s of
the tita n iu m a to m s.
It a p p e a r s th a t th e c h l o r o f o r m m o l e c u l e is h y d r o g e n b onded to
t h e o x y g e n s of t h e a c e t y l a c e t o n e g r o u p s .
The tita.nium -carbon-chlorine
b o n d a n g l e s a r e TO9. 5 ° , 1 0 8 . 1 ° , a n d 1 1 8 . 4 ° i n d i c a t i n g . t h a t the. h y d r o g e n
of t h e c h l o r o f o r m i s p o i n t i n g t o w a r d s t h e . t i t a n i u m a t o m .
The d istan ces
f r o m th e c h l o r o f o r m c a r b o n to the oxygen and t i t a n i u m a t o m s a r e as
follow s:
0 ( ' 4 ) - C ( l ) = 3. 35 A; O ( S ) - G ( I ) = 3 . 2 1 A; T i ( I ) - G ( I ) = 4. I 8 A .
T h u s , i t a p p e a r s that, t h e r e is w e a k h y d r o g e n b o n d i n g f r o m t h e c h l o r o ­
f o r m h y d ro g e n to the a to m s 0 (4 ) and 0 (5 ).
SUMMARY AND CONCLUSIONS
T h e s t r u c t u r e s , s tu d ie d .in th is d i s s e r t a t i o n h a v e p ro v id e d the
n e c e s s a r y f a c t s to u n d e r s t a n d , w ith m u c h m o r e c e r t a i n t y , the c h e m i s t r y
of o r g a n i c c o m p o u n d s of t i t a n i u m .
S ig n ific a n t c o n c l u s i o n s include:
(1) ' A l t h o u g h t h e n o r m a l b o n d a n g l e fo r - o x y g e n i s a r o u n d . I 09
degrees,
s e v e r a l la rg e oxygen bond angles have been re p o rte d p reviously.
'In a l l t h e t i t a n i u m c o m p o u n d s s t u d i e d h e r e s o m e o x y g e n a t o m h a d b o n d
an g les n e a r I 80°.
In e a c h c a s e the bond d is ta n c e s to th e s e , oxygens
w e r e s h o r t , i n d i c a t i n g d o u b l e b o n d c h a r a c t e r f r o m b a c k d o n a t i o n of
e l e c t r o n s b y t h e o x y g e n s t o e m p t y 3 - d o r b i t a l s of t h e t i t a n i u m .
Thus
tr b o n d i n g , is p o s t u l a t e d b e t w e e n t h e s e - o x y g e n s a n d t h e t i t a n i u m , w i t h
the oxygen being sp h y b rid ized .
(2)
T i t a n i u m i s n o r m a l l y o c t a h e d r a l l y c o o r d i n a t e d b u t in
d i c h l o r o d ip h e n o x y titan iu m (IV) the .titanium a to m s a r e p e n ta c o o rd in a te d .
T h i s a p p e a r s t o b e t h e f i r s t r e p o r t of f i v e c o o r d i n a t e d . t i t a n i u m .
It is
probable that m an y m o r e d im e ric o rganic titanium com pounds w ill be
found th a t exhibit five c o o rd in a te d tita n iu m .
(3)
T h e c i s c o n f i g u r a t i o n of t h e a c e t y l a c t o n a t e g r o u p s a r o u n d
t i t a n i u m a s in d i c a te d by s o lu tio n s tu d ie s h a s b e e n c o n f i r m e d . i n the
cry stal structure.
Since the cis c o n fig u ra tio n is l e s s s te r i c a l l y f a v o r ­
able, this is an in te re s tin g conclusion.
Bond d i s t a n c e s a r o u n d the
t i t a n i u m s u g g e s t c o n s i d e r a b l e i n t e r a c t i o n of t h e T o n e p a i r e l e c t r o n s , of
the- o x y g e n s w i t h t h e e m p t y 3 - d . o r b i t a l s of t i t a n i u m , t h u s , i m p l y i n g t h a t
the l e s s s t e r i c a l l y f a v o ra b le -c o n fig u ra tio n is s ta b i liz e d by in te ra c tio n
w i t h d o r b i t a l s of t i t a n i u m .
This conclusion has been previously
su g g e s te d by B ra d le y f r o m solution stu d ies.
(4)
T h e s t r u c t u r e : of t h e - f i r s t h y d r o l y s i s p r o d u c t of t e t r a e t h y l
tita n a te is d ecid ed ly d ifferen t f r o m th a t p ro p o se d .in th e - lite r a tu r e as a
r e s u l t of m o l e c u l a r w e i g h t s t u d i e s , a n a l y t i c a l r e s u l t s , a n d t h e p r o p o s e d
t r i m e r i c s tr u c t u r e fo r the te tr a e th y ltita n a te .
X - r a y studies have shown
th a t the f o r m u l a m u s t be T i-O
( C 0 H r )1 r a t h e r t h a n T i zO 0 0 ( C 0H r )1 .
/ Z4 id D I V
6 20 2 5 1 b
a n d t h a t t h e s t r u c t u r e i s f o r m e d b y v a r i o u s s p e c i e s s h a r i n g e d g e s of
T i O octahedra.
O ne c a n conclude f r o m this s t r u c t u r e th a t even though
m o l e c u l a r w e i g h t . s t u d i e s i n s o l u t i o n i n d i c a t e t h e e x i s t e n c e of p r e ­
d o m in ately t r i m e r i c s p e c ie s [ TifOC^Hg)^]
o t h e r m o l e c u l a r s p e c i e s . in t h e s o l u t i o n .
t h e r e m u s t b e a n u m b e r , of
T h is s u g g e s ts th a t the p r o p o s e d
m e c h a n i s m f o r h y d r o l y s i s n e e d s t o b e r e c o n s i d e r e d i n t h e - l i g h t of t h i s
new in fo rm a tio n .
F u r t h e r m o r e , t h e s t r u c t u r e s of o t h e r h y d r o l y s i s
p r o d u c t s s h o u l d b e d e t e r m i n e d , to p r o v i d e a d d i t i o n a l i n f o r m a t i o n f o r
t h e m e c h a n i s m , of h y d r o l y s i s .
(5) 1 A n o t h e r r e s u l t of this., r e s e a r c h is, t o i n d i c a t e t h e p o w e r of
d i r e c t m e t h o d s f o r t h e s o l u t i o n - of c e n t r o s y m m e t r i c c r y s t a l s t r u c t u r e s .
I n p a r t i c u l a r , t h e s y m b o l i c a d d i t i o n p r o c e d u r e h a s p r o v e d t o be a n
e x t r e m e l y ; p o w e r f u l m e t h o d f o r t h e s o l u t i o n of c o m p l e x s t r u c t u r e s e v e n
though nothing is known about the s t r u c t u r e .
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1.
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2.
D. C. B r a d l e y , R. G a z e , a n d W. W a r d l a w , J . C h e m . S o c. , 3937
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3.
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9 t h . I h t 1 C o h L on
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g r a p h N o. 3 ( E d w a r d s B r o t h e r s , A n n A r b o r , M i c h i g a n , (1953).
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£>, 68 (1 9 52 ).
TT
Til
87
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1 694 (1 95 0) .
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A . M c L . M a t h i e s on, D. P . M e l l o r , a n d N.-, C. S t e p h e n s o n ,
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33.
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;
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K t Z . . ■■
Watenpaugh, K. D.
Structural studies of organic
titanium compounds