4-Cyano-1-(4-nitro-benz-yl)pyridinium bis-(2-thioxo-1,3-dithiole-4,5-dithiol-ato-κS,S)nickelate(III).

In the title salt, (C(13)H(10)N(3)O(2))[Ni(C(3)S(5))(2)], the Ni(III) cation is S,S'-chelated by two 2-thioxo-1,3-dithiole-4,5-dithiol-ate anions in a distorted square-planar geometry. The complex anion is approximately planar with a maximum deviation of 0.097 (1) Å. In the 1-(4-nitro-benz-yl)-4-cyano-pyridinium cation, the pyridine ring is twisted at a dihedral angle of 73.84 (16)° with respect to the benzene ring. π-π stacking is observed between nearly parallel [dihedral angle = 4.71 (7)°] dithiole and benzene rings, the centroid-centroid distance being 3.791 (2) Å.

Related literature

For background to and applications of dithiol­ate metal complexes, see: Akutagawa & Nakamura (2000 ▶); Cassoux (1999 ▶). For the structure of a complex with a 2-thioxo-1,3-dithiole-4,5-dithiol­ate ligand, see: Zang et al. (2006 ▶). For weak inter­molecular inter­actions, see: Egli & Sarkhel (2007 ▶); Tian et al. (2007 ▶); Cundari et al. (2010 ▶).

Experimental

Crystal data

(C13H10N3O2)[Ni(C3S5)2]

M = 691.61

Monoclinic,

a = 8.4896 (17) Å

b = 25.789 (5) Å

c = 12.043 (3) Å

β = 106.181 (3)°

V = 2532.3 (9) Å3

Z = 4

Mo Kα radiation

μ = 1.62 mm−1

T = 296 K

0.20 × 0.17 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.738, T max = 0.794

12415 measured reflections

4423 independent reflections

3343 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.090

S = 1.02

4423 reflections

316 parameters

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037426/xu5018sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037426/xu5018Isup2.hkl

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

(C13H10N3O2)[Ni(C3S5)2]	F(000) = 1396
Mr = 691.61	Dx = 1.814 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 947 reflections
a = 8.4896 (17) Å	θ = 2.4–24.3°
b = 25.789 (5) Å	µ = 1.62 mm−1
c = 12.043 (3) Å	T = 296 K
β = 106.181 (3)°	Block, black
V = 2532.3 (9) Å3	0.20 × 0.17 × 0.15 mm
Z = 4

Bruker SMART APEXII CCD area detector diffractometer	4423 independent reflections
Radiation source: fine-focus sealed tube	3343 reflections with I > 2σ(I)
graphite	Rint = 0.043
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→10
Tmin = 0.738, Tmax = 0.794	k = −30→21
12415 measured reflections	l = −14→14

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0387P)2 + 0.150P] where P = (Fo2 + 2Fc2)/3
4423 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 0.57 e Å−3
0 restraints	Δρmin = −0.26 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	0.12504 (5)	0.535201 (17)	0.42287 (3)	0.04673 (14)
O1	0.2608 (4)	0.40743 (10)	−0.0690 (2)	0.0797 (9)
O2	0.5120 (4)	0.39512 (10)	0.0279 (2)	0.0754 (8)
N1	0.5275 (4)	0.80533 (13)	−0.0531 (3)	0.0746 (10)
N2	0.4084 (3)	0.64870 (9)	0.1936 (2)	0.0424 (6)
N3	0.3834 (4)	0.41930 (11)	0.0065 (2)	0.0552 (8)
S1	0.08507 (13)	0.76215 (4)	0.75005 (9)	0.0690 (3)
S2	−0.05329 (12)	0.69214 (4)	0.55265 (9)	0.0660 (3)
S3	0.27096 (11)	0.67162 (4)	0.69657 (8)	0.0602 (3)
S4	−0.05363 (11)	0.59682 (4)	0.40526 (8)	0.0620 (3)
S5	0.29798 (11)	0.57297 (4)	0.56561 (8)	0.0578 (3)
S6	−0.04453 (10)	0.49687 (4)	0.27893 (8)	0.0581 (3)
S7	0.30541 (10)	0.47438 (4)	0.44187 (8)	0.0559 (3)
S8	−0.01230 (12)	0.39818 (4)	0.15167 (8)	0.0661 (3)
S9	0.31466 (11)	0.37927 (4)	0.29563 (8)	0.0596 (3)
S10	0.16951 (15)	0.30728 (4)	0.10160 (11)	0.0842 (4)
C1	0.0997 (4)	0.71136 (13)	0.6712 (3)	0.0553 (9)
C2	0.0396 (4)	0.63686 (13)	0.5171 (3)	0.0514 (9)
C3	0.1933 (4)	0.62697 (13)	0.5861 (3)	0.0499 (9)
C4	0.0626 (4)	0.44299 (13)	0.2605 (3)	0.0510 (9)
C5	0.2162 (4)	0.43352 (13)	0.3297 (3)	0.0487 (8)
C6	0.1579 (4)	0.35837 (14)	0.1780 (3)	0.0602 (10)
C8	0.4722 (4)	0.72766 (12)	0.0638 (3)	0.0442 (8)
C9	0.5968 (4)	0.70593 (12)	0.1495 (3)	0.0480 (8)
H9	0.7035	0.7184	0.1643	0.058*
C10	0.5612 (4)	0.66582 (12)	0.2124 (3)	0.0472 (8)
H10	0.6451	0.6503	0.2693	0.057*
C11	0.2853 (4)	0.66928 (12)	0.1100 (3)	0.0458 (8)
H11	0.1793	0.6565	0.0976	0.055*
C12	0.3145 (4)	0.70877 (12)	0.0432 (3)	0.0484 (8)
H12	0.2295	0.7228	−0.0153	0.058*
C13	0.3706 (4)	0.60448 (12)	0.2623 (3)	0.0511 (9)
H13A	0.2637	0.6097	0.2749	0.061*
H13B	0.4516	0.6031	0.3372	0.061*
C14	0.5122 (4)	0.52460 (13)	0.2208 (3)	0.0485 (9)
H14	0.6052	0.5348	0.2781	0.058*
C15	0.3716 (4)	0.55425 (11)	0.1992 (2)	0.0404 (7)
C16	0.2328 (4)	0.53870 (12)	0.1150 (3)	0.0476 (8)
H16	0.1371	0.5581	0.1013	0.057*
C17	0.2358 (4)	0.49449 (12)	0.0513 (3)	0.0474 (8)
H17	0.1435	0.4841	−0.0064	0.057*
C18	0.3785 (4)	0.46620 (12)	0.0752 (2)	0.0415 (8)
C19	0.5162 (4)	0.48020 (13)	0.1588 (3)	0.0484 (8)
H19	0.6109	0.4602	0.1735	0.058*
C20	0.5035 (4)	0.77070 (14)	−0.0025 (3)	0.0538 (9)

	U11	U22	U33	U12	U13	U23
Ni1	0.0354 (2)	0.0605 (3)	0.0427 (3)	0.0008 (2)	0.00814 (19)	0.0116 (2)
O1	0.094 (2)	0.0649 (18)	0.0670 (18)	−0.0028 (15)	0.0001 (16)	−0.0202 (14)
O2	0.083 (2)	0.0650 (18)	0.0817 (19)	0.0176 (16)	0.0288 (16)	−0.0093 (14)
N1	0.084 (2)	0.070 (2)	0.068 (2)	−0.0089 (19)	0.0177 (19)	0.0166 (18)
N2	0.0533 (17)	0.0397 (15)	0.0352 (14)	−0.0012 (13)	0.0137 (13)	−0.0033 (12)
N3	0.075 (2)	0.0465 (19)	0.0471 (18)	−0.0005 (17)	0.0216 (17)	0.0048 (14)
S1	0.0714 (7)	0.0700 (7)	0.0707 (7)	0.0025 (5)	0.0282 (5)	0.0038 (5)
S2	0.0494 (6)	0.0619 (6)	0.0801 (7)	0.0097 (5)	0.0074 (5)	0.0082 (5)
S3	0.0480 (5)	0.0662 (6)	0.0623 (6)	0.0019 (5)	0.0082 (4)	0.0029 (5)
S4	0.0433 (5)	0.0683 (7)	0.0632 (6)	0.0080 (4)	−0.0037 (4)	0.0067 (5)
S5	0.0409 (5)	0.0680 (6)	0.0569 (6)	0.0088 (4)	0.0011 (4)	0.0029 (5)
S6	0.0376 (5)	0.0763 (7)	0.0546 (6)	0.0032 (4)	0.0031 (4)	0.0042 (5)
S7	0.0403 (5)	0.0726 (6)	0.0486 (5)	0.0074 (4)	0.0022 (4)	0.0011 (4)
S8	0.0549 (6)	0.0742 (7)	0.0610 (6)	−0.0100 (5)	0.0026 (5)	−0.0021 (5)
S9	0.0533 (6)	0.0602 (6)	0.0634 (6)	0.0004 (5)	0.0133 (5)	0.0046 (5)
S10	0.0937 (9)	0.0676 (7)	0.0933 (8)	−0.0168 (6)	0.0295 (7)	−0.0164 (6)
C1	0.051 (2)	0.058 (2)	0.062 (2)	−0.0038 (17)	0.0230 (18)	0.0135 (18)
C2	0.0419 (19)	0.051 (2)	0.061 (2)	0.0022 (16)	0.0148 (17)	0.0148 (17)
C3	0.046 (2)	0.051 (2)	0.052 (2)	−0.0036 (16)	0.0117 (16)	0.0121 (16)
C4	0.044 (2)	0.062 (2)	0.047 (2)	−0.0052 (17)	0.0128 (16)	0.0072 (17)
C5	0.0421 (19)	0.060 (2)	0.0463 (19)	−0.0017 (16)	0.0159 (16)	0.0101 (16)
C6	0.060 (2)	0.066 (2)	0.056 (2)	−0.0156 (19)	0.0190 (18)	0.0090 (18)
C8	0.057 (2)	0.0373 (19)	0.0412 (19)	−0.0013 (16)	0.0175 (16)	−0.0019 (15)
C9	0.049 (2)	0.049 (2)	0.046 (2)	−0.0029 (16)	0.0124 (16)	0.0001 (16)
C10	0.052 (2)	0.048 (2)	0.0385 (18)	0.0043 (17)	0.0067 (15)	−0.0020 (16)
C11	0.048 (2)	0.040 (2)	0.051 (2)	−0.0027 (16)	0.0153 (16)	−0.0069 (16)
C12	0.053 (2)	0.043 (2)	0.0460 (19)	0.0058 (16)	0.0087 (16)	−0.0009 (16)
C13	0.071 (2)	0.047 (2)	0.0395 (18)	−0.0047 (18)	0.0208 (17)	0.0023 (16)
C14	0.048 (2)	0.056 (2)	0.0364 (18)	−0.0059 (16)	0.0029 (15)	0.0038 (16)
C15	0.050 (2)	0.0405 (18)	0.0329 (16)	−0.0041 (15)	0.0144 (15)	0.0059 (14)
C16	0.0411 (18)	0.046 (2)	0.055 (2)	0.0015 (15)	0.0122 (16)	0.0055 (17)
C17	0.0404 (19)	0.046 (2)	0.050 (2)	−0.0060 (16)	0.0036 (16)	0.0034 (16)
C18	0.054 (2)	0.0370 (18)	0.0370 (17)	−0.0027 (15)	0.0175 (15)	0.0038 (14)
C19	0.047 (2)	0.050 (2)	0.046 (2)	0.0050 (16)	0.0102 (16)	0.0078 (16)
C20	0.061 (2)	0.052 (2)	0.047 (2)	−0.0031 (18)	0.0120 (18)	0.0024 (18)

Ni1—S5	2.1570 (10)	C2—C3	1.362 (4)
Ni1—S7	2.1591 (10)	C4—C5	1.360 (4)
Ni1—S6	2.1596 (10)	C8—C9	1.375 (4)
Ni1—S4	2.1661 (10)	C8—C12	1.380 (4)
O1—N3	1.215 (3)	C8—C20	1.434 (5)
O2—N3	1.220 (4)	C9—C10	1.365 (4)
N1—C20	1.132 (4)	C9—H9	0.9300
N2—C10	1.328 (4)	C10—H10	0.9300
N2—C11	1.343 (4)	C11—C12	1.362 (4)
N2—C13	1.495 (4)	C11—H11	0.9300
N3—C18	1.473 (4)	C12—H12	0.9300
S1—C1	1.643 (4)	C13—C15	1.503 (4)
S2—C1	1.714 (4)	C13—H13A	0.9700
S2—C2	1.740 (4)	C13—H13B	0.9700
S3—C1	1.735 (4)	C14—C19	1.373 (4)
S3—C3	1.744 (3)	C14—C15	1.379 (4)
S4—C2	1.707 (4)	C14—H14	0.9300
S5—C3	1.707 (4)	C15—C16	1.383 (4)
S6—C4	1.709 (4)	C16—C17	1.378 (4)
S7—C5	1.714 (3)	C16—H16	0.9300
S8—C6	1.728 (4)	C17—C18	1.375 (4)
S8—C4	1.730 (3)	C17—H17	0.9300
S9—C5	1.736 (4)	C18—C19	1.362 (4)
S9—C6	1.738 (4)	C19—H19	0.9300
S10—C6	1.626 (4)
S5—Ni1—S7	86.47 (4)	C9—C8—C20	120.7 (3)
S5—Ni1—S6	178.98 (4)	C12—C8—C20	119.6 (3)
S7—Ni1—S6	92.69 (4)	C10—C9—C8	118.9 (3)
S5—Ni1—S4	92.83 (4)	C10—C9—H9	120.6
S7—Ni1—S4	179.28 (4)	C8—C9—H9	120.6
S6—Ni1—S4	88.01 (4)	N2—C10—C9	120.9 (3)
C10—N2—C11	121.1 (3)	N2—C10—H10	119.5
C10—N2—C13	120.6 (3)	C9—C10—H10	119.5
C11—N2—C13	118.3 (3)	N2—C11—C12	120.4 (3)
O1—N3—O2	124.0 (3)	N2—C11—H11	119.8
O1—N3—C18	118.4 (3)	C12—C11—H11	119.8
O2—N3—C18	117.7 (3)	C11—C12—C8	119.0 (3)
C1—S2—C2	98.72 (17)	C11—C12—H12	120.5
C1—S3—C3	97.80 (16)	C8—C12—H12	120.5
C2—S4—Ni1	102.02 (12)	N2—C13—C15	110.2 (2)
C3—S5—Ni1	102.58 (11)	N2—C13—H13A	109.6
C4—S6—Ni1	102.50 (11)	C15—C13—H13A	109.6
C5—S7—Ni1	102.63 (12)	N2—C13—H13B	109.6
C6—S8—C4	98.39 (16)	C15—C13—H13B	109.6
C5—S9—C6	97.64 (17)	H13A—C13—H13B	108.1
S1—C1—S2	123.4 (2)	C19—C14—C15	120.7 (3)
S1—C1—S3	124.3 (2)	C19—C14—H14	119.6
S2—C1—S3	112.3 (2)	C15—C14—H14	119.6
C3—C2—S4	121.6 (3)	C14—C15—C16	119.5 (3)
C3—C2—S2	115.2 (3)	C14—C15—C13	120.6 (3)
S4—C2—S2	123.19 (19)	C16—C15—C13	119.8 (3)
C2—C3—S5	120.9 (3)	C17—C16—C15	120.3 (3)
C2—C3—S3	115.9 (3)	C17—C16—H16	119.9
S5—C3—S3	123.24 (19)	C15—C16—H16	119.9
C5—C4—S6	121.4 (3)	C18—C17—C16	118.3 (3)
C5—C4—S8	115.6 (3)	C18—C17—H17	120.9
S6—C4—S8	123.02 (19)	C16—C17—H17	120.9
C4—C5—S7	120.7 (3)	C19—C18—C17	122.6 (3)
C4—C5—S9	116.3 (3)	C19—C18—N3	118.7 (3)
S7—C5—S9	123.06 (19)	C17—C18—N3	118.6 (3)
S10—C6—S8	123.9 (2)	C18—C19—C14	118.5 (3)
S10—C6—S9	124.0 (2)	C18—C19—H19	120.8
S8—C6—S9	112.1 (2)	C14—C19—H19	120.8
C9—C8—C12	119.7 (3)	N1—C20—C8	178.6 (4)
S5—Ni1—S4—C2	−3.08 (12)	C6—S9—C5—C4	−0.8 (3)
S6—Ni1—S4—C2	177.50 (12)	C6—S9—C5—S7	−179.6 (2)
S7—Ni1—S5—C3	−177.63 (12)	C4—S8—C6—S10	−179.0 (2)
S4—Ni1—S5—C3	2.52 (12)	C4—S8—C6—S9	1.1 (2)
S7—Ni1—S6—C4	−2.01 (12)	C5—S9—C6—S10	179.7 (2)
S4—Ni1—S6—C4	177.84 (12)	C5—S9—C6—S8	−0.4 (2)
S5—Ni1—S7—C5	−176.49 (12)	C12—C8—C9—C10	0.2 (5)
S6—Ni1—S7—C5	2.94 (12)	C20—C8—C9—C10	178.5 (3)
C2—S2—C1—S1	−177.9 (2)	C11—N2—C10—C9	2.0 (5)
C2—S2—C1—S3	2.8 (2)	C13—N2—C10—C9	179.5 (3)
C3—S3—C1—S1	177.6 (2)	C8—C9—C10—N2	−1.7 (5)
C3—S3—C1—S2	−3.1 (2)	C10—N2—C11—C12	−0.7 (5)
Ni1—S4—C2—C3	3.3 (3)	C13—N2—C11—C12	−178.4 (3)
Ni1—S4—C2—S2	−175.84 (18)	N2—C11—C12—C8	−0.8 (5)
C1—S2—C2—C3	−1.3 (3)	C9—C8—C12—C11	1.0 (5)
C1—S2—C2—S4	177.9 (2)	C20—C8—C12—C11	−177.3 (3)
S4—C2—C3—S5	−1.5 (4)	C10—N2—C13—C15	−93.8 (3)
S2—C2—C3—S5	177.70 (18)	C11—N2—C13—C15	83.8 (4)
S4—C2—C3—S3	−179.97 (18)	C19—C14—C15—C16	0.7 (5)
S2—C2—C3—S3	−0.7 (4)	C19—C14—C15—C13	−176.3 (3)
Ni1—S5—C3—C2	−1.2 (3)	N2—C13—C15—C14	93.1 (3)
Ni1—S5—C3—S3	177.12 (18)	N2—C13—C15—C16	−84.0 (4)
C1—S3—C3—C2	2.4 (3)	C14—C15—C16—C17	−1.4 (5)
C1—S3—C3—S5	−176.0 (2)	C13—C15—C16—C17	175.7 (3)
Ni1—S6—C4—C5	0.3 (3)	C15—C16—C17—C18	1.1 (5)
Ni1—S6—C4—S8	−177.69 (18)	C16—C17—C18—C19	−0.1 (5)
C6—S8—C4—C5	−1.7 (3)	C16—C17—C18—N3	−179.2 (3)
C6—S8—C4—S6	176.4 (2)	O1—N3—C18—C19	−179.0 (3)
S6—C4—C5—S7	2.4 (4)	O2—N3—C18—C19	−0.1 (4)
S8—C4—C5—S7	−179.46 (18)	O1—N3—C18—C17	0.1 (4)
S6—C4—C5—S9	−176.42 (18)	O2—N3—C18—C17	179.0 (3)
S8—C4—C5—S9	1.7 (4)	C17—C18—C19—C14	−0.5 (5)
Ni1—S7—C5—C4	−3.7 (3)	N3—C18—C19—C14	178.5 (3)
Ni1—S7—C5—S9	175.08 (17)	C15—C14—C19—C18	0.2 (5)