The non-stoichiometry of tetracyanocomplexes

81

Journal of Molecular Structure, 75 (1981) 8144 ElswierScientific Publishing Company, Amsterdam -Printed

THE NON-STOICHIOMETRY

in The Netherlards

OF TETRACYANOCOMPLJZXES

A. SOPKOVi

Department

of Inorganic

and Analytical

P. J. Safirik's University,

Kogice

Chemistry,

Faculty

of Sciences,

(Czechoslovakia)

ABSTRACT

Tetracyanocomplexes

1. The preparation

can be non-stoichiometric

of,complexes

in three different ways:

such as M(N83)2M'(CN)4.nG

can result in a non-stoichiometric

product

and Z-f(en)mM'(CN)4.nG

i.e. n is non-integer

(refs. 1 and

2) -

2. Heating

a fully stoichiometric

compound such as M(NH3)2M'(CN)4.2G,

in the loss of some of the guest molecules

3. A stoichiometric molecule

or non-stoichiometric

of the appropriate

can result

(ref. 3).

compound can absorb an aromatic

size Crefs. 4-6) when heated

in the presence

of

the molecule.

INTRODLTCTION Non-stoichiometric

compounds

of tetracyanocomplexes

may be divided into three

groups.

The first group are the tetracyanocomplexes amount of guest molecule M(en)mM'(CN)4TnG,

which enclose a non-stoichiometric

G during their preparations

(M = NiII, CuII, CdII, Zn”

e.g. M(NH3)2M'(CN)4.nG

. . . . en = ethylenediamine,

NiII, Pt'I, PdII, m = 1,2,3,4, n = 0.1.2, G = C H

6 6' C6H5m2'

M' =

C6H50", clHq%

0022-2680/81/0000-0000/$02.50 0 1981 Elsevier Scientific Publishing Company

and

82 C4H5N,

C4H40

These being

. ..).

complaxes

also

the other

aromatic,

Examples

can

of such

be prepared

being

compounds

Ni(CN)4.0,28

(ref.

C6H6

second

group

the resultant

arises

loss

approaching

In

When

the original

the

case

(ref.

by varying

the number,

above

The

molecules

16)

The

formula.

sphere.

four

cannot

Compounds

third

and

remains

for

examples

of this

MB4X2.yB

temperature

C6H6.b

pit

are:

2), Ni(en)2Pt

(ref.

3) and Ni(en)3

base

this

11,12)

and

NiPt(CN)4.

the

cannot

act

which

removed

which

n,

is

as a host

lattice.

be correctly

non-stoichiometric

is equal

in the

retains

longer

should

it can become

are

no

with

(ref. 61,

compound

molecule,

compound

6H20,

molecules

can be

loss,

the

is heated

(ref. 91, H20

of guest

to zero,

inner

reversibly,

to 4 in the

coordination the other

but

and M(en)mM'(CN)4.nH2G

0 c n b 1 (ref.

with

as

tetracyanocomplex

two

reversibly.

tetracyanocomplexes form

guest

the guest

absorbed

of its decomposition.

molecule

be

that

(refs.

4,5,6).

formula

In

a

is heated In such

to be reabsorbed

the

when

or for the

approaches

cases, another

final the limiting

form.

behaviour

are

provided

and MB4X2. aG during pit

by

clathrates

sorption

. b,H20

as CU(NH_,)~NF(CN)~.~

(pit = piccoline)

arises

of a tetracyanocomplex

molecule

is such

will

6).

the products

Cu(NE3) 4Ni(C'N)4.a

higher

one

CsHs, Zn(NE3)2Ni(CN)4.0,1

amount

molecules

molecules

the stoichiometric

are

such'as

the original

the quantity

Examples

equal (refs.

of non-stoichiometric

to be absorbed

the type

the

P, of the water

when

species

for

n becomes

removed

in contact

by us (ref.

containing

as Ni(H2D)2Pt(CN)4.4H2D,

product, value

C6H6

Despite

or a non-stoichiometric

it is possible

prepared

C6H5NH2

as M(NH3)2M'(CN)4.nH20

group

stoichiometric

until

two remaining

be

such

9,4,5).

compound

water

non-stoichiometric

The

been

the nitrogen

(ref.

of a compound

formulated

molecules,

1,7).

a stoichiometric

parameters

zero.

resembles

when

of either

crystallographic

guest

2).

or the aromatic molecule its

have

(ref. lo), Ni(en)2Ni(CN)4.0,14

H20

The

(refs.

(ref. 81, Zn(NE3)2Ni(CIQ4.0.2

C&OH

C6R50H.

which

two different

Cu(en)ZNi(CN)4.0.14

Zn(en)2Ni(CN)4.0,14C6H6and

(CQOJ4

water

with

pit

and NiPt(CN)4.a

in GC

of Werner

and LC

(a = b = l), which

. b H2p,

exists

Zr~ihM~),~iilCN).~.

,GH3CH.b H20

complexes

(refs.

17-19). at a

a

(refs.. 4,5,6,16,20).

of Other

83 RESULTS

Compounds

which

Compounds

prepared

molecule guest

Figure guest

non-stoichiometric

from

be present

is sorbed

properties

the

will

are

into

as can be seen

1 illustrates

from

the

molecule(s)

lattice

Such

lattice.

time

of preparation

Non-stoichiometric

solution.

if the host

the

at the

Figures

forms

amounts

before

clathrates

have

of guest

the maximum

their

own

characteristic

situation

where

the host

lattice

is

the same,

but

is different.

I

1.

of

1-5.

Difractograms

of

two

clathrate

compounds

with

I

ro

IS

1

Fig.

amount

-“ze”

different

guest

molecules. (a) Ni(NH3)2Pt(CN)4.2C6H6 CuKol

Figure

Mikrometa

2 illustrates

with

changes

in either

host

lattice

(a and

Figure guest the

infrared

and spectra

3 (Chirana).

the situation its

where

concentration

the guest

(b and

molecule

c), or of

remains

the metals

the same, in the

b).

3 illustrates

molecule

2 Gon

(b) Ni(NH3)2Pt(CN)G.C6H50H.2H20

the differences

the metals (Fig.

4).

are

in the diffraction

changed.

Differences

can

photographs also

be

as the

observed

in

84

Fig. 2a

Y Cd3

IR spectra

‘. -. -. -. . . . . . . .

Fig. 2a and bi

IR spectra and derivatograms of compounds with different metals in the host (a and b) and with different concentration of enclosed guest 6

and c)

a

NiCNH_,)2Pt(CN)4.2C6R6

b

Zn(NH3)2Ni(CN)4-ZC6H6

c

ZU(N~~)~N~(~>~.O,ZC~H~

85

Used: Derivatograph OD 102 MOM (Hungary) and IR Model

Specord

IR 75 Zeiss.

Preparations

carried out in the solid state.

model the substitutional study and

the isolated

compare

it with

spectroscopy resp.

possibility

products

of

the

the original

of the enclosed

reaction

compound.

with

In thermal decomposition

the temperature

carried out to

guest, it was possible

two different

It is possible,

the characteristic

to differentiate

In experiments

Gl and G2

using IR

frequencies intervals

guests

to

for G

and G2 1 for the liberation

of

Gl and G2 were similar.

b,. I

I

60

50

I

I I

60

SO

40

2a

m

30

I

I

20

I

I

I

I,

I

40

0

40

0

I

d>.

Fig. 3.

Difractograms guest

of clathrate

compounds with non-stoichiometric

(a, b, c) and of the empty host lattice.

amounts of

86 a

Cu
b

Cu(en)2Ni(CN)4.0,14C6E6OH

c

Ni(en)2Pt(CN)4.0,14CgE50H

d

Cu(en)2Ni(CN)4

The void formed during the original

synthesis of Zn(NH3)2Ni(CN)4.0,2C6H6

capable of accormnodating more guest up to a maximum value of P = 2. of S-picoline up to the maximum The product

quantity

is

The sorption

can occur after the loss of 0,14 C6H6.

(Fig. 5) of this indirect synthesis

can be assigned

as

ZU(NHS)~N~(CN>~. a pic.b C6H6 (M-0, a=2).

Fig. 4

IR spectra of individual

clathrate

a

Ni(en),Ni(~),.O,28CgBg

b

Cu(en)2Ni(CN)4.0.14C6H6

c

Zn(NH3)2Ni(CN)4.2C,H6

d

Ni(NH3)2Pt(c=N)4.2C6H6

These modelling

experiments

with the organic component

solid host model compounds

ware made by contacting

for 48 hours.

washing with ether and, drying.

compounds

The'products

Zn(~3)2Ni(~>4.0.2CgHg were isolated after

Similar results were achieved by using other

such as Zn(NEg)2Ni(CN)4.0,5H20.

Fig. 5.

IR spectra of (a) Zn(NH3)2Ni(~)4.0,2C6Hg 6-picoline

Non-stoichiometric

Hofmann

and (b) after sorption of

in the solid state.

compounds obtained

as a result of thermal decomposition

type and similar clathrates.

Clathrate

compounds

such as

M(NH3)2Ni(CN)4. aG and M(en>,M'(CN)4. PG lose the guest molecule step of their thermal decomposition the amount

(n) of guest molecule

(ref. 3).

is approaching

clathrate

character, but when n becomes

clathrate

compounds.

The clathrate temperature

range where

zero, they still retain ?heir

equal to zero, they are no longer

are given below.

in a process giving a DTA maximum

compound Ni(NH3)2Pt(CN)4.C6H50H

in the 85-240-C

In Fig, 6 we compare to 235OC.

In the temperature

compound Ni(NH3)2Pt(CN)4. 2C6H50H loses all the phenol in the

range 55-244'C

The clathrate molecules

Some examples

G in the first

temperature

.PH,g

loses

at 184°C

hots

(ref. 8).

guest

range.

the difractogrsms

of the original

compound and after heating

These show that the host lattice remains intact after the loss of the

guest molecules

(refs. 3,22) and is still able to sorb other organic

compounds

(refs. 16,21,22).

Similar (ref.21).

results were

obtained

for Ni(NH3)4pt(CN)4. 2H23 after heating

to 235'G

I II I 60

I,

I,

I I

50

I .

I .

40

30

I

so

I

IK).

w

I

I

I

10

0

I

I II b* j,

I

20

I30

35

15

I

zo

9s

I

5

10

-

Fig.

6.

Difractograms

of

the clathrate

Ni(NH3)2Pt(CN)4.C6R50H.2H20 and

Model compounds i.e.

host

after

heating

lattices,

(ref.

3)

compounds (b)

synthesised

the host

stepwise

the hydrated

forms

of the Zn(NH3)2Ni(CN)4.2C6H6

lattice

ZnNi(CN)&. H 2 0, ZU(NH~)~N~(CN)~.O,~H~O

the compounds

20

(a)

it to 235'C

We

for

0I

Zn(NH,>mNi(CN>,.nH20 being

and

Zn(NH3)4Ni(CN)4.2H20,

dependant

of model clathrate the last

on the pH value

during

the

synthesis.

Powder after

photographs

heating

observed

to the

i values,

ZoNi(CN)4.H20 obtained water

and

of

the original

temperatures

the

products

dehydrates

by heating

up

compounds

shown could

in Table

of the products

1 were

be identified

to 15O"C,

ZU(NH~)~N~(CN)~-

and

0,5H20

obtained.

(ref.

the product

being

to 176'C,

when

formed From

the

23).

similar

to that

it loses

all

the

ammonia.

gn(N-H3)4Ni(CQ

2H20

loses

two ammonias

(CN)4.2H20 which then loses the water

The cl&hrate

between

25-70-C

to give

Zn(NH5)2Ni

and one other ammonia between

70-185°C.

Zn(NH,),Ni(CN),.2C,H, loses all the benzene between

26-130°C,

one ammonia ligand between

13&177'C,

and .then remains unchanged

as

89

TABLE1 Calculated 4 values

-10 (10 m) after thermal decomposition

0 N

E I

1,95

1,84

1,84

1,83

1,83

2,18

2,02

2,02

1,84

1,84

2,19

2,20

2,18

1,85

2,19

2,21

2,21

2,20

2,16

2,22

2.23

2,48

2,24

2,21

2,19

2,27

2,26

2,98

2,26

2,31

2,22

2,30

2,29

3,35

2,30

2,48

2,27

2,33

2,32

3,60

3,35

2,52

2,32

3,50

2,69

3,65

2,52

3,47

2,35

3,52

2,89

2,69

2,72

3,49

3,46

3,69

3,22

3.75

3,47

3,50

3,49

3,85

3,41

3,85

3,50

3,69

3,51

3,88

3,49

3,97

3,69

3,83

3,69

3,97

3,51

4,04

3,82

3,93

3,89

3,98

3,69

4,06

4,Ol

4,Ol

3,93

4,02

3,92

4,lO

4,05

4,04

3,97

4,05

3,97

4,15

4,09

4,09

4,00

4,lO

4,17

4,17

4,17

4,14

4,05

4,15

4,21

4,22

4,19

4,19

4,21

4,19

4,27

4,30

4,29

4,29

4,35

4,27

4,35

4,35

4,41

4,42

4,43

4,.78

4,48

4,54

4,49

4,44

4,50

4,49

5,43

Ni(CN)2N83

The

+ ZII(CN)~

dehydrated

A similar

form

product

345-c.

up to

of Z~i(~)~.~~O

could

ZnNi(CN)4.E20

be obtained from 15o'c

!ZU(N'H~~~N~(CN)~. the

Keating

of

*

znNi
+

Z~i(cN14

*

znNi(cN)4

heating

thermal

deficient

the compound

in amrmonia could

Nil?tCC!N)4.6B20

be obtained

in vaeuo

gives

Ni(H20)2PtfCN)4

remaining host lattice can absorb a variety of different (refs.

a clathrate

compound

of decomposition.

or a completely

different

a non-stoichiometric and

allouing

Under

guest

guest species such as alcohols,

such

molecule

compound can be obtained by

it to remain circumstances can be

phase in GC (ref. 24), modelling in the solid state

dlkanes

in contact

the

sorption

and resorption.

Hofmann

ry-pe compounds.

the

guest

molecule

reabsorbed.

clathrates compounds

containing

(refs. 4-6).

the compound as the stationary by heating

(ref. 23) and using a vacuum

desorption

with

the original

and heterocyclic

can be used: using

Three different methods

temperature

The

organic molecules

This method has been used to prepare non-stoichiometric

stationary

have been lost.

compounds obtained by the sorption of organic molecules

Under suitable condit?ons heating

where

6,16).

Non-stoichiometric

products

decompositions.

as follows

four water molecules which were present as guest molecules

reversibly

it to lSO°C.

345*c

2C6B6.

compound

after

the following

176OC

Zn~~~)~~i(~~~.O,5K~O

And

is abtatied

technique

the tetracyanocomplexes (ref. 14) Por

These clathrate._compounds can be used as the

phase in GC (refs. 4,5,22,21,25)

and they will sorb molecules

in the

range where n + o.

On heating Ni(Mtr3)2Pt(CrJ),.2C~H~OK in vacua, the phenol lost, and the voids can be reoccupied by phenol

guest molecules

or by another

guest

are

molecule

such as benzene.

Model host lattices. stoichiometrically.

The IT20 malecuies

in.Cu(NH3)4Ni(CN).4.ntf20 behave non-

After losing two NH3 ligands to give Cu(NH3)2Ni(CN)4.nG.

91 (G

= HZO),

it loses

molecules

The

between

product

y-picolina reaction

80 and

obtained

at 40°C at 120°C

The voids guest

molecules

during

gives

when

size

thermograms of

6H20)

(refs.

ZO-80°C

and

three

of Cu(NH3)4Ni(CN)4.3H20

a-s Cu(NH3)4Ni(CN)4 pit.

results are

are

both

bH20

water

(a i b G 1) whilst 20,21)(Fig.

(rafs.

sorb

In

8.

for

the

7).

by other

for ZnNi(CN)4.H20

(34-15O'C

can

with

can be reoccupied

in Fig.

water

compounds

(b + 0)

reported

displayed

the guest

b Hz0

.a pk.

r&I20

Mkf’(CN14.

Some

to loss

for NiPt(CN)4.

appropriate

the reaction

Cu(NH3)2Ni(CN)4.a

n + 0.

The

between

150°C.

is assigned

corresponding

30-135'C

two ammonias

in tetracyanocomplexes

NiPt(CN)4.6H20. range

a further

and

temperature

ZnNi(CN)4;4H20

organic

molecules

and

of the

6.21,25,26).

DISCUSSION The

study

of non-stoichiometric 2G, M(en),mM'(CN)4.2G

M(NH3)2M'(CN)4their

ability

to sorb

around

(a) molecules

the

the

case

The

ability

these

of guest range

molecules.

when

the

The

of tetracyanocomplexes

opens

(ref.

non-stoichiometry

single 29)

and

of

crystals, this

known that water of cyclodextrins

The

compounds

with

hydrogen

bonding

It is possible

ability

exists

lose

to clarify

the G or

H20

ligands,

when

guest

still

types

of finding

intact.

of nonnew

applications

can be fully data.

understood

Although

of Zn(en)_,Ni(CN)4.H20

only

it is difficult has been

to

solved

It is for example' of the H 0 molecule. 2 a significant role in the host lattice ability

play

30).

is known

the host

lattice

solely

to van

to be present

hydrogen of

lattice

they

the role

be attributed

that

This

the three

up the possibility

the structure

between

the non-stoichiometry

us

N containing

the'host

to form

and spectroscopic

molecules (ref.

cannot

enabled

compounds

tetracyanocomplexes

clarified

interaction

has

as

27).

with the aid of structural obtain

such

analysis;

compounds

compounds

tetracyanocomplexes

and MM'(CN)4:nH.20

of tetracyanocomplexes

steichiometric

(ref.

of some

the form of M(CN)2.M'(CN)2.NH_,. with

attain

for

a variety

temperature

in thermal in

(b)

forms

bonding

and

der Waals

in some

is also

tetracyanocomplexes.

guest

molecule forces

clathrates;

an important

of clathrate (ref.

(refs. factor

31),

since

3 -34).

in determining

92

Fig.

7.

y-picoline compared

IB spectra

and difractograms

on CU(N'H~)~N~(CN)~. 3H20 with

the original


CU(NIL,)~N~~CN)~-~H~O

(b)

Cu(NH,),Ni(CN),.3H,O

(c)

Cu<~314wm4.

X20

compound

of the products

at 120°C

(b) and

(a)

+ y-picoline.

(12OpC)

+ y-picoline

'<25'C)

of the sorption at room

temperature

of (c)

93

in

TA:

60-100°C. Xi20

NiPt(CN)4.6H20

ZnNi(CNJ4 .a20

Fig. 8.

1oo-135°c

III20

135-200°C

2H20

34-150°c

lH20

Derivatograms of ihNi(CN)4.H20 (a) and NiPt(CNI4.6H20

(b)

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