Physico-chemical study of first row transition metal ions coordination compounds with N,N′-bis(2-tosylaminobenzylidene)-1,3-diaminopropanol. The crystal structure of bis-azomethine and its cobalt(II) complex

Article abstract of DOI:10.1016/j.ica.2008.08.012

The novel Cu(II), Ni(II), Zn(II), Co(II) coordination compounds with Schiff base ligand - N,N′-bis(2-tosylaminobenzylidene)-1,3-diaminopropanol have been synthesized and studied. The structures of bis-azomethine as well as Co(II) and Zn(II) mononuclear me

Full text of DOI:10.1016/j.ica.2008.08.012

Inorganica Chimica Acta 362 (2009) 1673–1680
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Review
Physico-chemical study of first row transition metal ions coordination
compounds with N,N0-bis(2-tosylaminobenzylidene)-1,3-diaminopropanol.
The crystal structure of bis-azomethine and its cobalt(II) complex
a
a
a
b
a
L.D. Popov a, Yu.P. Tupolova a, , V.V. Lukov , I.N. Shcherbakov , A.S. Burlov , S.I. Levchenkov , V.A. Kogan ,
*
K.A. Lyssenko c, E.V. Ivannikova a
a Department of Chemistry, Southern Federal University, Zorge Street, 7, Rostov-on-Don 344090, Russia
b Department of Physical Organic Chemistry, Southern Scientific Centre of the RAS, 41, Chekhova Street, 344006 Rostov-on-Don, Russia
c A.N. Nesmeyanov Institute of Organoelement Compounds RAS, Vavilov Street, 28, Moscow, Russia
a r t i c l e i n f o
a b s t r a c t
The novel Cu(II), Ni(II), Zn(II), Co(II) coordination compounds with Schiff base ligand – N,N0-bis(2-tosy-
laminobenzylidene)-1,3-diaminopropanol have been synthesized and studied. The structures of bis-azo-
methine as well as Co(II) and Zn(II) mononuclear metallochelates have been determined by X-ray
analysis. The magnetic properties of all complexes were studied and interpreted in terms of HDVV theory.
It was shown that exchange interaction in binuclear copper(II) complexes was affected by tosyl groups.
Ó 2008 Elsevier B.V. All rights reserved.
Article history:
Received 18 April 2008
Received in revised form 27 June 2008
Accepted 22 August 2008
Available online 28 August 2008
Keywords:
Coordination compounds
Schiff base
Crystal structure
Magnetic properties
Leonid Dmitrievich Popov, was born in 1958, citizen of Russian Federation, in 1996 year he finished postgraduate course of the chemistry faculty of
Rostov State University. Now he works as a senior lecturer of physical and colloid chemistry at the chemistry faculty of Southern Federal University.
Basic scientific interests: synthesis and physical-chemical study of the polydentate ligands and their mono- and binuclear metal complexes; corre-
lation of a structure and physical and chemical properties of coordination compounds; search of ways of possible application of organic and
coordination compounds.
Yuliya Pavlovna Tupolova, was born in 1978 u., citizen of Russian Federation, in 2000 u. have graduated the chemistry faculty of Rostov State
University; in 2003 have finished postgraduate course of RSU. She was conferred the degree of Ph.D in physical and inorganic chemistry. The basic
scientific interests: synthesis and physical-chemical study of the polydentate ligands, forming mono- and binuclear complexes; NMR study; UV
spectroscopy, magnetochemical measurements. Currently Tupolova Yu.P. conducts seminars and practical courses on Physical Chemistry that address
Bachelor- degree senior students of the Faculty of Chemistry. In addition, among her responsibilities is to conduct lectures and practical courses on
special topics of the Faculty of Physical and Colloid Chemistry. She is one of the authors of 20 articles in Russian and International scientific journals.
She is a winner of Russia President’s Grant for young scientists.
* Corresponding author. Tel.: +7 863 2975148; fax: +7 863 2648817.
E-mail address: tup_u@mail.ru (Yu.P. Tupolova).
0020-1693/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2008.08.012

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L.D. Popov et al. / Inorganica Chimica Acta 362 (2009) 1673–1680
Vladimir Victorovich Lukov, full professor of Department of Chemistry, Southern Federal University. He was conferred the degree of Ph.D in
physical and inorganic chemistry in 1983, in 2000 he defended the doctoral dissertation titled ‘‘Magnetochemistry of mono-, bi- and threenuclear
transition metal complexes with hydrazone ligands”. He was conferred the degree of Doctor of Science in Chemistry. The area of scientific interest is
electronic and structural properties of inorganic transition-metal complexes. Magnetic studies to 4 K, single crystal anisotropy, electron spin reso-
nance spectroscopy, optical spectroscopy and paramagnetic NMR studies. He has published 170 articles in chemical periodicals and among them there
are 7 reviews and 2 monographs. He was granted as Soros Associated Professor (Soros Science Foundation) in 1995, 1997, 1998, 1999, 2000.
Igor Nikolaevich Shcherbakov, was born on 26/02/1964 in Rostov-on-Don, Russia, graduated from the Chemistry Faculty of the Rostov State
University in 1986 and from the same year started his career in this University first as assistant professor and from 1996 as Senior Lecturer at the
Department of the Physical and Colloid Chemistry of the Chemistry Faculty of the Southern Federal University (descendant of the Rostov State
University). The basic scientific interests: theoretical study of the electronic structure of the organic and metal-organic, coordination compounds,
quantum chemical modeling of the chemical reactions, molecular dynamics, theoretical modeling of the magnetic exchange interaction.
Anatoliy Sergeevich Burlov, Senior Researcher in the Southern Federal University, was born in 1943, graduated from the Chemistry Faculty of the
Rostov State University in 1971, conferred the degree of Ph.D in chemistry in 1975. The basic scientific interests: synthesis and physical-chemical
study of properties and structure metalocomplexes with azo- and azomethine ligands. Author of more than 350 articles in scientific periodicals.
Sergey Ivanovich Levchenkov, was born in 1966, graduated from the Rostov State University in 1990, conferred the degree of Ph.D in chemistry in
1994. At present time he is working as Senior Researcher in the Southern Scientific Center of the RAS and at the same time as Associated Professor of
the Department of Physical and Colloid Chemistry, Southern Federal University (Rostov-on-Don, Russia). The main fields of scientific interest are: the
coordination chemistry, magnetochemistry of transition metal coordination compounds.
Victor Alexandrovich Kogan, Head of Department of Physical and Colloid Chemistry, Full Professor. State Prize Winner, Chugaev Prize Winner of
Russian Academy of Sciences, Honored for Services to Science of Russian Federation. The sphere of primary scientific interests is the physico-chemistry
of coordination compounds, the relationship between structure and properties, nanochemistry. Author of more than 500 articles in scientific
periodicals.
Konstantin Alexandrovich Lyssenko, was born in 1973. Graduated from the High Chemical College of the Russian Academy of Sciences, Moscow in
1995. He was conferred the degree of Doctor of Science in physics in 2007. Now he works as Senior Researcher in the Institute of Organoelement
Compounds (INEOS), Russian Academy of Sciences. The basic scientific interests: the structure of the molecular crystals, low-temperature X-ray
investigations, crystallography of the small molecules and crystal properties, electron density distribution and dynamics of the molecular crystals,
solid state phase transitions the ab initio calculations of the organic and organometallic compounds.

L.D. Popov et al. / Inorganica Chimica Acta 362 (2009) 1673–1680
1675
Elena Vladimirovna Ivannikova, was born in 1979, graduated from the Department of Chemistry of the Rostov State University in 2001. She was
conferred the degree of Ph.D in chemistry in 2004. Now she works as a senior lecturer of the Department of Physical and Colloid Chemistry, Southern
Federal University. The basic scientific interests: synthesis and physical-chemical study of the polydentate ligands, transition metal complexes; study the
physical and chemical properties of coordination compounds. She has published 7 articles in chemical scientific journals.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1675
2. Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1675
2.1. Materials and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1675
2.2. Ligand synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
2.3. Synthesis of complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
2.3.1. [MHL] ꢀ H2O (M = Zn2+, Co2+, Ni2+) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
2.3.2. [Cu2L(X)], where X = CH3COOꢁ, CH2ClCOOꢁ, CCl3COOꢁ, CF3COOꢁ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
2.3.3. [Cu2L(Pz)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
2.4. X-ray crystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
3.1. Crystal structure of ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1676
3.2. Mononuclear complexes of Zn(II), Co(II), Ni(II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1677
3.2.1. Infrared spectroscopy of Zn(II), Co(II), Ni(II) complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1678
3.2.2. X-ray structures determination of [CoHL] ꢀ H2O, [ZnHL] ꢀ H2O. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1678
3.2.3. Magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1679
3.3. Binuclear Cu(II) complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1679
3.3.1. Infrared spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1679
3.3.2. Magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1679
4. Supplementary material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1680
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1680
1. Introduction
CH3
CH3
The metallochelates with Schiff bases produced from condensa-
tion of ortho-hydroxyaldehydes and b-diketones with 1,3-diamino-
propanol-2 have been studied in details [1–35]. The analysis of
published data has shown that above-stated azomethines form both
mononuclear [1–6] and polynuclear coordination compounds [7–
35]. In most cases the paramagnetic centres of bi- and polynuclear
complexes exhibit exchange interaction the character of which is
determined by the nature of exchange coupled ions and ligand’s do-
nor atoms as well as by bridging atoms of acidoligands (Hal, OAc) or
heterocycle molecules (pyrazol, azaindol, bipyridyl, etc.). It is also
known that presence of tosyl group in the molecules of ligand sys-
tems is frequently resulted in essential transformation of complex
structure and physical-chemical properties. The latter is caused by
both replacement of oxygen donor atom of phenoxide fragment by
the nitrogenone of tosylamino group and possible additionalcoordi-
nation of sulpho-group’s oxygen atoms to metal ion [36–45].
In this connection it was interesting to synthesize and study the
transition metal complexes with Schiff base produced from con-
densation reaction of ortho- aminotosylbenzaldehyde with 1,3-
diaminopropanol-2 (H3L, Fig. 1) in order to elucidate the tosyl
group’s influence on the structure and properties of obtained
metallochelates.
SO2
SO2
NH
HN
OH
N
N
C
H
C
C
H2
H2
Fig. 1. N,N0-Bis(2-tosylaminobenzylidene)-1,3-diamino-2-propanol (H3L).
standard procedures. 1,3-Diaminopropan-2-ol, 2-tosylaminobenz-
aldehyde, pyrazol were purchased from Aldrich and used without
further purification. Metal salts M(CH3COO)2 ꢀ nH2O were used in
their hydrated forms.
Microanalysis on C, H and N was performed on a Perkin–Elmer
240C Analyzer. The infrared spectra were recorded on a Varian
Scimitar 1000 infrared spectrophotometer in the range 4000–
400 cmꢁ1 1H NMR spectra were recorded on a ‘‘Unity-300” spec-
.
trometer using TMS as internal standard. The UV–Vis spectra were
recorded on ‘‘Unicam Helios Gamma” spectrometer in the 1100–
195 nm range. Magnetic susceptibility of powdered samples of
the complexes was measured in the temperature range 300–
77.4 K using a Faraday magnetometer employing magnetic field
strength 0.9 T. Corrections were made for diamagnetic contribu-
tions of the samples according to Pascal’s constants [46,47] and
2. Experimental
2.1. Materials and methods
All chemicals used for the preparative work were of reagent
grade. Solvents were dried and distilled before use according to

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L.D. Popov et al. / Inorganica Chimica Acta 362 (2009) 1673–1680
for temperature independent paramagnetism. The instrument was
calibrated with the use of Hg[Co(CNS)4]. The theoretical interpreta-
tion of binuclear complex’s magnetic properties was carried out in
terms of HDVV theory [48].
[Cu2L(CH3COO)]: Green solid. Yield 81%. M.p. > 250 °C. Anal. Calc.
for C33H32O7N4S2Cu2: C, 50.31; H, 4.09; N, 7.11; Cu, 16.13. Found:
C, 49.91; H, 3.68; N, 6.65; Cu, 15.81%. IR (NaCl, cmꢁ1):
m(C@N)
1636(s), m(C–N) 1294(s), mas(SO2) 1250(s), ms(SO2) 1141(s).
[Cu2L(CH2ClCOO)]: Green solid. Yield 74%. M.p. > 250 °C. Anal.
Calc. for C33H31O7N4S2CICu2: C, 48.22; H, 3.81; N, 6.84; Cu, 15.51.
Found: C, 48.51; H, 4.23; N, 7.16; Cu, 15.96%. IR (NaCl, cmꢁ1):
2.2. Ligand synthesis
N,N0-Bis(2-tosylaminobenzalidene)-1,3-diamino-2-propanol
was synthesized as follows. To a hot solution of 1,3-diaminopropa-
nol-2 (0.003 M) in 10 ml of ethanol 0.006 M o-tosylaminobenzalde-
hyde was added followed by the change of solution colour up to
yellow. Four drops of acetic acid were added and the solution was
refluxed for 4 h. Next morning the oil deposit was formed at the bot-
tom oh the flask. A day later it transformed into yellow precipitate.
The precipitate was left for one day more, after that it was sepa-
rated, washed with a minimum amount of ethanol and recrystal-
lized from the mixture of DMFA (2 ml) and methanol (6 ml). The
recrystallized product was washed with small amount of methanol.
Yellow precipitate. Yield 67%. M.p. 167 °C; lit. 161 °C [45]; 1H
NMR (DMSO-d6): 13.2 (s, 2H, NH), 8.5 (s, 2H, CHazomethene), 5.15
(d, 1H, OH), 7.1–7.7 (m, 16H, Ph-H), 3.7–3.9 (m, 4H, CH2), 4.2 (m,
1H, CHmethyn group), 2.2 (s, 6H, CH3). Anal. Calc. for C31H32N4O5S2:
C, 61.56; H, 5.29; N, 9.27. Found: C, 61.23; H, 6.04; N, 9.15%. IR
m
(C@N) 1642(s),
[Cu2L(CCI3COO)]: Green solid. Yield 72%. M.p. > 250 °C. Anal. Calc.
for C33H29O7N4S2CI3Cu2: C, 44.47; H, 3.35; N, 6.31; Cu, 14.34. Found:
C, 44.83; H, 3.92; N, 5.96; Cu, 14.64%. IR (NaCl, cmꢁ1):
(C@N)
1643(s), (C–N) 1285(s), as(SO2) 1264(s), s(SO2) 1137(s).
m(C–N) 1292(s), mas(SO2) 1255(s), ms(SO2) 1135(s).
m
m
m
m
[Cu2L(CF3COO)]: Green solid. Yield 77%. M.p. > 250 °C. Anal. Calc.
for C33H29O7N4S2F3Cu2: C, 47.14; H, 3.46; N, 6.72; Cu, 15.18. Found:
C, 46.85; H, 2.90; N, 7.04; Cu, 15.57%. IR (NaCl, cmꢁ1):
m(C@N)
1643(s),
m(C–N) 1290(s), mas(SO2) 1250(s), ms(SO2) 1137(s).
2.3.3. [Cu2L(Pz)]
To a hot suspension of ligand (0.0002 M) in 10 ml methanol the
solution of copper(II) acetate (0.0004 M) in 10 ml methanol was
added followed by the addition of pyrazole (0.0004 M). The dark
green solution was formed. In 5 min the complex has precipitated.
The mixture was refluxed for 5 h, then filtered off and washed with
methanol.
(NaCl, cmꢁ1):
(C–N) 1334 (s),
m
(O–H) 3525 (b),
m
(N–H) 3278 (b),
m(C@N) 1635 (s),
m
m
as(SO2) 1288 (s),
m
s(SO2) 1157 (s).
Green solid. Yield 71%. M.p. > 250 °C. Anal. Calc. for C34H32O5N6-
S2Cu2: C, 51.38; H, 4.06; N, 10.61; Cu, 16.05. Found: C, 50.93; H,
2.3. Synthesis of complexes
4.31; N, 10.22; Cu, 15.68%. IR (NaCl, cmꢁ1):
m(C@N) 1645(s), m(C–
N) 1290(s),
mas(SO2) 1263(s), ms(SO2) 1139(s).
Caution! It is very important to note that in all cases the molar
ratio of reagents M:L was 2:1 during the synthesis of complexes,
but in spite of this fact the coordination compounds possessing dif-
ferent structure have been obtained. Cu(CClH2COO)2, Cu(CCl3-
COO)2, Cu(CF3COO)2 have been obtained by a known method [49].
2.4. X-ray crystallography
Crystals of bis-azomethine and Co(II), Zn(II) complexes suitable
for X-ray diffraction were grown up by slow evaporation of solu-
tions in mixture C2H5OH and CH3Cl (2:1). X-ray diffraction exper-
iments were carried out with a Bruker SMART 1000 CCD in case of
Zn(II) complex and Bruker SMART APEX II CCD diffractometer in
case of Co(II) complex compound and free ligand, using graphite
2.3.1. [MHL] ꢀ H2O (M = Zn2+, Co2+, Ni2+
)
To a hot suspension of ligand (0.0002 M) in 10 ml of absolute
methanol
a hot solution of corresponding metal acetate
monochromated Mo Ka radiation ( = 0.71073 Å, x-scans). Reflec-
(0.0004 M) in 6 ml absolute methanol was added. The colour of
solution changed in each case. For the complexes with M = Co(II),
Ni(II) the precipitate was formed within 10 min, for Zn(II) complex
the precipitate was formed after 6 h of solution’s reflux. Complexes
were filtered off hot and washed with hot methanol followed by
the boiling in a small amount of ethanol for purification.
tion intensities were integrated using SAINT software and adsorption
correction was applied semi-empirically using SADABS program [50].
The structures was solved by direct method and refined by the full-
matrix least-squares against F2 in anisotropic approximation for
not-hydrogen atoms. The OH and NH hydrogen atoms were located
from the Fourier density synthesis and refined in isotropic approx-
imation, for all other ones the positions were calculated from geo-
metrical point of view. Analysis of Fourier density synthesis has
revealed that in complexes solvate water molecule and OH-group
are disordered by two positions with self occupancies factors
(s.o.f) equal to 0.8, 0.2 and 0.7, 0.3 for OH and H2O molecules,
respectively. In the crystal structure of the ligand one of phenyl
groups is disordered by two positions with equal occupancies.
The hydrogen atom for disordered OH-group was located only for
[ZnHL] ꢀ H2O: White solid. Yield 75%. M.p. 240 °C. Anal. Calc. for
C31H32N4O6S2Zn: C, 54.27; H, 4.70; N, 8.17; Zn, 9.53. Found: C,
54.46; H, 4.81; N, 8.31; Zn, 9.37%. IR (NaCl, cmꢁ1):
m
(O–H) 3523 (b),
s(SO2) 1135(s).
[CoHL] ꢀ H2O: Pink solid. Yield 71%. M.p. 238 °C. Anal. Calc. for
C31H32N4O6S2Co: C, 54.78; H, 4.75; N, 8.24; Co, 8.67. Found: C,
54.98; H, 4.81; N, 8.39; Co, 8.72%. IR (NaCl, cmꢁ1):
(O–H) 3520 (b),
(C@N) 1581(s), (C–N) 1342 (s), as(SO2) 1249(s), s(SO2) 1139(s).
7[NiHL] ꢀ H2O: Green solid. Yield 67%. M.p. 228 °C. Anal. Calc. for
C31H32N4O6S2Ni: C, 54.80; H, 4.75; N, 8.25; Ni, 8.64. Found: C,
55.15; H, 5.27; N, 8.76; Ni, 8.41%. IR (NaCl, cmꢁ1):
(O–H) 3522 (b),
(C@N) 1635(s), (C–N) 1290 (s), as(SO2) 1263(s), s(SO2) 1132(s).
m(C@N) 1639(s), m(C–N) 1289 (s), mas(SO2) 1263(s), m
m
m
m
m
m
position with s.o.f. equal to 0.8. The hydrogen atom of OH-group
1
for
of methanol molecule was not located. The positions of all
4
m
m
other hydrogen atoms were calculated geometrically. Crystal data
and structure refinement parameters for ligand and Co(II) and
Zn(II) complexes are given in Table 1. All calculations were per-
formed using the SHELXTL software [51].
m
m
m
2.3.2. [Cu2L(X)], where X = CH3COOꢁ, CH2ClCOOꢁ, CCl3COOꢁ, CF3COOꢁ
To a hot suspension of ligand (0.0002 M) in 10 ml of absolute
methanol the copper(II) salt (0.0004 M) solution in methanol was
added. For the complexes with X = CH3COOꢁ, CF3COOꢁ, CCl3COOꢁ
the precipitate was formed within 10 min, but for X = CH2ClCOOꢁ
the precipitate was formed after half-hour boiling. The solutions
of complexes were refluxed for 3–5 h, then filtered hot, followed
by the boiling of complexes with X = CF3COOꢁ, CCl3COOꢁ in
10 ml ethanol for purification. The compound with X = CH2ClCOOꢁ
is partially soluble in this solvent.
3. Results and discussion
3.1. Crystal structure of ligand
The molecular structure of H3L is obtained from single crystal X-
ray crystallographic studies. Selected bond distances and angles
are listed in Table 2 and the ORTEP views are given in Fig. 2.

L.D. Popov et al. / Inorganica Chimica Acta 362 (2009) 1673–1680
1677
Table 1
Selected crystallographic data for [H3L], [CoHL] ꢀ H2O, [ZnHL] ꢀ H2O
Table 2
Selected bond distance (Å) and angles (°) for ligand [H3L]
Compound
[H3L]
[CoHL] ꢀ H2O
C31H32CoN4O6S2
679.66
[ZnHL] ꢀ H2O
C31H32ZnN4O6S2
686.10
Bond lengths
C(1)–C(2)
C(1)–C(2’)
C(1)–O(1)
N(1)–C(3)
N(1’)–C(3’)
N(1)–C(2)
N(1’)–C(2’)
S(1)–O(2)
S(1)–O(3)
S(1’)–O(2’)
S(1’)–O(3’)
S(1)–N(2)
S(1’)–N(2’)
N(2)–C(5)
N(2’)–C(5’)
S(1)–C(10)
S(1’)–C(10’)
1.514(3)
1.529(2)
1.428(2)
1.279(3)
1.278(2)
1.467(2)
1.460(2)
1.4362(15)
1.4351(15)
1.4415(16)
1.4225(15)
1.6244(17)
1.6218(16)
1.408(2)
1.407(2)
1.760(2)
1.757(2)
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C31H32N4O5S2
604.73
100(2)
100(2)
120(2)
0.71073
triclinic
0.71073
orthorhombic
P212121
8.9953(8)
16.7289(15)
20.4180(16)
90
90
90
3072.5(5)
4
1.469
0.71073
orthorhombic
P212121
9.0591(6)
16.7557(12)
20.2064(14)
90
90
90
3067.2(4)
4
1.486
ꢀ
P1
8.0991(6)
12.0481(8)
15.9941(11)
79.5800(10)
82.8750(10)
71.8730(10)
1454.93(18)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (Mg/m3)
Absorption
coefficient
1.380
0.231
0.745
0.988
(mmꢁ1
)
Bond angles
O(1)–C(1)–C(2)
O(1)–C(1)–C(2’)
C(2)–C(1)–C(2’)
N(2)–S(1)–C(10)
C(5)–N(2)–S(1)
C(6)–C(5)–N(2)
N(2)–C(5)–C(4)
C(11)–C(10)–S(1)
C(15)–C(10)–S(1)
N(2’)–S(1’)–C(10’)
C(3’)–N(1’)–C(2’)
C(5’)–N(2’)–S(1’)
N(1’)–C(2’)–C(1)
C(6’)–C(5’)–N(2’)
N(2’)–C(5’)–C(4’)
C(11A)–C(10’)–S(1’)
C(15’)–C(10’)–S(1’)
C(3)–N(1)–C(2)
N(1)–C(2)–C(1)
106.77(15)
112.12(15)
113.01(15)
105.66(9)
126.53(13)
123.15(17)
117.20(17)
120.53(15)
118.80(15)
108.69(9)
117.09(14)
127.43(13)
111.92(14)
123.29(16)
116.75(15)
110.2(3)
F(000)
636
1412
1424
Crystal size (mm)
0.40 ꢂ 0.20 ꢂ 0.20
0.30 ꢂ 0.20 ꢂ 0.20
0.40 ꢂ 0.20 ꢂ 0.20
h Range (°)
1.80–29.00
ꢁ10 6 h 6 11,
ꢁ16 6 k 6 16,
ꢁ21 6 l 6 21
16711
1.99–29.00.
ꢁ12 6 h 6 11,
ꢁ16 6 k 6 22,
ꢁ22 6 l 6 27
16457
1.58–27.16
ꢁ11 6 h 6 11,
ꢁ21 6 k 6 21,
ꢁ21 6 l 6 25
31704
Index ranges
Reflections
collected
Independent
reflections
7662 (0.0213)
99.1
8000 (0.0237)
99.5
6805 (0.0806)
99.9a
(Rint
)
Completeness to
h = 29.00° (%)
Absorption
correction
Maximum and
minimum
117.3(2)
118.29(17)
108.10(15)
semi-empirical
from equivalents
0.9552 and
semi-empirical
from equivalents
0.8653 and
semi-empirical
from equivalents
0.8269 and
0.9132
0.8074
0.6934
transmission
Refinement
method
Data/restraints/
parameters
Goodness-of-fit
on F2
full-matrix least-
squares on F2
7662/0/413
full-matrix least-
squares on F2
8000/2/413
full-matrix least-
squares on F2
6805/2/413
1.030
1.051
1.015
Final R indices
R1 = 0.0497,
R1 = 0.0361,
R1 = 0.0427,
[I > 2
R indices (all data)
r
(I)]
wR2 = 0.1240
R1 = 0.0611,
wR2 = 0.0884
R1 = 0.0411,
wR2 = 0.0935
R1 = 0.0708,
wR2 = 0.1326
0.534 and ꢁ0.468
wR2 = 0.0914
0.669 and ꢁ0.492
wR2 = 0.1059
0.693 and ꢁ0.447
Largest difference
in peak and
hole (e Åꢁ3
)
a
Completeness to h = 27.16° (%).
Bis-azomethine crystallizes in an asymmetric conformation due
to flexibility of the propanol spacer. o-Aminobenzylidene frag-
ments are individually close to planar with the evidence of strong
intramolecular hydrogen bond NHꢀ ꢀ ꢀNaz (interatomic distances are
d(N(2)Hꢀ ꢀ ꢀN(1)) = 1.932 Å; d(N(20)Hꢀ ꢀ ꢀN(10)) = 1.914 Å). Aminopro-
panol fragment have the following structure: one of the azome-
thine nitrogen atoms is placed close to the plane, formed by
carbon atoms of the spacer (dihedral angle 172°), at the same time
other one is out of this plane due to rotation along (OH)C–C(N)
bond by 60°. OH-group participates in intermolecular hydrogen
bong with the oxygen atom of the SO2-group (d(OHꢀ ꢀ ꢀO) = 1.818 Å)
of another molecule, resulting in the formation of infinite supra-
molecular structure. It is worth noting that oxygen atoms of the
second tosyl moiety is not involved in the analogous Hꢀ ꢀ ꢀO hydro-
gen bond, but forms short intermolecular contact with proton of
the methyl group of the neighbouring molecule. (d(Oꢀ ꢀ ꢀHC) =
2.449 Å).
Fig. 2. Molecular structure of ligand H3L (50% probability).
Planes of the benzylidene fragment and phenyl ring of the tosyl
moiety are nearly mutually perpendicular with the angle 97° be-
tween them. Configuration of the bonds around amine nitrogen
is distorted pyramidal, bonds C–N and N–H lies in the plane of
the benzylidene fragment, but N–SO2 bond is turned from it by
the angle 19°. Thus, no conjugation of the benzylidene fragment
and S@O bond is observed.
3.2. Mononuclear complexes of Zn(II), Co(II), Ni(II)
The mononuclear type 1 metallochelates (Fig. 3) with the gen-
eral formula [MHL], where HL2ꢁ is the doubly deprotonated ligand

1678
L.D. Popov et al. / Inorganica Chimica Acta 362 (2009) 1673–1680
Table 3
Ts
N
Ts
N
Selected bond distance (Å) and angles (°) for [CoHL] ꢀ H2O, [ZnHL] ꢀ H2O
[CoHL] ꢀ H2O
[ZnHL] ꢀ H2O
Bond lengths
Co(1)–N(2’)
Co(1)–N(2)
Co(1)–N(1’)
Co(1)–N(1)
M
1.977(2)
1.9797(19)
2.006(2)
2.017(2)
Zn(1)–N(2)
Zn(1)–N(2’)
Zn(1)–N(1)
Zn(1)–N(1’)
1.971(3)
1.977(3)
2.026(3)
2.036(3)
N
CH
OH
N
C
C
H2
H2
Bond angles
N(2’)–Co(1)–N(2)
N(2’)–Co(1)–N(1’)
N(2)–Co(1)–N(1’)
N(2’)–Co(1)–N(1)
N(2)–Co(1)–N(1)
N(1’)–Co(1)–N(1)
C(3’)–N(1’)–Co(1)
C(2’)–N(1’)–Co(1)
C(5’)–N(2’)–Co(1)
S(1’)–N(2’)–Co(1)
C(5)–N(2)–Co(1)
S(1)–N(2)–Co(1)
C(3)–N(1)–Co(1)
C(2)–N(1)–Co(1)
130.78(8)
91.50(9)
123.17(8)
127.68(8)
90.19(8)
N(2)–Zn(1)–N(2’)
N(2)–Zn(1)–N(1)
N(2’)–Zn(1)–N(1)
N(2)–Zn(1)–N(1’)
N(2’)–Zn(1)–N(1’)
N(1)–Zn(1)–N(1’)
C(3’)–N(1’)–Zn(1)
C(2’)–N(1’)–Zn(1)
C(5’)–N(2’)–Zn(1)
S(1’)–N(2’)–Zn(1)
C(5)–N(2)–Zn(1)
S(1)–N(2)–Zn(1)
C(3)–N(1)–Zn(1)
C(2)–N(1)–Zn(1)
129.70(13)
91.51(13)
128.39(13)
123.16(13)
91.43(14)
87.87(14)
124.8(3)
114.4(3)
125.6(3)
111.16(18)
127.0(2)
110.51(17)
124.6(3)
M = Zn, Co, Ni
1
Fig. 3. Mononuclear Zn(II), Co(II), Ni(II) complexes.
88.77(9)
125.58(18)
114.62(16)
126.18(16)
111.47(11)
128.68(15)
108.61(10)
126.21(16)
114.67(16)
form have been obtained by the reaction between bis-azomethine
ligand and Zn(II), Co(II), Ni(II) salts. Similar complexes based on
bis-azomethines of hydroxycarbonyl compounds are known to
have polynuclear structure [24–28].
115.8(3)
3.2.1. Infrared spectroscopy of Zn(II), Co(II), Ni(II) complexes
In IR-spectra of Zn(II), Co(II), Ni(II) complexes the disappearance
of absorption band corresponding to bond stretches of NH-groups
(3278 cmꢁ1 region) is observed in comparison with the spectra of
ligand whereas the absorption band corresponding to OH-group
stretches (3520–3525 cmꢁ1 region) is preserved. The latter allow
to conclude that in these coordination compounds the OH-group
of diaminopropanol fragment doesn’t take part in coordination.
In the Co(II) complex metal ion is surrounded by 4 nitrogen
atoms (2 from azomethine and 2 from sulphamide fragments) in
a distorted tetrahedral configuration. Angle between planes of che-
late rings is 70° Alcoholic hydroxyl group does not participate in
coordination. Bond distances between Co(II) and the nearest donor
atoms are the following: 2.017 Å and 2.006 Å for azomethine nitro-
gen atoms, and 1.980 Å and 1.977 Å in case of nitrogens of tosyl
moieties. Oxygen atoms of sulpho-group are weakly coordinated
to metal ion with rather long not equal interatomic distances
Coꢀ ꢀ ꢀO@S (2.608 Å and 2.718 Å). Evidence of this interaction can
be also found in the lengthening of the coordinated O@S bond
compared to the non coordinated bond of the same group
(1.454 Å and 1.445 Å correspondingly) and this bond in free ligand
(1.436 Å). Four membered fragment Co–N–S@O is close to planar
(folding along Nꢀ ꢀ ꢀO line is only 6.3° and 5.6°).
The absorption band of
m
(C@N) bond stretches is observed in
1639 cmꢁ1 region whereas the absorption band
m(C–N) group of
diaminopropanol fragment is shifted to low-frequency region
(1289 cmꢁ1) that indicates the coordination of nitrogen atom to
the metal ion. The symmetric and asymmetric bond stretches of
SO2-group are shifted to low-frequency region on 20 cmꢁ1 in com-
parison with the spectra of ligand and observed at 1135 cmꢁ1 and
1263 cmꢁ1 correspondingly.
The molecular structures of the Zn(II) and Co(II) complexes are
established by X-ray analysis.
Six membered chelate rings formed with Co(II) ion by benzyli-
dene moieties are not planar and undergo typical distortions.
Atoms N(2) and C(3) (N(20) and C(30)) lies in the plane of the aro-
matic ring. Plane of the chelate rings are folded along N(2)ꢀ ꢀ ꢀC(3)
line by angle 12.6° (7.7°) and along N(2)ꢀ ꢀ ꢀN(1) line by 20.0°
(16.3°). Chelate ring formed by aminopropanol spacer due to three
sp3-hybridizated carbon atoms adopts distorted bath conforma-
tion, with nitrogen atom of one azomethine fragment and carbon
atom of the spacer in apical positions.
3.2.2. X-ray structures determination of [CoHL] ꢀ H2O, [ZnHL] ꢀ H2O
The crystal structure of [CoHL] ꢀ H2O is shown in Fig. 4. Selected
bond distances and angles are listed in Table 3.
The crystal structure besides the molecules of the complex
compounds is arranged by water molecules with molar ratio 1:1,
which due to formation of intermolecular hydrogen bonds with
donor centres of the complex molecules build up infinite hydrogen
bond supramolecular pattern (Fig. 5). Protons of each water
molecule interacts with oxygen atom of tosyl moiety of the first
complex molecule (d(HOHꢀ ꢀ ꢀO@S) = 2.013 Å) and with oxygen
atom of alcoholic hydroxyl group of the other molecule
(d(HOHꢀ ꢀ ꢀOH) = 1.720 Å), at the same time oxygen atom of each
water molecule is connected by hydrogen bond with the proton
of the hydroxyl group proton of the first molecule of the complex
(d(OHꢀ ꢀ ꢀOH2) = 1.884 Å).
The X-ray analysis of zinc(II) complex has been carried out by
our group in order to specify the structure of this complex being
synthesized previously [45]. Our data practically coincide com-
pletely with the results shown in the cited work. The zinc(II) com-
plex is isostructural with the cobalt(II) complex and has no any
peculiarities compared with it. Bond distances between Zn(II) do-
nor atoms are the following: 2.026 Å and 2.036 Å for azomethine
Fig. 4. Molecular structure of Co(II) complex (50% probability).

L.D. Popov et al. / Inorganica Chimica Acta 362 (2009) 1673–1680
1679
Ts
N
Ts
X
N
Cu
Cu
O
N
N
C
H
C
C
H2
H2
X=CH3COO, CH2ClCOO, CCl3COO, CF3COO, Pz
2
Fig. 6. Binuclear Cu(II) complexes.
3.3.1. Infrared spectroscopy
In IR-spectra of copper (II) complexes the absorption bands of
NH- and OH-groups disappear and the bands of C@N group bond
stretches are shifted to lower frequencies on 20–30 cmꢁ1. The sym-
metric and asymmetric bond stretches of SO2-group are shifted to
low-frequency region on 20–40 cmꢁ1 in comparison with the spec-
tra of ligand. These bands are observed in the 1135–1141 cmꢁ1 and
1250–1264 cmꢁ1 region correspondingly.
3.3.2. Magnetic properties
The type 2 binuclear structure of copper (II) complexes is con-
firmed by the data of magnetic measurements (Table 4). All com-
plexes exhibit the exchange antiferromagnetic interaction the
strength of which is determined by the nature of bridging acyl or
heterocyclic group included in an asymmetrical exchange frag-
ment. The values of 2J exchange parameters calculated in terms
of HDVV model [48] are shown in Table 4.
The analysis of these values has shown that for the complexes
under discussion there is no strict correlation between 2J values
and an electronic nature of substituents (halogen atom) in acetate
bridge. Recently the similar correlation has been revealed for the
Cu(II) binuclear metallochelates with ligands produced from con-
densation of salicylic aldehyde substituted derivatives with 1,3-
diaminopropanol-2 [53]. It should be noted that the absence of
similar correlation for the complexes under discussion is not sur-
prising since one should take into account the existence of rather
bulky tosyl substituents in the molecules of both ligand and com-
plexes. The possibility of H-bond formation as well as sterical hin-
drances due to tosyl group with respect to bridging acetate group
should result in distortion of exchange fragment’s structure. Thus
it is well-known that even small changes of bond angles in the ex-
Fig. 5. Infinite hydrogen bond supramolecular structure in the crystal structure of
Co(II) complex.
nitrogen atoms, and 1.971 Å and 1.977 Å in case of nitrogens of to-
syl moieties. Angle between planes of chelate rings is 69°.
3.2.3. Magnetic properties
The study of magnetic properties of Ni(II) and Co(II) complexes
revealed that these compounds exhibit trivial paramagnetism. The
values of leff at room temperature are 3.1 B.M. and 4.9 B.M. and
practically do not change up to the temperature of liquid nitrogen
(77.4 K). These values of leff support the suggested non-planar
structure of coordination unit, and as it is well-known [52] the
range of 2.8–3.2 B.M. is characteristic for octahedral environment
of nickel(II) ion. The octahedral coordination of nickel ion with
H3L ligand is taking place due to additional coordination of tosyl
fragment of sulpho-group. This assumption is supported by the
data of X-ray analysis of cobalt(II) complex (Fig. 5). In this com-
pound the additional coordination of tosyl group’s oxygen atom
is observed. The axial coordination to the central ion obviously
causes the essential orbital contribution in the resulting magnetic
moment of Co2+ cation (4.9 B.M.) the spin-only value being equal
3.77 B.M. (s = 3/2). It is known that the octahedral Co2+ complexes
as well as the complexes with tetrahedral-pyramidal configuration
are characterized by the values of leff in the range 4.7–5.1 B.M.
change fragment
usually results in significant changes
of exchange parameter’s values [52,54]. In would be interesting
to elucidate the influence of tosyl group having based on mag-
neto-structural correlations for these complexes but unfortunately
Table 4
Magnetic properties of copper(II) binuclear complexes
Compound
X
T (K)
leff (B.M.)
ꢁ2J (cmꢁ1
121
)
a
2
CH3COOꢁ
295
77.4
296
77.4
294
77.4
286
77.4
286
77.4
1.71
1.05
1.97
1.42
1.74
0.84
1.73
1.3
2
2
2
2
CH2ClCOOꢁ
CCl3COOꢁ
CF3COOꢁ
Pz
76
153
126
232
3.3. Binuclear Cu(II) complexes
1.47
0.78
The binuclear complexes (type 2, [Cu2LX]) with an asymmetri-
cal exchange fragment (Fig. 6) have been obtained by the reaction
between H3L ligand and copper (II) salts.
a
The effective magnetic moments are calculated per one metal ion.

1680
L.D. Popov et al. / Inorganica Chimica Acta 362 (2009) 1673–1680
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it is impossible to obtain them as monocrystals due to their poor
solubility in the most organic solvents.
Thus, as well as for previously studied complexes the replace-
ment of acetate bridge on heterocyclic (pyrazol) molecule leads
to significant increase of antiferromagnetic exchange interaction.
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