spectra were recorded from KBr pellets on a Bio-Rad FTS
135 spectrophotometer in the range 4000È600 cm~1. Electro-
spray mass spectra were obtained on a HewlettÈPackard
LC/MS spectrometer, in methanol as solvent. Room tem-
perature magnetic measurements were performed using a
Sherwood ScientiÐc magnetic susceptibility balance, calibrated
using mercury tetrakis(isothiocyanato)cobaltate(II).
cathode and a cobalt plate as the anode. The garnet solution
was reduced in volume and the precipitated solid isolated by
Ðltration, washed with diethyl ether and dried in air.
Crystallographic measurements
Crystal structures of CuL3(p-Tos)(H O), 1 and ZnL3(p-
2
Tos)(H O), 2. Crystals suitable for single X-ray di†raction
2
studies of 1 and 2 were obtained as previously described. Data
Synthesis of the complexes
were collected at 293 K using a CAD-4 di†ractometer
ML3(p-Tos)(H O) . These were obtained using an electro-
employing graphite-monochromated Mo-Ka (j \ 0.710 73 A)
2
n
chemical procedure, exempliÐed by the isolation of CuL3(p-
radiation, using the u/2h scan mode (2h \ 55.94¡ for 1 and
max
Tos)(H O), 1. An acetonitrile solution (70 mL) of L1 (0.2 g,
49.98¡ for 2). The structures were solved by direct methods
2
0.41 mmol) and p-toluenesulfonic acid (0.14 g, 0.82 mmol),
and reÐned by full matrix least squares on F2. All hydrogen
atoms were included in calculated positions, except those
attached to oxygen atoms, which were located in the Fourier
map and isotropically reÐned. Data processing and computa-
tion were carried out using the SHELX-97 program
package.29
containing about 10 mg of tetramethylammonium perchlorate
supporting electrolyte, was electrolysed for about 2 h using a
current of 10 mA. A platinum wire was used as the cathode
and a copper plate as the anode. The resulting suspension was
Ðltered, yielding the brown solid CuL3(p-Tos)(H O) . The
2
3
mother liquors were left to stand for one week. Evaporation of
the solution yielded small green crystals of CuL3(p-Tos)(H O),
Crystal structure of CoL3 , 3 . Brown plate crystals of 3
2
2
1, suitable for X-ray di†raction studies. Crystals of ZnL3(p-
were obtained as described above. All measurements were
Tos)(H O), 2, were obtained in exactly the same way, using a
made at 293(2) K on a Smart-CCD-1000 Bruker di†ractome-
2
zinc plate as the anode.
ter employing Mo-Ka (j \ 0.710 73 A) radiation, using the u
A grey solid of empirical formula Mn(p-Tos) (H O) was
scan mode (2h \ 52.98¡). An absorption correction from t
2
2
6
max
obtained by the same method, using manganese as the anode:
m.p. [300 ¡C; anal. found (calc.) for MnC C:
scans was applied. The structure was solved by direct methods
H
O S
and reÐned by full matrix least squares on F2. Non-hydrogen
atoms were reÐned anisotropically. All hydrogen atoms were
included in calculated positions. Data processing and compu-
tation were carried out using the SHELX-97 program
package.29
14 26 12 2
32.9 (33.3); H: 5.5 (5.1); N: 0 (0); S: 13.3 (12.7)%.
Slow recrystallisation of CoL3(p-Tos)(H O) in CH CN
2
3
3
yielded crystals of Co(p-Tos) (H O) : m.p. [300 ¡C; anal.
2 2 6
found (calc.) for CoC
H O S C: 33.7 (33.0); H: 5.4 (5.1);
0 (0); S: 13.6 (12.6)%. Unit cell: a \ 6.9867(1);
b \ 6.3049(1); c \ 25.2330(1) A; b \ 91.7544(8)¡.
14 26 12 2
N:
Crystal structures of CuL3 , 4 and ZnL3 Æ 2CH CN, 5.
2
2
3
Block-like dark red and orange plate crystals of 4 and 5,
respectively, were obtained as detailed above. All measure-
ments were made at 293(2) K on a Rigaku AFC5R di†ractom-
eter for 4 and on a Siemens CCD di†ractometer for 5,
employing Mo-Ka (j \ 0.710 73 A) radiation, using the 2h
ZnL3 (H O). This complex was isolated by two di†erent
2
2
methods. Method A (electrochemical synthesis): To an aceton-
itrile solution (70 mL) of L2 (0.2 g, 0.57 mmol), 10 mg of tetra-
methylammonium perchlorate were added as supporting
electrolyte. The resulting solution was electrolysed for 1.5 h
with a current of 10 mA, using a platinum wire as the cathode
and a zinc plate as the anode. During the experiment, an
orange solid precipitated. The solid was isolated by Ðltration,
washed with diethyl ether and dried in air.
scan mode (2h \ 56.56¡ for 4 and 49.94¡ for 5). The struc-
max
tures were solved by direct methods and reÐned by full matrix
least squares on F2. Non-hydrogen atoms were reÐned aniso-
tropically. All hydrogen atoms were included in calculated
positions. Data processing and computation were carried out
using the SHELX-97 program package.29
CCDC reference numbers 153998È154002. See http://
data in CIF or other electronic format.
Method B (chemical template synthesis): To a methanol
solution (80 mL) of Zn(acac) (0.25 g, 0.95 mmol), 2-
2
pyridinecarboxaldehyde (0.18 mL, 1.9 mmol) and N-tosyl-1,2-
diaminobenzene (0.5 g, 1.9 mmol) were added. The mixture
was reÑuxed for 3 h, removing the water with a DeanÈStark
device. The resultant suspension was Ðltered and the orange
solid was washed with diethyl ether and dried in air. Re-
crystallisation of the orange powder in hot acetonitrile yielded
crystals of ZnL3 É 2CH CN, 5, suitable for X-ray di†raction
Acknowledgements
The authors would like to thank the Ministerio de Educacion
y Ciencia (Spain) (PB98-0600) and Xunta de Galicia (Spain)
(PGIDT00PXI20910PR) for Ðnancial support.
2
3
studies. 1H NMR in DMSO-d : d 9.4 (s, 2H, CH2N), 8.08 (t,
6
2H, H ); 7.9È8.0 (m, 6H, 4H
16H, H ), 2.22 (s, 6H, methyl).
] 2H
) 6.76È7.47 (m,
arom
arom
apyridine
References
arom
1
D. A. Garnovskii, A. L. Nivorozhkin and V. I. Minkin, Coord.
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V. Alexander, Chem. Rev., 1995, 95, 273.
ML3 (H O) . All ML3 (H O) complexes (M \ Mn, Co,
2
2
n
2
2
n
Cu, Zn) can be obtained by method B. Recrystallisation of the
2
3
4
S. Yamada, Coord. Chem. Rev., 1999, 190–192, 537.
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dark brown solid CoL3 in CH CN and of the dark red
2
3
powder CuL3 , by slow evaporation of a methanolÈethanolÈ
2
dichloromethane solution, yielded crystals of CoL3 , 3, and
CuL3 , 4, respectively, suitable for X-ray di†raction studies.
2
2
CoL3 . This complex has also been obtained by two di†er-
2
ent procedures: chemical template synthesis (method B above)
5
6
7
8
M. R. Bermejo, A. Sousa, M. Fondo and M. Helliwell, New J.
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and by an electrochemical template synthesis: To an acetoni-
trile solution (70 mL) of N-tosyl-1,2-diaminobenzene (0.2 g,
0.76 mmol) and 2-pyridinecarboxaldehyde (0.8 mL, 0.8 mmol),
10 mg of tetramethylammonium perchlorate were added as
supporting electrolyte. The resultant solution was electrolysed
for 2 h with a current of 10 mA, using a platinum wire as the
S. Cabaleiro-Martoanez, J. Castro, J. Romero, J. A. Garc•a-
Vazquez and A. Sousa, Acta Crystallogr., Sect. C, 2000, 56, E249.
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Verschoor, J. Chem. Soc., Dalton T rans., 1984, 1349.
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653
Sousa
