4-Cyano-1-(4-nitro­benz­yl)pyridinium bis­(2-thioxo-1,3-dithiole-4,5-dithiol­ato-κ2S4,S5)nickelate(III)

Li, K.-H.; Lei, Q.-D.; Mei, C.-Z.

doi:10.1107/S1600536810037426

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1311

doi:10.1107/S1600536810037426

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4-Cyano-1-(4-nitrobenzyl)pyridinium bis(2-thioxo-1,3-dithiole-4,5-dithiolato-κ²S⁴,S⁵)nickelate(III)

Kai-Hui Li,^a Qing-Duo Lei ^a and Chong-Zhen Mei ^a ^*

^aInstitute of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011, People's Republic of China
^*Correspondence e-mail: meichongzhen@163.com

(Received 15 August 2010; accepted 18 September 2010; online 30 September 2010)

In the title salt, (C₁₃H₁₀N₃O₂)[Ni(C₃S₅)₂], the Ni^III cation is S,S′-chelated by two 2-thioxo-1,3-dithiole-4,5-dithiolate 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-nitrobenzyl)-4-cyanopyridinium 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_r = 691.61
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.090
S = 1.02
4423 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −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.

Supporting information

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

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

checkCIF report

Comment top

Bis-dithiolate metal ion-pair complexes have been actively studied for a long time as a wide range of conducting and magneticmaterials as well as nonlinear opticalmaterials (Cassoux, 1999). 2-Thioxo-1,3-dithiole-4,5-dithiolate metal complex also is excellent building block employed for the construction of molecular magnetic materials (Zang et al., 2006) apart from its well known electric conductivity molecular conductors (Akutagawa & Nakamura, 2000). We report herein the synthesis and crystal structure of the new ion-pair complex.

The title compound (I) comprises [Ni^III(dmit)₂]^- anions (where dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate) and 1-(4-nitrobenzyl)-4-cyanopyridinium cations (Figure 1). The Ni^III ion adopts a square-planar geometry coordinated by four S atoms of two dmit ligands, with Ni—S bond lengths ranging from 2.157 to 2.166 Å. Two [Ni^III(dmit)₂]^- anions form pairs across centres of inversion, with their least squares planes parallel and Ni1···Ni1ⁱ= 3.668 Å, S1···S10ⁱ= 3.636 Å, [symmetry code: (i) -x, 1 - y, 1 - z]. Neighbouring anion pairs are nearly vertical or parallel arrangements so that S···S interactions in this region include S5···S7ⁱⁱ = 3.606, S5···S9ⁱⁱ = 3.473, S7···S5ⁱⁱ= 3.506, S7···S7ⁱⁱ= 3.471 and S10ⁱ···S2ⁱⁱⁱ = 3.496 Å [symmetry codes: (ii) 1 - x, 1 - y, 1 - z; (iii) x, 1.5 - y, 1/2 + z]. The adjacent [NO₂CNbzpy]⁺cations adopting edge-to-face inversion arrangements are associated together through lone pair-aromatic interactions (lp···π: O2-centroid distance 2.953 Å) (Egli & Sarkhel, 2007) between the oxygen atom of nitro group and the pyridine ring from neighboring cation and CN···π interactions (C10···N1ⁱⁱⁱ distance 3.010 Å) (Tian et al., 2007) between the CN group at the end of the cations and the pyridine ring of the adjacent cation. In addition, there is π···π interaction (centroid-centroid distance 3.625 Å) between phenyl ring of [NO₂CNbzpy]⁺cation and the ethylene group (C4═C5) of [Ni^III(dmit)₂]^- anion and donor-acceptor interaction between anion and cation (S1···C11ⁱⁱⁱ distance 3.234 Å [symmetry codes (iii) x, 1.5 - y, 1/2 + z]) (Cundari et al., 2010). The weak S···S, CN···π, lp···π, donor-acceptor and π···π interactions lead a three-dimensional supramolecular structure (Figure 2).

Related literature top

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 top

4,5-Bis(thiobenzoyl)-1,3-dithiole-2-thione (812 mg, 2.0 mmol) was suspended in dry methanol (20 ml) and sodium (92 mg, 4.0 mmol) was added under a nitrogen atmosphere at room temperature to give a bright-red solution. NiCl₂.6H₂O (238 mg, 1 mmol) was then added, followed successively by I₂ (127 mg, 0.5 mmol) and a solution of 1-(4-nitrobenzyl)-4-cyanopyridinium chloride (276 mg, 1 mmol) in methanol at an interval of approximately 20 min. The solution was stirred for a further 30 min and the resulting solid collected by filtration. Single crystals of the title complound were obtained by evaporation of a dilute acetone solution over 2 weeks at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The cation and anion in (I), showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Three-dimensional supramolecular structure of (I). Hydrogen atoms have been omitted for clarity. Dashed lines indicate weak S···S, CN···π, lp···π, donor-acceptor and π···π interactions.

4-Cyano-1-(4-nitrobenzyl)pyridinium bis(2-thioxo-1,3-dithiole-4,5-dithiolato- κ²S⁴,S⁵)nickelate(III) top

Crystal data top

(C₁₃H₁₀N₃O₂)[Ni(C₃S₅)₂]	F(000) = 1396
M_r = 691.61	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0387P)² + 0.150P] where P = (F_o² + 2F_c²)/3
4423 reflections	(Δ/σ)_max = 0.001
316 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

(C₁₃H₁₀N₃O₂)[Ni(C₃S₅)₂]	V = 2532.3 (9) Å³
M_r = 691.61	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4896 (17) Å	µ = 1.62 mm⁻¹
b = 25.789 (5) Å	T = 296 K
c = 12.043 (3) Å	0.20 × 0.17 × 0.15 mm
β = 106.181 (3)°

Data collection top

Bruker SMART APEXII CCD area detector diffractometer	4423 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3343 reflections with I > 2σ(I)
T_min = 0.738, T_max = 0.794	R_int = 0.043
12415 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.02	Δρ_max = 0.57 e Å⁻³
4423 reflections	Δρ_min = −0.26 e Å⁻³
316 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₀N₃O₂)[Ni(C₃S₅)₂]
M_r	691.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.4896 (17), 25.789 (5), 12.043 (3)
β (°)	106.181 (3)
V (Å³)	2532.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.62
Crystal size (mm)	0.20 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.738, 0.794
No. of measured, independent and observed [I > 2σ(I)] reflections	12415, 4423, 3343
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.090, 1.02
No. of reflections	4423
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.26

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported financially by the North China University of Water Conservancy and Electric Power, China.

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