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Z. anorg. allg. Chem.

615 (1992) 155-160

Zeitschrift fur anorganische


und allgemeine Chemie
0 Johann Ambrosius Barth 1992

Electrochemical Synthesis of Metal Complexes of Schiff Bases:


The Crystal Structure of
Bis~2-[(4-methylphenyl)~m~nomethyl]pyrrolat~~copper(II)
J. A. Castro, J. Romero, J. A. Garcia-Vazquez, A. CastiFieiras, M. L. Duran, and A. Sousa"
Santiago de Compostela/Spain, Universidad, Departamento de Quimica Inorginica
Received February 6th, 1992.

Abstract. The electrochemical oxidation of anodic nickel,


copper, zinc or cadmium in acetonitrile solutions of
Schiff bases (HL) derived from H-pyrrole-2-carbaldehyde
and substituted anilines gives compounds of general formula ML,. The crystal structure of bis(2-[(4-methylphenyl)iminomethyl]pyrrolato)copper(II) has beeii determined by X-ray diffraction. The compound crystallizes in
the rnonoclinic space group P2,/n with a = 9.356(2),
b = 16.697(2), c = 14.145(2) A a n d p = 108.47(2)". The

crystal structure consists of monomeric molecules in


which the central CuN, unit has distorted square-planar
geometry with a dihedral angle of 25.8(3)" between the
coordination planes. The IR, 'H NMR and UV-visible
spectra of the complexes are discussed and related to the
structure.

Key words: Electrochemical synthesis; Schiff bases metal


complexes

Elektrochemische Synthese von Metall(I1)-Komplexen mit Schif fschen Basen:


Kristallstruktur von Bis(2-[(4-methylphenyl)iminomethyl]pyrrolato)kupfer(II)
Inhaltsiibersicht. Die elektrochemische Oxidation von
anodischem Metal1 (Nickel, Kupfer, Zink, Cadmium) in
einer Acetonitril-Lijsung mit einer aus H-pyrrol-Zcarbaldehyd abgeleiteten Schiffschen Base eines
substitutierten Anilins (HL) liefert die gemischten
Komplexe ML,. Die Kristallstruktur von Bis(2-[(4rnethylphenyl)iminomethyl]pyrrolato]kupfer(II) wurde
rontgenographisch bestimmt. Der Komplex kristallisiert

monoklin in der Raumgruppe P2,/n, a = 9,356(2),


b = 16,697(2), c = 14,145(2)A, p = 108,47(2)", Z = 4,
und er besteht aus monomeren Molekulen, von denen die
zentrale CuN,-Einheit
eine verzerrt-tetraedrische
Ceometrie besitzt mit einem Diederwinkel der Fliichen
von 25,8(3)". Die IR, 'H-NMR und UV-VIS Spektren
werden im Zusammenhang mit der Struktur diskutiert.

Introduction

complexes with arylpyrrolealdimines (HL),

The synthesis of metal complexes by electrochemical oxidation of a sacrificial anode in an electrolytic cell has
been extensively developed by Tuck et al. [l], in whose
laboratory this procedure has been applied to the
preparation of metal complexes of anionic ligands such
as diketonates [2, 31, catecolates [4] and thiolates [5]. In
our laboratory we have used this method to synthesise
metal complexes with Schiff bases containing weakly acid
groups [6 - 121. We now report its application to the synthesis of copper(II), nickel(II), zinc(I1) and cadmium(I1)

@H=N-@,
H

where R = H (HL'); 2-CH3 (HL2); 4-CH3 (HL3); 2-C1


(HL4); 4-C1 (HL'); 2-OCH3 (HL6); 4-OCH3 (HL') or
2-OCH3-5-CH, (HL').
The weakly acid behaviour of these Schiff bases is due
to the N-H group of the pyrrole ring. Some of these
compounds have previously been synthezised by conventional methods [131, and the crystal structures of some

Z. anorg. allg. Chem. 615 (1992)

156
copper alkylpyrrolealdimines have been reported; in these
complexes, the coordination sphere of the metal is
markedly determined by the substituent on the
azomethine nitrogen. Thus bis[(2-iminomethyl)pyrrolato]copper(II) has square-planar geometry [ 141, but in
bis~[2-(tert-butyl)iminomethyl]pyrrolato]copper(Il) the
arrangement around the copper atom can be described as
distorted tetrahedral, with a dihedral angle of 61.3(4)"
between the two coordination planes [15]. No crystal
structures to copper(I1) complexes of arylpyrrolealdimines have previously been described, but on the basis
of ESR data Addison suggested they have square-planar
geometry [16]. We report here the crystal structure of

bis~[2-(4-methylphenyl)iminomethyl]pyrrolatojcopper(II),
in which the environment of the copper atom can be
described as distorted square-planar, with a dihedral
angle of 25.8(3)".
Experimental
Acetonitrile, pyrrole-2-aldehyde and amines were all commercial products and were used as supplied. Metals (Ega Chemie)
were used as ca. 2 x 2 cm plates.
The ligands were prepared by reaction of the aldehyde and the
appropriate amine in chloroform until the theoretical amount
of water had been collected in a Dean-Stark trap. After removal
of the solvent, the solid was crystallized from n-hexane. Its purity was checked by recording its IR and 'H NMR spectra.

The electrochemical synthesis


The electrochemical procedure used in the synthesis of the complexes is based on the work of Tuck et al. [17]. The cell was a

100ml tall-form beaker fitted with a rubber bung through


which the electrochemical leads passed. The foil anode was
suspended from a platinum wire, and the cathode was also a
platinum wire. The ligand was dissolved in acetonitrile, and a
small amount of tetraethylammonium perchlorate (ca. 20 mg)
was added to the solution as a current carrier. Direct current
was obtained from a purpose-built d.c. power supply. In these
conditions the cell can be summarized as
Pt( -)/CHjCH

+ HL/M( +)

During electrolysis, hydrogen was evolved at the cathode. Solids


precipitated during the electrolysis were collected, washed with
acetonitrile and diethylether, and dried in vacuo. In some cases
concentration of the solution was required to obtain a solid product. The working conditions are detailed in Table 1.

Physical measurements
Microanalysis was performed using a Carlo-Erba EAI 108
microanalyser. The analytical data are given in Table 2. IR spectra were recorded in KBr mulls on a Perkin-Elmer 180 spectrophotometer. Solid reflectance spectra were recorded on a
Perkin-Elmer Lambda 9 spectrophotometer. Solution electronic
spectra were recorded on a Uvikon 81OP spectrophotometer using CHCI, as solvent. Magnetic measurements were taken using a SQUID. Proton NMR spectra of the ligands were recorded
on a Bruker WM 250MHz using CDCI, as solvent; chemical
shifts were determined against TMS as internal standard.

Determination of the Crystal Structure of CuL:


An amber prismatic crystal of approximate dimensions
0.12x0.2~0.16mmwas mounted on a glass fiber and used for
data collection on a CAD4 Enraf-Nonius fourcicle automatic
diffractometer. Cell contants and an orientation matrix for data

Table 1 Experimental Conditions for the Electrochemical Synthesis


Metal

Ligand

Amount
of ligand (g)3

Initialb)
Potential(V)

Time (h)

Ni
Ni
Ni
Ni
Ni
Ni
Ni

HL'
HLZ
HL'
HL'
HL6
HL'
HL'

0.13
0.29
0.27
0.32
0.30
0.31
0.23

25
25
20
20
22
20
15

2.0
2.0
2.0
2.0
2.0
2.0
2.5

48.0
42.8
47.6
42.6
43.2
43.6
44.1

0.55
0.49
0.5 1
0.49
0.49
0.50
0.40

cu
cu
cu
cu

0.20
0.21
0.60
0.50
0.55
0.30
0.30
0.20

20
20
15
20
16
20
30

0.75
0.75
1.5
1.5
1.5
1.o
1.o
1.o

35.0
40.0
72.0
69.0
70.0
49.0
45.0
53.3

0.98
1.12
1.01
0.97

cu
cu
cu

HL'
HLZ
HL'
HL4
HLS
HL6
HL7
HL'

1.03
0.95
1.12

Zn
Zn

HL'
HL'

0.40
0.70

18
15

3.0
1.5

75
40

0.51
0.54

Cd
Cd
Cd

HL3
HL'
HL7

0.50
0.50
0.55

20
20
15

3.0
3.0
3.0

3 30

0.5 1
0.51
0.53

cu

") Plus "Me4]


b,

CIO, (ca. 10 mg)


Voltage to produce a current of 20 mA

15

Metal
dissolved (mg)

131
135

Ef
(mol F-I)

1 .oo

157

J. A. Castro et al., Bis(2-[(4-methylphenyl)iminomethyl]-pyrrolato)copper(II)


Table 2 Analytical Data
9'0 found (calc.)

Compound

NIL:
NIL:
NiL:
NiL:
NiLq
NIL:
NiL:

63.9(63.7)
65.4(65.3)
65.7(65.3)
56.6(56.7)
60.1(60.7)
60.9(60.6)
64.7(64.4)

13.1(13.5)
12.7(12.7)
12.7(12.7)
14.3(13.8)
11.8(11.8)
12.8(11.8)
11.8(11.6)

4.7(4.8)
5.0(4.9)
4.9(4.9)
4.0(3.8)
5.0(5.1)
4.9(5.1)
5.3 (5.4)

CUL:
CULl
CUL:
CUL:
CULS
CUL: 2 H2O
CUL:
CUL!

65.1 (65.7)
66.6(67.1)
67.2(67.1)
55.9(55.4)
54.7(55.4)
57457.9)
62.3(62.4)
62.7(63.7)

13.7(13.9)
12.8( 13.O)
13.2( 13.O)
11.9(11.8)
1I S ( 11.8)
11.8(11.3)
12.0(12.1)
11.1 (11.4)

4.5(4.5)
5.1(5.1)
5.2(5.1)
3.4(3.4)
3.4(3.4)
5.7(5.2)
4.9(4.8)
5.4(5.3)

ZnL:
ZnL:

66.8(66.8)
56.2(55.9)

13.2(13.0)
12.3(11.9)

5.2p.1)
3.5 (3.4)

CdL:
CdLI
CdLz

60.1(60.2)
50.5(50.6)
56.1(56.4)

11.7(11.7)
10.7(10.7)
11.0(11.O)

4.7(4.6)
3.1(3.4)
4.4(4.3)

HzO
H20
CH,CN
.H20
.H20

collection were obtained by least-squares refinement of the


diffraction data for 25 reflections in the range of 5 - 12". The
monoclinic space group P2,/n was assumed due to the extinctions observed. Data were collected at 293 "C using MoKa
radiation (A = 0.71073 A) and the w / O scan technique. The
data were corrected for Lorentz and polarization effects. An
empirical absorption correction [I 81 and a secondary extinction
correction was also applied [19]. The final coefficient, refined
in the last least-square cycle was 7.01(1)x
The structure was solved by direct methods [20] which revealed the position of all non-hydrogen atoms, and refined on F by
full-matrix least-square procedure using anisotropic
temperature factors for the Cu and N atoms, and isotropic for
the non-hydrogen atoms [21]. Hydrogen atoms were located
from geometrical considerations (C-H = 0.95 A), A d added
to the structure factor calculations as fixed contributions

(BISO
= 4.0 A) and their positional parameters were not
refined. The final R value was 0.057, with R, = 0.058
(weighting scheme w - ' = a2(F); 143 parameters; S = 2.13;
maximum A / a in final cycle 0.001; maximum
A , = 0.35 e k 3Computations
)
were performed on a DECMicroVAXII computer.
For a summary of crystal data, see Table 3. The final atomic
positional parameters are listed in Table4. These and others
crystallographic data have been deposited as Supplementary
Publication no CSD-56056. Copies can be obtained through the
Fachinformationszentrum Energie, Physik, Mathematik,
D-75 14 Eggenstein-Leopoldshafen.

Results and discussion


The electrochemical oxidation of nickel, copper, zinc and
cadmium in acetonitrile in the presence of
2-pyrrolearylaldimines proved to be a simple, direct route
to compounds of general formula ML,. The reaction
can be represented as
M

+ HL+ML2 + H2

With copper as the anode, a current of 1OmA rapidly


produced a dark green solution, and crystalline solids
could be collected from the bottom of the cell after 1-2
hours. These brown-green compounds were air-stable and
have melting points in the range 190-220C.
With nickel as anode and a working current of 20 mA,
two hours electrolysis gave a dark solution from which
solid product was obtained by air-concentration.
Not all the experiments with zinc or cadmium electrodes, yielded well characterized compounds. In some
experiments in which the cathode rapidly became coated
with a black solid that markedly reduced the current, no
useful products could be isolated from the solution.
In keeping with our usual practice, we measured the
electrochemical efficiency defined as moles of metal
dissolved per Faraday of charge (Er, mol F-I). When the
metal was nickel, zinc or cadmium, E, was close to
0.5 mol F-', corresponding to the process
Cathode: 2HL + 2e- + H2@)+ 2LAnode: M + 2L- +ML2 + 2e-

Table 3 Summary of crystal data


Formula
M
Crystal system
space group
a, A
b, A
c, A
P, d,es
V, A 3
Z
F(000)
density (calc.), g * cm-'
radiation
P,(cm-'1
wavelength, A

CJLCuN,
430.01
monoclinic
P2,/n
9.356(2)
16.697(2)
14.145(2)
108.47(2)
2095.4(6)
4
892
1.363
MoKa
10.593
0.71073

min.-max. abs. correction


Total No. refl. measured
(0 Range)
No. of observ.
refl. criterion)
max. (sin 0 ) / A
No. of unique
refl. (Rim)
R
R,

0.69-1.10
4 526 (3 - 26 deg)
1518 (I > 3a(T))
0.616
4 000(0.022)
0.057
0.058

Z . anorg. allg. Chem. 615 (1992)

158
Table 4 Positional parameters for CuL: with e.s.d.'s. in Parentheses

Atom

cu
Nt
N2
N21
N22

0.1903( 1)
0.1988(7)
0.2137(7)
0.1 103(7)
0.2225(7)
0.202( 1)
0.215(1)
0.223(1)
0.2129(9)
0.217(1)
0.2169(9)
0.329(1)
0.336(1)
0.236(1)
0.123( 1)
0.1 12(1 )
0.042(1)
- 0.008(1)
0.027(1)
0.10 16(9)
0.16 t2(9)
0.2834(9)
0.1988(9)
0.255(1)
0.3949(9)
0.254(1)
0.481(1)
0.4247(9)
0.454(1)

0.6 1012(7)
0.6868(4)
0.7091(4)
0.5364(4)
0.5081 (4)
0.6912(6)
0.7724(6)
0.8168(6)
0.7637(5)
0.7723(6)
0.7 173(S)
0.6787(6)
0.6892(6)
0.7364(6)
0.7720(6)
0.7604(6)
0.5348(6)
0.4584(6)
0.4104(6j
0.4600(5)
0.4488(5)
0.5013(5)
0.4686(5)
0.4698(6)
0.5014(6)
0.7486(7)
0.5287(6)
0.5305(5)
0.5064(7)

ct

c2
c3
c4

c5
C6
c7
C8
c9
c10
Cli

c 21
c22
C23
C24
C25
C26
C27
C28
C29
C9 1
c210
C211
C29 t

0.36559(8)
0.47 18(5)
0.2896(5)
0.2555(5)
0.4463( 5)
0.5683(7)
0.5962(7)
0.5202(7)
0.4399(6)
0.3435(6)
0.1908(6)
0.1626(7)
0.0674(7)
-0.0019(6)
0.0246(7)
0.1 295(7)
0.1562(7)
0.1258(73
0.2088(7)
0.2890(6)
0.3923(6)
0.5525(6)
0.6084(6)
0.71 i6(6)
0.7597(6)
-- 0.1028(8)
0.7033(6)
0.5998(6)
0.8738(8)

With copper as anode, the average E, was always close to


1.O mol F-', which together with the formation of H, at
the cathode points to the process
Cathode: HL + e- --t 1/2H2(g)+ L
Anode: Cu + L- [CuL] + e-

[CUL] + HL+CuLz

+ 1/2H2,,

these oxidation steps have been observed in other electrochemical processes involding copper as anode [8, 101.
An ORTEP view of the structure of CuLi is shown in
Fig. 1 with the atom labelling used in Tables. A
stereoscopie view of the complex is shown in Fig. 2.
Selected bond distances and angles, together with their
estimated standard deviations, are listed in Tables 5 and
6. The complex consists of discrete molecules in which
the copper atom is bound to two bidentate ligands. The
environment of the copper atom can be described as
distorted square-planar, with two nitrogen atoms
0.289(7) above and the other two 0.288(7)A below the
best plane defined by the four nitrogen donor atoms. The
dihedral angle between the planes, defined by the copper
atom and the two nitrogen atoms of each chelate ring is
25.8(3)' as a consequence of steric hindrance by the
phenyl groups bound to the atomethine nitrogen atoms;

Fig. 1 The molecular structure of CuL:

Fig. 2 Stereoscopic view of structure of CuL:

this value falls between the 0" found in the perfect planar
bis[(2-iminomethyl)pyrrolato]copper(II) [ 141, and the
6 1.3(4)" of bis{[2-(te~t-butyl)iminomethyl]pyrrolato)copper(I1) [I 51, with its bulky N-sustituent. The N-Cu-N
bond angles are correspondingly distorted: those involving adjacent nitrogen atoms are 83.6(3)", 82.4(3)",
99.0(3)" and 99.9(3)" instead of the required 90", the
smaller values being for angles with both nitrogens in the
chelate ring, and those involving opposite nitrogens are
165.6(3)" and 160.6(3)", instead of 180". The Cu-N
bond distances are also dissimilar, the copper atom being
closer to the pyrrole nitrogen (average distance
1.948(7) A) than to the imine nitrogen (average distance
2.020(7) A); both distances are in agreement with those
observed in tetracoordinated copper complexes with
alkylpyrrolealdimines [14, 15, 221
The five membered imino-pyrrole ring is essentially
planar. The average value of the C(5)-N(2) bond is
1.29(1)
close to the 1.30 A,close to the 1.30 A of a
C = N bonds [23].
All the ligand distances are essentially identical to
those found in other complexes containing those ligands.

A,

J. A. Castro et al., Bis(2-[(4-rnethylphenyl)iminomethyl]-pyrrolato

Table 5 Select Bond Distances ( A ) for CuL: with e.s.d.'s. in


Parentheses
CU-N1
Cu-N21
N1-C1
N2-C5
N21-C21
N22-C25
c1-c2
c3-c4
C6-C7
C7-C8
C9-CIO
c1o-c11
C22-C23
C24-C25
C26-C2 11
C28-C29
C29-C291

1.956(8)
1.940(6)
1.36(1)
1.30(1)
1.35(2)
1.28(2)
1.41(1)
1.42(1)
1.39(1)
1.38(1)
1.331)
1.39( 1)
1.37(1)
1.40(2)
1.37(2)
1.37(1)
1.53(1)

CU-N~
Cu-N22
N 1-C4
N2-C6
N21 -C24
N22-C26
C2-C3
c4-c5
C6-ClI
C8-C9
C9-C91
c21 -c22
C23-C24
C26-C27
C27-C28
C29-C210
c210-c211

2.020(7)
2.020(7)
1.39(1)
1.41(1)
1.37(1)
1.43(1)
1.33(1)
1.38(1)
1.40(1)
1.37(1)
1SO(2)
1.38(1)
1.40(1)
1.40(1)
1.39(1)
1.38(1)
1.39(1)

Table 6 Select Bond Angles (") for CuL: with e.s.d.'s. in


Parentheses

about 1 1.8 ppm in the ligands is absent in the complexes,


indicating that in the latter the ligand is in its monoanionic form. The azomethine hydrogens signals
(8.4 - 8.6 ppm) are slightly shifted in the complexes from
their positions in the free ligand (8.1 -8.3 ppm). In the
complexes with an alkyl group on the phenyl ring, the
alkyl hydrogen signal appears at higher field.
For each of the nickel(I1) complexes, the electronic
reflectance and CHCl, solution spectra, are approximately the same, suggesting that the complexes probably
retain the same structure in both states. The solid state
electronic spectra of the nickel complexes show a very
broad band in the region 16000- 18000 cm-' (extinction coeffient in solution c.a. 300mol-' 1cm-') (v,) and
another in the region 7 000 - 9 300 cm-' (vJ, consistent
with a pseudo-tetrahedral geometry [25]. These spectra
are also very similar to that found in bis{[2-(terf-butyl)
iminomethyl]pyrrolatojnickel(II) whose tetrahedral structure has been determinated by X-ray diffraction [I51 and
therefore the bands can be assigned similarly to
3T,+ 3T,(P) (v3) and 3T,+ 3A, (VJ respectively. A weak
band observed in some cases ca. 11 800 cm-' is assigned
to the 3T, 'E spin forbidden transition.
The solid reflectance spectra of the copper complexes
show one broad band in the range of 1460015900 cm-' in keeping with a square-planar stereochemistry of the metal.
The magnetic moments of the nickel complexes at
room temperature lie in the range of 2.8 - 3.2 B.M. and
these values are the expected for tetrahedral complexes.
For the copper complexes the values of the magnetic
moments at room temperature lie in the range of
1.7 - 1.8 B.M., corresponding to one unpaired electron.
-+

N1 -Cu-N2
N1 -Cu-N22
N2-Cu-N22
C1 -N1 -C4
C21-N21 -C24
Nl-Cl-C2
c2-c3-c4
N1 -C4-C5
N2-C5-C4
N2-C6-C
11
C6-C7-C8
C8-C9-C10
c1o-c9-c91
C6-CI1-CIO
c21-c22-c23
N21-C24-C23
c23-c24-c25
N22-C26-C27
I
C27-C26-C21
C27-C28-C29
C28-C29-C291
c29-c21o-c211

83.6(3)
99.0(3)
165.6(3)
107.7(7)
106.3(7)
107.9(8)
107.0(9)
1 17.0(8)
119.5(9)
122.5(9)
119.7(8)
1 17.9(9)
122.1(8)
119.8(9)
108.0(8)
109.8(7)
134.2(8)
121.1(7)
119.7(7)
120.9(9)
121(1)
121.4(8)

N1-Cu-N21
N2-Cu-N21
N21-Cu-N22
C5-N2-N6
C25-N22-C26
c1-c2-c3
Nl-C4-C3
c3-c4-c5
N2-C6-C7
C7-C6-C11
C7-~8-~9
C8-C9-C91
C9-ClO-C11
N21-C21-C22
C22-C23--C24
N21-C24-C25
N22-C25-C24
N22-C26-C211
C26-C27-C28
C28-C29-C210
C21O-C29-C291
C26-C211-C210

160.6(3)
99.9(3)
82.4(3)
120.0(8)
121.4(8)
109.5(9)
108.0(8)
135.0(9)
119.6(7)
118.0(9)
123(1)
120.1(9)
122.1(8)
110.2(8)
105.6(8)
115.9(7)
118.5(8)
119.1(9)
119.8(8)
118.6(8)
120.7(8)
119.5(9)

Spectroscopic studies

In general, the spectroscopic data are similar to those


reported previously, and confirm that all the complexes
have similar structures. Thus none of the I R spectra have
the band present at 3 300 cm-' in the spectrum of the
free Schiff base, confirming that it is the deprotonated
ligand that is present in the complexes. The band attributable to the azomethine group, v(C=N), shifts to
lower frequences in the complexes as a consequence of
coordination through the imine nitrogen [24].
The ' H N M R spectra of the zinc and cadmium complexes are as expected. The pyrrole hydrogen signal at

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Address for correspondence:


Prof. Dr. A. Sousa
Depto. Quimica Inorghnica, Universidad de Santiago
E-15706 Santiago de Compostela, Spain