Synthesis, spectral and X-ray structural studies of Ni(II) complexes of N′-acylhydrazine carbodithioic acid esters containing ethylenediamine or o-phenanthroline as coligands

Article abstract of DOI:10.1016/j.poly.2010.12.043

The new complexes [Ni(Hbstbh)₂(en)] (1) and [Ni(Hpchce)(o-phen) ₂]Cl·CH₃OH·H₂O (2) with N′-benzoyl hydrazine carbodithioic acid benzyl ester (H₂bstbh) and [N′-(pyridine-4-carbonyl)-hydrazine]-carbodit

Full text of DOI:10.1016/j.poly.2010.12.043

Polyhedron 30 (2011) 990–996
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis, spectral and X-ray structural studies of Ni(II) complexes
of N0-acylhydrazine carbodithioic acid esters containing ethylenediamine
or o-phenanthroline as coligands
M.K. Bharty a, A.K. Srivastava a, Ram Dulare a, R.J. Butcher b, N.K. Singh a,
⇑
a Department of Chemistry, Banaras Hindu University, Varanasi 221 005, India
b Department of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
a r t i c l e i n f o
a b s t r a c t
The new complexes [Ni(Hbstbh)2(en)] (1) and [Ni(Hpchce)(o-phen)2]ClꢀCH3OHꢀH2O (2) with N0-benzoyl
hydrazine carbodithioic acid benzyl ester (H2bstbh) and [N0-(pyridine-4-carbonyl)-hydrazine]-carbo-
dithioic acid ethyl ester (H2pchce) have been synthesized, containing ethylenediamine (en) or o-phenan-
throline (o-phen) as coligands. The ligands and their complexes have been characterized by elemental
analyses, IR, magnetic susceptibility and single crystal X-ray data. [Ni(Hbstbh)2(en)] (1) and [Ni(Hpch-
ce)(o-phen)2]ClꢀCH3OHꢀH2O (2) crystallized in the monoclinic and triclinic systems, space group C2/c
and P ꢁ 1, respectively. The (N, O) donor sites of the bidentate ligands chelate the Ni(II) center and form
a five-membered CN2ONi ring. The resulting complexes are paramagnetic and have a distorted octahedral
geometry.
Article history:
Received 26 October 2010
Accepted 28 December 2010
Available online 9 January 2011
Keywords:
Carbodithioic acid ester
Ni(II) complexes
Mixed ligand complexes, Supramolecular
architectures
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
reports the syntheses, spectral characterization and X-ray crystal-
lography of [Ni(Hbstbh)2(en)] (1) and [Ni(Hpchce)(o-phen)2]Clꢀ-
S-Alkyldithiocarbazates behave as versatile ligands, either act-
ing as monodentate (S or N2) donors or bidentate anionic (via
N3-S or S, S) chelating ligands [1–3]. They have been widely stud-
ied for their biological activities and chemotherapeutic properties
[4,5] which may be highly dependent on the nature of the metal
ion and binding sites of the ligand. Some Schiff bases of S-alkyl es-
ters of dithiocarbazic acid and their complexes were found to dis-
play antifungal and antibacterial properties [6–8]. Several papers
are available on the syntheses and spectral characterization of me-
tal complexes of dithiocarbazates [9–15]. Recently, bis chelated
complexes of S-benzyl-b-N-(benzoyl) dithiocarbazate, a oxygen–
sulfur donor ligand, have been reported [16], but there is no work
on the mixed ligand complexes of the dithioester of N-acyl hydra-
zide, RC(O)NH–NH–C(S)SR which may coordinate via N, O/O, S/N, S.
Following our interest in the coordination property of ligands con-
taining the H–N–C@S moiety and with the aim of elucidating the
coordination geometry of this class of biologically important li-
gands, N0-benzoyl hydrazine carbodithioic acid benzyl (H2bstbh)
and [N0-(pyridine-4-carbonyl)-hydrazine]-carbodithioic acid ethyl
(H2pchce) esters have been synthesized and the present paper
CH3OH (2) (o-phen = o-phenanthroline).
2. Experimental
2.1. Materials and methods
Commercial reagents were used without further purification
and all experiments were carried out in the open atmosphere.
Ethyl benzoate and isonicotinic acid hydrazide (Sigma–Aldrich),
CS2 (SD Fine Chemicals, India) and KOH (Qualigens) were used as
received. All the solvents were purchased from Merck Chemicals,
India and used after purification. Benzoic acid hydrazide and
[Ni(en)2(NCS)2] were prepared by reported methods [17,18].
2.2. Preparation of N0-benzoyl hydrazine carbodithioic acid benzyl
ester (H2bstbh)
H2bstbh was prepared by the reaction of CS2 (1.5 ml, 20 mmol)
with a suspension of benzoic acid hydrazide (2.7 g, 20 mmol) in
CHCl3 (20 ml) in the presence of triethylamine (2.0 ml, 14 mmol).
Benzyl chloride was added dropwise to the above clear solution
and stirred continuously for 4 h at room temperature. The solvent
was evaporated at room temperature and the residue was washed
with water, which gave a colorless solid. Yield 66%; m.p. 426 K.
⇑
Corresponding author. Tel.: +91 542 6702452.
E-mail addresses: mkbharty@bhu.ac.in (M.K. Bharty), singhnk_bhu@yahoo.com,
nksingh@bhu.ac.in (N.K. Singh).
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.12.043

M.K. Bharty et al. / Polyhedron 30 (2011) 990–996
991
Anal. Calc. for C15H14N2OS2 (302): C, 59.60; H, 4.63; N, 9.27; S,
21.19. Found: C, 59.45; H, 4.80; N, 9.36; S, 21.30%. IR (
, cmꢁ1
KBr): (NH) 3205 and 3175, (C@O) 1685s; (N–N) 1060; (C@S)
Found: C, 53.55; H, 4.90; N, 11.95; S, 17.85%; IR (
m
, cmꢁ1, KBr):
m
,
m
(NH) 3165; (C@O) 1640s; (N–N) 1096; m(C@S) 956; m(Ni–N)
m
m
m
m
m
m
450 and 475. The structure was further confirmed by XRD.
966. 1H NMR (DMSO-d6; d ppm): 11.80 and 11.60 (s, 2H, NH), 3.7
(s, 2H, CH2) 7.0–7.8 (m, 10H aromatic protons). 13C NMR (DMSO-
d6; d ppm): 119.25 (C1), 129.10 (C2, C6), 121.10 (C3, C5), 130.95
(C4), 164.69 (C7@O), 202.30 (C8@S), 38.08 (C9H2), 134.05 (C10),
128.52 (C11, C15), 130.65 (C12, C14), 127.30 (C13) (Fig. 1).
2.5. Preparation of [Ni(Hpchce)(o-phen)2]ClꢀCH3OHꢀH2O (2)
NiCl2ꢀ6H2O (0.237 g, 1 mmol) and H2pchce (0.482 g, 2 mmol)
were dissolved separately in 20 ml MeOH, mixed together and stir-
red for 1 h. The brown solid which separated was filtered, washed
successively with ethanol and air dried. A methanol solution of o-
phen (0.400 g, 2 mmol) was added to the methanol suspension of
the above compound and stirred for 2 h. The resulting clear brown
solution was filtered and kept for crystallization. Brown single
crystals of 2 suitable for X-ray analyses were obtained by slow
evaporation of its methanol solution over a period of 10 days. Yield
2.3. Preparation of N0-(pyridine-4-carbonyl)-hydrazinecarbodithioic
acid ethyl ester
The ligand H2pchce was prepared as described earlier [19].
2.4. Preparation of [Ni(Hbstbh)2(en)]
55%; m.p. 483 K.
(741.92): C, 54.99; H, 3.90; N, 13.20; S, 8.62. Found: C, 55.00; H,
3.95; N, 13.30; S, 8.82%. IR ( (OH) 3457 and 3426;
, cmꢁ1, KBr):
(NH) 3179; (C@O) 1630s; (N–N) 1097; (C@S) 985; (Ni–N)
455 and 478.
leff = 2.9 BM. Anal. Calc. for C34H29ClN7NiO3S2
[Ni(Hbstbh)2(en)] was prepared by adding a MeOH–CHCl3 solu-
tion of freshly prepared N0-benzoyl hydrazine carbodithioic acid
benzyl ester (H2bstbh) (0.604 g, 2 mmol) to a MeOH solution of
[Ni(en)2(NCS)2] (0.230 g, 1 mmol). The resulting solution was fil-
tered and kept for crystallization. Light pink single crystals of
[Ni(Hbstbh)2(en)] suitable for X-ray analyses were obtained by
slow evaporation of its MeOH-CHCl3 solution over a period of
m
m
m
m
m
m
m
2.6. Physical measurements
Carbon, hydrogen and nitrogen contents were estimated on a
Carlo Erba 1108 model microanalyser. Magnetic susceptibility
measurements were performed at room temperature on a Cahn
Faraday balance using Hg[Co(NCS)4] as the calibrant. Electronic
spectra were recorded on a Shimadzu 1700 UV–Vis spectropho-
tometer as Nujol mulls [20]. IR spectra were recorded in the
4000–400 cmꢁ1 region as KBr pellets on a Varian 3100-FTIR spec-
trophotometer. 1H and 13C NMR spectra were recorded in DMSO-
d6 on a JEOL AL 300 FT NMR spectrometer using TMS as an internal
reference.
15 days. Yield 60%; m.p. > 573 K.
l
eff = 3.0 BM. Anal.
Calc. for
C32H34N6NiO2S4 (721.60): C, 53.21; H, 4.71; N, 11.64; S, 17.73.
14
15
13
12
O
1
H
N
2
6
S
1
7
10
5
N
8
1
9
11
H
3. Crystal structure determination
S
4
2
2
Data for the structure of 1 were obtained at 173(2) K on a Bru-
ker three-circle diffractometer equipped with SMART 6000 CCD
software, whereas the data for the structure of 2 were obtained
3
Fig. 1. N’-Benzoyl hydrazinecarbodithioic acid benzyl ester.
O
O
H
NH2
CS2 + NEt3
MeOH
N
SNEt3
N
H
N
H
S
MeOH
PhCH2Cl
S
H
N
S
N
O
O
H
N
H2N
S
Ni(en)2(NCS)2
MeOH + H2O
N
H
Ni
N
S
H2
S
O
N
HN
S
Scheme 1. Preparation of complex 1.

992
M.K. Bharty et al. / Polyhedron 30 (2011) 990–996
at 293(2) K on an Oxford Diffraction Gemini diffractometer
equipped with CrysAlis Pro., using a graphite monochromated
methanol and ethanol, while complexes 1 and 2 dissolve in DMF
and DMSO.
Mo Ka (k = 0.71073 Å) radiation source for both complexes. The
structures were solved by direct methods (SHELXL-97) and refined
against all data by full matrix least-square on F2 using anisotropic
displacement parameters for all non-hydrogen atoms. All hydrogen
atoms were included in the refinement at geometrically ideal posi-
tions and refined with a riding model [21]. The MERCURY package and
ORTEP-3 for Windows program were used for generating molecular
graphics [22,23].
4.1. IR spectra
The IR spectrum of the ligand N0-benzoyl hydrazine carbo-
dithioic acid benzyl ester (H2bstbh) shows absorptions due to the
stretching modes of NH at 3205 and 3175, C@O at 1685, C@S at
966 and N–N at 1060 cmꢁ1. The IR spectrum of complex 1 shows
a band at 3165 cmꢁ1, indicating the presence of one NH group
upon complexation. The appearance of two new bands for
N) at 450 and 475 cmꢁ1 suggests bonding of Ni(II) with en and
one hydrazinic nitrogen after loss of a proton. The (C@O) and
m(Ni–
4. Results and discussion
m
m
(N–N) bands suffer negative and positive shifts of 45 and
The ligand N0-benzoyl hydrazine carbodithioic acid benzyl
(H2bstbh) ester reacts with [Ni(en)2(NCS)2] yielding [Ni(Hbstb-
h)2(en)] (1), whereas [N0-(pyridine-4-carbonyl)-hydrazine]-carbo-
dithioic acid ethyl ester (H2pchce) on reaction with NiCl2ꢀ6H2O
and then with o-phen yields [Ni(Hpchce)(o-phen)2]ClꢀCH3OHꢀH2O
(2). The complexes 1 and 2 are stable towards air and moisture,
and melt at >573 and 483 K, respectively. Schemes 1 and 2 depict
the formation of the complexes, which contain Hbstbh and Hpchce
as ligands and en/o-phen as coligands. Both ligands are soluble in
36 cmꢁ1, respectively, indicating that H2bstbh is acting as a uni-
negative bidentate ligand, bonding through the carbonyl oxygen
and hydrazinic nitrogen in complex 1. The IR spectrum of
[Ni(Hpchce)(o-phen)2]ClꢀCH3OHꢀH2O (2) shows two bands at
3457 and 3426 cmꢁ1 for
m
(OH) of H2O and CH3OH, and a band at
(NH) band,
(Ni–N) at 455
and 478 cmꢁ1, suggest bonding of Ni(II) with one hydrazinic nitro-
3185 cmꢁ1 for
together with the appearance of two new bands for
m(NH) of the ligand. The absence of one m
m
gen after loss of a proton and o-phen nitrogen. The m(C@O) and
O
S
O
H
N
EtOH
NH2
CS
2
+
KOH
N
+
N
H
SK
N
N
H
C2H5I
+
(i) NiCl2.6H2O
N
O
S
O
N
H
(ii) o-phen
MeOH
N
N
N
N
H
HN
·
Ni
N
SCH2CH3
Cl- MeOH. H2O
S
N
H3CH2CS
N
Scheme 2. Preparation of complex 2.
Fig. 2. ORTEP diagram of [Ni(Hbstbh)2(en)] (1) at the 30% ellipsoids probability level. Hydrogen atoms are omitted for clarity.

M.K. Bharty et al. / Polyhedron 30 (2011) 990–996
993
Table 1
Crystallographic data for [Ni(Hbstbh)2(en)] and [Ni(Hpchce)(o-phen)2]ClꢀCH3OHꢀH2O.
Table 2
Selected bond lengths (Å) and angles (°) for [Ni(Hbstbh)2(en)] (1).
Compound
1
2
Bond length
Bond angle
Empirical formula
Formula weight
T (K)
C
32H34N6NiO2S4 C34H29ClN7NiO3S2
S(1)–C(8)
S(1)–C(9)
S(2)–C(8)
O(1)–C(7)
N(1)–C(8)
N(2)–C(7)
N(1)–N(2)
N(3)–C(16)
C(1)–C(6)
C(1)–C(2)
Ni(1)–O(1)
Ni(1)–N(3)
Ni(1)–N(1)
1.770(14)
1.809(13)
1.700(13)
1.251(15)
1.321(16)
1.336(16)
1.395(13)
1.480(2)
1.387(18)
1.394(19)
2.081(10)
2.097(12)
2.111(11)
O(1)–C(7)–N(2)
O(1)–C(7)–C(1)
N(1)–C(8)–S(2)
N(1)–C(8)–S(1)
(S2)–C(8)–S(1)
C(10)–C(9)–S(1)
O(1)–Ni(1)–O(1)
O(1)–Ni(1)–N(3)
N(3)–Ni(1)–N(3)
O(1)–Ni(1)–N(1)
O(1)–Ni(1)–N(1)
N(3)–Ni(1)–N(1)
N(3)–Ni(1)–N(1)
N(1)–Ni(1)–N(1)
C(16)–Ni(1)–N(3)
120.51(10)
721.62
173(2)
0.71073
monoclinic
C2/c
741.92
293(2)
0.71073
triclinic
P ꢁ 1
121.60(11)
125.64(9)
111.47(9)
122.83(7)
107.97(9)
174.42(5)
89.68(5)
83.08(7)
78.43(4)
105.57(4)
94.52(5)
164.41(4)
91.77(6)
k (Å)
Crystal system
Space group
Unit cell dimensions
a (Å)
b (Å)
c (Å)
22.430(7)
9.073(3)
18.385(6)
90.0
117.486(4)
90.0
3319.1(18)
4
1.444
10.813(8)
12.633(11)
12.823(13)
104.066(8)
96.496(7)
96.042(7)
1672.3(3)
2
a
(°)
b (°)
c
(°)
V (Å3)
Z
107.68(9)
qcalc (g/cm3)
1.473
0.832
l
(mmꢁ1
)
0.876
F(0 0 0)
1504
766
Crystal size (mm)
0.50 x 0.40 x
0.23
0.27 x 0.25 x 0.23
Table 3
Hydrogen bonding parameters for [Ni(Hbstbh)2(en)] (1).
h Range for data collection (°)
Index ranges
2.50 – 30.52
ꢁ31 6 h 6 32
ꢁ12 6 k 6 12
ꢁ25 6 l 6 23
18 356
2.03 - 28.93
ꢁ14 6 h 6 14
ꢁ15 6 k 6 17
ꢁ16 6 l 6 17
12 249
D–Hꢀ ꢀ ꢀA
D–H (Å)
0.88
Hꢀ ꢀ ꢀA (Å)
Dꢀ ꢀ ꢀA (Å)
\D–Hꢀ ꢀ ꢀA (°)
110.6
N2–H2Bꢀ ꢀ ꢀS2
2.42
2.854(13)
No. of reflections collected
No. of independent reflections (Rint
)
5073 (0.0228)
8835 (0.0493)
8835/0/425
1.089
0.0608, 0.1932
0.0807, 0.2008
1.014 and ꢁ0.988
Number of data/restraints/parameters 5073/0/204
Goodness-of-fit on F2
1.057
0.0274, 0.0702
0.0319, 0.0721
2 [24]. On the basis of IR data alone, How et al. have concluded that
the bonding in bis chelated complexes of S-benzyl-b-N-(benzoyl)
dithiocarbazate takes place through oxygen and sulfur, which is
in contrast to the present finding. The bonding through oxygen
and nitrogen in our mixed ligand complexes is supported by
X-ray data.
a,b
R1, wR2 [(I > 2
r
(I))]
a,b
R1, wR2 (all data)
Largest difference in peak and hole (e 0.321 and
Åꢁ3
)
ꢁ0.365
a
R1
=
R
||Fo| ꢁ |Fc||
R|Fo|.
P
P
2
2 1=2
R2 ¼ ½ wðjF2oj ꢁ jFc2jÞ = wjFo2j ꢂ
.
b
4.2. 1H and 13C NMR spectra
m
(N–N) bands suffer negative and positive shifts, indicating bond-
The 1H NMR spectrum of H2bstbh in DMSO-d6 shows two sig-
ing through the carbonyl oxygen and one hydrazinic nitrogen.
Thus, H2pchce acts as a uninegative bidentate ligand in complex
nals at d 11.80 and 11.60 ppm for the amide and thioamide
Fig. 3. Crystal packing of complex 1 along the c axis.

994
M.K. Bharty et al. / Polyhedron 30 (2011) 990–996
Fig. 4. Showing N–Hꢀ ꢀ ꢀS hydrogen bonding, leading linear chain structure.
protons, respectively. Phenyl ring protons appear as a multiplet be-
tween d 7.0 and 7.8 ppm. The 13C NMR spectrum of H2bstbh shows
signals at d 202.30 (C8) and 164.69 (C7) ppm due to the >C@S and
>C@O carbons, respectively. The phenyl ring carbons appear in the
region d 119.25–134.05 ppm.
The values of the dihedral angles suggest that the extended copla-
nar ring system of the two ligands approach each other orthogo-
nally and shows an unsymmetrical coordination of the two
ligands. In the solid state the complex is stabilized via intermolec-
ular N–Hꢀ ꢀ ꢀS interactions between dithio sulfur atoms and NH2
hydrogen atoms of the en molecule, leading to the formation of a
symmetrical linear chain structure (Fig. 4).
4.3. Electronic spectra and magnetic moments
A magnetic moment of 3.0 BM for [Ni(Hbstbh)2(en)] and the
presence of two bands at 15 040 and 22 320 cmꢁ1 assigned to
4.5. Crystal structure description of [Ni(Hpchce)(o-phen)2]
ClꢀCH3OHꢀH2O (2)
the 3A2g ? 3T1g(F) (
m
2) and 3T1g(P) (
m
3) transitions, respectively,
suggest a distorted octahedral geometry for the complex [25].
Fig. 5 shows an ORTEP diagram of complex 2 together with the
atom numbering scheme. The structural refinement data related
to complex 2 are listed in Table 1 and the selected bond distances
and bond angles are listed in Table 4. The (N, O) donor sites of the
uninegative bidentate ligand chelate the Ni(II) center to form a
five- membered CN2ONi ring. The resulting complex has a dis-
torted octahedral geometry. The average bond lengths in complex
2 are: O1–C6 = 1.295(5), N3–C7 = 1.326(5), N2–N3 = 1.397(5), N2–
C6 = 1.311(5) Å which suggest considerable delocalization of
A
magnetic moment of 2.9 BM for [Ni(Hpchce)(o-phen)2]Clꢀ
CH3OHꢀH2O (2) and the presence of a band at 17 275 cmꢁ1 assigned
to the 3A2g ? 3T1g(F) transition, suggests a distorted octahedral
geometry for the complex [25].
4.4. Crystal structure description of [Ni(Hbstbh)2(en)] (1)
Fig. 2 shows an ORTEP diagram of the complex [Ni(Hbstb-
h)2(en)] (1) together with the atom numbering scheme, which con-
tains a pair of monodeprotonated ligands and one en coordinated
to Ni(II) ion via a carbonyl oxygen, b-nitrogen (N2) and both nitro-
gens of en, forming three five membered chelate rings. The crystal-
lographic data and structural refinement details are given in Table
1 and the selected bond distances and bond angles are presented in
Table 2. The elements of the structure are joined to each other in
the crystal packing (Fig. 3) by means of an extended system of
H-bonds where hydrogen atoms belonging to the en ligand are par-
ticipating in the structure. The hydrogen bonding parameters of
complex 1 are given in Table 3. The deprotonation of the hydrazinic
nitrogens adjacent to carbonyl group, viz. N2/N20, in complex 1 re-
sults in a narrowing of the endocyclic angles C(7)–N(2)–N(1) by 9°
(Table 2). The environment around the metal atoms may be de-
scribed as a distorted octahedral with bite angles of 78.43(4)
[N(1)–Ni–O(1)] and 83.08(7) [N(3)–Ni–N(3)]. The formation of a
five membered chelate ring, C2N2Ni, with
a bite angle of
82.71(9)° represents a major deviation from an octahedral geome-
try. The geometry and bonding parameters within the en molecule
agree with those of the related compound [Ni(trans(L)2(en)2]
{L = N-(5-chlorouracilato)} [26]. The distances within the chelate
rings are intermediate between single and double bond lengths.
The average bond lengths, N2–N1 = 1.395(13), N2–C7 = 1.336(16),
N1–C8 = 1.321(16), C7–O1 = 1.251(15) Å, suggest considerable
delocalization of charge [27]. In complex 1 the chelate rings and
the phenyl ring lie nearly in the same plane. The phenyl ring thus
makes an extended coplanar system with the two chelate rings.
Fig. 5. ORTEP diagram of [Ni(Hpchce)(o-phen)2]ClꢀCH3OHꢀH2O (2) at the 30% ellip-
soids probability level. Hydrogen atoms and solvent molecules are omitted for
clarity.

M.K. Bharty et al. / Polyhedron 30 (2011) 990–996
995
Fig. 6. C–Hꢀ ꢀ ꢀCl, N–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀO hydrogen bonding forming a six membered C, Cl, O arrangement (shown as a Ball and Stick model).
atoms and NH2 hydrogen atoms of the en molecule. The crystal
structure of complex 2 is stabilized in the solid state by weak inter-
molecular C–Hꢀ ꢀ ꢀCl interactions between the phenyl ring hydro-
gens and chlorine atoms and N–Hꢀ ꢀ ꢀO interaction between the
hydrazinic hydrogen and oxygen of water molecule, as well as
C–Hꢀ ꢀ ꢀO interactions between the hydrogens of methanol and
the oxygen of the water molecule.
Table 4
Selected bond lengths (Å) and angles (°) for [Ni(Hpchce)(o-phen)2]ClꢀCH3OHꢀH2O (2).
Bond lengths
Bond angles
Ni–O1
Ni–N3
Ni–N4
Ni–N5
Ni–N6
Ni–N7
S2–C7
S1–C8
S1–C7
O1–C6
N3–C7
N3–N2
N2–C6
C5–C6
C8–C9
O3–C34
N7–C29
N7–C30
2.033(3)
2.079(3)
2.099(3)
2.109(3)
2.109(3)
2.139(3)
1.677(4)
1.804(6)
1.810(4)
1.295(5)
1.326(5)
1.397(5)
1.311(5)
1.475(5)
1.464(9)
1.339(10)
1.303(6)
1.352(5)
O1–Ni–N3
O1–Ni–N4
N3–Ni–N4
O1–Ni–N5
N3–Ni–N5
N4–Ni–N5
O1–Ni–N6
N3–Ni–N6
N4–Ni–N6
N5–Ni–N6
O1–Ni–N7
N3–Ni–N7
N4–Ni–N7
N5–Ni–N7
N6–Ni–N7
N2–N3–Ni
S2–C7–S1
O1–C6–N2
78.60(12)
91.20(12)
95.89(13)
169.15(12)
107.05(13)
79.11(13)
95.03(12)
95.15(13)
168.21(12)
93.69(12)
87.72(12)
164.32(13)
91.98(13)
87.73(13)
78.31(13)
112.4(2)
Acknowledgements
The authors are thankful to Dr. S. Bhattacharya, Department of
Chemistry, Faculty of Science, Banaras Hindu University, for ana-
lyzing the crystal structure of compound 2.
Appendix A. Supplementary material
121.7(2)
126.2(4)
CCDC 792156 and 795157 contain the supplementary
crystallographic data for [Ni(Hbstbh)2(en)] (1) and [Ni(Hpchce)(o-
phen)2]ClꢀCH3OHꢀH2O (2). These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
charge [27]. Complex 2 is stabilized in the solid state by weak
intermolecular C–Hꢀ ꢀ ꢀCl interactions between the phenyl ring
hydrogens and chlorine atoms, and N–Hꢀ ꢀ ꢀO interaction between
the hydrazinic hydrogen and oxygen of water molecule, as well
as C–Hꢀ ꢀ ꢀO interactions between the hydrogens of methanol and
the oxygen of the water molecule (Fig. 6). Masui suggested that
if active electron delocalization within a metal–N–heterocyclic
chelate ring is present, it would exhibit some degree of metalloaro-
maticity [28,29]. In the complex the chelate rings and the pyridine
rings lie nearly in the same plane, forming a dihedral angle of 7.88°.
The Ni–O, Ni–N and Ni–N(phen) bond distances of 2.033(3),
2.079(3) and 2.099(3) Å, respectively are comparable to the bond
lengths reported earlier [19].
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