1-(2,4-Dichloro-benz-yl)pyridinium bis-(2-sulfanyl-idene-1,3-dithiole-4,5-dithiol-ato-κS,S')nickelate(III).

Abstract

In the title compound, (C(12)H(10)Cl(2)N)[Ni(C(3)S(5))(2)], the Ni(III) atom is chelated by two bidentate 2-sulfanyl-idene-1,3-dithiole-4,5-dithiol-ate (dmit) dianions and shows a distorted square-planar geometry. The two dmit ligands are twisted with respect to each other by 3.21 (2)°. In the cation, the two aromatic groups linked by the methyl-ene bridging group form a dihedral angle of 68.09 (2)°. S⋯S [3.6212 (11) and 3.5573 (9) Å] and Ni⋯S [3.566 (2)Å] inter-actions influence the arrangement of the anions in the crystal.

Full text

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1-(2,4-Dichlorobenzyl)pyridinium bis(2-
sulfanylidene-1,3-dithiole-4,5-dithiolato-
j2S,S0 0 0)nickelate(III)
Guang-Xiang Liu
Department of Chemistry, Nanjing Xiaozhuang University, Nanjing 211171,
People’s Republic of China
Correspondence e-mail: njuliugx@gmail.com
Received 7 October 2011; accepted 27 October 2011
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.005 A ˚;
R factor = 0.034; wR factor = 0.092; data-to-parameter ratio = 15.9.
In the title compound, (C12H10Cl2N)[Ni(C3S5)2], the NiIII
atom is chelated by two bidentate 2-sulfanylidene-1,3-dithiole-
4,5-dithiolate (dmit) dianions and shows a distorted square-
planar geometry. The two dmit ligands are twisted with respect
to each other by 3.21 (2)?. In the cation, the two aromatic
groups linked by the methylene bridging group form a
dihedralangleof68.09 (2)?.
3.5573 (9) A˚] and Ni???S [3.566 (2)A˚] interactions influence
the arrangement of the anions in the crystal.
S???S[3.6212 (11)and
Related literature
For potential applications of bis(dithiolate)-metal complexes,
see: Cassoux (1999). For the oxidation of NiIIcompounds, see:
Cassoux et al. (1991). For the synthesis, see: Wang et al. (1998).
Experimental
Crystal data
(C12H10Cl2N)[Ni(C3S5)2]
Mr= 690.48
Monoclinic, P21=c
a = 14.4614 (5) A˚
b = 8.2158 (3) A˚
c = 21.8894 (8) A˚
? = 107.231 (1)?
V = 2484.00 (15) A˚3
Z = 4
Mo K? radiation
? = 1.85 mm?1
T = 293 K
0.26 ? 0.12 ? 0.10 mm
Data collection
Bruker SMART APEX CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
Tmin= 0.645, Tmax= 0.837
18903 measured reflections
4615 independent reflections
3992 reflections with I > 2?(I)
Rint= 0.085
Refinement
R[F2> 2?(F2)] = 0.034
wR(F2) = 0.092
S = 1.04
4615 reflections
290 parameters
H-atom parameters constrained
??max= 0.59 e A˚?3
??min= ?0.69 e A˚?3
Data collection: SMART (Bruker, 2000); cell refinement: SAINT
(Bruker, 2000); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97(Sheldrick,
SHELXTL (Sheldrick, 2008); software used to prepare material for
publication: SHELXTL.
2008); moleculargraphics:
This work was supported by the National Natural Science
Foundation of China (No. 20971004), the Key Project of the
Chinese Ministry of Education (No. 210102) and the Natural
Science Foundation of Anhui Province (No. 11040606M45).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: GK2414).
References
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Cassoux, P. (1999). Coord. Chem. Rev. 185–186, 213–232.
Cassoux, P., Valade, L., Kobayashi, H., Kobayashi, A., Clark, R. A. &
Underhill, A. (1991). Coord. Chem. Rev. 110, 115–160.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wang, C.-S.,Batsanov,A.S.,Bryce, M.R.& Howard,J. A.K. (1998).Synthesis,
pp. 1615–1618.
metal-organic compounds
m1654
Guang-Xiang Liudoi:10.1107/S1600536811045004
Acta Cryst. (2011). E67, m1654
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
sup-1
Acta Cryst. (2011). E67, m1654 [ doi:10.1107/S1600536811045004 ]
1-(2,4-Dichlorobenzyl)pyridinium
2S,S')nickelate(III)
bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-
G.-X. Liu
Comment
The bis(dithiolate)-metal complexes and their analogues with interesting structures and/or potential applications such as
conducting/magnetic or non-linear optical (NLO) materials have been reported in recent years (Cassoux, 1999). We report
herein the crystal structure of the title bis-dithiolate-metal complex. In this compound, the NiII cations of NiCl2.6H2O have
been oxidized to NiIII cation by I3- (Cassoux et al., 1991). The NiIII cation is coordinated with two dmit2- anions. As shown in
Fig. 1, the asymmetric unit of the title compound contains one [Ni(dmit)2]- anion and one [DiClPy]+ cation. Each nickel(III)
ion is coordinated by four S atoms from two dmit ligands to complete a square-planar geometry, with Ni—S bond lengths
ranging from 2.1589 (7) to 2.1640 (7) Å. The [Ni(dmit)2]- anions related by inversion center form dimers with the S atom of
one anion placed directly above the Ni atom of another anion with Ni···S distance of 3.566 (2)Å (Ni1···S2i: symmetry code:
(i) -x, -y, -z], indicating the existence of electrostatic Ni···S interactions. The dimers linked through S3···S5ii [3.6212 (11)Å]
and S4···S8iii [3.5573 (9)Å] [symmetry code: (ii) -x, 1/2 + y, 1/2 - z; (iii) x, 1/2 - y;1/2 + z] interactions form a two-dimensional
layer structure, as depicted in Fig 2. The (C12H10Cl2N)+ cation adopts a Λ-shaped conformation, and the dihedral angles
formed by the C12/C13/N1 plane with the benzene and pyridinium rings are 76.44 (2) and 86.75 (2)°, respectively.
Experimental
4,5-Di(thiobenzoyl)-1,3-dithiole-2-thione (812 mg, 2 mmol) was suspended in methanol (10 ml). Sodium methoxide in
methanol (prepared form 184 mg of sodium in 10 ml of methanol) was added to the above mixture under argon atmosphere
at room temperature from 30 min to give a dark red solution. To this solution, NiCl2.6H2O (238 mg, 1 mmol) was added.
After 30 min, a solution of I2 (127 mg, 1 mmol) and NaI (150 mg, 1 mmol) in methanol (20 ml) was added (the monoanion-
ic [Ni(dmit)2]- are obtained from the dianionic [Ni(dmit)2]2- by I3- oxidation). After another 10 min, a solution of 1-(2,4-
dichlorobenzyl)pyridinium bromide [(DiClPy)Br] (317 mg, 1 mmol) in methanol (20 ml) was added to the reaction mixture.
The solution was stirred for 30 min and cooled in a refrigerator overnight. The resultant dark green crystal was collected by
filtration, and purified by recrystallization using a mixed solvent of acetonitrile and benzene.
Refinement
H atoms were positioned geometrically, with C—H = 0.93 and 0.97 Å for aromatic and methylene H atoms, respectively,
and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C).

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Figures
Fig. 1. The cation and anion in the title compound with displacement ellipsoids drawn at
the30% probability level. Hydrogen atoms have been omitted for clarity.
Fig. 2. Two-dimensional supramolecular structure of [Ni(dmit)2]- anions through S···S and
Ni···S contacts. Dashed lines indicate weak interactions.
1-(2,4-Dichlorobenzyl)pyridinium bis(2-sulfanylidene-1,3-dithiole- 4,5-dithiolato-κ2S,S')nickelate(III)
Crystal data
(C12H10Cl2N)[Ni(C3S5)2]
F(000) = 1388
Dx = 1.846 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9920 reflections
θ = 2.7–27.6°
µ = 1.85 mm−1
T = 293 K
Needle, black
Mr = 690.48
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 14.4614 (5) Å
b = 8.2158 (3) Å
c = 21.8894 (8) Å
β = 107.231 (1)°
V = 2484.00 (15) Å3
Z = 4
0.26 × 0.12 × 0.10 mm
Data collection
Bruker SMART APEX CCD area-detector
diffractometer
Radiation source: sealed tube
graphite
phi and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
Tmin = 0.645, Tmax = 0.837
18903 measured reflections
4615 independent reflections
3992 reflections with I > 2σ(I)
Rint = 0.085
θmax = 25.5°, θmin = 2.0°
h = −14→17
k = −9→9
l = −26→26
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map

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Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
R[F2 > 2σ(F2)] = 0.034
H-atom parameters constrained
wR(F2) = 0.092
w = 1/[σ2(Fo2) + (0.0486P)2 + 0.8363P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.59 e Å−3
Δρmin = −0.69 e Å−3
Extinction correction: SHELXL97 (Sheldrick, 2008),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
S = 1.04
4615 reflections
290 parameters
0 restraints
Primary atom site location: structure-invariant direct
methods
Extinction coefficient: 0.0070 (5)
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance mat-
rix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations
between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of
cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
0.11672 (2)
0.17227 (5)
−0.02108 (5)
−0.10016 (4)
0.07706 (5)
−0.07945 (6)
0.25347 (5)
0.06384 (5)
0.15951 (5)
0.33185 (5)
0.31807 (6)
0.07448 (18)
−0.00959 (17)
−0.03719 (18)
0.24237 (18)
0.16105 (18)
0.27173 (19)
0.47163 (18)
0.5031 (2)
0.5673
y
0.16527 (4)
−0.00117 (9)
0.18995 (9)
0.02836 (9)
−0.14743 (9)
−0.17259 (11)
0.13324 (9)
0.33985 (9)
0.48291 (9)
0.28997 (9)
0.49623 (10)
−0.0249 (3)
0.0580 (3)
−0.1004 (3)
0.2678 (3)
0.3563 (3)
0.4270 (3)
0.4200 (3)
0.5037 (3)
0.4975
z
0.035816 (14)
0.11477 (3)
0.05446 (3)
0.15211 (3)
0.20813 (3)
0.26887 (4)
0.01601 (3)
−0.04061 (3)
−0.13470 (3)
−0.08385 (3)
−0.19673 (4)
0.14306 (11)
0.11635 (11)
0.21241 (12)
−0.04584 (11)
−0.07046 (11)
−0.14143 (12)
0.30763 (12)
0.36482 (13)
0.3900
Uiso*/Ueq
0.03166 (12)
0.03781 (17)
0.04024 (18)
0.03853 (18)
0.03956 (18)
0.0588 (2)
0.04044 (18)
0.03918 (18)
0.04262 (19)
0.04294 (19)
0.0494 (2)
0.0311 (5)
0.0319 (5)
0.0372 (6)
0.0337 (5)
0.0326 (5)
0.0375 (6)
0.0369 (6)
0.0424 (7)
0.051*
Ni1
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
C1
C2
C3
C4
C5
C6
C7
C8
H8