Bis[1-(3-cyano-benz-yl)pyridinium] bis-(1,2-dicyano-ethene-1,2-dithiol-ato)nickelate(II).

In the ionic title complex, (C(13)H(11)N(2))(2)[Ni(C(4)N(2)S(2))(2)], the Ni(II) ion is located on an inversion centre so the asymmetric unit contains one-half [Ni(mnt)(2)](2-) dianion (mnt(2-) is maleonitrile-dithiolate) and one 1-(3-cyano-benz-yl)pyridinium cation ([CNBzPy](+)). The Ni(II) ion in the [Ni(mnt)(2)](2-) anion is coordinated by four S atoms of two mnt(2-) ligands, and exhibits square-planar coordination geometry. In the [CNBzPy](+) cation, the benzene and pyridine rings are twisted with respect to the C/C/N plane incorporating the methyl-ene C atom that links them. The crystal structure is stabilized by Coulombic inter-actions.

Related literature

For background to the development of new functional mol­ecule-based materials, see: Robertson & Cronin (2002 ▶). For the applications of mol­ecular solids based on M[dithiol­ene]2 complexes in mol­ecular-based materials showing magnetic, superconducting and optical properties, see: Ni et al. (2004 ▶, 2005 ▶); Nishijo et al. (2000 ▶). For bond lengths and angles in related structures, see: Ren et al. (2004 ▶).

Experimental

Crystal data

(C13H11N2)2[n class="Chemical">Ni(C4N2S2)2]

M = 729.57

Monoclinic,

a = 11.633 (3) Å

b = 8.709 (2) Å

c = 16.692 (4) Å

β = 91.278 (5)°

V = 1690.7 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.86 mm−1

T = 293 K

0.4 × 0.3 × 0.2 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.702, T max = 0.741

13953 measured reflections

3068 independent reflections

2154 reflections with I > 2σ(I)

R int = 0.092

Refinement

R[F 2 > 2σ(F 2)] = 0.076

wR(F 2) = 0.130

S = 1.18

3068 reflections

214 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810051263/bx2332sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051263/bx2332Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C13H11N2)2[Ni(C4N2S2)2]	Z = 2
Mr = 729.57	F(000) = 748
Monoclinic, P21/c	Dx = 1.433 Mg m−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71070 Å
a = 11.633 (3) Å	θ = 3.0–25.4°
b = 8.709 (2) Å	µ = 0.86 mm−1
c = 16.692 (4) Å	T = 293 K
β = 91.278 (5)°	Block, red
V = 1690.7 (7) Å3	0.4 × 0.3 × 0.2 mm

Bruker SMART CCD area-detector diffractometer	3068 independent reflections
Radiation source: fine-focus sealed tube	2154 reflections with I > 2σ(I)
graphite	Rint = 0.092
phi and ω scans	θmax = 25.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
Tmin = 0.702, Tmax = 0.741	k = −9→10
13953 measured reflections	l = −20→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.18	w = 1/[σ2(Fo2) + (0.0263P)2 + 1.4994P] where P = (Fo2 + 2Fc2)/3
3068 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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 matrix. 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, conventional 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.

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.0000	1.0000	0.0420 (3)
S1	0.08308 (11)	0.02743 (15)	0.88570 (8)	0.0527 (4)
S2	−0.06667 (12)	0.23125 (15)	0.98459 (8)	0.0543 (4)
N1	0.2335 (5)	−0.2035 (6)	0.7340 (3)	0.0840 (16)
N2	−0.2202 (5)	0.5312 (6)	1.0989 (3)	0.0818 (16)
N3	0.5244 (5)	1.6046 (6)	0.9022 (4)	0.0906 (17)
N4	0.7437 (3)	0.8647 (4)	0.9068 (2)	0.0440 (10)
C1	0.1400 (4)	−0.1530 (6)	0.8694 (3)	0.0460 (12)
C2	0.1931 (5)	−0.1824 (6)	0.7942 (3)	0.0557 (14)
C3	−0.1341 (4)	0.2636 (6)	1.0743 (3)	0.0477 (13)
C4	−0.1819 (4)	0.4130 (6)	1.0888 (3)	0.0522 (13)
C5	0.5193 (5)	1.4752 (6)	0.8943 (3)	0.0636 (15)
C6	0.5134 (4)	1.3103 (5)	0.8838 (3)	0.0476 (12)
C7	0.4315 (4)	1.2492 (6)	0.8324 (3)	0.0560 (14)
H11A	0.3794	1.3125	0.8053	0.067*
C8	0.4284 (4)	1.0918 (6)	0.8219 (3)	0.0567 (14)
H10A	0.3741	1.0489	0.7868	0.068*
C9	0.5040 (4)	0.9987 (6)	0.8625 (3)	0.0502 (12)
H9A	0.4994	0.8928	0.8559	0.060*
C10	0.5869 (4)	1.0600 (5)	0.9132 (3)	0.0425 (12)
C11	0.5915 (4)	1.2165 (5)	0.9241 (3)	0.0481 (13)
H13A	0.6468	1.2592	0.9584	0.058*
C12	0.6706 (4)	0.9595 (6)	0.9596 (3)	0.0561 (14)
H7A	0.7197	1.0239	0.9932	0.067*
H7B	0.6279	0.8921	0.9945	0.067*
C13	0.7754 (4)	0.7251 (6)	0.9321 (3)	0.0587 (14)
H4A	0.7510	0.6900	0.9815	0.070*
C14	0.8426 (5)	0.6340 (7)	0.8868 (4)	0.0729 (17)
H3A	0.8637	0.5367	0.9047	0.087*
C15	0.8784 (5)	0.6860 (8)	0.8156 (4)	0.0707 (17)
H2A	0.9225	0.6233	0.7833	0.085*
C16	0.8498 (5)	0.8310 (8)	0.7906 (3)	0.0674 (16)
H1A	0.8761	0.8686	0.7422	0.081*
C17	0.7823 (4)	0.9196 (6)	0.8379 (3)	0.0568 (14)
H6A	0.7632	1.0188	0.8220	0.068*

	U11	U22	U33	U12	U13	U23
Ni1	0.0495 (5)	0.0381 (5)	0.0383 (5)	0.0040 (4)	0.0040 (4)	−0.0014 (4)
S1	0.0691 (9)	0.0437 (8)	0.0457 (8)	0.0070 (7)	0.0132 (6)	0.0017 (6)
S2	0.0716 (9)	0.0436 (8)	0.0482 (8)	0.0121 (7)	0.0119 (7)	0.0030 (6)
N1	0.109 (4)	0.071 (4)	0.074 (4)	−0.005 (3)	0.038 (3)	−0.009 (3)
N2	0.107 (4)	0.057 (3)	0.082 (4)	0.028 (3)	0.022 (3)	−0.001 (3)
N3	0.113 (4)	0.041 (3)	0.117 (5)	0.000 (3)	−0.003 (4)	−0.004 (3)
N4	0.049 (2)	0.038 (2)	0.045 (3)	0.005 (2)	−0.004 (2)	0.003 (2)
C1	0.045 (3)	0.046 (3)	0.047 (3)	0.005 (2)	0.006 (2)	−0.012 (3)
C2	0.064 (3)	0.046 (3)	0.057 (4)	−0.003 (3)	0.013 (3)	−0.007 (3)
C3	0.050 (3)	0.042 (3)	0.052 (3)	0.006 (3)	0.003 (2)	−0.005 (3)
C4	0.057 (3)	0.051 (3)	0.048 (3)	0.008 (3)	0.004 (3)	−0.001 (3)
C5	0.070 (4)	0.046 (4)	0.074 (4)	0.005 (3)	−0.004 (3)	−0.001 (3)
C6	0.056 (3)	0.031 (3)	0.055 (3)	0.001 (2)	0.004 (3)	0.003 (2)
C7	0.054 (3)	0.054 (3)	0.060 (4)	0.014 (3)	−0.008 (3)	0.002 (3)
C8	0.054 (3)	0.055 (4)	0.060 (4)	0.003 (3)	−0.011 (3)	−0.009 (3)
C9	0.056 (3)	0.035 (3)	0.060 (3)	0.003 (3)	0.002 (3)	−0.005 (3)
C10	0.044 (3)	0.037 (3)	0.046 (3)	0.006 (2)	0.006 (2)	−0.002 (2)
C11	0.049 (3)	0.043 (3)	0.051 (3)	−0.003 (3)	0.000 (2)	−0.007 (2)
C12	0.069 (3)	0.052 (3)	0.048 (3)	0.018 (3)	0.008 (3)	0.000 (3)
C13	0.068 (4)	0.046 (3)	0.063 (4)	0.010 (3)	0.004 (3)	0.010 (3)
C14	0.092 (4)	0.049 (4)	0.078 (5)	0.021 (3)	−0.003 (4)	−0.010 (3)
C15	0.065 (4)	0.080 (5)	0.067 (4)	0.016 (3)	−0.006 (3)	−0.033 (4)
C16	0.061 (3)	0.093 (5)	0.049 (4)	0.008 (4)	0.005 (3)	0.003 (3)
C17	0.058 (3)	0.055 (3)	0.057 (4)	−0.002 (3)	−0.001 (3)	0.014 (3)

Ni1—S1	2.1710 (13)	C7—H11A	0.9300
Ni1—S1i	2.1710 (13)	C8—C9	1.365 (6)
Ni1—S2	2.1713 (14)	C8—H10A	0.9300
Ni1—S2i	2.1713 (13)	C9—C10	1.377 (6)
S1—C1	1.729 (5)	C9—H9A	0.9300
S2—C3	1.729 (5)	C10—C11	1.376 (6)
N1—C2	1.134 (6)	C10—C12	1.510 (6)
N2—C4	1.135 (6)	C11—H13A	0.9300
N3—C5	1.136 (6)	C12—H7A	0.9700
N4—C17	1.332 (6)	C12—H7B	0.9700
N4—C13	1.336 (6)	C13—C14	1.356 (7)
N4—C12	1.489 (6)	C13—H4A	0.9300
C1—C3i	1.348 (6)	C14—C15	1.347 (8)
C1—C2	1.435 (7)	C14—H3A	0.9300
C3—C1i	1.348 (6)	C15—C16	1.368 (8)
C3—C4	1.438 (7)	C15—H2A	0.9300
C5—C6	1.449 (7)	C16—C17	1.365 (7)
C6—C7	1.374 (7)	C16—H1A	0.9300
C6—C11	1.385 (6)	C17—H6A	0.9300
C7—C8	1.382 (7)
S1—Ni1—S1i	180.0	C8—C9—H9A	119.7
S1—Ni1—S2	87.64 (5)	C10—C9—H9A	119.7
S1i—Ni1—S2	92.36 (5)	C11—C10—C9	119.3 (5)
S1—Ni1—S2i	92.36 (5)	C11—C10—C12	119.0 (5)
S1i—Ni1—S2i	87.64 (5)	C9—C10—C12	121.7 (4)
S2—Ni1—S2i	180.0	C10—C11—C6	119.8 (5)
C1—S1—Ni1	102.59 (18)	C10—C11—H13A	120.1
C3—S2—Ni1	102.48 (17)	C6—C11—H13A	120.1
C17—N4—C13	120.3 (4)	N4—C12—C10	112.8 (4)
C17—N4—C12	121.3 (4)	N4—C12—H7A	109.0
C13—N4—C12	118.3 (4)	C10—C12—H7A	109.0
C3i—C1—C2	120.8 (4)	N4—C12—H7B	109.0
C3i—C1—S1	120.9 (4)	C10—C12—H7B	109.0
C2—C1—S1	118.3 (4)	H7A—C12—H7B	107.8
N1—C2—C1	178.5 (6)	N4—C13—C14	120.9 (5)
C1i—C3—C4	120.2 (4)	N4—C13—H4A	119.5
C1i—C3—S2	121.2 (4)	C14—C13—H4A	119.5
C4—C3—S2	118.5 (4)	C15—C14—C13	119.3 (6)
N2—C4—C3	178.9 (6)	C15—C14—H3A	120.4
N3—C5—C6	179.6 (8)	C13—C14—H3A	120.4
C7—C6—C11	120.9 (5)	C14—C15—C16	120.1 (6)
C7—C6—C5	119.4 (5)	C14—C15—H2A	120.0
C11—C6—C5	119.8 (5)	C16—C15—H2A	120.0
C6—C7—C8	118.6 (5)	C17—C16—C15	119.0 (6)
C6—C7—H11A	120.7	C17—C16—H1A	120.5
C8—C7—H11A	120.7	C15—C16—H1A	120.5
C9—C8—C7	120.7 (5)	N4—C17—C16	120.4 (5)
C9—C8—H10A	119.6	N4—C17—H6A	119.8
C7—C8—H10A	119.6	C16—C17—H6A	119.8
C8—C9—C10	120.6 (5)

Ni1—S1	2.1710 (13)
Ni1—S2	2.1713 (14)

S1—Ni1—S2	87.64 (5)
S1i—Ni1—S2	92.36 (5)

Symmetry code: (i) .