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Synthesis and Reactivity in

Inorganic and Metal-Organic
Chemistry
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A Method for the

Preparation of the cisBis(Glycinato)Copper(II)
Monohydrate Complex in the
Solid State
A. K. Saxena

Department of Physics and Astrophysics ,

University of Delhi , Delhi, 110007, India
Published online: 14 Apr 2008.

To cite this article: A. K. Saxena (1998) A Method for the Preparation of the
cis-Bis(Glycinato)Copper(II) Monohydrate Complex in the Solid State, Synthesis
and Reactivity in Inorganic and Metal-Organic Chemistry, 28:10, 1653-1663, DOI:
10.1080/00945719809349420
To link to this article: http://dx.doi.org/10.1080/00945719809349420

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SYNTH. REACT. INORG. MET.-ORG. CHEM., 28(10), 1653-1663 (1998)

A METHOD FOR THE PREPARATION OF THE

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cis-BIS(GLYCINATO)COPPER(II) MONOHYDRATE COMPLEX IN THE

SOLID STATE

A. K. Saxena
Department of Physics and Astrophysics
University of Delhi
Delhi-110007
India

ABSTRACT
A

method has

been

described

for the preparation of the

bis(glycinato)copper(II) monohydrate complex in the

in the solid state.

cis

form

The complex was characterised by IR

spectra, elemental analyses and X-ray spectroscopy using a

compact

X-ray

diffraction

analyser.

The

blue

complex

prepared in the solid phase has an identical structure when

compared with one prepared by the wet method.

INTRODUCTION
During Ley's

early work' on heavy metal salts of organic

acids, he interpreted the constitution of salts of amino

acids by means of his concept of inner-complex salts.

In

his first paper' he recognized that a characteristic colour

1653
Copyright 0 1998 by Marcel Dekker. Inc.

www.dckker.com

SAXENA

1654

was one of the most important and distinguishing features of

these types of complexes.
the complex

Bis(glycinato)copper(II),

to

formulate

his

concept

of

inner

compound that led Ley

complexes,

discovered in 1841 by Boussingault'.

Suida'

discovered

modifications

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and

bluish

[ NH,CH,COO

that

the

was

first

In 1890 Hauthner and

compound

exists

in

two

as blue needles in *-[NH,CH,COO],Cu.

violet

glistening

] ,Cu. 2H20.

These

two

in

trans-

have

planer

scales
forms

H,O,

configurations.
Ley

and

Wiegner'

and

later

Grinberg

and

Gol'braikh'

attributed this fact to geometric (cis-trans) isomerism.

cis and

1961 T ~ m i t a ~
confirmed
'~
the

the

basis

of

his

X-ray

In

trans forms (Fig. 1) on

diffraction

and

IR

studies,

respectively.
Finally,

three

isolated.
were

Out

crystalline
of

assigned

these,

the

forms

of

the

complex

were

a dihydrate6 and a monohydrate'

trans

structures

and

t'he

third

modification, which crystallized as a deep blue monohydrate,

was assigned the

cis

structure.

The

form was later

confirmed by X-ray diffraction studiesg.

The preparation of the
previously

cis

form of the above complex was

reported by Abderhalden and Schnitzer".

on, Quagliano et al.

11

also prepared it, in a modified way

by dissolving 4.98 g CuSO,.SH,O

cold

distilled

water

and

(0.02 mole)

adding

solution of sodium hydroxide

precipitated

cupric

Later

hydroxide

20

mL

in

200 mL

of

an

(1.70 g, 0.41 mole).

was

filtered

and

of

aqueous
The
washed

1655

cis-btr(GLYCMATO)COPPER(II)MONOHYDRATE

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c i s = blue needles

trans

Fig. 1.

violet scales

Bis (glycinato)copper(Iu Complex

quickly and thoroughly with cold water until it was free

alkali.

from

This

alkali-free

cupric

hydroxide

was

dissolved in 150 mL of an aqueous solution of glycine (3.09,

0.04

mole).

water

bath

The resulting solution was then warmed on the

at

60C

for

concentration and cooling

30

min.

and

filtered.

crystallization occurred and

On
the

blue flakes of the complex were collected by filtration.

The blue crystals were washed quickly with ice-cold water
several times.

The washed crystals were again dissolved in

warm water and the crystallization process was repeated.

Finally, the crystals were dried in a vacuum desicator over
concentrated sulphuric acid for several days.
a

50%

yield of the complex.

They reported

SAXENA

1656

RESULTS AND DISCUSSION

Basic copper carbonate and glycine were mixed as solids in
the mole ratio of 1:4, respectively,

This corresponds to

the stoichemetry of the reaction shown below.

CuCO,. Cu ( OH ) 2 . H20 + 4NH,CH2COOH

+ 3H,O + CO,

2Cu(NH,CH,COO),.H20

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At the reaction temperature of 120 C, water and carbon

dioxide gas are given off as the reaction proceeds.

The

difference in weight between reactants and the products at

120' C is equivalent to the loss of water and carbon dioxide

gas

only,

showing

that

the

mobility

of

the

other

constituents of the reaction mixture were negligible at this

stage.

The ease with which the reaction occurs, suggests

that the degree of mixing the solids is not a limiting

factor.

This,

in turn, suggests that

reactants plays an important role.

the mobility

of

Provided the particles

of the two substances are in reasonably close proximity,

reaction

will

occur

because

of

the

mobility

of

the

moleculesi2.
The pure complex was obtained by dissolving the product in
water, filtering and crystallizing it, after quickly washing
the crystals with ice-cold distilled water several times.
The

process

was

repeated

two

or

three

times.

The

experimental yield of complex was found to be 4 2 . 5 5 .

reactants and
diffraction.
product

products

subjected

to

X-ray

powder

The X-ray powder diffraction pattern of the

obtained

obtained by

were

The

the

by

this method

was

vet method (Table I).

identical
Analytical

to

that

results

cis-bis(GLYCINATO)COPPER(II)
MONOHYDRATE
are given in Table 11.

IR spectra

1657

obtained for the complex

by the wet method and the present method were also found to
be identical (Table 111).

EXPERIMENTAL
Materials
Basic

copper

carbonate

(May and

Baker),

acetic acid

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(glacial), potassium iodide, potassium thiosulphate all were

AR,

BDH (England). Starch was LR, BDH grade.

Synthesis
Basic copper carbonate (0.2391 g, 1 mmole) and

glycine

(0.3003 g, 4 mmole) were mixed

and the

in an

open vessel

temperature was first kept at 100' C for 1 h and then was

raised to 120'
After cooling

and maintained at that level for 4 h.

to

room temperature, 150 mL double-distilled

water

was added to the product and the mixture heated at

for 1 h on a water bath. Finally, after cooling to

60'

room

temperature

it

was

filtered.

The

filtrate was

concentrated on a water bath and kept for a few days at 2 5 ' C

for crystallization.

Subsequently, the blue flakes were

collected by filtration and washed quickly with a small

quantity of ice-cold distilled water several times and the
yield was found to be 1.08 g (22%) of the complex.

The

filtrate and washings were collected and concentrated for

crystallizations which

further gave

1.3

(29%) of

the

complex.
The total product (2.8 g) was again dissolved in 100 mL warm
water

and

concentrated,

repeating

the

crystallization

SAXENA

1658

TABLE I
X-ray Powder Diffraction Data

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Compound
Basic Copper
Carbonate
[ CuCO,. Cu ( O H )

d = h/2sin J
Peak
( A = 1.5441838)

2e0

Remarks
Definite
structure

,. H,O ]
11.74
12.68
24.05
25.58
31.22
32.04
33.44
33.58
36.58
39.64
43.44

7.531
6.975
3.698
3.479
2.862
2.791
2.677
2.666
2.455
2.271
2.081

7.5380
6.9812
3.7018
3.4824
2.8649
2.7935
2.6796
2.6688
2.4565
2.2737
2.0832

and many more

G 1 ycine
NH,CH,COOH

Definite
structure
12.02
12.30
14.00
14.62
21.82
29.24
35.68
38.92

7.356
7.189
6.320
6.058
4.069
3.051
2.514
2.312

7.3630
7.1960
6.3258
6.0589
4.0732
3.0543
2.5164
2.3140

and many more

Blue Complex
DRY METHOD
[ NH,CH,COO ] ,Cu. H,O

Definite
structure
9.760
10.100
10.340

9.054
8.750
8.548

9.0623
8.8453
8.5552

cis-bis(GLY CINATO)COPPER(II) MONOHYDRATE

1659

TABLE I
Continued

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Compound

d = A/2sin 8
( A = 1.5441838)

29

15.260
15.420
16.200
17.500
20.940
24.480
25.400
27.920
33.100
46.540

5.801
5.741
5.467
5.063
4.238
3.633
3.504
3.193
2.704
1.950

Peak

5.8674
5.7463
5.5324
5.1854
4.2423
3.6363
3.5012
3.1956
2.7064
1.9514

Remarks

Definite
structure

and many more

Blue Complex
WET METHOD
[ NH,CH,COO],Cu.

Definite
structure
H,O
9.780
9.960
10.300
10.540
15.220
15.340
17.440
17.700
20.160
20.280
20.920
25.400
25.520
27.880
33.360
46.620

-~

9.036
8.873
8.581
8.386
5.816
5.771
5.081
5.007
4.401
4.375
4.243
3.504
3.487
3.197
2.704
1.946

9.0438
8,8807
8.5883
8.3933
5.8214
5.7761
6,1340
6.0261
4.4047
4.3789
4.2463
3.5066
3.4904
3.2001
2.7661
1.9482

and many more

process. Finally, the blue crystals were collected and dried

in a vacuum desiccator over silica gel for three days, the
experimental yield was

1.9

g (42.5%).

The

complex was determined by a standard method.

copper in the

1660

SAXENA

In

u)

In

15

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pl

N
Y

u)

00

pl

In
m

r(

u)

15

l-i

I4

pl

l-i

cl

m
4

In
0

15

l-i

0
N

--

v)

In

u)

u)

CI

CI

u)

0
0
X

tiI:
b

cis-bi.s(GLYCINATO)COPPER(II) MONOHYDRATE

1661

TABLE I11
IR Spectral Data of The Complex (cm-')

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DRY METHOD

WET METHOD

3300
3200
2970
1680
1620
1580
1430
1380
1330
1270
1115
1050
1030
950
920
740
670
560

3300
3200
3000
1679
1610
1590
1420
1390
1320
1270
1140
1060
1035
940
910
145
655
575

Instrumentation
X-ray powder diffraction patterns were obtained on a Philips
Compact X-ray Diffraction Analyser model with the following
operating conditions: P.W. 1840/04/11 at 40kV, 25 ma, and a
slit width of 0.2 nun, copper-LFF tube, angular range 3.0' to
65. Oo,

scan speed 0.2028/s

speed 20 nun /2O8, chart

(standard default value), chart

range 1 to IxlO',

second, nickel filter and at 20'

spectra

were

spectrophotometer
subjected

recorded
as

KBr

on

temperature.

discs.

to microanalyses at

time constant 1.0

200-91527

The

Shimadzu

complexes

the Chemistry

Catholic University, Nijmegen, Holland.

The IR

were

Department,

SAXENA

1662

ACKNOWLEDGEMENT
My thanks to the Chemistry Department of the University of
Dar Es Salaam, Tanzania, for research facilities.

THe paper

is dedicated to the memory of the late Prof. A, Steyermark

of the Department of Chemistry, Rutgers University, Newark,
New

Jersey,

USA,

who

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Microchemical Journal.

was

the

founding

Editor

of

the

I am also thankful to C.S.I.R.,

India, for financial assistance and

Prof. Abhai Man Singh

of the Department of Physics and Astrophysics, University of

Delhi, Delhi-7,

for providing space for completing this

work.

REFERENCES

10, 954

1.

H. Ley, Z. Elektrochem.,

2.

J. B. Boussingault, Ann. Chim. Phys.,

Ann., 2, 304 (1841).

3.

J. Mauthner and W. Suida, Monatsh. Chem.,

(1904).

3,

257 (1841);

11, 373

(1890).

11, 585

4.

H. Ley and G. Wiegner, Z. Electrochem.,

5.

A. A. Grinberg and Z. E. Gol'braikh, Zhur Obshchei

Khim, 11, 1039 (1941); Chem. Abstr., 2, 4538 (1945).

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K. Tomita, Bull. Chem.

7.

K. Tomita

and

SOC.

Japan.,

I. Nitta, Bull.

34,

(1905).

280 (1961).

Chem. SOC. Japan., 2,

286 (1961).
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T. Yasui

and

Y. Shimura, Bull. Chem.

SOC.

Japan.,

2,

604 (1966).
9.

H. C. Freeman, M. R. Snow, I. Nitta and K. Tomita, Acta

C r y s t . , __
17, 1463 (1964).

cis-bis(GLYCINATO)COPPER(II)MONOHYDRATE
10.

E. Abderhalden and E. Schnitzler, 2. Phys. Chem.,

1663

163,

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96 (1927).
11.

D. N. Sen, S. Mizushima, C. Curran and J. V. Quagliano,

J. Am. Chem. SOC.,
211 (1955).

12.

G. C. Bond, "Heterogeneous Catalysis: Principles and

Applications", Second Edition, Clarendon Press, Oxford
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A. I. Vogel, "A Textbook of Quantitative

Inorganic
Analysis", Third Edition (ELBS), Longman, London,
p. 358 (1973).

z,

Received: 8Octobe.r 1997

Accepted: 25 June 1998

Referee I: G . J. Meyer
Referee 11: E. J. Valente