Bis(1-ethyl-4,4′-bipyridin-1-ium) bis­(1,2-di­cyano­ethene-1,2-di­thiol­ato-κ2S,S′)nickelate(II)

Chen, Y.; Ning, W.; Liu, J.-L.

doi:10.1107/S1600536813015493

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page m428

doi:10.1107/S1600536813015493

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Bis(1-ethyl-4,4′-bipyridin-1-ium) bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickelate(II)

Yao Chen,^a Wei-hua Ning ^a and Jian-Lan Liu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: njutljl@163.com

(Received 27 May 2013; accepted 4 June 2013; online 3 July 2013)

In the anion of the title compound, (C₁₂H₁₃N₂)[Ni(C₄N₂S₂)₂], the Ni^II atom is coordinated by four S atoms from two 1,2-dicyanoethene-1,2-dithiolate (mnt) ligands in a suqare-planar geometry. Weak C—H⋯N and C—H⋯S hydrogen bonds between the 1-ethyl-4,4′-bipyridin-1-ium cations and mnt anions and weak π–π interactions between the pyridine rings of the cations [centroid–centroid distances = 3.808 (3) and 3.972 (3) Å] lead to a two-dimensional network parallel to (010).

Related literature

For general background to bis(1,2-dithiolene) complexes acting as magnetic materials or showing non-linear optical properties, see: Duan et al. (2010 ); Kato (2004 ). For the synthesis of the compound, see: Pei et al. (2010 ). For related structures, see: Duan et al. (2011 ); Liu et al. (2011 ).

Experimental

Crystal data

(C₁₂H₁₃N₂)[Ni(C₄N₂S₂)₂]
M_r = 709.58
Triclinic, $[P \overline 1]$
a = 7.4505 (13) Å
b = 12.793 (2) Å
c = 17.745 (3) Å
α = 78.664 (2)°
β = 86.558 (2)°
γ = 80.344 (2)°
V = 1634.2 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 296 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.808, T_max = 0.876
14954 measured reflections
7631 independent reflections
3616 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.128
S = 0.97
7631 reflections
408 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯S2ⁱ	0.93	2.78	3.549 (4)	141
C17—H17⋯N4ⁱ	0.93	2.55	3.441 (6)	161
C21—H21⋯N3ⁱⁱ	0.93	2.42	3.342 (6)	170
C22—H22⋯N4ⁱⁱ	0.93	2.50	3.372 (5)	156
C24—H24⋯N2	0.93	2.46	3.364 (5)	163
C25—H25⋯N1	0.93	2.52	3.411 (6)	161
C27—H27⋯N4ⁱⁱ	0.93	2.58	3.498 (6)	172
C30—H30⋯N2	0.93	2.60	3.526 (6)	176
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x-1, y, z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 D, I. DOI: 10.1107/S1600536813015493/hy2630sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813015493/hy2630Isup2.hkl

checkCIF report

Comment top

Bis(1,2-dithiolene) complexes of transition metals as an important part of the molecular-based materials have been widely studied due to their novel applications in the areas of materials science, medicines and biology (Duan et al., 2010; Kato, 2004). It is known that weak inter- or intramolecular interactions in the complexes could influence on their properties. Herein we report the crystal structure of the title compound. The bond lengths and angles in the title compound (Fig. 1) are within normal ranges (Duan et al., 2011; Liu et al., 2011). Weak C—H···N and C—H···S hydrogen bonds between the 1-ethyl-4,4'-bipyridin-1-ium cations and 1,2-dicyanoethene-1,2-dithiolate anions and weak π–π interactions between the pyridine rings of the cations [centroid–centroid distances = 3.808 (3) and 3.972 (3) Å] lead to a two-dimensional network parallel to (010) (Fig. 2).

Related literature top

For general background to bis(1,2-dithiolene) complexes acting as magnetic materials or showing non-linear optical properties, see: Duan et al. (2010); Kato (2004). For the synthesis of the compound, see: Pei et al. (2010). For related structures, see: Duan et al. (2011); Liu et al. (2011).

Experimental top

The title compound was prepared by a method similar to that reported in literature (Pei et al., 2010). Nickel chloride hexahydrate (238 mg, 1.00 mmol) and disodium maleonitriledithiolate (365 mg, 2.00 mmol) were mixed under stirring in water (50 ml) and heated to boiling for about 20 min. After filtering the red solution, an aequeous solution of 1-ethyl-4,4'-bipyridin-1-ium bromide (554 mg, 2.00 mmol) was added dropwise to the filtrate. The immediately formed dark red precipitate was filtered off, washed with water and dried in vacuum oven, giving the crude product (yield: 511 mg, 72%). Red block-like single crystals were obtained by slow evaporation of the crude in an acetonitrile solution at room temperature in about two weeks.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound viewed down the a axis. Dashed lines indicate hydrogen bonds.

Bis(1-ethyl-4,4'-bipyridin-1-ium) bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nickelate(II) top

Crystal data top

(C₁₂H₁₃N₂)[Ni(C₄N₂S₂)₂]	Z = 2
M_r = 709.58	F(000) = 732.0
Triclinic, P1	D_x = 1.442 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4505 (13) Å	Cell parameters from 1518 reflections
b = 12.793 (2) Å	θ = 2.3–19.7°
c = 17.745 (3) Å	µ = 0.89 mm⁻¹
α = 78.664 (2)°	T = 296 K
β = 86.558 (2)°	Block, red
γ = 80.344 (2)°	0.25 × 0.20 × 0.15 mm
V = 1634.2 (5) Å³

Data collection top

Bruker APEX CCD diffractometer	7631 independent reflections
Radiation source: fine-focus sealed tube	3616 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ and ω scans	θ_max = 28.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.808, T_max = 0.876	k = −16→16
14954 measured reflections	l = −23→20

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0418P)²] where P = (F_o² + 2F_c²)/3
7631 reflections	(Δ/σ)_max < 0.001
408 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

(C₁₂H₁₃N₂)[Ni(C₄N₂S₂)₂]	γ = 80.344 (2)°
M_r = 709.58	V = 1634.2 (5) Å³
Triclinic, P1	Z = 2
a = 7.4505 (13) Å	Mo Kα radiation
b = 12.793 (2) Å	µ = 0.89 mm⁻¹
c = 17.745 (3) Å	T = 296 K
α = 78.664 (2)°	0.25 × 0.20 × 0.15 mm
β = 86.558 (2)°

Data collection top

Bruker APEX CCD diffractometer	7631 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3616 reflections with I > 2σ(I)
T_min = 0.808, T_max = 0.876	R_int = 0.050
14954 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 0.97	Δρ_max = 0.49 e Å⁻³
7631 reflections	Δρ_min = −0.37 e Å⁻³
408 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.82715 (7)	0.22869 (4)	0.39454 (3)	0.04134 (16)
S1	0.73997 (14)	0.35458 (7)	0.46177 (6)	0.0484 (3)
S2	0.76184 (16)	0.10350 (7)	0.48848 (6)	0.0547 (3)
S3	0.87246 (15)	0.35324 (8)	0.29580 (6)	0.0528 (3)
S4	0.93428 (17)	0.10088 (8)	0.33202 (6)	0.0613 (3)
C2	0.6768 (5)	0.2822 (3)	0.5502 (2)	0.0441 (9)
C1	0.6135 (6)	0.3411 (3)	0.6099 (2)	0.0499 (10)
C3	0.6833 (5)	0.1733 (3)	0.5608 (2)	0.0440 (10)
C4	0.6232 (6)	0.1130 (3)	0.6311 (2)	0.0551 (11)
C6	0.9759 (5)	0.2797 (3)	0.2284 (2)	0.0465 (10)
C5	1.0367 (6)	0.3382 (3)	0.1563 (2)	0.0565 (12)
C7	1.0008 (5)	0.1697 (3)	0.2436 (2)	0.0479 (10)
C8	1.0813 (6)	0.1076 (3)	0.1876 (2)	0.0558 (11)
C9	0.2604 (6)	0.3605 (3)	0.4593 (3)	0.0606 (12)
H9	0.2870	0.4231	0.4273	0.073*
C10	0.1955 (5)	0.3644 (3)	0.5330 (3)	0.0576 (12)
H10	0.1772	0.4301	0.5497	0.069*
C11	0.1563 (5)	0.2723 (3)	0.5835 (2)	0.0461 (10)
C12	0.1837 (6)	0.1787 (3)	0.5540 (2)	0.0577 (12)
H12	0.1594	0.1148	0.5850	0.069*
C13	0.2461 (6)	0.1784 (3)	0.4801 (3)	0.0609 (12)
H13	0.2615	0.1140	0.4618	0.073*
C14	0.0815 (5)	0.2768 (3)	0.6632 (2)	0.0481 (10)
C15	0.0630 (6)	0.3698 (3)	0.6932 (3)	0.0672 (13)
H15	0.1012	0.4316	0.6645	0.081*
C16	−0.0124 (6)	0.3709 (4)	0.7661 (3)	0.0713 (14)
H16	−0.0215	0.4345	0.7849	0.086*
C17	−0.0516 (7)	0.1977 (4)	0.7814 (3)	0.0785 (15)
H17	−0.0891	0.1368	0.8117	0.094*
C18	0.0220 (6)	0.1890 (3)	0.7087 (3)	0.0645 (13)
H18	0.0309	0.1244	0.6911	0.077*
C19	0.3576 (6)	0.2552 (4)	0.3530 (2)	0.0682 (13)
H19A	0.4785	0.2126	0.3566	0.082*
H19B	0.2795	0.2159	0.3312	0.082*
C20	0.3667 (7)	0.3600 (4)	0.3003 (3)	0.0956 (17)
H20A	0.2507	0.4057	0.3006	0.143*
H20B	0.3972	0.3476	0.2491	0.143*
H20C	0.4582	0.3943	0.3170	0.143*
C21	0.2644 (6)	0.2746 (4)	0.9515 (3)	0.0754 (14)
H21	0.2103	0.3136	0.9883	0.090*
C22	0.2539 (6)	0.1671 (4)	0.9611 (2)	0.0686 (13)
H22	0.1919	0.1345	1.0040	0.082*
C23	0.3346 (5)	0.1053 (4)	0.9076 (2)	0.0567 (11)
C24	0.4248 (6)	0.1605 (4)	0.8456 (2)	0.0688 (13)
H24	0.4823	0.1231	0.8085	0.083*
C25	0.4311 (7)	0.2679 (4)	0.8376 (3)	0.0796 (15)
H25	0.4917	0.3027	0.7951	0.095*
C26	0.3254 (6)	−0.0126 (4)	0.9179 (2)	0.0572 (11)
C27	0.2592 (6)	−0.0700 (4)	0.9857 (3)	0.0676 (13)
H27	0.2166	−0.0359	1.0264	0.081*
C28	0.2581 (6)	−0.1785 (4)	0.9909 (3)	0.0759 (14)
H28	0.2132	−0.2155	1.0367	0.091*
C29	0.3719 (8)	−0.1787 (5)	0.8721 (3)	0.0989 (19)
H29	0.4079	−0.2151	0.8318	0.119*
C30	0.3822 (7)	−0.0688 (4)	0.8589 (3)	0.0785 (15)
H30	0.4259	−0.0341	0.8121	0.094*
C31	0.3614 (8)	0.4438 (4)	0.8812 (3)	0.0931 (17)
H31A	0.3367	0.4788	0.8284	0.112*
H31B	0.2689	0.4765	0.9140	0.112*
C32	0.5411 (9)	0.4616 (4)	0.9009 (4)	0.120 (2)
H32A	0.5715	0.4209	0.9512	0.181*
H32B	0.5383	0.5370	0.9005	0.181*
H32C	0.6308	0.4386	0.8640	0.181*
N1	0.5638 (5)	0.3873 (3)	0.6585 (2)	0.0711 (11)
N2	0.5710 (6)	0.0624 (3)	0.6863 (2)	0.0819 (13)
N3	1.0878 (6)	0.3863 (3)	0.1002 (2)	0.0855 (13)
N4	1.1447 (6)	0.0573 (3)	0.1433 (2)	0.0788 (13)
N5	0.2860 (4)	0.2673 (3)	0.4330 (2)	0.0513 (9)
N6	−0.0723 (5)	0.2883 (3)	0.8109 (2)	0.0716 (11)
N7	0.3506 (5)	0.3244 (3)	0.8906 (2)	0.0708 (11)
N8	0.3154 (6)	−0.2354 (4)	0.9367 (3)	0.0889 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0509 (3)	0.0353 (3)	0.0370 (3)	−0.0089 (2)	0.0064 (2)	−0.0055 (2)
S1	0.0639 (7)	0.0369 (5)	0.0446 (6)	−0.0108 (5)	0.0060 (5)	−0.0085 (4)
S2	0.0809 (8)	0.0356 (6)	0.0452 (7)	−0.0104 (5)	0.0182 (6)	−0.0072 (5)
S3	0.0705 (8)	0.0391 (6)	0.0450 (7)	−0.0087 (5)	0.0151 (6)	−0.0043 (5)
S4	0.0992 (10)	0.0382 (6)	0.0447 (7)	−0.0145 (6)	0.0226 (6)	−0.0081 (5)
C2	0.045 (2)	0.046 (2)	0.041 (2)	−0.0056 (18)	0.0023 (19)	−0.0091 (18)
C1	0.055 (3)	0.049 (2)	0.045 (3)	−0.006 (2)	0.001 (2)	−0.009 (2)
C3	0.051 (3)	0.041 (2)	0.037 (2)	−0.0031 (19)	0.0066 (19)	−0.0056 (18)
C4	0.069 (3)	0.048 (2)	0.045 (3)	−0.005 (2)	0.014 (2)	−0.009 (2)
C6	0.054 (3)	0.049 (2)	0.034 (2)	−0.009 (2)	0.003 (2)	−0.0032 (18)
C5	0.077 (3)	0.048 (3)	0.043 (3)	−0.008 (2)	0.010 (2)	−0.010 (2)
C7	0.065 (3)	0.044 (2)	0.036 (2)	−0.010 (2)	0.009 (2)	−0.0108 (18)
C8	0.079 (3)	0.050 (3)	0.035 (3)	−0.012 (2)	0.002 (2)	0.000 (2)
C9	0.064 (3)	0.047 (3)	0.070 (3)	−0.015 (2)	−0.001 (3)	−0.004 (2)
C10	0.066 (3)	0.035 (2)	0.074 (3)	−0.014 (2)	0.003 (3)	−0.011 (2)
C11	0.047 (2)	0.035 (2)	0.057 (3)	−0.0102 (18)	−0.007 (2)	−0.0064 (19)
C12	0.075 (3)	0.040 (2)	0.059 (3)	−0.015 (2)	0.002 (3)	−0.007 (2)
C13	0.077 (3)	0.046 (3)	0.061 (3)	−0.012 (2)	0.002 (3)	−0.011 (2)
C14	0.045 (2)	0.041 (2)	0.058 (3)	−0.0047 (19)	0.000 (2)	−0.011 (2)
C15	0.086 (4)	0.048 (3)	0.070 (3)	−0.014 (2)	0.012 (3)	−0.018 (2)
C16	0.089 (4)	0.054 (3)	0.075 (4)	−0.016 (3)	0.004 (3)	−0.021 (3)
C17	0.101 (4)	0.057 (3)	0.076 (4)	−0.019 (3)	0.014 (3)	−0.008 (3)
C18	0.083 (3)	0.046 (3)	0.064 (3)	−0.013 (2)	0.003 (3)	−0.009 (2)
C19	0.056 (3)	0.092 (4)	0.053 (3)	−0.020 (3)	−0.005 (2)	0.005 (3)
C20	0.098 (4)	0.098 (4)	0.093 (4)	−0.020 (3)	0.003 (3)	−0.021 (4)
C21	0.083 (4)	0.089 (4)	0.047 (3)	−0.003 (3)	0.016 (3)	−0.010 (3)
C22	0.078 (3)	0.080 (3)	0.041 (3)	−0.007 (3)	0.017 (2)	−0.007 (2)
C23	0.049 (3)	0.075 (3)	0.042 (3)	−0.002 (2)	0.002 (2)	−0.009 (2)
C24	0.086 (4)	0.077 (3)	0.043 (3)	−0.016 (3)	0.017 (3)	−0.012 (2)
C25	0.090 (4)	0.088 (4)	0.054 (3)	−0.013 (3)	0.020 (3)	−0.007 (3)
C26	0.049 (3)	0.081 (3)	0.041 (3)	−0.010 (2)	0.003 (2)	−0.013 (2)
C27	0.066 (3)	0.085 (4)	0.049 (3)	−0.014 (3)	0.012 (2)	−0.008 (3)
C28	0.071 (4)	0.090 (4)	0.064 (4)	−0.018 (3)	0.001 (3)	−0.007 (3)
C29	0.121 (5)	0.095 (4)	0.086 (4)	−0.027 (4)	0.033 (4)	−0.031 (4)
C30	0.100 (4)	0.082 (4)	0.053 (3)	−0.017 (3)	0.022 (3)	−0.017 (3)
C31	0.109 (5)	0.070 (4)	0.084 (4)	0.010 (3)	−0.003 (4)	0.005 (3)
C32	0.144 (6)	0.083 (4)	0.137 (6)	−0.017 (4)	−0.003 (5)	−0.026 (4)
N1	0.094 (3)	0.067 (3)	0.054 (3)	−0.006 (2)	0.009 (2)	−0.026 (2)
N2	0.112 (3)	0.075 (3)	0.051 (3)	−0.016 (2)	0.025 (2)	−0.001 (2)
N3	0.124 (4)	0.074 (3)	0.053 (3)	−0.024 (3)	0.029 (3)	−0.001 (2)
N4	0.123 (4)	0.062 (3)	0.052 (3)	−0.014 (2)	0.023 (2)	−0.021 (2)
N5	0.046 (2)	0.047 (2)	0.060 (2)	−0.0098 (17)	−0.0047 (18)	−0.0043 (18)
N6	0.088 (3)	0.062 (3)	0.068 (3)	−0.011 (2)	0.006 (2)	−0.020 (2)
N7	0.078 (3)	0.073 (3)	0.052 (3)	0.001 (2)	0.005 (2)	−0.003 (2)
N8	0.101 (4)	0.087 (3)	0.080 (3)	−0.022 (3)	0.013 (3)	−0.018 (3)

Geometric parameters (Å, º) top

Ni1—S1	2.1796 (11)	C17—H17	0.9300
Ni1—S2	2.1668 (11)	C18—H18	0.9300
Ni1—S4	2.1703 (11)	C19—C20	1.485 (6)
Ni1—S3	2.1760 (11)	C19—N5	1.515 (5)
S1—C2	1.740 (4)	C19—H19A	0.9700
S2—C3	1.723 (4)	C19—H19B	0.9700
S3—C6	1.731 (4)	C20—H20A	0.9600
S4—C7	1.730 (4)	C20—H20B	0.9600
C2—C3	1.362 (5)	C20—H20C	0.9600
C2—C1	1.431 (5)	C21—N7	1.331 (5)
C1—N1	1.149 (4)	C21—C22	1.367 (6)
C3—C4	1.422 (5)	C21—H21	0.9300
C4—N2	1.148 (5)	C22—C23	1.398 (5)
C6—C7	1.362 (5)	C22—H22	0.9300
C6—C5	1.440 (5)	C23—C24	1.388 (5)
C5—N3	1.143 (5)	C23—C26	1.496 (6)
C7—C8	1.434 (5)	C24—C25	1.362 (6)
C8—N4	1.145 (5)	C24—H24	0.9300
C9—N5	1.346 (5)	C25—N7	1.350 (5)
C9—C10	1.374 (5)	C25—H25	0.9300
C9—H9	0.9300	C26—C27	1.390 (5)
C10—C11	1.395 (5)	C26—C30	1.390 (5)
C10—H10	0.9300	C27—C28	1.374 (6)
C11—C12	1.378 (5)	C27—H27	0.9300
C11—C14	1.498 (5)	C28—N8	1.326 (5)
C12—C13	1.366 (5)	C28—H28	0.9300
C12—H12	0.9300	C29—N8	1.317 (6)
C13—N5	1.338 (5)	C29—C30	1.394 (6)
C13—H13	0.9300	C29—H29	0.9300
C14—C18	1.370 (5)	C30—H30	0.9300
C14—C15	1.379 (5)	C31—C32	1.468 (7)
C15—C16	1.380 (6)	C31—N7	1.519 (6)
C15—H15	0.9300	C31—H31A	0.9700
C16—N6	1.316 (5)	C31—H31B	0.9700
C16—H16	0.9300	C32—H32A	0.9600
C17—N6	1.346 (5)	C32—H32B	0.9600
C17—C18	1.388 (6)	C32—H32C	0.9600

S2—Ni1—S4	87.25 (4)	C20—C19—H19B	108.9
S2—Ni1—S3	175.30 (5)	N5—C19—H19B	108.9
S4—Ni1—S3	91.97 (4)	H19A—C19—H19B	107.7
S2—Ni1—S1	92.18 (4)	C19—C20—H20A	109.5
S4—Ni1—S1	175.51 (5)	C19—C20—H20B	109.5
S3—Ni1—S1	88.96 (4)	H20A—C20—H20B	109.5
C2—S1—Ni1	102.87 (13)	C19—C20—H20C	109.5
C3—S2—Ni1	103.49 (13)	H20A—C20—H20C	109.5
C6—S3—Ni1	103.08 (13)	H20B—C20—H20C	109.5
C7—S4—Ni1	103.58 (13)	N7—C21—C22	121.2 (4)
C3—C2—C1	121.6 (3)	N7—C21—H21	119.4
C3—C2—S1	120.4 (3)	C22—C21—H21	119.4
C1—C2—S1	117.9 (3)	C21—C22—C23	121.3 (4)
N1—C1—C2	179.2 (5)	C21—C22—H22	119.4
C2—C3—C4	121.5 (3)	C23—C22—H22	119.4
C2—C3—S2	121.0 (3)	C24—C23—C22	115.5 (4)
C4—C3—S2	117.5 (3)	C24—C23—C26	122.8 (4)
N2—C4—C3	177.3 (5)	C22—C23—C26	121.7 (4)
C7—C6—C5	121.0 (3)	C25—C24—C23	121.6 (4)
C7—C6—S3	121.0 (3)	C25—C24—H24	119.2
C5—C6—S3	118.0 (3)	C23—C24—H24	119.2
N3—C5—C6	177.9 (5)	N7—C25—C24	120.8 (5)
C6—C7—C8	121.7 (3)	N7—C25—H25	119.6
C6—C7—S4	120.3 (3)	C24—C25—H25	119.6
C8—C7—S4	118.0 (3)	C27—C26—C30	117.4 (4)
N4—C8—C7	179.4 (5)	C27—C26—C23	122.0 (4)
N5—C9—C10	120.8 (4)	C30—C26—C23	120.6 (4)
N5—C9—H9	119.6	C28—C27—C26	118.4 (5)
C10—C9—H9	119.6	C28—C27—H27	120.8
C9—C10—C11	121.6 (4)	C26—C27—H27	120.8
C9—C10—H10	119.2	N8—C28—C27	125.9 (5)
C11—C10—H10	119.2	N8—C28—H28	117.0
C12—C11—C10	115.7 (4)	C27—C28—H28	117.0
C12—C11—C14	122.7 (3)	N8—C29—C30	125.5 (5)
C10—C11—C14	121.6 (3)	N8—C29—H29	117.3
C13—C12—C11	121.0 (4)	C30—C29—H29	117.3
C13—C12—H12	119.5	C26—C30—C29	118.0 (5)
C11—C12—H12	119.5	C26—C30—H30	121.0
N5—C13—C12	122.4 (4)	C29—C30—H30	121.0
N5—C13—H13	118.8	C32—C31—N7	111.8 (4)
C12—C13—H13	118.8	C32—C31—H31A	109.3
C18—C14—C15	117.0 (4)	N7—C31—H31A	109.3
C18—C14—C11	120.9 (4)	C32—C31—H31B	109.3
C15—C14—C11	122.0 (4)	N7—C31—H31B	109.3
C14—C15—C16	119.7 (4)	H31A—C31—H31B	107.9
C14—C15—H15	120.1	C31—C32—H32A	109.5
C16—C15—H15	120.1	C31—C32—H32B	109.5
N6—C16—C15	124.8 (4)	H32A—C32—H32B	109.5
N6—C16—H16	117.6	C31—C32—H32C	109.5
C15—C16—H16	117.6	H32A—C32—H32C	109.5
N6—C17—C18	124.4 (4)	H32B—C32—H32C	109.5
N6—C17—H17	117.8	C13—N5—C9	118.5 (4)
C18—C17—H17	117.8	C13—N5—C19	117.0 (3)
C14—C18—C17	119.1 (4)	C9—N5—C19	124.5 (4)
C14—C18—H18	120.5	C16—N6—C17	114.9 (4)
C17—C18—H18	120.5	C21—N7—C25	119.6 (4)
C20—C19—N5	113.4 (4)	C21—N7—C31	120.4 (4)
C20—C19—H19A	108.9	C25—N7—C31	120.0 (4)
N5—C19—H19A	108.9	C29—N8—C28	114.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···S2ⁱ	0.93	2.78	3.549 (4)	141
C17—H17···N4ⁱ	0.93	2.55	3.441 (6)	161
C21—H21···N3ⁱⁱ	0.93	2.42	3.342 (6)	170
C22—H22···N4ⁱⁱ	0.93	2.50	3.372 (5)	156
C24—H24···N2	0.93	2.46	3.364 (5)	163
C25—H25···N1	0.93	2.52	3.411 (6)	161
C27—H27···N4ⁱⁱ	0.93	2.58	3.498 (6)	172
C30—H30···N2	0.93	2.60	3.526 (6)	176

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z+1.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₃N₂)[Ni(C₄N₂S₂)₂]
M_r	709.58
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.4505 (13), 12.793 (2), 17.745 (3)
α, β, γ (°)	78.664 (2), 86.558 (2), 80.344 (2)
V (Å³)	1634.2 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.808, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	14954, 7631, 3616
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.128, 0.97
No. of reflections	7631
No. of parameters	408
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.37

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···S2ⁱ	0.93	2.78	3.549 (4)	141
C17—H17···N4ⁱ	0.93	2.55	3.441 (6)	161
C21—H21···N3ⁱⁱ	0.93	2.42	3.342 (6)	170
C22—H22···N4ⁱⁱ	0.93	2.50	3.372 (5)	156
C24—H24···N2	0.93	2.46	3.364 (5)	163
C25—H25···N1	0.93	2.52	3.411 (6)	161
C27—H27···N4ⁱⁱ	0.93	2.58	3.498 (6)	172
C30—H30···N2	0.93	2.60	3.526 (6)	176

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z+1.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University of Technology, for support.

References

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