Synthesis of cobalt(II), nickel(II) and copper(II) complexes with 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene and crystal structures of {bis(methanol)[2-(2′-N-tosylaminophenyl)iminomethyl]phenolato}nickel(II) and {bis(2,2′-bipyridine)[2-(2′-N-tosylaminophenyl)iminomethyl] phenolato}copper(II)

Article abstract of DOI:10.1016/S0277-5387(98)00372-6

Electrochemical oxidation of metal anodes (cobalt, copper and nickel) in acetonitrile solutions of 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene (H₂L) gave [CoL], [CuL] and [NiL] complexes. When 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) was added to the electrolytic cell, the mixed complexes [MLL′] (M=Co, Cu, L′=bipy or M=Ni, L′=phen) were obtained. A binuclear compound of composition [Ni₂L₂(MeOH)₄] (1) was synthesized by reaction of the ligand H₂L and nickel(II) acetate in methanol. X-ray structure determination showed the compound to be binuclear, with each nickel atom coordinated to two nitrogen and two bridging phenol oxygen atoms of two dianionic ligands and two methanol molecules, in an octahedral environment. The crystal structure of [CuLbipy] (2) was determined by X-ray diffraction; with the copper atom in a distorted bipyramidal environment defined by the two bipyridine nitrogen atoms and by the phenolic oxygen and the nitrogen atoms of the dianionic ligand. The electronic and vibrational spectral data of the complexes are discussed and related to the structure.

Full text of DOI:10.1016/S0277-5387(98)00372-6

Polyhedron 18 (1999) 863–869
Synthesis of cobalt(II), nickel(II) and copper(II) complexes with 2-(2-
hydroxyphenyliminomethyl)-1-(4-methyl-phenylsulfonamido)benzene and
crystal structures of hbis(methanol)[2-(29-N-
tosylaminophenyl)iminomethyl]phenolatojnickel(II) and hbis(2,29-
bipyridine)[2-(29-N-tosylaminophenyl)iminomethyl]phenolatojcopper(II)
a
a
a
b
A.D. Garnovskiia, , A.S. Burlov , D.A. Garnovskii , I.S. Vasilchenko , A.S. Antsichkina ,
G.G. Sadikovb, A. Sousac, J.A. Garcia-Vazquezc, J. Romeroc, M.L. Duranc, A. Sousa-Pedraresc,
C. Gomezc
*
aResearch Institute of Physical and Organic Chemistry, Rostov State University, 344090, Rostov-on-Don, Russia
bKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
c
´
´
Departamento de Quımica Inorganica, Universidad de Santiago de Compostela, 15706 Santiago de Compostela, Spain
Received 27 July 1998; accepted 9 October 1998
Abstract
Electrochemical oxidation of metal anodes (cobalt, copper and nickel) in acetonitrile solutions of 2-(2-hydroxyphenyliminomethyl)-1-
(4-methyl-phenylsulfonamido)benzene (H2L) gave [CoL], [CuL] and [NiL] complexes. When 1,10-phenanthroline (phen) or 2,29-
bipyridine (bipy) was added to the electrolytic cell, the mixed complexes [MLL9] (M5Co, Cu, L95bipy or M5Ni, L95phen) were
obtained. A binuclear compound of composition [Ni2L2(MeOH)4] (1) was synthesized by reaction of the ligand H2L and nickel(II)
acetate in methanol. X-ray structure determination showed the compound to be binuclear, with each nickel atom coordinated to two
nitrogen and two bridging phenol oxygen atoms of two dianionic ligands and two methanol molecules, in an octahedral environment. The
crystal structure of [CuLbipy] (2) was determined by X-ray diffraction; with the copper atom in a distorted bipyramidal environment
defined by the two bipyridine nitrogen atoms and by the phenolic oxygen and the nitrogen atoms of the dianionic ligand. The electronic
and vibrational spectral data of the complexes are discussed and related to the structure.
reserved.
1999 Elsevier Science Ltd. All rights
1. Introduction
phenyliminomethyl)-1-(4-methyl-phenylsulfonamido)ben-
zene (X5O, Y5NTs), H2L were hitherto unknown.
In this paper, the synthesis of cobalt(II), nickel(II) and
copper(II) complexes of H2L and the crystal structures of
[Ni2L2(MeOH)4] and [CuL(bipy)] are described.
Most ligands of type I [1,2] are binuclear compounds of
types II [3–6] and III [7–10] with bridging phenolato
oxygen groups, although there many examples of mononu-
clear structures such as IV [10–19]. In the case of
vanadium, a compound formed by two monomer frag-
ments bridged by an oxo group,V, has been described [20].
Until recently, most of the tridentate dianionic ligands
were salyciliden-2-aminophenol derivatives, I (X5Y5O)
[1,7,10,11,21–24]. In the last few years, some studies on
these types of ligands with X5O, but Y5S or Se have
been carried out [12,17,25–28]. However, as far as we
know, coordination compounds of 2-(2-hydroxy-
2. Experimental
All solvents and 2-hydroxyaniline were commercial
products used without further purification.
2-(2-Hydroxyphenyliminomethyl)-1-(4-methyl-phenyl-
sulfonamido)benzene (H2L) was prepared by refluxing 2-
formyl-1-(4-methylphenylsulfonamido)benzene [29] (2.75
g, 10 mmol) and 2-hydroxyaniline (1.09 g, 10 mmol) in
benzene (20 cm3) as solvent until the theoretical amount of
water was collected in a Dean-Stark trap. The resulting
*
Corresponding author.
0277-5387/99/$ – see front matter
PII: S0277-5387(98)00372-6
1999 Elsevier Science Ltd. All rights reserved.

864
A.D. Garnovskii et al. / Polyhedron 18 (1999) 863–869
solution was concentrated in a rotary evaporator to a final
volume of 5 cm3 and the solid was precipitated by the
addition of 10 cm3 of methanol. Recrystallization from hot
methanol yielded yellow crystals (2.75 g; yield, 75%).
Anal. Found: C, 65.6; H, 5.0; N, 7.9; S, 8.9. Calc. for
C20H18N2O3S: C, 65.6; H, 5.0; N, 7.6; S, 8.8%. IR, n(NH)
3400, n(OH) 3100–2800, n(C5N) 1610, nas(SO2) 1322
methanol. The solid was recrystallized in the same solvent
and brown crystals, suitable for X-ray studies, were
obtained and characterized as C44H48N4O10S2Ni2. Anal.
calculated: C, 54.8; H, 5.0; N, 5.8; S, 6.7. Found: C, 55.1;
H, 5.0; N, 5.6; S, 6.8%. IR, n (C5N) 1593, nas(SO2) 1286
and ns(SO2) 1173 cm21
.
and ns(SO2) 1140 cm21
.
2.3.3. [NiLphen]
The electrolysis of a solution containing 0.136 g (0.371
mmol) of H2L and 0.073 g (0.371 mmol) of 1,10-phen-
anthroline in 50 cm3 of CH3CN for 2 h and using a current
of 16 V, 10 mA dissolved 22.1 mg of nickel metal
(Ef50.50). The product of the reaction was a brown
precipitate, which was isolated following the same pro-
cedure as described above. Anal: calculated for [NiLphen],
[C32H24NiN4SO3]: C, 63.67, N, 9.28, H, 3.97%. Found: C,
63.30, N, 9.48, H, 3.78%. IR, n(C5N) 1590, nas(SO2)
2.1. Preparation of complexes
The complexes were obtained following an electro-
chemical procedure [30]. An acetonitrile solution of the
ligand containing about 15 mg of tetramethylammonium
perchlorate as a current carrier was electrolyzed using a
platinum wire as the cathode and a metal plate as the
sacrificial anode. The cell can be summarized as Pt(2)/
MeCN1H2L/M(1); M5Co, Cu, Ni.
1280 and ns(SO2) 1155 cm21
2.4. Copper(II) complexes
2.4.1. [CuL]
.
2.2. Cobalt(II) complex
2.2.1. [CoL].CH3CN
The electrochemical oxidation of cobalt in a solution of
H2L (0.136 g, 0.371 mmol) in CH3CN (50 M) containing
20 mg of tetramethylammonium perchlorate for 2 h at 10
V and 10 mA resulted in the loss of 22.8 mg of cobalt from
the anode (Ef50.52). Hydrogen was evolved at the cathode
during the electrolysis. The room temperature concen-
tration of the reaction mixture produced a microcrystalline
dark brown precipitate, which was collected by filtration
and identified as [CoL].CH3CN. Anal.: calculated for
[CoC22H19N3SO3]: C, 56.90, N, 9.05, H, 4.12%. Found:
C, 56.93, N, 9.06, H, 4.19%. IR, n(C;N) 2190, n(C5N)
Electrolysis of a solution of H2L (0.136 g, 0.371 mmol)
and tetramethylammonium perchlorate (20 mg) in CH3CN
(50 cc) for 2 h at 6 V and 10 mA using a copper anode led
to the dissolution of 46.2 mg of copper (Ef50.97). Brown
crystals of [CuL] were isolated from the resulting solution.
Anal.: calculated for [C20H16CuN2SO3]: C, 56.13, N, 6.53,
H, 3.78%. Found: C, 55.70, N, 6.54, H, 3.74%. IR,
n(C5N) 1590, nas(SO2) 1285 and ns(SO2) 1170 cm21
.
1600, nas(SO2) 1290 and ns(SO2) 1160 cm21
2.3. Nickel(II) complexes
2.3.1. [NiL]
.
2.4.2. [CuLbipy]
The electrolysis of an acetonitrile solution containing
H2L (0.136 g, 0.371 mmol) and 2,29-bipyridine (0.058 g,
0.371 mmol), using a current of 11 V and 10 mA over 2 h,
resulted in the loss of 44.9 mg of copper (Ef50.94).
Brown crystals of [CuLbipy] that were suitable for X-ray
studies were isolated from the reaction solution. Anal.:
calculated for [C30H24CuN4SO3]: C, 61.65, N, 9.59, H,
4.11%. Found: C, 61.94, N, 9.72, H, 4.01%. IR, n(C5N)
A brown powder was isolated from the solution re-
sulting from the electrolysis (20 V, 10 mA, 2 h) of a
solution of H2L (0.136 g; 0.371 mmol) in 50 cm3 of
CH3CN using a nickel anode. Under these conditions, 21
mg of nickel were dissolved (Ef50.48). The precipitate
was collected, washed with acetonitrile and diethyl ether,
dried in vacuo and identified as [NiL]. Anal.: calculated for
[NiC20H16N2SO3]: C, 56.76, N, 6.62, H, 3.78%. Found: C,
56.27, N, 6.55, H, 3.18%. IR, n(C5N) 1590, nas(SO2)
1600, nas(SO2) 1285 and ns(SO2) 1160 cm21
.
2.5. Physical measurements
Microanalyses were performed using a Carlo-Erba
EA1108 microanalyser. IR spectra were recorded in KBr
disks on a Perkin-Elmer 180 spectrophotometer.
1280 and ns(SO2) 1155 cm21
.
2.3.2. [Ni2L2(MeOH)4 ]
The magnetic susceptibility for [Ni2L2(MeOH)4] was
measured by the Faraday method in the temperature range
78–300 K (Table 1), using Hg[Co(CNS)4] as the calibrant.
The exchange parameter, J, was deduced from a least-
squares fitting procedure by minimizing the deviation from
the experimental values of the calculated theoretical mag-
netic susceptibilities using the equation.
This compound was alternatively obtained by the slow
addition of 2-(2-hydroxyphenyliminomethyl)-1-(4-methyl-
phenylsulfonamido)benzene (0.36 g, 1 mmol) in methanol
(15 cm3) to a solution of nickel acetate (0.248 g, 1 mmol)
in the same solvent (10 cm3). After refluxing for 1 h, the
brown crystalline precipitate was filtered and washed with

A.D. Garnovskii et al. / Polyhedron 18 (1999) 863–869
865
Table 1
Magnetic data for [Ni2L2(MeOH)4]a
b
c
b
T (K)
xM exp.
meff (exp.) B.M.
xM calc.
meff (calc.) B.M.
290
269
251
233
216
199
185
170
159
150
132
98
7311
7820
8235
8710
9540
10 251
11 081
11 555
12 385
12 741
14 638
19 210
21 571
23 010
2.91
2.90
2.88
2.85
2.87
2.86
2.86
2.80
2.81
2.77
2.78
2.74
2.77
2.76
7156
7680
8196
8789
9437
10 191
10 910
11 806
12 565
13 264
14 927
19 583
21 348
22 713
2.88
2.88
2.87
2.86
2.86
2.85
2.84
2.83
2.83
2.82
2.81
2.77
2.76
2.75
89
83
a
J524 cm21; g52.03; estimated error r51.83%.
xM, molar magnetic susceptibility.
b
c
meff, per one nickel (II) atom in a binuclear molecule.
3g2
4T
e24J /KT 1 5
e26J /KT 1 3e24J /KT 1 5
recorded on a Syntex P21 automatic diffractometer for (1)
and on a Siemens CCD Smart system for (2), with graphite
monocromated MoKa radiation (l50.71073 A) at 298
]
xM 5
˚
where g, T and K have their usual meanings.
2.6. X-ray data collection and processing
and 293 K using the v/2u scan technique, 2umax 5568 for
(1) and 66.3 for (2). 1523 reflections were collected, of
which, 1367 with I.2sI were used for calculations for (1)
and 23 409, of which, 9901 with I.2sI for (2).
The crystal data and a summary of the data collection
and structure refinement for these compounds are given in
Table 2. Crystals of complexes [NiL(MeOH)4] (1) and
[CuLbipy] (2) were mounted on glass fibres and data were
The structure of (1) was solved by the heavy-atom
method and that of (2) by the direct method. In both
compounds, non-hydrogen atoms and hydrogen atoms,
except for those from CH3 groups, were located from
Fourier difference synthesis. The structures were refined
using a full-matrix least-squares technique, isotropically
for the hydrogen atoms and anisotropically for all remain-
ing non-hydrogen atoms. All calculation were performed
using SHELXS-93 [31] for (1) and SHELXS-97 [32] for
(2). Interatomic bond distances and angles are given in
Tables 3 and 4, respectively. Atom positions, bond lengths
and bond angles, and other crystallographic data, have
been deposited as Supplementary Publication No. CSD
59422 for (1) and 408953 for (2): copies can be obtained
through Fachinformationszentrum Karlsruhe, 76344, Ener-
gie Physik Mathematik, D-7514 Eggenstein-Leopolshafen.
Table 2
Summary of crystal data for [Ni2L2(MeOH)4] (1) and [CuLbipy] (2)
[Ni2L2(MeOH)4]
[CuLbipy]
Empirical formula
Formula weight
Size
Crystal system
Space group
C44H48N4O10S2Ni2
974.5
0.130.0830.05
Triclinic
C30H24CuN4O3S
584.13
0.7530.6030.20
Monoclinic
P2(1)/c
P21 ([2)
Unit cell dimensions,
˚
a, A
10.271(2)
10.523(2)
11.460(2)
113.59(3)
105.21(3)
91.03(3)
1084.7(4)
1
17.2716(9)
8.6945(4)
17.9165(9)
90
92.7220(10)
90
2687.4(2)
4
1.444
˚
b, A
˚
c, A
a, 8
b, 8
g, 8
3
˚
Volume, A
3. Results and discussion
Z
dcalc, g cm23
1.492
0.71073
1.027
˚
l, A (MoKa radiation)
0.71073
0.930
The electrochemical oxidation of cobalt, copper and
nickel in the presence of the Schiff base H2L led to
complexes of general formulae [ML], where L stands for
the dianionic form of the Schiff base.
m (MoKa), mm21
T, K
293(2)
1523
1400
298(2)
23 409
9901
no. of reflns collected
no. of indept. reflns.
For cobalt and nickel, the electrochemical efficiency, Ef,
defined as moles of metal dissolved per Faraday of charge,
was close to 0.5 mol F21, in accordance with the following
process:
F(000)
508
0.070
0.1447
1204
0.0591
0.1131
Ra
Rwb
aR5S(uFou2uFcu)/SuFou. bRw 5[(Sw(uFou2uFcu)2 /SwuFou2]1 / 2
.

866
A.D. Garnovskii et al. / Polyhedron 18 (1999) 863–869
Table 3
˚
Selected bond distances (A) and angles (8) for [Ni2L2(MeOH)4]
Ni–N(1)
Ni–O(3)
Ni–O(4)
S–N(2)
2.002(12)
2.051(11)
2.111(14)
1.602(14)
1.460(12)
1.41(2)
1.41(2)
1.43(2)
1.37(2)
1.37(2)
Ni–N(2)
Ni–O(39)
Ni–O(5)
S–O(1)
S–C(14)
N(1)–C(7)
O(3)–C(1)
O(5)–C(22)
C(1)–C(6)
C(3)–C(4)
C(5)–C(6)
C(17)–C(20)
2.093(13)
2.063(10)
2.191(13)
1.419(12)
1.77(2)
1.30(2)
1.33(2)
1.40(2)
1.42(2)
S–O(2)
N(1)–C(6)
N(2)–C(13)
O(4)–C(21)
C(1)–C(2)
C(2)–C(3)
C(4)–C(5)
C(7)–C(8)
1.38(2)
1.40(2)
1.51(2)
1.36(2)
1.46(2)
N(1)–Ni–N(2)
N(1)–Ni–O(39)
N(1)–Ni–O(5)
N(2)–Ni–O(39)
N(2)–Ni–O(5)
O(3)–Ni–O(4)
O(39)–Ni–O(4)
O(4)–Ni–O(5)
N(2)–S–O(2)
87.3(4)
159.0(4)
94.8(5)
113.6(4)
92.3(5)
N(1)–Ni–O(3)
N(1)–Ni–O(4)
N(2)–Ni–O(3)
N(2)–Ni–O(4)
O(3)–Ni–O(39)
O(3)–Ni–O(5)
O(39)–Ni–O(5)
N(2)–S–O(1)
N(2)–S–C(14)
O(1)–S–C(14)
Ni–N(1)–C(6)
Ni–N(2)–C(13)
Ni–O(3)–Ni9
79.7(4)
94.6(5)
166.9(4)
94.2(6)
79.4(5)
89.0(4)
86.8(5)
86.7(4)
82.4(4)
168.8(4)
106.3(7)
113.9(7)
107.9(8)
125.9(11)
118.5(10)
112.7(9)
121.4(11)
125.1(14)
120(2)
115.3(8)
105.2(6)
107.6(7)
113.5(8)
117.4(9)
100.6(4)
124.1(11)
113.1(13)
125(2)
O(1)–S–O(2)
O(2)–S–C(14)
Ni–N(1)–C(7)
S–N(2)–C(13)
Ni–O(3)–C(1)
Ni–O(5)–C(22)
N(1)–C(7)–C(8)
N(2)–C(13)–C(8)
Ni–O(4)–C(21)
N(1)–C(6)–C(1)
C(7)–C(8)–C(13)
˚
with a 3.165 (1) A intermetallic Ni . . . Ni distance. Each
nickel atom is coordinated to two nitrogen and two oxygen
atoms from the ligands and two oxygen atoms from two
methanol molecules. Both nickel atoms are bridged by two
phenol oxygen atoms. The donor atoms [N(1), N(2), O(3)]
of one tridentate ligand and the oxygen bridge atom of the
other ligand (O(3)9) are coplanar and occupy the equatori-
al positions of a tetragonally distorted pseudo-octahedral
nickel(II) centre, with two methanol ligands at the axial
sites. The deviation from perfect geometry around the
nickel atom is illustrated by the values of the angles
defined by the nickel atom and two equatorial cis donor
atoms, which are very different from the expected value of
908 [N(1)–Ni–O(3)579.7(4)8]. On the other hand, the
NiN(1)O(3), O(3)C(1)C(16)N(1) fragments and the
phenyl ring C(1)–C(6) form dihedral angles with
[Ni2O(3)]2 of 2, 11 and 198, respectively. In the same way,
the six-membered chelate ring NiN(1)C(7)C(8)C(13)N(2)
and the phenyl ring C(8)–C(13) are not coplanar with the
plane NiO(3)NiO(3)9. In addition, the dihedral angles
between the N(1)NiN(2) fragment and the C(8)–C(13)
phenyl ring with the NiO(3)NiO(3)9 plane are 2 and 48,
respectively. The dihedral angle between the phenyl ring
C(14)–C(19) and the central square Ni2(O(3))2 is 548.
Cathode: H2L 1 2e2 → L22 1 H2
Anode: L22 1 M → [ML] 1 2e2
or L22 1 Ni 1 phen → [NiLphen] 1 2e2
In the case of copper, Ef was close to 1 mol F21
,
indicating that the formation of copper (I) at the anode is
followed by oxidation to copper (II) in solution. This
behaviour has already been observed in other copper
systems in which low-oxidation-state species are the initial
electrochemical products. This fact suggests that a possible
mechanism could be:
2
2
1
]
Cathode: H2L 1 e → HL 1 2 H2
Anode: Cu → Cu1 1 e2
1
2
1
]
Cu 1 HL → [CuL] 1 2 H2
2
1
1
]
or HL 1 Cu 1 bipy → [CuLbipy] 1 2 H2
3.1. Structure of [Ni2L2(MeOH)4 ]
The analytical data of the compound obtained by
reaction
of
nickel
acetate
and
2-(2-hydroxy-
phenyliminomethyl)-1-(4-methyl-phenylsulfonamido) ben-
zene, H2L, in methanol are compatible with a NiL?
2MeOH formulation. An X-ray diffraction study of this
compound showed that it consists of discrete neutral
dinuclear centrosymmetric [Ni2L2(MeOH)4] units (Fig. 1)
˚
The Ni–Nimine distance of 2.002(12) A is slightly
shorter than those found in other hexacoordinate
salicylidenealdiminate nickel(II) complexes [2.050(6)–

A.D. Garnovskii et al. / Polyhedron 18 (1999) 863–869
867
˚
Table 4
Selected bond lengths (A) and angles (8) for [CuLbipy]
2.066(3) A] [33,34]. The Ni–Namide bond distance of
˚
˚
2.093(13) A is longer than the Ni–Nimine one and, as
expected, significantly longer than those found in tetra-
hedral nickel amide complexes [1.916(3) [35], 1.839(6) A
[16]]. This is a reflection of the lower coordination number
in these latter compounds. The Ni–Ophenol bond distances
of 2.051(11) and 2.063(10) A are longer than observed in
mononuclear hexacoordinate salicylidenealdiminate nickel
complexes [2.005(4), 2.032(3) A] [33,34,36], whereas the
other two Ni–O bonds between the metal atom and the
methanol oxygen atom are considerably longer, being
Cu(1)–O(1)
Cu(1)–N(2)
Cu(1)–N(3)
S(1)–O(2)
1.9403(17) Cu(1)–N(1)
1.9737(17)
2.0037(18)
1.4448(18)
1.5950(18)
1.281(3)
1.407(3)
1.343(3)
1.347(3)
1.403(3)
1.386(4)
1.387(3)
1.451(3)
1.428(3)
1.379(4)
1.393(3)
1.385(4)
1.379(5)
1.509(5)
1.390(5)
1.369(6)
1.475(4)
1.373(5)
1.383(3)
2.003(2)
2.354(2)
Cu(1)–N(4)
S(1)–O(3)
˚
1.4482(18) S(1)–N(2)
S(1)–C(14)
N(1)–C(6)
N(3)–C(21)
N(4)–C(30)
O(1)–C(1)
C(1)–C(6)
C(3)–C(4)
C(5)–C(6)
C(8)–C(9)
C(9)–C(10)
C(11)–C(12)
C(14)–C(15)
C(15)–C(16)
C(17)–C(18)
C(18)–C(19)
C(22)–C(23)
C(24)–C(25)
C(26)–C(27)
C(28)–C(29)
O(1)–Cu(1)–N(1)
N(1)–Cu(1)–N(2)
1.774(2)
1.415(3)
1.340(4)
1.330(3)
1.314(3)
1.420(3)
1.392(4)
1.391(3)
1.401(3)
1.381(4)
1.383(4)
1.378(4)
1.387(4)
1.373(5)
1.381(5)
1.368(6)
1.395(4)
1.396(4)
1.362(5)
84.24(7)
86.30(7)
N(1)–C(7)
˚
N(2)–C(13)
N(3)–C(25)
N(4)–C(26)
C(1)–C(2)
C(2)–C(3)
C(4)–C(5)
˚
˚
2.118(14) and 2.191(13) A. The C(7)–N(1) distance
C(7)–C(8)
˚
C(8)–C(13)
C(10)–C(11)
C(12)–C(13)
C(14)–C(19)
C(16)–C(17)
C(17)–C(20)
C(21)–C(22)
C(23)–C(24)
C(25)–C(26)
C(27)–C(28)
C(29)–C(30)
[1.30(2) A] is as expected for azomethine C5N bonds
˚
[37]. C(1)–O(3) [1.33(2) A] is shorter than a C–O single
bond, but longer than a C5O double bond [38].
3.2. Structure of [CuLbipy]
Fig. 2 shows the molecular structure of [CuLbipy] and
the atom numbering system used. Selected bond distances
and angles are listed in Table 4.
O(1)–Cu(1)–N(2) 154.69(9)
O(1)–Cu(1)–N(4)
N(2)–Cu(1)–N(4)
92.00(7)
99.04(8)
The compound consists of discrete molecules with a
pentacoordinated copper atom. The geometrical parameter,
t, [t5(b2a)/60], where a and b are O(1)–Cu–N(3)
and N(1)–Cu–N(4) bond angles, respectively [39], has a
value of 0.9885. This suggests that the complex has a
geometry closer to that of a trigonal bipyramide (t51)
than of a square–pyramide (t50). The environment
around the copper metal is formed by one of the bipyridine
nitrogen atoms, the phenolate oxygen atom and the amide
deprotonated nitrogen of the 4-toluenesulfonamide group
atom, occupying the equatorial sites, and the azomethine
nitrogen atom and the other bipyridine nitrogen atoms in
the axial sites. The copper atom and the equatorial donor
N(1)–Cu(1)–N(4) 173.92(8)
O(1)–Cu(1)–N(3) 114.61(8)
N(1)–Cu(1)–N(3) 101.63(8)
N(2)–Cu(1)–N(3)
O(3)–S(1)–O(2)
O(2)–S(1)–N(2)
O(2)–S(1)–C(14)
C(7)–N(1)–C(6)
C(6)–N(1)–Cu(1)
C(13)–N(2)–Cu(1) 117.27(14)
C(21)–N(3)–C(25) 117.5(3)
C(25)–N(3)–Cu(1) 107.59(16)
C(30)–N(4)–Cu(1) 121.22(17)
90.27(8)
N(4)–Cu(1)–N(3)
O(3)–S(1)–N(2)
O(3)–S(1)–C(14)
N(2)–S(1)–C(14)
C(7)–N(1)–Cu(1)
C(13)–N(2)–S(1)
S(1)–N(2)–Cu(1)
C(21)–N(3)–Cu(1) 130.7(2)
C(30)–N(4)–C(26) 119.0(2)
C(26)–N(4)–Cu(1) 119.76(16)
75.57(8)
115.88(12)
114.53(11)
106.69(11)
124.37(18)
110.88(13)
106.12(11)
107.67(11)
105.28(10)
123.89(15)
120.66(16)
120.38(11)
C(1)–O(1)–Cu(1)
O(1)–C(1)–C(6)
112.01(14)
119.95(19)
O(1)–C(1)–C(2)
122.5(2)
Fig. 1. Crystal structure of hbis(methanol)[2-(29-N-tosylaminophenyl)iminomethyl] phenolatojnickel(II).

868
A.D. Garnovskii et al. / Polyhedron 18 (1999) 863–869
possessing the exchange fragment mentioned above [42–
46] reveal weak exchange coupling in contrast with copper
(II) complexes [46].
3.4. Spectroscopic studies
The IR data are consistent with the chelating behaviour
of the ligand. The bands attributable to n(NH) and n(OH)
are absent in the complexes, confirming the loss of the
phenolic and amide group hydrogen atoms during the
electrolysis. The n(C5N) shifts to lower frequency in
going from the free ligand, 1609 cm21, to the complexes,
1590–1600 cm21. These observations suggest that the
Schiff base coordinates the metallic atoms in the dianionic
form through the phenolate oxygen atom, and the amide
and azomethine nitrogen atoms. This conclusion is con-
firmed by the X-ray structures of [Ni2L2(MeOH)4] and
[CuLbipy]. In the IR spectra of the mixed compounds,
additional bands due to coordinated bipyridine and phen-
anthroline ligands are observed (720 and 750 cm21, and
725, 845 and 1510 cm21, respectively) [47,48].
Fig.
2.
Crystal
structure
of
hbis(2,29-bipyridine)[2-(29-N-
tosylaminophenyl)iminomethyl] phenolatojcopper(II).
atoms are coplanar within the limits of experimental
accuracy. Distortion was observed in the equatorial plane
(Table 4), with the angles O(1)–Cu–N(3), 114.61(8)8,
N(3)–Cu–N(2),
154.69(9)8, and along the axial direction of the trigonal
bipyramide, with a N(1)–Cu–N(4) angle of 173.92(8)8.
The Cu–O bond length, 1.940(18) A, is similar to the
values observed for other five-coordinated copper com-
plexes with Schiff-bases as ligands [14,40]. The Cu–Nimine
bond length [1.973(17) A] is shorter than those found in
other five-coordinated copper compounds, for example, in
bis(dimethylaminosalicyaldiminato)copper(II), with
mean value of 1.946 A [40]. The Cu–Nbipy bond distances
are different, with the axial bond, 2.0037(18)A, being
shorter than the equatorial one, 2.354(2) A. The shorter
Cu–Nbipy bond length is similar to the bond distances
found in other five-coordinated copper(II) complexes with
2,29-bipyridine; (2.002(4) A in di-m-hydroxo-bis[(2,29-
The diffuse reflectance spectrum of the [CuL] compound
shows a band at a ca. 15 000 cm21, in agreement with
those reported for square–planar copper(II) complexes. A
square–planar dimeric structure is therefore tentatively
assigned to the copper(II) complexes.
90.27(8)8,
and
O(1)–Cu–N(2),
˚
The diffuse reflectance spectra of nickel(II) complexes
exhibit two d–d bands that are well within the range for
six-coordinate octahedral complexes of nickel(II) (ca.
9100–8900 and 17 500–16 100 cm21), which can be
˚
3
3
assigned to the A2g →3T2g and A2g →3T1g transitions
respectively [49]. This octahedral environment has been
found in the X-ray structure determination of
[Ni2L2(MeOH)4]. Consequently, a six-coordinate poly-
meric structure is therefore tentatively assigned to the
[NiL] complex.
a
˚
˚
˚
The cobalt complex spectrum shows three bands at
4
7500, 11 900 and 18 200 cm21, assigned to T2g →4T1g
˚
4
4
(n3), A2g →4T1g (n2) and T1g(P)→4T1g(F) (n3) transi-
tions in a distorted octahedral field, respectively [48].
Therefore, a six-coordinated polymeric structure is tenta-
tively assigned to the cobalt(II) complex.
bipyridine)(trifluoromethanesulfonato-O)-copper(II)] [41].
3.3. Magnetic studies
The study of the magnetic properties of
[Ni2L2(MeOH)4] shows that the effective magnetic mo-
ment [per nickel (II) atom] decreases with temperature
down to a value that is less than the ‘spin-only’ value, 2.83
B.M., Table 1. This behaviour can be attributed to weak
antiferromagnetic exchange interaction between two para-
magnetic nickel atoms. The value of the exchange parame-
ter J is 24 cm21. In spite of the fact that the
NiO(3)NiO(3)9 fragment is nearly planar, implying the
overlap of equatorial plane magnetic orbitals and corre-
spondingly strong antiferromagnetism, the relatively small
J value should not be considered as anomalous. It is well
known that the majority of high spin nickel (II) complexes
Acknowledgements
We thank the Russian Science Foundation N960332026a
for financial support.
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