Cobre Con Glicina
Cobre Con Glicina
Cobre Con Glicina
1464
STRUCTURE
OF B I S G L Y C I N O - C O P P E R ( I I )
MONOHYDRATE
Matrix
approximation
1-3
Diagonal
4-7
Temperature
factor
Final
R*
Weighting
scheme
T r e a t m e n t of
Funobs
Mean
isotropie
0" 146
omitted
ZEBRA
Schoone
(1961)
Diagonal
Individual
isotropic
0.126
As above
omitted
ZEBRA
Schoone
(1961)
8-9
Full
matrix
Individual
isotropie
0.129
I/w= 1/(~(Fo)
from B, Fig. 2
IBM
7090
Busing &
L e v y (1961)
10-16
Full
matrix
Individual
anisotropic
0.091
As above
IBM
7090
Busing &
L e v y (1961)
Machine program
2~u = Fmin
~(Fu) = 2'rain/I/(12)
As above
3. Refinement
Least-squares refinement was commenced with the
TN positional parameters. Six observed and three
unobserved reflections were given zero weights, so
t h a t 877 reflections were actually included. Details
of the refinement are given in Table 2.
A revision of the weighting scheme was made
after cycle 7 (see 4). Corrections for extinction were
made to the 18 largest structure amplitudes, all of
low 0, after cycle 13. The correction factor for the
Fo values, found by the method of Pirmock, Taylor
6 ~o/~
260
~.._o
2020
0
I0
~
o o
20
o
30
"
,
hO
,~'T---------~, /3 ,
50
60
70
Fo
I t . C. F R E E M A N ,
M. R . S N O W , I . N I T T A
AND K. T O M I T A
1465
Table 3(a). The positional parameters and their estimated standard deviations
All values have been multiplied by 104
Average s.d.
Atom
x
a(x)
y
a(y)
z
(~(z)
(A x 104)
Cu
1031
2
3403
4
4013
1
16
O(1)
813
8
5772
17
2903
6
82
0(2)
1242
9
6286
19
1314
6
90
0(3)
104
10
5568
18
4919
6
96
0(4)
-- 664
10
5797
22
6444
7
104
O(5w)
2878
10
5558
28
4530
8
112
N(1)
1842
9
1152
21
3025
7
100
N(2)
1196
11
989
24
5176
8
110
C(1)
1938
13
2519
25
2074
10
124
C(2)
1285
9
5047
24
2085
9
114
C(3)
623
12
2162
34
6065
9
137
C(4)
-- 45
11
4676
26
5803
8
120
Table 3(b). The final temperature factor parameters from the isotropic (B) and anisotropic (B~j) refinements
and their estimated standard deviations (in/~2)
The anisotropic temperature parameters have been multiplied by 104
Atom
B
Bn
Cu
1.86(0.05)
58(2)
O(1)
1.86(0"17)
46(8)
0(2)
2.22(0.19)
78(9)
0(3)
2.53(0.22)
102(10)
0(4)
2.86(0.24)
84(10)
O(5w)
4.10(0.30)
74(10)
N(1)
2.00(0.22)
36(8)
N(2)
2.74(0.27)
64(10)
C(1)
2.50(0.30)
73(12)
C(2)
1.55(0.23)
22(8)
C(3)
2.42(0.28)
43(9)
C(4)
1.62(0.24)
43(9)
Anisotropic temperature factor: exp
B22
B33
B1,
B13
B23
161(7)
20(1)
17(3)
1(1)
4(2)
179(35)
25(4)
13(13)
3(4)
-- 12(10)
205(37)
23(4)
20(17)
12(5)
11(11)
178(37)
23(4)
40(18)
9(6)
11(11)
341(48)
31(5)
20(18)
20(6)
0(13)
588(68)
50(6)
--88(22)
--35(7)
60(18)
159(41)
32(5)
15(15)
--4(5)
11(13)
266(51)
34(5)
37(21)
12(6)
28(14)
130(46)
36(6)
1(20)
3(8)
6(15)
129(44)
35(6)
-- 10(16)
-- 10(6)
2(2)
476(79)
28(6)
5(22)
74(7)
32(20)
219(51)
22(6)
1(19)
2(6)
-- 1(14)
[ -- (Bllh~ + B~k 2 B3al~+ 2B12h/c+ 2Blahl + 2B2z/cl)].
4. Weip, h t i n g a n d e r r o r a n a l y s i s
To o b t a i n a n e s t i m a t e of t h e errors i n t h e s t r u c t u r e
a m p l i t u d e s 12,o] (from here on called m e r e l y 2,o),
comparisons were m a d e a m o n g t h e 93 s t r u c t u r e
a m p l i t u d e s which were recorded twice. The v a r i a t i o n
of t h e m e a n discrepancy, / i F (average difference
between t h e scaled observations in a range of 2,o),
with 2,0 is shown in Fig. 1. The p o p u l a t i o n d i s t r i b u t i o n
of 2'0 based on all d a t a is also given.
F o r t h e diagonal m a t r i x calculations on t h e Z E B R A
computer, a t w o - p a r a m e t e r weighting f u n c t i o n w - 2 0 0 / ( 2 0 0 + ( 2 , o - 2 0 ) ~} was f i t t e d to a plot of 1/(z]2,) 2
versus 2,0. The agreement between t h e weighting
f u n c t i o n a n d t h e inverse of curve A i n Fig. 1 was
best in the range 1 0 < 2 , o < 2 0 near t h e p o p u l a t i o n
m a x i m u m . The weighting f u n c t i o n diverged in t h e
sense of higher weights a t high values of 2,0.
For t h e f u l l - m a t r i x calculations on a n IBM 7090
computer, t h e observed reflections were given weights
w, where w- = cr(Fo) a n d t h e (I(Fo) were read from
a plot of (1/~/2)AF versus 2'0 (Fig. 2, curve B). This
doubled t h e weights which h a d been assigned in t h e
diagonal m a t r i x calculation, a l t h o u g h t h e a c t u a l
weighting f u n c t i o n now more a c c u r a t e l y represented
the calculated weights. Our use of t h e ' p o p u l a t i o n
s t a n d a r d d e v i a t i o n ' (~(x)=~[Z,(xi-~)~/(n-1)]
for
small samples followed the m e t h o d of Davies &
._
(F) 5
A
B
3
x
1'o
2?
3'0 ~'o
s'o 6'o
7'o
Fo
Fig. 2. A: ]/[[Fo--Fc]2], the r.m.s, difference between the
observed and calculated structure factors after cycle 13,
found in ranges of 2'o, plotted versus 2' o. B: The standard
deviation of 2'o, a(F)----0-707A2', plotted versus .Fo.
Pearson (1934). For two observations of 2,0, t h e
s t a n d a r d d e v i a t i o n of a(2,) is t h e n 0.6033(F). The
'range estimate' of T i p p e t t (1925), used b y Ibers
(1956), gives a(2,)---0.89F with s t a n d a r d d e v i a t i o n
0.7563(F).
A t t h e end of t h e refinement, t h e r.m.s, s t a n d a r d
d e v i a t i o n in an observed s t r u c t u r e a m p l i t u d e of u n i t
weight, ~[Zw[Fo-Ec]2/(m-n)], was f o u n d to be 2.14
i n s t e a d of u n i t y , t h e value expected when t h e weighting factors are given b y w = 1/a2(F). This discrepancy
1466
STRUCTURE
T~ble
OF
BISGLYCINO-COPPER(II)
MONOHYDRATE
h Fcalc Pobs
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1o
i 1.43
11 .
21.44
22,1q
1.4 @ 1.14
.0?
11 .~4
12.41
15.15
14.7
1?.??
9.25
5.85
3.80
5.51
17.37
9.96
le.56
11.52
12.18
z 2.0
4.25
4.am
15.15
8.00
4.q5
~ 1.5o
.04
7.34
~.71
I,
8.14
4
12.47
36.N
q.o
12.44
.33
15.41
4.47
11.33
9.4~
2.35
4.47
5,72
17.31
4.~
q.~
21.04
5.
?.~
X 3.24
II
22.75
10
.eo
25..,b
18.37
38.18
23,13
16.47
f'2.51
X 2.09
25.29
17.~
20.84
21.25
14,74
t.21
4
o
4.85
11.?5
24,10
7.1m
|8.5;
8.14
14.14
4.8'8
11.95
I.23
11.15
5
14.37
|.14
5
4.5
5.53
16.75
18.35
5
15.99
11.8
5
}?.41
4.94
5
7.42
1,*.96
5
15,79
IO.85
8.?4
3.?t
? .52
14
12.11
5
3.43
12.56
14.85
11.23
,42
13
14,25
*.55
5.?4
3.~
6.8
36.81
5
19.23
18.46
10.6~
S.5
15.23
12
9.34
11
6
23,2
~4.1o
~. 17
8.~
10.35
1~,0~
14.4~
25.08
13.31
10.22
1".63
16.44
9.2~
7.4
13.27
2.85
10.85
12.57
9.59
5,23
1q.56
I1.~
.42
1.51
15.04
%?6
10.56
n?.S
I0.3~
4,85
4.14
0
4
o
t
13.47
27.61
24.e
22.14
15o18
8.37
19.?4
15.44
18.0"
5.14
14
~0.76
10.47
~.14
13.85
11.54
6.16
?
q
13
24,10
6.
12.5.~
3.72
12.$
3
15 57
10"27
4,41
17.05
16.'3
#.41
10.20
l?.~
9.*?
3,4q
2.0
12
4.45
5
8
II
7.38
17,08
12.51
14.3.3
11.44
25.a~
1o. . . .
5.~
16.37
.5~P
13.84
11.83
5.71
14.46
1.42
4.0
8.3'8
26.72
27,41
IO.Ol
lO.~9
10.99
11.42
.3
11.23
22.5
23.41
2,12 ~ 1.57
tT.~'3
I?.~S'
?.10
4.00
8,M
4.09
4
39.21
39.03
14.48
44,87
21.53
19.35
19.31
30.35
4.04
3.43
t4.50
14.~
?.84
14.0~
?34
33.~0
8.1)4
2.50
13.02
30.?2
4.~S
9.48
k l
h FeM c F o b s
3
31,57
2.1
11,0~
12.90
14.23
1.54
10.04
7.40
10.52
14.23
12.71
2.05
4 .~'J
24.84
I$.80
14,44
14.46
25,13
? .52
3.52
14.09
12.18
11 .~3
22.52
31.74
21,42
22.45
5.32
13.3')
12,87
l#.4n
12,33
4.30
4.08
1
IO
t2
2.?3
14,52
2~ .72
15.2~
~.53
14.78
17.2
9,?
19.17
5.?
6.9
35.4
6.30
2~ .~3
14.00
22.20
7.52
4.9
12.40
10.43
51 . 3
16.34
14,42
13.~
2~.87
8.01
17,56
q.31
15.84
2.54
14.51
0
Z3.94
3.72
51,33
10.52
3,0
5.32
38,04
3.31
4.q~
2,43
11.15
h Fcalc F o b s
16
?.47
14.25
10.22
e,O
35.12
10.85
5.?1
4 .oo
?6.94
17.25
17.2.5
6.47
9.43
Fcmlc F o b s
13
35.3
8 .9
5.73
5.24
29.2
18.37
16.75
6.65
5.04
4.07
I1o
11,4
14.47
7.~5
1o
11
I~.15
2? . ?
18.44
~.89
8.09
11.~6
17.8~
13,9 ~
5.03
~.57
4
?~
2
io
5
15.n2
~.54
I?.~T
3'8.35
4.14
15.~0
18.5~
14.14
4.1E
.23
16,52
22,16
7.25
.2O
11.03
39.83
15.40
.33
IO
15:3
4.2')
IO
~.715
11.69
44,84
3t.56
34.24
41.11
54.45
4.40
14.57
24.45
0.72
,41
1,54 4[" 2 . 5 7
22.64
21 .?~
17.471
17.?0
34.74
24.08
14,74
14.37
3.14 It 3.05
12.43
13.13
21.42
18.36
I0,04
10.q5
,]
I~
0
10,34
21,10
49.24
25.2q
40,47
22,06
48.?2
31.~
4,89
?t.??
39,79
63,49
34.36
1?.51
4.47
35.31
1.04
15.13
9,3~
13.04
5.57
2
I
4
33.47
45 89
31.12
22.18
22.94
q.45
~.75
~.3
23.O3
5.14
11.53
2~.13
x 2.5?
X 2.?4
X 1.9'?.
39.79
71.10
21,89
25.13
27.79
16.37
5.66
2~,32
25.03
~.46
14.37
e.47
15.83
17.13
0.53
21.51
30.34
31.50
23,25
34.45
1.43 ~ 2 , 5
12.599 13.71
~.58
23.51
4,83
5.43
12.14
11.42
10.19
5.~
x 2.09
8.5?
,?:5 . . . . . .
O
21.80
?.53
15.32
14,75
15.13
10.15
11.9 ~
ll.qO
~- 2.19
5
4 4
67:?6
42.13
5.0?
30,04
15.13
?.~
35.61
18.65
15,52
? .33
1~.44
.12
to
h Fcalc F o b s
4
44.2~
65.
21.24
24.2
27.44
14.70
q.3
24,19
25.5't
7.~3
14.43
10,06
14
2~,4~
16.24
1.05
q,44
2?.74
=1.14
2~, IO
4.?
IO.~
2?.44
2.qt
?.55
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29.13
t5.712
21.51
12.28
20.18
17.50
17.5~
~,43
11,~o
11.6t
13
13*87
I .o?
8
~,64
27.22
26.4
Id" 3.14
21.42
* 3.14
25. ~-)
q .6~
I0.55
16.94
t0.47
12
31.22
13.58
21.13
11.6!
19,4
16.71
|q.23
3,37
11.42
It.S9
k 1
h Fcalc F o b s
11
12
II
36.14
25.18
24.70
4.47
21 .t~6
6.32
23.?3
6,93
?.74
15.16
12.34
23.3o
4.e5
15.64
14.56
12.4n
11.'9
13.47
I
21.84
52,35
41,21
34,12
s~ ..H*
3?.90
3?.72
3.~4J
24.2
5.54
34.19
14,3
11.20
2.84
14.87
7
8
37.~27"48
,.50
12.15
"17.42
21,~
tl- 2.?6
~ 2.38
?.45*
.1....3.7. . . . . 2 1 , 4 5
20.5~
20.18
4.9~ ~ t . 9 5
?.53
11.52
8.03
.41
4
~
15,.44
12.2~
5.43
x 2.35
t4.56 i
.55
io,.,,
3. . . . . . . . .
16
1"].76
14.~5
11.42
4.45
1o ,,,,55'
28.3
X 2,95
15.t3
X 2.67
15.13
3
T~
2<).4O
O
t
. . . . . . . . . . 46.07
43.04
3.2t5
38,45
42,4
3?.O6
Z~.34
5
4
2
~
4
9
I0
11
12
to
-~.74
2o.os
95,57
65.24
~k~.84
4?.59
~P2.36
57.01
42.24
12.89
2~ .93
21 .~
15
3.O.2
4..T~
14.15
2.30
16.32
46.23
29.20
4~.93
2?.4?
~8.~
42.29
10.18
2~ ,92
~1.47
Iv.
~t.49
IS.4?
12.37
5.72
....
10.43
18,43
1,53
4.54
4.~
5.54
I
3
4
5
?~
24.58
35.44
Io
II
12
13
14.75
I1.71
x 3.51
8.6'~
....
2?.46
k l
h Fc~flc F o b s
~ ,.,6
20.2.S
. . . . . . . . . 1.70
I~*~1
14,37
2.?? X $.14
14.72
15.q0
15,33
14.75
8
23.51
24.61
32,16
55.01
21.~0
12.21
12.93
32.~
15.41
II.S q
.57
12.?1
I0
It
12
13
39.9~
53.02
15,42
22.2?
11,14
16.94
x 3.14
22,56
11,14
!.~9
37.51
52,82
37,50
15.27
15.94
2?.?3
15.49
11.5o
2.S?
9,14
26.41
2?.?O
I0.45
11.23
40.?4
41.88
54.33
52.25
24.95
28.94
31.'~4
34.0?
21.54
23.32
51,92
49.59
11.50
14.56
q.72
9.9O
9.? * 3.~4
I].2~
11.42
11.~5
11.14
15.25
11.90
2
3
12
5,54
1.16
5,57
0
21
35.12
~.n,~3 I 2.38
10.13
13.04
32.40
32.71
37.~4
~.74
9.81
I1. ~
30.04
32.~
23.63
~.oq
.95
12.1q
4.44 X 3.90
15.*.7
23.22 1
11.24
12.28
?
4.42
17.15
3O.93
":;I
I 3,45
.,
II
35.79
56,27
10.60
16.33
?.O2
13.17
4.70
20,O4
9.66
6.2
13.01
IO.17
1.75
8.54
o
I
1o
11
12
13
?5.65
"3.471
14 .qo
19.2}
24.2?
28.55
IC.30
11.61
36.12
51.~9
t4.53
18.57
13.09
iii, ~+i
4.5o x 3.Z,=
13.17
11.33
6,82 x 3.24
23.86
22.65
5.~
4
93.?4
3.
34.14
6.4?
57.23
14.28
49.6O
31.0q
5.29
2.99
10.34
2O.5?
3.~
7~
. .3.!6
. . . . . . . . 5,14
14.75
22.19
11.27
12.56
3?,57
55.59
35.52
13.~?
15.75
2?.2
14.}0
IO.72
.74,~
.?2
37.31
40.45
52.?3
50,35
56.39
35.69
33.5O
35.03
34 79
35.03
~'Ts#-A 3.90
22.2~
25.32
22.56
23 .?~
5.95
9.14
.?5 x 3.24
.4? X. 3.62
18.,4
k l
h Fcalc F o b s
9.85
to.S?
22.18
It. C. FREEMAN,
M. R. SNOW,
I. NITTA
AND
"')
S(2.x) c ( 3 ~
1467
3-dimensional
N u m b e r of reflections
Final R value
254
0.165
877
0.091
#(1)* ( C a - O )
~(1)* ( C u - N )
0.03 A
0.03
0.010 A
0.010
~(l)* (O-C)
0.05
0.015
d(l)* (N-C)
~(/)* (C-C)
0.06
0.06
0.016
0.017
_ ~ N ( 1
K. TOMITA
Discussion
of
the
structure
L=_~
Fig. 3. Bisglycino-copper(II) m o n o h y d r a t e : t h e a s y m m e t r i c
u n i t a t (x, y, z) w i t h its i m m e d i a t e e n v i r o n m e n t . Covalent
bonds,
; hydrogen-bonds, - - ,
weak coppero x y g e n interactions,
* D r J. A. I b e r s has p o i n t e d o u t to us t h a t e v e n if the
s t a n d a r d d e v i a t i o n s of t h e o b s e r v e d s t r u c t u r e a m p l i t u d e s h a d
b e e n on an a b s o l u t e scale, we b l u n d e r e d b y using incorrect
values for some of t h e .Fu a n d (l(Fu) (Table 2). F o r 36 uno b s e r v e d reflections in centric projections, our values were
correct. F o r 32 general reflections we used ] F u l = 0 " 5 F m i n
i n s t e a d of 0"67Fmin a n d cr(Fu)= Fmin/V12 i n s t e a d of Fmin/VI8
(Ibers, 1956). Owing to t h e over-weighting of t h e 808Fo,
t h e 32 slightly incorrect values of _Fu were included w i t h t o o
low relative weights. The effect on t h e final p a r a m e t e r s is
considered to be negligible.
Distance
Cu-O(1)
Ca-O(3)
Ca-N(1)
Cu-N(2)
Ca-O(5)
N(1)-C(1)
N(2)-C(3)
C(1)-C(2)
C(3)-C(4)
C(2)-0(1)
C(2)-O(2)
C(4)-0(3)
C(4)-O(4)
C u - . . O(2 viii)
N(1) O(1)
N(2) 0(2)
N(1) N(2)
O(1) 0(2)
d
1.95~ A
1.946
1.984
2.021
2.404
1.473
1.484
1.49 s
1.54 z
1.275
1.226
1-291
1.24 a
2.742
2.663
2.691
2-989
2.831
a( d)
0.009 /~
0.009
0.010
0.011
0.011
0.016
0.017
0.017
0.018
0.014
0.015
0.015
0.015
0.009
0.014
0.016
0.014
0.012
H y d r o g e n b o n d distances
Distance
0(5) . - " 0 ( 2 ix)
0 ( 5 ) . ' ' O(4 v)
O(1) N(1 ii)
Equivalent
distance
0(2) . . - 0 ( 5 x)
0 ( 4 ) . . . O(5 xi)
N(1) O(1 iii)
d
2.765 A
2.80 a
3.027
0(3) .. N(2~)
N ( 2 ) O ( 3 iii)
3-086
2.982
a(d)
0.014 A
0.015
0.013
0.015
0.014
S h o r t e s t n o n - b o n d e d i n t e r - c o m p l e x distances
0 ( 1 ) - . " C(1 vii)
O(1) N(1 vii)
0 ( 1 ) . . - C(2 vii)
C ( 1 ) . . . O(1 vili)
N(1) O(1 viii)
C ( 2 ) . . . O(1 viii)
3.13/~
3.15
3.19
1468
STRUCTURE
OF BISGLYCINO-COPPER(II)
T h e a s y m m e t r i c u n i t s are d e n o t e d as follows"
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(ix)
(x)
(xi)
~
x
x
+x
+x
-+x
~
~
--x
--x
--+x
y
1+ y
- 1+ y
--y
1--y
--y
+y
-+y
1--y
1--y
1--y
z
z
z
1--z
l--z
1--z
-z
-z
+z
--+z
1-z
MONOHYDRATE
The ligands
T h e c a r b o x y l o x y g e n a t o m s n o t s t r o n g l y b o u n d to
t h e c o p p e r ( I I ) ion, 0(2) a n d 0(4), e a c h h a v e t w o w e a k
i n t e r a c t i o n s (Fig. 3), w h e r e a s of t h e t w o a m i n o
n i t r o g e n a t o m s , N(2) h a s one h y d r o g e n b o n d a n d
N(1) h a s two. A l t h o u g h t h e g l y c i n e l i g a n d s t h u s h a v e
d i f f e r e n t e n v i r o n m e n t s , t h e g r e a t e s t difference bet w e e n t h e m occurs i n t h e c a r b o n - c a r b o n b o n d - l e n g t h s
(0.04 A or 2.23(d)). T h i s is n o t c o n s i d e r e d s i g n i f i c a n t .
standard deviations
Angle
O(1)-Cu-N(1)
O(3)-Cu-N(2)
N(1)-Cu-N(2)
O(1)-Cu-O(3)
N(1)-Cu-O(2 ~ii)
N(2)-Cu-O(2vm)
O(1)-Cu-O(2~)
o(3)-Cu-O(2~-u)
o(5)-Cu-O(2V~U)
N(1)-Cu-O(5)
N(2)-Cu-O(5)
o(1)-Cu-O(5)
o(3)-Cu-O(5)
Cu-N(1)-C(1)
Cu-N(2)-c(3)
Cu-O(1)-C(2)
0u-O(3)-C(4)
N(1)-C(1)-C(2)
N(2)-C(3)-C(4)
C(I)-C(2)-O(I)
C(I)-C(2)-0(2)
O(1)-C(2)-O(2)
C(3)-C(4)-O(3)
C(3)-C(4)-O(4)
O(3)-C(4)-O(4)
CuVit-O (2)-C(2)
Hydrogen bond angles
eu-o(5) 0(2=)
Cu-O(5) o(4v)
o ( 2 ~ ) - o ( 5 ) . . , o(4v)
0
85.0
85.4
96.6
92.9
93.O
87.3
91.2
82.5
170.9
95.9
89.6
91.7
88.8
109.3
109.6
115-3
115.8
112.6
111.3
117.4
118.3
124.3
117.5
119.7
122.8
112.6
a(0)
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.8
0-8
0.8
0.8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.8
a(O)
112.3
130-8
116.7
C~-N(I) O(1~)
115.0
eu-N(1)-.
0(4i,,)
116.3
C(I)-N(1)
O(lm)
115.4
C(1)-N(1)
O(4 iv)
108.1
Cu-N(2) 0(3 iii)
116-8
C(3)-N(2)
O(3~)
108.0
C(2)-0(1)
N(lm)
100.0
Cu-0(1) N(1 )
120.0
c(2)-0(2)
o(5x)
122.9
Cu~-O(2) .. o(5x)
108.2
Cu-O(3) N(2)
113.8
C(4)-O(3) N(2 m)
106.0
C(4)-O(4) N(1 vi)
119.9
C(4)-O(4) .. O(5 xi)
107.4
N(lVi) . . . 0 ( 4 ) . . . 0(5 xi) 80.2
0.8
0-8
0.9
0.8
0.8
1.0
1-0
0.8
0.8
1.0
0.8
1.0
0.8
0.8
1.0
1.0
1.0
0.9
Atom
Cu
+0.0059*
O(1) +0.0003
0(2) +0.0005
0(3)
0(4)
N(1) --0.1027"
N(2)
C(1) +0.00002
C(2) -0.0010
C(3)
C(4)
--0.1256"
+0.0512"
+0.0189
+ 0.0028
+0.0034
- 0.0268
--0.1623"
--0.0288
+0.0368
+0.0054
-- 0.0088
Coordinate
. s.d. (a)
(A)
0.0016
0.0082
0.0090
0.0096
0.0104
0.0100
0.0110
0.0124
0.0114
0.0137
0.0120
w---
K/a s
0
131
111
100
88
89
63
47
67
43
63
Plane
2
3
3
6.2
--
T h e C ~ - C O - O g r o u p s are p l a n a r (planes 1, 2 of
T a b l e 7). T h e g r e a t e s t d e v i a t i o n is 0.009 _~ of a t o m
C(4) f r o m p l a n e 2. T h e angle b e t w e e n p l a n e s 1 a n d 2
is 5.4 , i n d i c a t i n g t h a t t h e chelate p a r t of t h e c o m p l e x
is o n l y a p p r o x i m a t e l y p l a n a r . T h e a m i n o n i t r o g e n
a t o m s N(1) a n d N(2) d e v i a t e f r o m p l a n e s 1 a n d 2
b y 0.103 A a n d 0.162 ~ r e s p e c t i v e l y . T h e t e t r a h e d r a l
e n v i r o n m e n t of N(1) w i t h t w o h y d r o g e n b o n d s is
m o r e s y m m e t r i c a l t h a n t h a t of N(2) w i t h one h y d r o g e n
bond. T h i s q u a l i t a t i v e l y a c c o u n t s for t h e difference
of 0.059 A b e t w e e n t h e i r r e s p e c t i v e d e v i a t i o n s .
H . C. F R E E M A N ,
M. R . S N O W ,
I. NITTA
AND
K. TOMITA
1469
Atom
Cu
Axis i
~l(o'~i)
0il (o'011)
0i2(0"0i2 )
0i3 (0"0~3)
~9~(0"~9i)
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
I
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
133(3)
145(4)
191(3)
134(16)
165(13)
174(14)
134(13)
164(16)
227(13)
136(16)
150(17)
257(13)
144(15)
213(15)
245(14)
137(17)
208(17)
331(17)
132(20)
150(18)
182(15)
154(18)
165(19)
236(17)
133(24)
181(17)
210(18)
98(24)
136(22)
186(16)
139(21)
172(20)
263(21)
142(19)
161(17)
174(20)
84(4)
71(3)
20(3)
113(17)
111(64)
41(57)
105(9)
71(12)
25(9)
88(18)
71 (6)
19(6)
117(6)
73(18)
33(12)
41(7)
63(9)
138(4)
45(39)
127(42)
112(18)
95(58)
160(14)
51(10)
90(13)
79(31)
11(31)
24(20)
75(28)
109(10)
127(25)
143(25)
86(9)
109(43)
161(45)
87(73)
113(11)
149(9)
71(3)
51(18)
64(51)
50(43)
102(23)
160(16)
74(11)
125(48)
141 (46)
74(6)
84(10)
157(20)
68(20)
85(7)
50(6)
41(5)
135(37)
144(41)
114(19)
124(49)
56(50)
52(10)
8(20)
98(20)
88(13)
73(29)
162(28)
85(19)
100(10)
78(10)
16(9)
87(28)
87(76)
4(61)
24(12)
113(12)
87(2)
48(20)
137(26)
98(53)
19(10)
96(23)
72(6)
34(49)
123(50)
81(5)
28(7)
75(12)
67(8)
49(8)
128(9)
63(4)
93(30)
125(23)
35(23)
34(39)
72(64)
62(9)
98(20)
167(28)
79(31)
73(11)
80(20)
20(12)
39(22)
124(24)
75(9)
19(43)
109(43)
92(36)
81(3)
100(3)
13(3)
84(17)
117(70)
27(69)
94(7)
98(11)
9(10)
90(11)
101 (6)
11 (6)
97(6)
94(20)
8(10)
30(10)
59(10)
88(4)
73(44)
155(37)
106(22)
95(28)
110(12)
21(10)
68(13)
98(29)
23(16)
8(29)
97(29)
90(11)
113(20)
138(16)
58(9)
90(40)
152(76)
62(76)
O(1)
0(2)
O(3)
0(4)
0(5)
N(1)
N(2)
C(1)
C(2)
C(3)
C(4)
/~~%11~
111'~'
(:(I)
C(I)
~~I
11~ 11~0'
1174"~117.I"
,,.
o(I)
073
(a)
o<11
o~)
(b)
1470
"
S T R U C T U R E OF B I S G L Y C I N O - C O P P E R ( I I ) M O N O H Y D R A T E
financial assis-
References