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Acta Cryst. (2007). E63, m3003    [ doi:10.1107/S1600536807056620 ]

Bis[1-(3,5-dibromobenzyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato-[kappa]2S,S')nickelate(II)

Q.-B. Liao, M.-G. Liu and C.-L. Ni

Abstract top

In the title compound, (C12H10Br2N)2[Ni(C4N2S2)2], the NiII atom of the anion lies on an inversion centre and exhibits a square-planar coordination geometry. The benzene and pyridine rings of the cation make a dihedral angle of 74.6 (3)°. The cations (C1 and C2) and anions (A) are arranged in a ...C1C2AC1C2AC1C2... pattern along the [\overline{1}10] direction and are linked by C-H...S hydrogen bonds and [pi]-[pi] stacking interactions involving the benzene ring [centroid-centroid separation = 3.778 (3) Å].

Comment top

Recently, some substituted benzylpyridinium cations have been introduced into the Ni(mnt)2 system (mnt is maleonitriledithiolate) in order to obtain some Ni(mnt)2-based molecular solids showing unusual magnetic properties (Ni et al., 2005; Xie et al., 2002; Ren et al., 2002). We report here the crystal structure of the title compound, in which 1-(3,5-dibromobenzyl)pyridinium functions as a counterion of Ni(mnt)2 anion.

As shown in Fig.1, the asymmetric unit of the title compound consists of one C12H10Br2N+ cation and one-half of a [Ni(C4N2S2)2]2− anion. The NiII ion lies on an inversion centre and exhibits a square-planar coordination geometry. The CN groups of the [Ni(mnt)2]2− unit are slightly tipped out of the C1/S1/Ni1/S2i/C3i plane, and the deviations from the plane are −0.116 (6) Å for N1 and 0.009 (6) Å for N2i [symmetry code: (i) 1 − x, 2 − y, 1 − z]. The benzene and pyridine rings of the C12H10Br2N+ unit form a dihedral angle of 74.6 (3)°. Atoms Br1 and Br2 deviate from the plane of the benzene ring by 0.038 (1) and 0.077 (1) Å, respectively.

Two C12H10Br2N+ units are linked to a [Ni(C4N2S2)2]2− unit through C16—H16···S1 hydrogen bonds (Table 1). The adjacent hydrogen-bonded units are cross-linked via weak π-π interactions between the benzene ring of the cation at (x, y, z) and (2 − x, 1 − y, 1 − z), with a centroid-centroid separation of 3.778 (3) Å. The cations and anions involved in the above interactions are arranged alternately along the [1 1 0] direction (Fig. 2).

Related literature top

For related literature, see: Liu & Ni (2006a,b); Ni et al. (2005); Ren et al. (2002); Xie et al. (2002).

Experimental top

The title compound was prepared by the direct reaction of NiCl2·6H2O (0.24 g, 1.0 mmol), disodium maleonitriledithiolate (0.37 g, 2.0 mmol) and 1-(3,5-dibromobenzyl)pyridinium bromide (0.85 g, 2.1 mmol) in water (50 ml). Red block-shaped single crystals were obtained by slow evaporation of a CH3CN-i-PrOH (1:1) solution at room temperature over three weeks.

Refinement top

All H atoms were placed in geometrically calculated positions (C—H = 0.93–0.97 Å) and treated as riding, with Uiso = 1.2 Ueq(parent atom).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The cation and anion of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted. Unlabelled atoms are related to the labelled atoms by the symmetry operation (1 − x, 2 − y, 1 − z).
[Figure 2] Fig. 2. The packing of the title compound, showing a column of anions and cations.
Bis[1-(3,5-dibromobenzyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ2S,S')nickelate(II) top
Crystal data top
(C12H10Br2N)2[Ni(C4N2S2)2]Z = 1
Mr = 995.13F000 = 486
Triclinic, P1Dx = 1.913 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.843 (3) ÅCell parameters from 904 reflections
b = 9.415 (3) Åθ = 2.7–27.9º
c = 10.861 (4) ŵ = 5.46 mm−1
α = 77.701 (5)ºT = 291 (2) K
β = 78.427 (6)ºBlock, red
γ = 84.221 (5)º0.35 × 0.30 × 0.21 mm
V = 864.0 (5) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		3309 independent reflections
Radiation source: fine-focus sealed tube2482 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 291(2) Kθmax = 26.0º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −5→10
Tmin = 0.165, Tmax = 0.323k = −11→11
4584 measured reflectionsl = −13→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.06P)2 + 0.99P]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3309 reflectionsΔρmax = 0.59 e Å−3
214 parametersΔρmin = −0.96 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C12H10Br2N)2[Ni(C4N2S2)2]γ = 84.221 (5)º
Mr = 995.13V = 864.0 (5) Å3
Triclinic, P1Z = 1
a = 8.843 (3) ÅMo Kα
b = 9.415 (3) ŵ = 5.46 mm−1
c = 10.861 (4) ÅT = 291 (2) K
α = 77.701 (5)º0.35 × 0.30 × 0.21 mm
β = 78.427 (6)º
Data collection top
Bruker SMART APEX CCD
diffractometer		3309 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2482 reflections with I > 2σ(I)
Tmin = 0.165, Tmax = 0.323Rint = 0.033
4584 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055214 parameters
wR(F2) = 0.117H-atom parameters constrained
S = 0.99Δρmax = 0.59 e Å−3
3309 reflectionsΔρmin = −0.96 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.36658 (7)0.41523 (7)0.40770 (6)0.03356 (18)
Br20.95637 (7)0.72824 (8)0.73580 (6)0.04073 (19)
C10.4467 (7)0.8563 (6)0.7832 (6)0.0340 (13)
C20.3762 (8)0.7687 (7)0.9091 (6)0.0384 (15)
C30.4290 (7)1.0569 (7)0.2308 (6)0.0323 (13)
C40.3562 (7)1.0604 (7)0.1245 (6)0.0349 (13)
C51.0417 (7)0.7617 (7)0.3449 (6)0.0317 (13)
C61.1611 (7)0.6488 (6)0.3263 (5)0.0298 (12)
H61.20190.63030.24500.036*
C71.2118 (7)0.5708 (7)0.4307 (6)0.0397 (15)
C81.1544 (7)0.5909 (7)0.5510 (5)0.0340 (13)
H81.18900.53200.62140.041*
C91.0407 (7)0.7037 (7)0.5658 (6)0.0339 (13)
C100.9816 (7)0.7898 (7)0.4667 (6)0.0358 (14)
H100.90520.86340.47970.043*
C110.9801 (7)0.8528 (6)0.2317 (5)0.0330 (13)
H11A1.06440.87740.16000.040*
H11B0.92900.94260.25360.040*
C120.9136 (8)0.6867 (7)0.1004 (6)0.0404 (15)
H121.01340.69120.05260.048*
C130.8089 (7)0.6021 (7)0.0802 (6)0.0362 (14)
H130.84140.53650.02580.043*
C140.6588 (7)0.6107 (6)0.1371 (6)0.0335 (13)
H140.58800.55710.11650.040*
C150.6095 (7)0.7000 (7)0.2271 (6)0.0361 (14)
H150.50770.70510.27020.043*
C160.7215 (7)0.7806 (6)0.2484 (6)0.0356 (14)
H160.69310.84720.30230.043*
N10.3176 (7)0.7000 (6)0.9957 (5)0.0456 (14)
N20.2845 (6)1.0553 (6)0.0475 (5)0.0373 (12)
N30.8642 (6)0.7645 (6)0.1946 (4)0.0350 (12)
Ni10.50001.00000.50000.0337 (3)
S10.34573 (18)0.87197 (16)0.65724 (15)0.0358 (4)
S20.35180 (18)0.96071 (17)0.37648 (15)0.0367 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0360 (3)0.0317 (3)0.0297 (3)0.0000 (2)0.0024 (2)−0.0077 (2)
Br20.0298 (3)0.0566 (4)0.0336 (3)−0.0010 (3)0.0058 (2)−0.0158 (3)
C10.037 (3)0.023 (3)0.043 (3)−0.008 (2)−0.010 (3)−0.004 (2)
C20.038 (3)0.030 (3)0.040 (3)−0.008 (3)0.010 (3)−0.005 (3)
C30.029 (3)0.033 (3)0.035 (3)−0.013 (3)0.001 (2)−0.010 (2)
C40.031 (3)0.029 (3)0.046 (3)−0.007 (2)−0.003 (3)−0.013 (3)
C50.026 (3)0.037 (3)0.034 (3)−0.007 (2)0.005 (2)−0.019 (3)
C60.030 (3)0.028 (3)0.027 (3)−0.010 (2)0.005 (2)−0.001 (2)
C70.028 (3)0.043 (4)0.048 (4)−0.011 (3)−0.001 (3)−0.012 (3)
C80.035 (3)0.037 (3)0.026 (3)−0.018 (3)0.005 (2)0.000 (2)
C90.037 (3)0.035 (3)0.031 (3)−0.007 (3)−0.008 (3)−0.006 (2)
C100.033 (3)0.031 (3)0.040 (3)−0.001 (3)0.001 (3)−0.007 (3)
C110.036 (3)0.028 (3)0.029 (3)0.002 (3)0.000 (2)0.000 (2)
C120.049 (4)0.041 (3)0.029 (3)0.003 (3)−0.018 (3)0.006 (3)
C130.033 (3)0.044 (4)0.029 (3)0.010 (3)−0.012 (3)−0.002 (3)
C140.034 (3)0.024 (3)0.047 (3)−0.004 (2)−0.022 (3)−0.001 (3)
C150.032 (3)0.035 (3)0.038 (3)−0.005 (3)0.003 (3)−0.006 (3)
C160.035 (3)0.028 (3)0.038 (3)0.007 (3)0.000 (3)−0.002 (3)
N10.044 (3)0.045 (3)0.042 (3)−0.026 (3)−0.003 (3)0.010 (3)
N20.036 (3)0.039 (3)0.031 (3)−0.007 (2)−0.006 (2)0.009 (2)
N30.032 (3)0.034 (3)0.031 (3)0.023 (2)−0.006 (2)0.000 (2)
Ni10.0298 (6)0.0282 (5)0.0365 (6)0.0150 (4)−0.0035 (4)−0.0020 (4)
S10.0322 (8)0.0298 (7)0.0382 (8)0.0141 (6)−0.0039 (6)−0.0009 (6)
S20.0331 (8)0.0325 (8)0.0396 (8)−0.0079 (6)0.0034 (6)−0.0026 (6)
Geometric parameters (Å, °) top
Br1—C71.923 (7)C10—H100.93
Br2—C91.901 (6)C11—N31.543 (9)
C1—C3i1.400 (8)C11—H11A0.97
C1—C21.490 (8)C11—H11B0.97
C1—S11.751 (7)C12—C131.359 (10)
C2—N11.088 (8)C12—N31.360 (8)
C3—C1i1.400 (8)C12—H120.93
C3—C41.424 (9)C13—C141.349 (9)
C3—S21.694 (6)C13—H130.93
C4—N21.158 (8)C14—C151.400 (9)
C5—C101.393 (8)C14—H140.93
C5—C61.437 (8)C15—C161.388 (9)
C5—C111.507 (9)C15—H150.93
C6—C71.344 (9)C16—N31.288 (7)
C6—H60.93C16—H160.93
C7—C81.350 (9)Ni1—S2i2.1607 (18)
C8—C91.399 (9)Ni1—S22.1607 (18)
C8—H80.93Ni1—S1i2.1795 (16)
C9—C101.363 (9)Ni1—S12.1795 (16)
C3i—C1—C2122.6 (6)C5—C11—H11B110.0
C3i—C1—S1120.0 (5)N3—C11—H11B110.0
C2—C1—S1116.4 (5)H11A—C11—H11B108.4
N1—C2—C1174.1 (8)C13—C12—N3116.2 (6)
C1i—C3—C4119.8 (5)C13—C12—H12121.9
C1i—C3—S2120.8 (5)N3—C12—H12121.9
C4—C3—S2119.1 (4)C14—C13—C12121.7 (6)
N2—C4—C3172.6 (6)C14—C13—H13119.2
C10—C5—C6121.1 (6)C12—C13—H13119.2
C10—C5—C11118.8 (5)C13—C14—C15120.1 (6)
C6—C5—C11120.1 (5)C13—C14—H14119.9
C7—C6—C5117.6 (5)C15—C14—H14119.9
C7—C6—H6121.2C16—C15—C14116.2 (6)
C5—C6—H6121.2C16—C15—H15121.9
C6—C7—C8123.6 (6)C14—C15—H15121.9
C6—C7—Br1118.0 (5)N3—C16—C15121.0 (6)
C8—C7—Br1118.3 (5)N3—C16—H16119.5
C7—C8—C9117.5 (6)C15—C16—H16119.5
C7—C8—H8121.3C16—N3—C12123.8 (6)
C9—C8—H8121.3C16—N3—C11116.5 (5)
C10—C9—C8123.8 (6)C12—N3—C11119.4 (5)
C10—C9—Br2118.9 (5)S2i—Ni1—S2180
C8—C9—Br2117.3 (4)S2i—Ni1—S1i86.58 (6)
C9—C10—C5116.4 (6)S2—Ni1—S1i93.42 (6)
C9—C10—H10121.8S2i—Ni1—S193.42 (6)
C5—C10—H10121.8S2—Ni1—S186.58 (6)
C5—C11—N3108.5 (5)S1i—Ni1—S1180
C5—C11—H11A110.0C1—S1—Ni1101.1 (2)
N3—C11—H11A110.0C3—S2—Ni1103.4 (2)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C16—H16···S1i0.932.753.591 (5)151
Symmetry codes: (i) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C16—H16···S1i0.932.753.591 (5)151
Symmetry codes: (i) −x+1, −y+2, −z+1.
Acknowledgements top

The authors thank the Science and Technology Project (grant No. 2007B011000008) of Guangdong Science and Technology Department and the President's Science Foundation of South China Agricultural University (grant No.2005 K092) for financial support.

references
References top

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Liu, M.-G. & Ni, C.-L. (2006b). Acta Cryst. E62, m2851–m2852.

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