ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2009, Vol. 54, No. 3, pp. 396–402. © Pleiades Publishing, Inc., 2009.
Original Russian Text © Z.G. Rezinskikh, P.A. Slepukhin, I.G. Pervova, G.N. Lipunova, T.I. Maslakova, I.N. Lipunov, G.I. Sigeikind, 2009, published in Zhurnal Neorganicheskoi
Khimii, 2009, Vol. 54, No. 3, pp. 443–449.
COORDINATION
COMPOUNDS
Synthesis and Structure of Cobalt(II) 1-Aryl-3-aryl(alkyl)-5-
(benzothiazol-2-yl)formazanates
Z. G. Rezinskikha, P. A. Slepukhinb, I. G. Pervovaa, G. N. Lipunovac, T. I. Maslakovaa,
I. N. Lipunova, and G. I. Sigeikind
a Ural State Forestry Engineering University, Sibirskii trakt 37, Yekaterinburg, 620100 Russia
b Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences,
ul. S. Kovalevskoi 20, Yekaterinburg, 620219 Russia
c Ural State Technical University, ul. Mira 19, Yekaterinburg, 620002 Russia
d Interdepartmental Center of Analytical Studies at the Presidium of the Russian Academy of Sciences, Moscow, Russia
Received December 26, 2007
Abstract—New mono- and binuclear cobalt(II) complexes based on 1-aryl-3-aryl(alkyl)-5-(benzothiazol-2-
yl)formazans were synthesized. The structure of the synthesized compounds was determined by electronic and
IR absorption spectroscopy, mass spectrometry, and X-ray crystallography.
DOI: 10.1134/S0036023609030115
Previously [1, 2], the structure of nickel(II) and was stirred for 30 min and evaporated to a volume of
cobalt(II) formazanates based on some benzothiazolyl- 10 mL. The resulting precipitate was filtered off, washed
formazans was studied. It was shown that the ligands with warm distilled water and ethanol, and dried.
are coordinated to the metal atom through the nitrogen
Elemental analysis was carried out on a Perkin
atoms of the heterocycle and the N1 and N4 atoms of the
Elmer PE2400SII CHN analyzer. The metal content of
formazan chain, forming the ML2 complex. At the same
time, for benzothiazolylformazans that have additional
complexing groups in the aryl substituent at the
N1 atom, complexes ML and M2L2 are most typical [3].
a complex was determined by the rapid gravimetric
method on the equipment of Khimlaborpribor OAO
(Klin, Russia).
Electronic absorption spectra were recorded on a
Beckman UV-5260 double-beam spectrophotometer in
the wavelength range 350–800 nm.
IR spectra of benzothiazolylformazans II, III, and
V–VII and complexes IICo, IIICo, and VCo–VIICo
were recorded as KBr disks and Nujol mulls on a
Specord 75IR spectrophotometer in the range 400–
4000 cm–1.
Liquid chromatography/positive- and negative-ion
atmospheric pressure chemical ionization (APCI)
mass spectrometry studies of cobalt formazanates IICo,
IIICo, and VCo–VIICo were carried out on a Shimadzu
LCMS-2010 liquid chromatograph/mass spectrometer.
Samples were introduced into the mass spectrometer
through the chromatograph with an SPD-M10Avp diode
matrix using direct injection into the ion source.
In continuation of these studies, we synthesized
seven Co(II) complexes with seven different benzothi-
azolylformazan molecules (I–VII) and studied the
effect of denticity of the organic ligand on the structure
of the forming complexes.
EXPERIMENTAL
Cobalt(II) 1,3-diphenyl-5-(benzothiazol-2-yl)for-
mazanate (ICo) was synthesized as described in [4].
Synthesis of cobalt 1-(2-carboxyphenyl)-3-phenyl-
5-(benzothiazol-2-yl)formazanate (IICo), cobalt 1-(4-
carboxyphenyl)-3-phenyl-5-(benzothiazol-2-yl)forma-
zanate (IIICo), cobalt 1-phenyl-3-isopropyl-5-(ben-
zothiazol-2-yl)formazanate (IVCo), cobalt 1-(2-car-
boxyphenyl)-3-isopropyl-5-(benzothiazol-2-yl)forma-
X-ray crystallography. The crystallographic data,
zanate (VCo), cobalt 1-(2-hydroxy-4-nitrophenyl)-3- experimental details, and refinement parameters for
methyl-5-(benzothiazol-2-yl)formazanate (VICo), and compounds ICo and VICo are presented in Table 1.
cobalt 1-(2-hydroxy-4-nitrophenyl)-3-butyl-5-(ben- The unit cell parameters and a set of experimental data
zothiazol-2-yl)formazanate (VIICo). A solution of were measured on an Xcalibur 3 four-circle automated
cobalt(II) chloride (0.6 mmol for IICo, VCo–VIICo and diffractometer with a CCD detector (295(2) K; ω scan
0.3 mmol for IIICo and IVCo) in a minimal amount of with an increment of 1° and an exposure time of 30 s
acetone was added dropwise to a continuously stirred per frame; the crystal–detector distance, 50 mm). Data
solution of 0.6 mmol of corresponding formazan II–VIII collection and editing and the refinement of the unit cell
in 50 mL of acetone at 40 5°ë. The resulting mixture parameters were performed with the CrysAlis CCD
396