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1463

Acta Cryst. (1964). 17, 1463

A Refinement of the Structure of Bisglycino-Copper(II)


Monohydrate, Cu(NH2CH2COO)2. H20
BY H. C. FR~,~,MA~ AND IV[. 1~. SNOW*

School of Chemistry, University of Sydney, Sydney, Australia


AND I. I~ITTAt AND K. TOMITA:~

Chemistry Department, Faculty of Science, Osaka University, Osaka, Japan


(Received 31 October 1963)
The crystal structure of bisglycino-copper(II) m o n o h y d r a t e , which was originally determined b y
Tomita & N i t t a in 1961, has been refined b y three-dimensional least-squares methods. The molecular geometry of this cis complex is essentially the same as reported earlier, but the s t a n d a r d
deviations of the distances have been reduced to a t h i r d of their previous values. The groups
C~-CO-O of b o t h glycine molecules are highly planar, the entire chelate p a r t of the complex only
a p p r o x i m a t e l y so. The e n v i r o n m e n t of the water molecule is trigonal. An error analysis of the reflection data is presented.
1. Introduction
T h e c r y s t a l 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 was d e t e r m i n e d f r o m W e i s s e n b e r g p r o j e c t i o n
d a t a b y T o m i t a & N i t t a (1961). T h e y s h o w e d t h a t
two g l y c i n e molecules are c o o r d i n a t e d to t h e c o p p e r ( I I )
ion, f o r m i n g a p l a n a r cis c o n f i g u r a t i o n . T h e i r r e g u l a r
o c t a h e d r a l c o o r d i n a t i o n is c o m p l e t e d b y two o x y g e n
a t o m s : one b e l o n g i n g to a w a t e r m o l e c u l e a n d t h e
o t h e r a 'free' c a r b o x y l o x y g e n a t o m of a n a d j a c e n t
asymmetric unit.
A t t h e t i m e of p u b l i c a t i o n of t h e O s a k a p a p e r
( T o m i t a & N i t t a , 1961), t h e s t r u c t u r e h a d b e e n
solved i n d e p e n d e n t l y in S y d n e y as p a r t of a p r o g r a m
of a c c u r a t e s t r u c t u r e a n a l y s e s of m e t a l - p e p t i d e
complexes. Since c o m p l e t e t h r e e - d i m e n s i o n a l d a t a

were available in Sydney, it was agreed that an


accurate refinement should be carried out and submitted as a joint publication. Unfortunately
a
systematic comparison of the Osaka (TN) and Sydney
(FS) observations was impossible because the original
Osaka records had been lost.
In this paper we do not make a detailed comparison
of our results with the three metal glycinate structures
which have been previously reported: bisglycinonickel(II) dihydrate (Stosick, 1945a) and bisglycinocadmium and zinc monohydrates (Low, Hirshfeld &
l~ichards, 1959). These are trans structures and were
not refined to high precision. Other structure determinations of trans a-amino acid chelate complexes,
in increasing order of precision, are those of bis-a* Present address: Chemistry Department, University
College, London, W.C. 1, England.
Present address: Kwansei Gakuin University, Nishinomiya, Japan.
Present address: Biology Department, Massachusetts
Institute of Technology, Cambridge 39, Massachusetts, U.S.A.

a m i n o b u t y r a t o - c o p p e r ( I I ) (Stosick, 1945b), bis-DLp r o l i n a t o - c o p p e r ( I I ) d i h y d r a t e (Mathieson & Welsh,


1953) a n d b i s - l ' - a m i n o c y c l o p e n t a n e c a r b o x y l a t o - c o p p e r ( I I ) ( B a r c l a y & S t e p h e n s , 1963).
2. Experimental

Crystals prepared from a neutral solution of copper(II)


ion and glycine always grow as fine, light blue needles
which are unsuitable for structure analysis on account
of their small size. Okaya, Pepinsky, Takeuchi,
Kuroya, Shimada, Gallitelli, Stemple & Beevers (1957)
first reported the space group and approximate unitcell dimensions of such crystals, but did not proceed
with structure analysis.
It was accidentally found that triglycine present in
the preparation allowed much larger crystals to form.
Apparently the triglycir.e-copper(II) complex is both
more stable and soluble than the glycine complex.
It buffers the copper(II) ion concentration at a low
value, allowing comparatively large (0"3 x 0-15 x 0.15
T a b l e 1. Unit-cell data of Tomita & .Nitta (1961)

and Freeman & Snow for bisglycino-copper(II)


monohydrate
CuCaHsN204 . It20
F.W. = 228.67
Orthorhombic TN
FS
a(aa) = 10.78 (0.010)
10.866(0.017 ) A
b(ab) ---- 5.208(0.004)
5.220(0.007) A
c(ac) = 13.47 (0.020)
13.502(0.021 ) A
U -- 756.5
765.9 A3
Dm---- 1"99s
1-99 g.cm -3
Z =
4
4
Dx = 2.01
1.98 g.cm -3
# =
-42.6 cm -1
~t(Cu Ka) = 1.542
1.5405(a~), 1.5443(a2) A
Space group: P212~21 (from systematic absences).

1464

STRUCTURE

OF B I S G L Y C I N O - C O P P E R ( I I )

MONOHYDRATE

Table 2. Summary of the details of the least-squares refinement


Cycle
Nos.

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

]/w = 1/zJ (Fo)


from A, Fig. 1

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

* R: Cycles 1-7, observed reflections only; cycles 8-16, all reflections.

ram3) crystals of bisglycino-copper(II) monohydrate


to form slowly. The crystals are ortho~hombic needles
exhibiting predominantly the form {101}. TN prepared
similar crystals by buffering the pH of the solution
with carbon dioxide.
The two sets of unit-cell data are compared in
Table 1.
The unit-cell dimensions of TN had been fitted to
the diffraction angles of eight planes in the range
10 _< 20 _< 20 . Their diffractometer measurements
were calibrated only for zero error by means of silica
powder lines.
The values determined by FS were fitted by leastsquares to the spacings of the al and a2 components
of twelve reflections at high angles on Weissenberg
photographs calibrated with platinum powder lines.
These values were used in the subsequent structure
refinement.
A 0.29 mm long crystal of rhombic cross-section,
with diagonals 0.16 x 0.175 mm 2, was rotated about
the needle axis to obtain hO1 to h41 multiple-film
Cu K a eqni-inclination Weissenberg data. For interlayer scaling the hk0 and 0kl spectra were recorded
with crystals 0.15 x 0.22 x 0.175 mm 3 and 0.19 x 0.16
0.18 mm~; the last mentioned length corresponds
to the rotation axis in each case. The intensities were
estimated visually and corrected for Lorentz-polarization and Tunnel effects, but not for absorption.
The 93 reflections which were recorded twice were
used to correlate 886 non-symmetry-related reflections
(85% of the accessible data), of which 71 were too
weak to be observed.

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

& Lipson (1956), was 1/V(1-klo), where Io is the


observed intensity and k was determined to be
6 x 10 -5.
The scattering factors used were those of Berghuis,
Haanappel, Potters, Loopstra, MacGillavry & Veenendaal (1955) for carbon, nitrogen, oxygen and copper.
The Cu + curve was used for copper for reasons mentioned in previous communications (Freeman, Smith
& Taylor, 1961 ; Freeman, Robinson & Schoone, 1964).
The real part of the anomalous scattering by copper
was allowed for by subtracting 2.1 electrons from the
scattering curve over the whole sin 0 range (Dauben
& Templeton, 1955).
At the end of the least-squares refinement the
unweighted and weighted reliability factors for all
reflections were, respectively, R = 0-091 and R' -- 0.103.
The final r.m.s, shifts in the coordinates were 6x=
0.014, ~y=0.0002, (5z=0.0002 /~. A final difference
Fourier synthesis had only two peaks of probable
significance: these peaks were close to the copper
atom. They could be explained by only slight differences between the copper atom parameters required,
respectively, by the Fourier and least-squares weighting schemes.
The final coordinates are shown in Table 3(a),
and the thermal parameters in Table 3(b). The observed and calculated structure factors are compared
in Table 4.
ZV~-

6 ~o/~

260

~.._o

2020
0

I0

~
o o
20

o
30

"
,
hO

,~'T---------~, /3 ,
50
60
70

Fo

Fig. 1. A: The m e a n discrepancy / I F (average difference


between two estimates of _Fo in a range of _Fo) plotted
versus
Fo. B : The population distribution of -/~o: the n u m b e r
of reflections, n, in a range of fie plotted versus ~'o.

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

Observed and calculated structure amplitudes for bisflycino-copper(II) monohydrate

E a c h group is h e a d e d b y ]c a n d 1. S u b s e q u e n t lines c o n t a i n h, Fca~c a n d Fobs. The Eca~c h a v e been scaled b y a f a c t o r of 1.0506.


Values m a r k e d 'x' represent Fmin; values m a r k e d * represent ~Fmin; double-starred F ' s were excluded from least-squares
cycles 8-16
k

h Fcalc Pobs
0
4
6

. .t.57
...
o

7
q~
l
II

"
2

?
*
i~
11
12
1.5
O
1

IO
II
12
13
o

2
4~

7
8
19
^
11
12

,121
X 2.2~

74

I
IO
11

o
1
3
4
?
5

I~.. 37

35.0~
33.69
29,96
39.12
61.17
51.97
19.95
22.2"
20.61
24. ceJ
.?." X :=.5
32.5?
714.62
2=-.56 31.60
25.4
2.79
11.31
13.90
12.59
14.7~
1.44 X 3 , ~
17.72
21,~2

54.~Z
92.93
41. :~
14.61

75. 654~f~5 I.~?


71.75
42.~2
6.B3
52.~1
57/'?
56.25
47.3?
47.?=
40.35
4O.}6
l*lO 3.24
22.?7
2" .9"
22.73
27.6C
.~
I( 3.5?
13.23
14.47
11.43

':
66.92
~6.42
45.('7
17.53

I?

k l
h Pc,Mc F o b s

3
76

tO
0

3
2.82
IO.S5
22.42
15.08
11.2~
15.32
?.3
13.42
??.?6
81.47
14.61
18.66
12.~
14.0
19.94
22.4
2e.31
30.4';
15,02
15.32
8.?u
11.271
4.98 x ~.24
q.o$
IO.15

O
2

47.02
36.07
3~.17
5.43
53.30
2Z.37
43,85
30.93~
.04
x 3,~
14.1q
2.~. 57
x 4.00

T~

11
12
o
o

5,q
45,?5
~0.44
1.41
1o.??
2.5?
12.74
25.51
13.t~

3.91
4.38

.42
34.45
arP.4 ~ ,
24,=~
2o.15
31.12
14.T5
30.55
IS.25

'}

7
;
9
Ir,
11

3.42
39.9
3? .44
38 . 3
34,?6
34.~4 I
33.2?
3? .22
56.6
54,25
12.24
13.0
4.52
10.7~
17.76
15.91
32.46
32,~q
IZ.~"
14.~4
4.34 ]L 3.0~

3
5

IC
11

I
4

o
o

14

IO
II

24.46
34,~
36.64
56.~
~.ge
23.51
~,1~
3~.45
15.83
13.93
x 71.24
13.~4

~t

?~

I
ii
12
13

X 4.0 ~
21.7~
23.51

e.54

.5}

22.,,

x 2.,41

I'

13

,5,

x ..24 #
1, 2 . }
P, 2o3~
I0.2:1

14

225

9.03

I0.2'~

.........

3
8
o

3
5

20.15'
8.24
6.5?
3.36
13.85
11.1o

17

8.39
o

IO
It
I
o

4
5
I

O
2
3

t
o

_t
3
I

23.60
o

,.o,?'2
38,93
3?,03
5.14
3HI.4I
9.41
32,34
17.70
12.94
~ 2.86
15,52

4
?
1o
It
12
2
o

2o.2 et
23.6
1~.51

1.7~
~.65
21.32

5
~
?
8

37,45
36.24
33.1
4.75
I1.??

3?,03
35.12
31.69
8.95
12,47

19.94

In.lq

6
?.?1

55.~
44,45
~1 ,~,..~17..
42.93
3.59

17.19
1.40
4.t
4O.2

. .2. ,. ?. ...2. .5 7

In
II
12
13
31

4
7

I
II
12
13

3.11
14.27
14.33
I,Ot

i~' 22.0
15.46
5.12
3.51

14.37
II
8,04
5.?6 ~
t
3/.,=

3
~

1
~.15

59.99
8P~,42
32.26
23.~2
41.94
41.69
.q6
11.9
23,37
25.51 '
14.5
14,23:
14.42
15.61 ;
2.~. 95
21.?o
1 . ~ t[" 2 . 5 7
I0.57
tO.S7

31.0"
52.62

4
tot
I1
12
2

1O 42.57
. . . . . . . . . . 40,4q

2.57
14.47
13.13
I =.05*

34.0?
49.11 i

?
IO
II
1
o
/

11.47
2?.O0
31.04
10.29

!),99
26.17
2.8
12.2~

I?.O?
12.~0
I t.40
8.45
12.~8

17.13
12.28
I t .04
9.23
11,90

12,59
15.~4
5.6~
2q.3!
6.15
12.39
5.46
22.88
9.25

6
15
o

11
12

11.44
3.e

?
10
11
12
2

2
]

?
13.71
t?.SL
It.23
25.7
5,9O,
11.=.~
5,43
18.94
4.76

IO
I1
12
2
tO

I?.2o
t.37
8,~
1.76
30.42
Iq.27
4 , 8 ~ 2.?6
3O.4O
14.23
14.14
12.1q
.54
10.47
?,27
4,47
10,56
7.50
15

16
11.83
9.16
t?.2~
,95
.~3

11.47
.33
15.~
5.5?
-.'~?

I?

6
q
IO
11
12

4
=
o~

I
11

4,1 ][ 3.52
3 42
34 , 3
94:'~
4?.?8
21.345
21,80
11.55
13,42
24.'~t
24.t5
34.'16
31.711
1~.41
14.54
IO.'~
9.41
4.~t"
4. I
1o.??
11.33
1,90 41 2 . 5 ?

I1

14,25
24,54
43.1~
2?.22
40,07
22.?5
45,21
39.36

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o

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3
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0
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h Fcalc F o b s

16
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h Fcalc F o b s

4
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k 1
h Fcalc F o b s
11
12

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36.14
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I
21.84
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3?.90
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7
8

37.~27"48
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20.5~
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11.52
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3. . . . . . . . .

16

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4.45

1o ,,,,55'

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t

. . . . . . . . . . 46.07
43.04
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4

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8
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13

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3

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21

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11
12
13

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4
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40.45
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35.03
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18.,4

k l
h Fcalc F o b s

9.85

to.S?

22.18

It. C. FREEMAN,

M. R. SNOW,

might be attributed to factors such as the presence


of systematic errors in the experimental data.
On the other hand, the function

V [ z IFo - F~l=/z (~FF],


which was derived in intervals of increasing 2'o from
the curves in Fig. 2, was found to be 2.15+0.035.
This is consistent with the greater part of the
discrepancy being attributed to an over-estimation
of the weighting factors by a factor of about two.
This corresponds to an under-estimate of ~(F) from
the limited selection of the doubly estimated intensities, a result which is not unexpected. (An error
only in the scale of the weights does not affect the
final parameters or their calculated standard deviations in the computational method used in this
refinement).*
Aspects of the two-dimensional (TN) and three-

I. NITTA

AND

"')

S(2.x) c ( 3 ~

1467

dimensional (FS) refinements of the structure are


compared below:
2-dimensional

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

* T N : a v e r a g e e.s.d.'s from f o r m u l a e of Cruickshank (1949).


F S : a v e r a g e e.s.d.'s from final l e a s t - s q u a r e s cycle.

The bond lengths found by TN do not differ by


more than 1.5 e.s.d.'s from the new values. The
e.s.d.'s, however, have been reduced to less than
one-third of their previous values by the threedimensional refinement.
5.

_ ~ N ( 1

K. TOMITA

Discussion

of

the

structure

Fig. 3 illustrates the asymmetric unit at (x, y, z)


and its immediate environment. Interatomic distances
and intervector angles are listed in Tables 5 and 6.
Arabic numerals have been used to distinguish atoms
of the same type within an asymmetric unit and
Roman superscripts for atoms not belonging to the
asymmetric unit at (x, y, z).
Table 5. Interatomic distances and their estimated
standard deviations

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

N(1) O(4 iv)

0(4) . . . N(1 vi)

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

Molecules are l i n k e d i n spirals p a r a l l e l to b b y b o n d s


f r o m c a r b o x y l o x y g e n a t o m s to c o p p e r ( I I ) ions
(0(2 ~m) . . . Cu, 0 ( 2 ) - - " Cu vii etc. i n Fig. 3). T h i s
c o p p e r - o x y g e n i n t e r a c t i o n a n d t h e c o o r d i n a t i o n of
T a b l e 6. Intervector angles and their estimated

MONOHYDRATE

one w a t e r m o l e c u l e m a k e t h e c o p p e r ( I I ) i o n coordinat i o n sixfold. C h e l a t e molecules r e l a t e d b y t h e l a t t i c e


t r a n s l a t i o n b are l i n k e d b y t w o h y d r o g e n b o n d s f r o m
a m i n o n i t r o g e n to c a r b o x y l o x y g e n ( N ( 1 ) . . - 0(1) =
3"03 ~ , N ( 2 ) - . . 0 ( 3 ) = 3 . 0 9 A). T h e s p i r a l c h a i n s
are cross-linked b y h y d r o g e n b o n d s f r o m w a t e r to
c a r b o x y l o x y g e n ( 0 ( 5 ) . . . 0 ( 4 v ) = 2 . 8 0 A, 0 ( 5 ) - . . 0 ( 2 i~)
= 2 . 7 6 J~. T h e r e is also a h y d r o g e n bond, N ( 1 ) . - . 0 ( 4 iv)
= 2 . 9 9 _~, a c t i n g c h i e f l y p a r a l l e l to (101).

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

T a b l e 7. Details of plane of best fit


Each plane is represented by lx" + my' + nz" + k = 0 with respect
to orthogonal axes, where x', y', z" are coordinates in /k
Plane
1
m
n
k
1
+0.856039
+0.456178
+0-243102
--3-081509
2
+0.806339
+0.511710
+0.296596
--3.544961
3
+0-865199
+0.437638
+0.244753
-- 3-021608

Atom

Deviation from plane (A)


^
1
2
3

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

The starred deviation values correspond to atoms not


included in the least-squares plane.

Plane
2
3

Angles between planes


1
2
5.4
-0.2
6-2

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

T a b l e 8. Parameters of thermal vibration ellipsoids


/~t, r.m.s, component of thermal displacement along principal axes i (A x 10a); OiL angles with respect to the cell axes/~ (degrees);
~0i, angles between principal axes and the normal to the plane of the coordination square (degrees). Estimated standard deviations
in these quantities are also given

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)

Fig. 4. Comparison of the average bond lengths and angles


of the chelate rings of bisglycino-copper(II) monohydrate
(a) with those obtained for glycine (b) by Marsh (1958).

The average bond lengths and angles of the chelate


are compared with those obtained by Marsh (1957)
for c-glycine in Fig. 4. The standard deviations in
the averages have not been estimated since the two
chelate molecules do not represent independent
determinations. It can be seen that the bond lengths
and angles agree well except for those of the carboxyl
group. In the chelate the C(2)-O(1) bond has lengthA C 17--95

ened and the C(2)-0(2) bond has shortened compared


with the glycine values; the difference of 0.05 A has
probable significance. Differences of this magnitude
are observed in amino acid salts (Hahn, 1957) and
chelates (Barclay & Stephens, 1963), in carboxylic
acids when the proton is attached to the carboxyl
oxygen (Nardelli, Fava & Giraldi, 1962) and in
peptide-metal complexes (Strandberg, Lindqvist &
Rosenstein, 1961; Freeman et al., 1964). Coordination
to a metal presumably stabilizes the resonance form
in which C(2)-O(1) is a single bond.
Environments of the copper ion and water molecule
Two glycine molecules are chelated to the copper(II)
ion. The ligand atoms, 0(1), 0(3), ~(1) and N(2) are
not strictly co-planar, the deviations from their best
least-squares plane (plane 3, Table 7) ranging from
0.019 A to 0.037 A. The copper(II) ion lies 0.05 A
out of this plane on the side of the water molecule
(Cu-O(5)=2.405 ~). A weak interaction (Cu-O(2vui)
--2.74 ~) with an adjacent carboxyl oxygen completes
the distorted octahedral coordination of the copper(II)
ion.
The water molecule additionally makes two close

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

approaches to carboxyl oxygen atoms at distances of


2.76 and 2.80/~ (Fig. 3). The angle O(2L~)--O(5)--O(4v)
is 116"7, making the assignment of these contacts
as hydrogen bonds reasonable. The distance of the
water oxygen atom from the best plane fitted to itself
and its three neighbours Cu, 0(2 ix) and O(4 v) is 0"06 A,
and the sum of the three angles about it is 359.8 .
Approximately trigonal water environments of this
kind, whilst occurring in the minority of structures,
are not uncommon (Clark, 1963).
Thermal analysis
The parameters #i2 and 0i~ of the thermal vibration
ellipsoids for all atoms (other than hydrogen) are
shown in Table 8. These were calculated by the function and error program of Busing & Levy (1961, p. 140)
and represent, respectively, the magnitudes of the
principal axes of the vibration ellipsoids and their
angles with respect to the cell axes. The angles
between the same principal axes and the normal to
the plane of the atoms O(1), 0(3) and N(1) have also
been calculated. Except for the atoms C(2), C(3) and
N(1) the atoms of the chelate have their maximum
amplitudes of vibration roughly normal to the coordination plane. The water molecule has the largest
maximum vibration of any atom and this makes an
angle of 8.6 with the normal to the plane of the atoms
to which it is bonded (O(4v), 0(2 '-~) and Cu).
The vibrations of the atoms :N(1), O(1), C(1), C(2)
and 0(2) are smaller than those of the corresponding
atoms of the other glycine molecule. The general
trend of the magnitudes of the thermal vibrations
is the same in both glycine molecules. In particular,
the trigonal carbon atoms C(2) and C(4) have the
smallest thermal parameters and the 'outer' oxygen
atoms 0(2) and 0(4) the largest.
We cannot explain the behaviour of atoms C(2)
and C(3). The atom C(2) has a relatively large vibrational component in the plane of the chelate in a
direction approximately parallel to the vector between
carboxyl oxygen atoms 0(1) and 0(2). A similar
result was found for this atom in glycine by Marsh
(1957) who thought it might be an artifact caused
by the electron density associated with the C(2)-0(1)
bond (i.e. C(1)-0(1) using Marsh's labels). Anomalous
values of the thermal vibrations of trigonal carbon
atoms in potassium bisbiureto cuprate(II) tetrahydrate
h~ve ~1~o been reported (Freeman et a~,, 1961), Little
physical significance, however, is accorded these
phenomena, especially in view of the omission of
hydrogen atoms from the present refinement.
2Von-bonded contacts
The three shortest contacts between adjacent complexes are made by 0(1) with the atoms C(lvii), N(1 vii)
and C(2~ii). These distanccs arc included in Table 5.
All other contacts exceed 3.2 A.
The authors gratefully acknowledge

financial assis-

tance from the U.S. Public Health Service through


the :National Institutes of Health, Bethesda, Md.
(Grant :No. GM10867), and the award of a Research
Scholarship from the Commonwealth of Australia
(for M.R.S.).
The computations were carried out with the help
of Prof. J. M. Bennett and the staff of the Basser
Computing Laboratory, University of Sydney, on
SILLIAC; Mr T. M. Prentice and Standard Telephone
and Cables Ltd., on ZEBRA; and Mr P. N. L. Goddard
and the staff of the computing centre of the Weapons
Research Establishment at Salisbury, South Australia
on the IBM 7090. The SILLIAC programs were
written by Dr F. M. Lovell and Dr J. G. Sime, who
also assisted in carrying out the other calculations.
The authors also wish to thank Drs J. A. Ibers and
B. M. Craven, who gave helpful criticism and advice.

References

BARCLAY, C. A. & STEPHENS, F. S. (1963). J. Chem. Soc.


p. 2027.
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(1955). Acta Cryst. 8, 478.
BUSING, W. L. & LEVY, H. (1961). In Comput~:ng Methods
and the Phase Problem in X-ray Crystallography.
Pergamon Press.
CLARK, J. R. (1963). The Water Molecule in Hydrated
Organic Crystals. Rev. Pure Appl. Chem. 1S, 50.
CRUICKSHANK, D. W. J. (1949). Acta Cryst. 2, 65.
DAUBEN, C. H. & TEMPLETON, D. H. (1955). A c t a Cryst.
8, 841.
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