O,O′-dimethyl diphenyldithiophosphates of nickel(II) with N-donor ligands

Article abstract of DOI:10.1007/s00706-015-1569-6

The present work demonstrates the synthesis and characterization of donor stabilized addition complexes of nickel(II) with O,O0-dimethyl diphenyldithiophosphates [[(ArO)2PS2]2NiL2] (Ar= 2,4-(CH3)2C6H3, 3,4-(CH3)2C6H3, and 3,5-(CH3)2C6H3; L = pyridine, 4-ethylpyridine, and 3,4-dimethylpyridine). These complexes were successfully isolated and structurally characterized by single crystal X-ray analysis. The complexes [[(2,4-CH3)2C6H3O]2PS2]2Ni(C5H5N), [[(2,4-CH3)2C6H3O]2PS2]2Ni[4-(C2H5)C5H4N]2, and [[(3,4-CH3)2C6H3O]2PS2]2Ni(C5H5N)2 were crystallized in the monoclinic crystal system with space group P21/n, whereas the complex [[(3,5-CH3)2C6H3O]2PS2]2Ni[3,4-(CH3)2C5H3N]2 was crystallized in the monoclinic crystal system with different space group P21/c. X-ray diffraction analysis of complexes reveals a six-coordinated octahedral geometry for the NiS4N2 chromophore, defined by two chelating diphenyldithiophosphate anions as well as two N-donor ligands. Two diphenyldithiophosphate ligands are coordinated to the nickel ion as a bidentate chelating via the two thiolate S atoms, forming a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Ni atom in trans position.

Full text of DOI:10.1007/s00706-015-1569-6

Monatsh Chem
DOI 10.1007/s00706-015-1569-6
ORIGINAL PAPER
O,O0-Dimethyl diphenyldithiophosphates of nickel(II)
with N-donor ligands
Sandeep Kumar1 Ruchi Khajuria1 Atiya Syed1 Amanpreet Kaur Jassal2
•
•
•
•
Love Karan Rana2 Geeta Hundal2 Sushil K. Pandey1
•
•
Received: 2 January 2015 / Accepted: 3 September 2015
Ó Springer-Verlag Wien 2015
Abstract The present work demonstrates the synthesis
and characterization of donor stabilized addition complexes
of nickel(II) with O,O0-dimethyl diphenyldithiophosphates
[[(ArO)2PS2]2NiL2] (Ar = 2,4-(CH3)2C6H3, 3,4-(CH3)2
C6H3, and 3,5-(CH3)2C6H3; L = pyridine, 4-ethylpyridine,
and 3,4-dimethylpyridine). These complexes were success-
fully isolated and structurally characterized by single crystal
X-ray analysis. The complexes [[(2,4-CH3)2C6H3O]2PS2]2
Graphical abstract
Ni(C5H5N),
[[(2,4-CH3)2C6H3O]2PS2]2Ni[4-(C2H5)C5H4
N]2, and [[(3,4-CH3)2C6H3O]2PS2]2Ni(C5H5N)2 were crys-
tallized in the monoclinic crystal system with space group
P21/n, whereas the complex [[(3,5-CH3)2C6H3O]2PS2]2
Ni[3,4-(CH3)2C5H3N]2 was crystallized in the monoclinic
crystal system with different space group P21/c. X-ray
diffraction analysis of complexes reveals a six-coordinated
octahedral geometry for the NiS4N2 chromophore, defined
by two chelating diphenyldithiophosphate anions as well as
two N-donor ligands. Two diphenyldithiophosphate ligands
are coordinated to the nickel ion as a bidentate chelating via
the two thiolate S atoms, forming a four-membered chelate
ring in the equatorial plane. The N atoms from two donor
ligands are axially coordinated to the Ni atom in trans
position.
Keywords Diphenyldithiophosphates Á Single crystal Á
Donor stabilized Á Nickel
Introduction
Transition metal ions react with dialkyl/diaryl dithiophos-
phoric acid to give complexes of the type [M[S2P(OR)]n]
(M = Fe, Co, Mn, Ni, Pd, Pt, Hg, Zn, or Sn; R = alkyl or
aryl; n = 2 or 3), which are either square-planar or tetra-
hedral and octahedral with a MS4 and MS6 chromophore,
respectively [1, 2]. The family of nickel(II) dithiophos-
phates have been intensively investigated structurally [3].
The homoleptic dithiophosphates Ni[S2P(OR)2]2 (R = Me
[4], Et [5], n-Pr [6], iso-Pr [7], iso-Bu [8], cyclo-C6H11 [9],
benzyl, ortho-tolyl, meta-tolyl [10], para-tolyl [11] ) are
square-planar complexes. Many six-coordinated adducts
like Ni[S2P(OR)2]2Á2L (L = pyridine [12, 13], 2,20-bipyr-
idyl [14], 1,10-phenanthroline [15–18], 2,9-dimethyl-1,10-
phenanthroline [19] ) have been reported. Few five coor-
dinated adducts like Ni[S2P(OR)2]Á2L (R = Et; L = PPh3
[20] or quinoline [16]) are also known. In general dithio-
phosphates complexes have been extensively studied and
are of wide practical use. These have been employed for
Electronic supplementary material The online version of this
article (doi:10.1007/s00706-015-1569-6) contains supplementary
material, which is available to authorized users.
& Sushil K. Pandey
kpsushil@rediffmail.com
1
Department of Chemistry, University of Jammu, Jammu
180006, J & K, India
2
Department of Chemistry, Guru Nanak Dev University,
Amritsar 143005, India
123

S. Kumar et al.
the vulcanization of rubber [21], as insecticides [22, 23], or
may be applied as analytical agents [24]. The amines in
lubricating oil have a great influence on the properties of
metal dialkyldithiophosphates as additives [25]. The donor
stabilized dialkyl/alkylene dithiophosphates of nickel(II)
have consistently retained interest for the last few decades
[26–28]. Continuation of our interest in nickel dithio-
phosphate complexes [29, 30] led us to work on the
reactions of nickel(II) diphenyldithiophosphate complexes
with nitrogen donor moieties to examine the influence of
the aromatic moiety upon coordination with the nickel. In
our recent publication on donor stabilized complexes of
nickel(II) diphenyldithiophosphates [30], we have reported
the synthesis along with the X-ray structures of some of the
nickel complexes. In this publication, we have also repor-
ted the synthesis of the complexes [[(2,4-CH3)2C6H3O]2
PS2]2Ni(C5H5N)2 (1), [[(2,4-CH3)2C6H3O]2PS2]2Ni[4-(C2-
H5)C5H4N]2 (2), and [[(3,4-CH3)2C6H3O]2PS2]2Ni(C5-
H5N)2 (3), but X-ray structures could not be reported for
these complexes owing to the non-formation of suitable
crystals. We now report herein on the synthesis of a new
complex [[(3,5-CH3)2C6H3O]2PS2]2Ni[3,4-(CH3)2C5H3N]2
(4) and structural characterization of the complexes 1–4.
be ascribed to the [m(P)-O-C] and [mP-O-(C)] vibrations of
the diphenyldithiophosphate moiety, respectively. The
bands for [vP-S]asym and [vP-S]sym of the diphenyldithio-
phosphate moiety were observed at 660 and 573 cm-1
,
respectively. The bands [mNi-S] and [mNi–N] appeared at
374 and 447 cm-1, respectively [30]. The band at the
1595 cm21 has been assigned for [vC-N] stretching
vibrations of the aromatic ring of the Lewis base.
Magnetic moment measurements
The magnetic moment analysis of the adduct established
octahedral geometry and the paramagnetic nature. The
magnetic moment of complex 4 is found to be 3.18 B.M. at
298 K, which corresponds to two unpaired electrons [30].
Crystal and molecular structures of complexes 1–4
The complexes 1–3 were crystallized in the monoclinic
crystal system with space group P21/n, whereas complex 4
was crystallized in the monoclinic crystal system with
different space group P21/c. The X-ray crystal structure
analysis reveals that the nickel atom lies on a crystallo-
graphic center of symmetry and has octahedral
coordination geometry (Figs. 1, 2, 3, 4). The nickel atom is
six-coordinated by the tertiary nitrogen of two donor
moiety (pyridine, 4-ethylpyridine, and 3,4-dimethylpyr-
idine) and four sulfur atoms of two coordinated
dithiophosphate ligands, which are situated in the equato-
rial plane. Selected bond distances and bond angles for the
complexes 1–4 are listed in Tables 1, 2, 3 and 4. In the
complexes 1, 2, 3 and 4, the Ni–N1 bond distances are
Results and discussion
The complexes 1–4 are prepared by the facile reactions of
bis(O,O0-diphenyldithiophosphato)nickel(II)
complexes
[[(ArO)2PS2]2Ni] (Ar = 2,4-(CH3)2C6H3, 3,4-(CH3)2C6H3,
and 3,5-(CH3)2C6H3) with pyridine, 4-ethylpyridine, and 3,4-
dimethylpyridine in 1:2 stoichiometric ratio at room temper-
ature in chloroform. The purple colour changed on addition of
nitrogen base to give a consistent green colour on addition of a
slight excess of base which yielded the adducts of nickel(II)
diphenydithiophosphates formulated as [[(ArO)2PS2]2NiL2]
(Scheme 1). In each case complexes were obtained as green
powder, which were soluble in common organic solvents.
˚
2.0961(17), 2.108(2), 2.108(12), and 2.098(2) A, which are
comparable with the corresponding octahedral Ni-N bond
distances reported for Ni[S2P(OC6H4Me-p)2]2(C10H8N2)
˚
(2.060(1) A) [14] and [[(3,5-CH3)2C6H3O]2PS2]2-
˚
Ni(C5H5N)2 [2.1310(11) A] [30]. The Ni-S1 and Ni-S2
bond lengths for the complex 1 are 2.5061(5) and
˚
˚
2.5475(5) A, complex 2 are 2.4636(6) and 2.4986(6) A,
˚
complex 3 are 2.492(3) and 2.494(4) A, and complex 4 are
IR spectra
˚
2.4746(8) and 2.5015(9) A. These bond lengths are in
The characteristic stretching bands in the IR spectra were
assigned by comparison with literature data [10, 14, 29,
30]. In the complex 4 the band at 1120 and 854 cm-1 may
reasonable agreement with those of Ni[S2P(OC6H4Me-
˚
p)2]2(C10H8N2) [2.4757(7) and 2.5049(4) A] [14] and
[[(3,5-CH3)2C6H3O]2PS2]2Ni(C7H9N)2 [2.5213(5) and
˚
2.5164(4) A] [30]. However, these bond distances are
longer than that of the square-planar complexes [[2,4-
˚
(CH3)2C6H3O]2PS2]2Ni [2.229(11) and 2.229(11) A] [29],
scheme 1
˚
Ni(S2P(OC6H4CH3-o)2]2 [2.2415(6) and 2.2241(6) A], and
˚
Ni[S2P(OC6H4CH3-m)2]2 [2.2421(6) and 2.2421(6) A]
[10]. This shows that adduct formation reduces the net
positive charge on the N atom and increases the net neg-
ative charge on the S atoms [30, 31]. The steric and
123

O,O0-Dimethyl diphenyldithiophosphates of nickel(II) with N-donor ligands
Fig. 1 Molecular structure of [[(2,4-CH3)2C6H3O]2PS2]2Ni(C5H5N)2 (1) with displacement ellipsoids drawn at 50 % probability level
Fig. 2 Molecular structure of
[[(2,4-CH3)2C6H3O]2PS2]2Ni[4-
(C2H5)C5H4N]2 (2) with
displacement ellipsoids drawn
at 50 % probability level
electronic effect results in an increase of the S–P–S angle,
lengthens the Ni–S distance and decreases the S–Ni–S
angle. The phosphorus-sulfur bond lengths in all the
complexes fall between the bond lengths of P–S and P=S
bonds, since the phosphorus-sulfur bond distances of these
complexes are marginally shorter than the single P–S
bonds found in [Ni(S2P[O]OCH2CH2Ph)(dppe)] [2.042(2)
˚
and 2.038(2) A] [32] and larger than the P=S bond
123

S. Kumar et al.
˚
Table 1 Selected bonds lengths/A and angles/° for complex 1
N1–Ni1
2.0961(17)
1.6035(14)
1.6162(15)
1.9698(7)
1.9747(7)
96.93(8)
106.57(6)
113.35(6)
115.11(6)
111.37(6)
112.54(3)
83.83(2)
82.63(2)
180.00(10)
89.06(5)
90.94(5)
90.94(5)
a
S1–P1i
1.9697(7)
2.5061(5)
2.5475(5)
2.0960(17)
2.5060(5)
89.06(5)
O1–P1
S1–Ni1
O2–P1
P1–S1a
S2–Ni1
Ni1–N1a
Ni1–S1a
P1–S2
O1–P1–O2
O1–P1–S1a
O2–P1–S1a
O1–P1–S2
O2–P1–S2
S1a–P1–S2
P1a–S1–Ni1
P1–S2–Ni1
N1a–Ni1–N1
N1a–Ni1–S1a
N1–Ni1–S1a
N1a–Ni1–S1
N1–Ni1–S1
S1a–Ni1–S1
N1a–Ni1–S2a
N1–Ni1–S2a
S1a–Ni1–S2a
S1–Ni1–S2a
N1a–Ni1–S2
N1–Ni1–S2
S1a–Ni1–S2
S1–Ni1–S2
S2a–Ni1–S2
180.0
88.93(5)
91.07(5)
99.047(17)
80.952(17)
91.06(5)
88.94(5)
80.952(17)
99.049(17)
179.999(1)
Symmetry code(s): -x ? 1, -y, -z
Fig. 3 Molecular structure of [[(3,4-CH3)2C6H3O]2PS2]2Ni(C5H5N)2
(3) with displacement ellipsoids drawn at 50 % probability level
˚
Table 2 Selected bonds lengths/A and angles/° for complex 2
N1–Ni1
2.108(2)
1.9751(9)
2.4635(6)
1.9699(8)
2.4986(6)
98.19(9)
106.69(7)
113.99(7)
114.39(7)
110.37(7)
112.44(4)
180.0
O1–P1
1.6055(17)
1.6065(18)
2.108(2)
2.4636(6)
2.4986(6)
180.0
S1–P1
O2–P1
Ni1–N1a
Ni1–S1a
S1–Ni1
S2–P1
S2–Ni1
Ni1–S2a
O1–P1–O2
O1–P1–S2
O2–P1–S2
O1–P1–S1
O2–P1–S1
S2–P1–S1
N1a–Ni1–N1
N1a–Ni1–S1
N1–Ni1–S1
N1a–Ni1–S1a
N1–Ni1–S1a
S1–Ni1–S1a
N1a–Ni1–S2a
N1–Ni1–S2a
S1–Ni1–S2a
S1a–Ni1–S2a
N1a–Ni1–S2
N1–Ni1–S2
S1–Ni1–S2
S1a–Ni1–S2
S2a–Ni1–S2
90.17(6)
89.83(6)
97.28(2)
82.72(2)
89.84(6)
90.16(6)
82.72(2)
97.28(2)
180.0
90.67(6)
89.33(6)
89.33(6)
90.67(6)
a
Symmetry code(s): -x ? 2, -y, -z
delocalisation of the p-electron density over the four-
membered metallocycles (NiS2P) [30, 31]. The phosphorus
atoms in dithiophosphato groups are in a tetrahedral
neighbouring (O2S2) environment.
Fig. 4 Molecular structure of [[(3,5-CH3)2C6H3O]2PS2]2Ni[3,4-
(CH3)2C5H3N]2 (4) with displacement ellipsoids drawn at 50 %
probability level
The S1–Ni–S2 and S1–P1–S2 bond angles for the
complex 1 are 80.952(17)° and 112.54(3)°, complex 2 are
82.72(2)° and 112.44(4)°, complex 3 are 82.46(11)° and
113.5(2)°, and complex 4 are 83.17(2)° and 114.02 (4)° are
in reasonable proximity with that of Ni[S2P(OC6H4Me-
p)2]2(C10H8N2) [81.33(2)° and 110.34(2)°] [14] and [[(3,4-
˚
observed in HS2POCMe2CMe2O [1.923(2) A] [33] and
˚
also intermediate between hypothetical single (2.14 A) and
˚
double (1.94 A) P–S bonds [34]. This is an evidence of
123

O,O0-Dimethyl diphenyldithiophosphates of nickel(II) with N-donor ligands
˚
S1–Ni–S2 bond angle [31]. In the complexes 1 and 2 O1–
P1–O2 bond angle bond angles are 96.93(8)° and 98.19(9)°
while in the parent square planar complex [[2,4-(CH3)2-
C6H3O]2PS2]2Ni [29] is 92.85(10)°, this increase in bond
angle in complexes 1 and 2 is may also due to the coor-
dination of aromatic N-donor ligand with nickel atom. In
the complex 4, no large deviation is observed in O1–P1–O2
bond angle when compared to the parent square planar
complex. The pyridine ring is fairly planar with the con-
junction of P1 and Ni atom in the all four compounds. It is
pertinent to state that there is no prominent effect on the
structure and geometry of final complexes were observed
by exchanging the O,O0-dimethyl diphenyldithiophos-
phates and N-donor ligands.
Table 3 Selected bonds lengths/A and angles/° for complex 3
N1–Ni1
2.108(12)
1.599(9)
1.607(9)
1.964(4)
2.492(3)
81.87(14)
81.80(15)
180.000(1)
90.1(3)
S2–P1
1.966(5)
2.494(4)
2.108(12)
2.492(3)
2.494(4)
90.5(3)
O1–P1
S2–Ni1
Ni1–N1a
Ni1–S1a
O2–P1
S1–P1
S1–Ni1
Ni1–S2a
P1–S1–Ni1
P1–S2–Ni1
N1a–Ni1–N1
N1a–Ni1–S1a
N1–Ni1–S1a
N1a–Ni1–S1
N1–Ni1–S1
S1a–Ni1–S1
N1a–Ni1–S2a
N1–Ni1–S2a
S1a–Ni1–S2a
S1–Ni1–S2a
N1a–Ni1–S2
N1–Ni1–S2
S1a–Ni1–S2
S1–Ni1–S2
S2a–Ni1–S2
O1–P1–O2
O1–P1–S1
O2–P1–S1
O1–P1–S2
O2–P1–S2
S1–P1–S2
89.5(3)
97.54(11)
82.46(11)
180.0
89.9(3)
89.9(3)
97.0(4)
90.1(3)
113.6(4)
112.2(4)
107.1(4)
112.2(3)
113.5(2)
180.0
89.5(3)
90.5(3)
Experimental
82.46(11)
97.54(11)
Solvents were distilled and dried using standard methods
before use. Chloroform (Thomas Baker, b.p. 61 °C) was dried
over P2O5. All the disubstituted phenols and Ni(NO3)2Á6H2O
were procured from Sigma Aldrich and used without further
purification. Pyridines were procured from Himedia. Mois-
ture was carefully excluded for the synthesis of ligands
throughout the experimental manipulations by using standard
Schlenk techniques. The sodium salts of O,O0-dimethyl
diphenyldithiophosphates, i.e., [(2,4-CH3)2C6H3O]2PS2Na,
[(3,4-CH3)2C6H3O]2PS2Na, and [(3,5-CH3)2C6H3O]2PS2Na
were synthesized according to a literature procedure [35].
Nickel was estimated gravimetrically as nickel(II)dimethyl-
glyoximate [36]. Elemental analyses (C, H, N, S) were
conducted using the Elemental Analyser Vario EL-III (Indian
Institute of Integrative Medicine, Jammu). Infrared spectra
were recorded in the range of 4000–340 cm-1 on a Shimadzu
FT-IR spectrophotometer at the Department of Chemistry,
University of Jammu, Jammu.
a
Symmetry code(s): -x, -y, -z
˚
Table 4 Selected bonds lengths/A and angles/° for complex 4
N1–Ni1
2.098(2)
1.6053(18)
1.6111(19)
1.9661(10)
1.9717(10)
2.4746(8)
97.83(10)
107.92(7)
112.01(8)
112.39(8)
111.51(7)
114.02(4)
81.51(3)
S2–P1a
1.9662(10)
2.5015(9)
2.098(2)
O1–P1
S2–Ni1
Ni1–N1a
Ni1–S1a
Ni1–S2a
O2–P1
P1–S2a
2.4746(8)
2.5015(9)
P1–S1
S1–Ni1
O1–P1–O2
O1–P1–S2a
O2–P1–S2a
O1–P1–S1
O2–P1–S1
S2a–P1–S1
P1–S1–Ni1
P1a–S2–Ni1
N1a–Ni1–N1
N1a–Ni1–S1
N1–Ni1–S1
N1a–Ni1–S1a
N1–Ni1–S1a
S1–Ni1–S1a
N1a–Ni1–S2
N1–Ni1–S2
S1–Ni1–S2
S1a–Ni1–S2
N1a–Ni1–S2a
N1–Ni1–S2a
S1–Ni1–S2a
S1a–Ni1–S2a
S2–Ni1–S2a
88.88(6)
180.0
89.42(6)
90.58(6)
96.83(2)
83.17(2)
90.58(6)
89.42(6)
83.17(2)
96.83(2)
180.0
Bis(O,O0-bis(dimethylphenyl)dithiophosphato)nickel(II)
[[(ArO)2PS2]2Ni]
80.92(3)
180.00(7)
88.88(6)
To the stirred aqueous solution of 0.40 g Ni(NO3)2Á6H2O
(1.37 mmol), an aqueous solution of 1.00 g (ArO)2PS2Na
(2.77 mmol) [Ar = 2,4-(CH3)2C6H3, 3,4-(CH3)2C6H3, or
3,5-(CH3)2C6H3] was added in 1:2 molar ratio with
constant stirring. A solid precipitated immediately. After
30 min of stirring the reaction contents were filtered to
obtain the complex [[(ArO)2PS2]2Ni] as purple powdery
solid [29].
91.12(6)
91.12(6)
a
Symmetry code(s): -x ? 1, -y, -z
CH3)2C6H3O]2PS2]2Ni(C7H9N)2
[82.666(16)
and
113.15(3)°] [30]. In square planar complexes like [[2,4-
(CH3)2C6H3O]2PS2]2Ni [29] and Ni[S2P(OC6H4CH3-o)2]2
[10], S1–P1–S2 bond angles are 102.65(5)° and 103.32(3)°,
respectively, which are very small when compared to
angles present in complexes 1–4. It reveals that coordina-
tion of aromatic N-donor ligand with nickel atom caused
widening of S1–P1–S2 bond angle due to steric and elec-
tronic effect of Lewis base and also resulted in decrease in
Synthesis of complexes 1–3
The complexes bis(O,O0-bis(2,4-dimethylphenyl)dithio-
phosphato)bis(pyridine)nickel(II) (1, C42H46N2NiO4P2S4),
bis(O,O0-bis(2,4-dimethylphenyl)dithiophosphato)bis
123

S. Kumar et al.
Table 5 Summary of the crystal structure, data collection, and structure refinement parameters for complexes 1–4
Complex
1
2
3
4
Chemical formula
Formula weight
C42H46N2NiO4P2S4
891.72
C46H54N2NiO4P2S4
947.82
C42H46N2NiO4P2S4
891.72
C46H54N2NiO4P2S4
947.82
Crystal system, space group
Temperature/K
Monoclinic, P21/n
100
Monoclinic, P21/n
100
Monoclinic, P21/n
296
Monoclinic, P21/c
100
˚
a, b, c/A
15.1620(17),
9.8310(11),
15.6320(14)
10.1800(9),
15.3596(14),
15.3141(15)
7.159(5), 21.756(16), 8.033(2), 16.062(5),
14.015(10) 18.788(5)
b/°
V/A
117.759(3)
2061.9(4)
2
102.639(4)
2336.5(4)
93.10(3)
99.246(5)
3
˚
2180(3)
2
2392.7(11)
Z
2
2
l/mm-1
0.80
0.71
0.75
0.69
Crystal size/mm
Absorption correction
0.11 9 0.09 9 0.06
Multi-scan
0.608, 0.745
0.15 9 0.09 9 0.07
Multi-scan
0.664, 0.745
19845, 4839, 4062
0.14 9 0.12 9 0.08 0.12 9 0.10 9 0.07
Multi-scan
Multi-scan
Tmin, Tmax
0.497, 0.746
0.599, 0.746
No. of measured, independent and observed 16,802, 4341, 3863
[I [ 2r(I)] reflections
15,829, 5544, 1458
20,790, 5576, 4245
Rint
0.068
0.057
0.133
0.092
-1
˚
(sin h/k)max/A
0.634
0.628
0.704
0.655
R[F2 [ 2r(F2)], wR(F2), S
No. of reflections
0.039, 0.113, 1.04
0.041, 0.111, 0.95
0.136, 0.459, 1.04
0.054, 0.154, 0.99
4341
4839
5544
5576
No. of parameters
No. of restraints
253
277
250
274
0
5
0
0
-3
˚
Largest difference in peak/hole/e A
0.45, -0.52
1.07, -1.04
0.58, -0.77
0.59, -0.56
(4-ethylpyridine)nickel(II) (2, C46H54N2NiO4P2S4) and bis
(O,O0-bis(3,4-dimethylphenyl)dithiophosphato)bis(pyridine)-
nickel(II) (3, C42H46N2NiO4P2S4) were synthesized accord-
ing to the reported procedure [30].
structures of the complexes 1–4 were determined by single
crystal X-ray diffraction analysis. X-ray data of complexes 1–
4 were collected on a Bruker’s Apex-II CCD diffractometer
(Department of Chemistry, Guru Nanak Dev University,
˚
Amritsar) using Mo Ka (k = 0.71069 A). The data were
Bis(O,O0-bis(3,5-dimethylphenyl)dithiophosphato)bis(3,4-
dimethylpyridine)nickel(II) (4, C46H54N2NiO4P2S4)
To a stirred chloroform solution of 0.25 g [[(3,5-CH3)2-
C6H3O]2PS2]2Ni (0.34 mmol), 3,4-dimethylpyridine was
added until the purple colour of the solution changed to
green, then a slight excess of pyridine was added. The
contents were stirred for further 30 min at room temper-
ature. The solvent was then evaporated under vacuum,
which results the complex 4 as green solid. The resulting
solid was recrystallized from a chloroform/n-hexane mix-
ture at room temperature. Yield: 87 %; IR (KBr): v
= 1595 m [vC-N], 1120 s [v(P)-O-C], 854 s [vP-O-(C)],
660 s [vP-S]asym, 573 m [vP-S]sym, 374 w [vNi-S], 447 w
[vNi-N] cm-1; leff = 3.18 BM.
processed by SAINT correcting for Lorentz and polarization
effects. An empirical absorption correction was applied using
SADABS from Bruker. The solution was obtained by direct
methods, using SIR-92 [37] and refined by full-matrix least
squares refinement methods [38] based on F-2, using
SHELX-97. All non-hydrogen atoms were refined
anisotropically. In complex 3, large residual value (R1) may
be due to incomplete scans, possibly based on erroneously
assumed higher than actual symmetry. All calculations were
performed using Wingx package [39]. Molecular drawings
were obtained using DIAMOND version 2.1 [40]. Crystal-
lographic data, details of the data collection, structure solution
and refinements are listed in Table 5.
CCDC 1041257, 1041258, 1041259, and 1041260 con-
tain the supplementary crystallographic data for complexes
1, 2, 3, and 4, respectively. 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.
Crystallography data collection and refinement
The green colored crystals of complexes 1–4 were obtained
by very slow evaporation of their saturated solution in chlo-
roform/n-hexane mixture (3:1) at room temperature. The
123

O,O0-Dimethyl diphenyldithiophosphates of nickel(II) with N-donor ligands
21. McCleverty JA, Gill S, Kowalski RSZ, Bailey NA, Adams H,
Lumbard KW, Murphy MA (1982) J Chem Soc Dalton Trans 493
22. Gupta AKS, Srivastava RC, Parma SS (1967) Can J Chem
45:2293
23. Rufenacht K (1968) Helv Chim Acta 51:518
24. Sacconi L, Lombardo G, Ciafalo R (1960) J Am Chem Soc
82:4182
25. Shiomi M, Tokashiki M, Tomizawa H, Kuribayashi T (1989)
Lubr Sci 1:131
26. Ooi S, Fernando Q (1967) Inorg Chem 6:1558
27. Bhasin CP, Panchal DG (2004) Phosphorus Sulfur Silicon Relat
Elem 179:1545
References
1. Cavell RG, Day ED, Byers W, Watkins PM (1972) Inorg Chem
11:1759
2. Livingstone SE, Mihkelson AE (1970) Inorg Chem 9:2545
3. Haiduc I, Sowerby DB, Lu SF (1995) Polyhedron 14:3389
4. Kastalsky V, McConnell JF (1969) Acta Crystallogr B 25:909
5. McConnell JF, Kastalsky V (1967) Acta Crystallogr 22:853
6. Yordanov ND, Gochev G, Angelova O, Macicek J (1990) Poly-
hedron 9:2597
7. Hoskins BF, Tiekink ERT (1985) Acta Crystallogr C 41:322
8. Ivanov AV, Antzutkin ON, Forsling W, Bostroem D, Yegao Y,
Rodionova NA (2002) Doklady Phys Chem 387:299
9. Tas M, Yagan M, Bati H, Bati B, Bueyuekguengoer O (2005)
Acta Crystallogr E61:1684
10. Bingham AL, Drake JE, Light ME, Nirwan M, Ratnani R (2006)
Polyhedron 25:945
11. Zhang SS, Yang B, Wang YF, Li XM, Jiao K, Kassim MB,
Yamin BM (2004) Acta Crystallogr E60:485
12. Jian FF, Xiao H, Li Y, Jiao K (2003) J Chem Crystallogr 33:705
13. Lei W, Hao Q, Lu L, Yang X, Wang X (2004) J Chem Crys-
tallogr 34:387
14. Bingham AL, Drake JE, Hursthouse MB, Light ME, Nirwan M,
Ratnani R (2007) Polyhedron 26:2672
¨
28. Bolundut L, Haiduc I, Ilyes E, Kociok-Kohn G, Molloy KC,
´
Gomez-Ruiz S (2010) Inorg Chim Acta 363:4319
29. Kumar S, Khajuria R, Gupta VK, Kant R, Pandey SK (2014)
Polyhedron 72:140
30. Kumar S, Khajuria R, Jassal AK, Hundal G, Hundal MS, Pandey
SK (2014) Acta Crystallogr B 70:761
31. Jian F, Xiao H, Li Y, Jiao K (2014) J Chem Crystallogr 33:705
32. Li Y, Xie B, Zou L, Lin X, Yang Y, Zhu S, Wang T (2014)
Polyhedron 67:490
33. Drake JE, Khasrou LN, Mislankar AG, Ratnani R (2000) Poly-
hedron 19:407
34. Lawton SL, Kokotailo GT (1969) Inorg Chem 8:2410
35. Khajuria R, Kumar S, Kour G, Anthal S, Gupta VK, Kant R,
Pandey SK (2014) J Coord Chem 67:2925
36. Vogel AI (1978) A Textbook of Quantitative Inorganic Analysis,
4th edn. Longman, London
37. Altomare A, Cascarano G, Giacovazzo C, Guagliardi A (1993) J
Appl Crystallogr 26:343
38. Sheldrick GM (2008) Acta Crystallogr A 64:112
39. Farrugia LJ (1999) J Appl Crystallogr 32:837
40. Brandenburg K (1998) DIAMOND version 2.1 crystal impact
GbR. Bonn, Germany
15. Fernando Q, Shiro M (1971) J Chem Soc D Chem Commun 350
16. Shetty PS, Fernando Q (1970) J Am Chem Soc 92:3964
17. Craig DC, Pallister ET, Stephenson NC (1971) Acta Crystallogr
B 27:1163
18. Hao QG, Fun HK, Chantrapromma S, Razak IA, Jian FF, Yang
XJ, Lu LD, Wang X (2001) Acta Crystallogr C 57:717
19. Shetty PS, Ballard RE, Fernando Q (1969) J Chem Soc D Chem
Commun 717
20. Liu SX, Lin CC, Yu YP, Zhu DL, Xu Z, Gou SH, You XZ (1991)
Acta Crystallogr C 47:43
123