1-(4-Cyano­benz­yl)-3,5-dimethyl­pyridinium bis­(benzene-1,2-dithiol­ato)nickelate(III)

Dong, Y.-J.; Kong, X.-J.

doi:10.1107/S1600536811004971

metal-organic compounds

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Volume 67| Part 3| March 2011| Page m339

doi:10.1107/S1600536811004971

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1-(4-Cyanobenzyl)-3,5-dimethylpyridinium bis(benzene-1,2-dithiolato)nickelate(III)

Yan-Jie Dong ^a and Xue-Jun Kong ^a ^*

^aSchool of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246003, People's Republic of China
^*Correspondence e-mail: liugx@aqtc.edu.cn

(Received 28 January 2011; accepted 9 February 2011; online 16 February 2011)

The asymmetric unit of the title compound, (C₁₅H₁₅N₂)[Ni(C₆H₄S₂)₂], contains half each of two independent centrosymmetric anions and a single cation in a general position. The Ni^III ions are coordinated by four S atoms in a square-planar geometry. The anions exhibit two packing modes, viz. stacked along the a axis in a face-to-face fashion with an alternate arrangement of anions and cations, and stacked in a side-by-side fashion, forming ribbons parallel to (011).

Related literature

For general background to molecular-based magnetic materials, see: Jones (1997 ); Akutagawa et al. (2009 ). For the role played by the size and shape of the counter-cations in determining the ground-state properties of the resulting materials, see: Ren et al. (2003 ). For related structures, see: Sellmann et al. (1991 ); Xie et al. (2002 , 2003 ); Ren et al. (2002 ).

Experimental

Crystal data

(C₁₅H₁₅N₂)[Ni(C₆H₄S₂)₂]
M_r = 562.42
Triclinic, $[P \overline 1]$
a = 7.1517 (7) Å
b = 12.8190 (13) Å
c = 15.3294 (16) Å
α = 69.774 (1)°
β = 77.740 (1)°
γ = 87.721 (1)°
V = 1287.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 296 K
0.36 × 0.30 × 0.28 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.694, T_max = 0.749
6530 measured reflections
4530 independent reflections
3728 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 1.02
4530 reflections
312 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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/S1600536811004971/rz2554sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004971/rz2554Isup2.hkl

checkCIF report

Comment top

Molecular solids with particular functionality are continuously paid much attention by chemists and physicists in the field of materials science (Jones, 1997). The preparation of new molecular based spin-bearing systems, among others, has been pursued from the viewpoint of materials/physical organic chemistry to develop novel molecular-based magnetic materials (Akutagawa et al., 2009). In our previous research using benzylpyridinium derivatives ([RBzPy]⁺) as the counter-cation of [M(mnt)₂]^- (where M = Ni, Pd and Pt and mnt^2- = maleodinitriledithiolate), a series of ion-pair compounds with segregated columnar stacks of cations and anions has been prepared (Ren et al., 2002; Ren et al., 2003; Xie et al., 2002). The quasi one-dimensional magnetic nature of these compounds was attributed to intermolecular orbital interactions within the anionic columns. As an extension of our work on this series of complexes, we report here the crystal structure of the title compound, (I).

The asymmetric unit of (I) contains half each of two independent centrosymmetric [Ni(C₆H₄S₂)₂]^- anions and one (C₁₅H₁₅N₂)⁺ cation. In the anions, the nickel(III) ions are coordinated by four S atoms in a square-planar geometry; the Ni—S bonds and S—Ni—S angles are in agreement with the corresponding values found in analogous complexes (Sellmann et al., 1991; Xie et al., 2003). The centrosymmetric [Ni(C₆H₄S₂)₂]^- anions are almost planar. The dihedral angle between the two benzene rings of the cation is 86.49 (6)°. In the crystal structure, the packing of the two anions is different (Fig. 2). The Ni1-containing anions stack in a side-by-side fashion, forming one-dimensional ribbons parallel to (011); the shortest distance between the adjacent nickel(III) ions is 7.152 (6) Å. The Ni2-containing anions stack in a face-to-face fashion along the a axis with an alternating arrangement of [Ni(C₆H₄S₂)₂]^- anions and [C₁₅H₁₅N₂]⁺ cations such that the pyridine ring of the cation lies above the benzene ring of the anion. The shortest distance between adjacent nickel(III) ions is also 7.152 (6) Å. A Ni···Ni distance of 8.155 (9)Å is found between adjacent Ni1-containing and Ni2-containing anions.

Related literature top

For general background to molecular-based magnetic materials, see: Jones (1997); Akutagawa et al. (2009). For the role played by the size and shape of the counter-cations in determining the ground-state properties of the resulting materials, see: Ren et al. (2003). For related structures, see: Sellmann et al. (1991); Xie et al. (2002, 2003); Ren et al. (2002).

Experimental top

Benzene-1,2-dithiol (142 mg, 1.0 mmol) was added to a solution of sodium metal (46 mg, 2.0 mmol) in absolute ethanol (25 ml), under a nitrogen atmosphere at room temperature. A solution of NiCl₂.6H₂O (120 mg, 0.5 mmol) in ethanol (25 ml) was added, resulting in the mixture turning a muddy red-brown colour. Following this, [CNBzPy(CH₃)₂]Br (304 mg, 1.0 mmol) was added and the mixture allowed to stand with stirring for 1 h, and then stirred for an additional 24 h in air. The colour of the mixture gradually turned green, indicating oxidation from a dianionic species to the more stable monoanionic form. The precipitate was washed with absolute ethanol and diethyl ether and then dried. The crude product was recrystallized twice from dichloromethane to give the title compound (yield 198 mg, 54%).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (A) 1-x, 1-y, 1-z; (B) 1-x, 2-y, -z.
	Fig. 2. Packing diagram of (I) viewed along the a axis.

1-(4-Cyanobenzyl)-3,5-dimethylpyridinium bis(benzene-1,2-dithiolato)nickelate(III) top

Crystal data top

(C₁₅H₁₅N₂)[Ni(C₆H₄S₂)₂]	Z = 2
M_r = 562.42	F(000) = 582
Triclinic, P1	D_x = 1.450 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1517 (7) Å	Cell parameters from 3577 reflections
b = 12.8190 (13) Å	θ = 2.6–27.0°
c = 15.3294 (16) Å	µ = 1.10 mm⁻¹
α = 69.774 (1)°	T = 296 K
β = 77.740 (1)°	Block, dark green
γ = 87.721 (1)°	0.36 × 0.30 × 0.28 mm
V = 1287.8 (2) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4530 independent reflections
Radiation source: sealed tube	3728 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
T_min = 0.694, T_max = 0.749	k = −12→15
6530 measured reflections	l = −18→15

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0581P)²] where P = (F_o² + 2F_c²)/3
4530 reflections	(Δ/σ)_max = 0.001
312 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

(C₁₅H₁₅N₂)[Ni(C₆H₄S₂)₂]	γ = 87.721 (1)°
M_r = 562.42	V = 1287.8 (2) Å³
Triclinic, P1	Z = 2
a = 7.1517 (7) Å	Mo Kα radiation
b = 12.8190 (13) Å	µ = 1.10 mm⁻¹
c = 15.3294 (16) Å	T = 296 K
α = 69.774 (1)°	0.36 × 0.30 × 0.28 mm
β = 77.740 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4530 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3728 reflections with I > 2σ(I)
T_min = 0.694, T_max = 0.749	R_int = 0.042
6530 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	Δρ_max = 0.25 e Å⁻³
4530 reflections	Δρ_min = −0.39 e Å⁻³
312 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	0.5000	0.5000	0.5000	0.05051 (14)
Ni2	0.5000	1.0000	0.0000	0.06279 (16)
S1	0.38833 (9)	0.43210 (6)	0.41084 (5)	0.06354 (19)
S2	0.78410 (8)	0.44650 (5)	0.45826 (4)	0.05774 (17)
S3	0.52163 (10)	0.85288 (5)	0.11833 (6)	0.0751 (2)
S4	0.44027 (9)	1.09946 (6)	0.09034 (6)	0.0758 (2)
C1	0.5817 (3)	0.3696 (2)	0.36074 (16)	0.0563 (6)
C2	0.5622 (4)	0.3134 (2)	0.29922 (18)	0.0710 (7)
H2	0.4429	0.3068	0.2862	0.085*
C3	0.7171 (4)	0.2681 (3)	0.2582 (2)	0.0800 (8)
H3	0.7024	0.2306	0.2177	0.096*
C4	0.8974 (4)	0.2777 (2)	0.2765 (2)	0.0779 (8)
H4	1.0026	0.2472	0.2480	0.093*
C5	0.9189 (4)	0.3322 (2)	0.33656 (18)	0.0674 (7)
H5	1.0394	0.3392	0.3482	0.081*
C6	0.7616 (3)	0.37727 (19)	0.38061 (15)	0.0544 (5)
C7	0.4721 (4)	0.8937 (2)	0.2174 (2)	0.0750 (8)
C8	0.4671 (4)	0.8185 (3)	0.3089 (3)	0.0933 (10)
H8	0.4884	0.7438	0.3178	0.112*
C9	0.4315 (5)	0.8526 (4)	0.3851 (3)	0.1155 (14)
H9	0.4298	0.8014	0.4456	0.139*
C10	0.3978 (5)	0.9626 (5)	0.3733 (3)	0.1139 (14)
H10	0.3753	0.9851	0.4261	0.137*
C11	0.3969 (4)	1.0402 (3)	0.2847 (3)	0.0971 (10)
H11	0.3712	1.1140	0.2779	0.116*
C12	0.4356 (3)	1.0061 (2)	0.2045 (2)	0.0734 (7)
C13	0.7251 (6)	0.5985 (3)	−0.0472 (2)	0.0964 (10)
C14	0.8167 (5)	0.6096 (2)	0.0246 (2)	0.0708 (7)
C15	1.0079 (5)	0.6423 (2)	0.0003 (2)	0.0809 (8)
H15	1.0773	0.6544	−0.0612	0.097*
C16	1.0958 (4)	0.6572 (2)	0.06717 (19)	0.0723 (7)
H16	1.2245	0.6796	0.0505	0.087*
C17	0.9938 (4)	0.63901 (18)	0.15919 (17)	0.0571 (6)
C18	0.8028 (4)	0.60457 (19)	0.18304 (18)	0.0614 (6)
H18	0.7338	0.5916	0.2447	0.074*
C19	0.7138 (4)	0.5892 (2)	0.1172 (2)	0.0713 (7)
H19	0.5858	0.5654	0.1343	0.086*
C20	1.0872 (4)	0.65782 (19)	0.23205 (18)	0.0632 (6)
H20A	1.0577	0.5944	0.2906	0.076*
H20B	1.2250	0.6635	0.2093	0.076*
C21	0.9853 (4)	0.7593 (2)	0.34242 (17)	0.0622 (6)
H21	0.9952	0.6936	0.3918	0.075*
C22	0.9338 (4)	0.8545 (2)	0.36168 (17)	0.0648 (7)
C23	0.9208 (3)	0.9501 (2)	0.28705 (17)	0.0597 (6)
H23	0.8853	1.0150	0.2995	0.072*
C24	0.9592 (3)	0.95288 (18)	0.19364 (15)	0.0512 (5)
C25	1.0102 (3)	0.85467 (18)	0.17933 (15)	0.0509 (5)
H25	1.0374	0.8532	0.1177	0.061*
C26	0.8910 (5)	0.8506 (3)	0.46412 (19)	0.0950 (10)
H26A	0.8574	0.9231	0.4661	0.142*
H26B	1.0023	0.8277	0.4907	0.142*
H26C	0.7864	0.7985	0.5004	0.142*
C27	0.9439 (3)	1.0558 (2)	0.11151 (17)	0.0617 (6)
H27A	1.0669	1.0761	0.0692	0.093*
H27B	0.9012	1.1153	0.1346	0.093*
H27C	0.8536	1.0422	0.0781	0.093*
N1	0.6563 (6)	0.5905 (3)	−0.1048 (2)	0.1353 (14)
N2	1.0217 (3)	0.76078 (14)	0.25195 (12)	0.0528 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0451 (2)	0.0580 (3)	0.0509 (2)	−0.00616 (18)	−0.01511 (17)	−0.01801 (19)
Ni2	0.0386 (2)	0.0489 (3)	0.0962 (4)	0.00137 (17)	−0.0198 (2)	−0.0160 (2)
S1	0.0478 (3)	0.0842 (4)	0.0722 (4)	−0.0036 (3)	−0.0202 (3)	−0.0387 (3)
S2	0.0473 (3)	0.0721 (4)	0.0593 (3)	−0.0029 (3)	−0.0192 (3)	−0.0244 (3)
S3	0.0622 (4)	0.0528 (4)	0.1011 (5)	0.0018 (3)	−0.0223 (4)	−0.0121 (3)
S4	0.0527 (4)	0.0594 (4)	0.1193 (6)	0.0036 (3)	−0.0267 (4)	−0.0308 (4)
C1	0.0559 (14)	0.0622 (14)	0.0501 (12)	−0.0090 (11)	−0.0119 (10)	−0.0171 (11)
C2	0.0641 (16)	0.0864 (18)	0.0730 (16)	−0.0116 (14)	−0.0170 (13)	−0.0376 (15)
C3	0.083 (2)	0.090 (2)	0.0773 (18)	−0.0109 (16)	−0.0060 (15)	−0.0465 (16)
C4	0.0702 (18)	0.088 (2)	0.0779 (18)	0.0033 (15)	−0.0050 (14)	−0.0381 (16)
C5	0.0548 (15)	0.0792 (18)	0.0669 (15)	0.0004 (12)	−0.0127 (12)	−0.0235 (14)
C6	0.0538 (13)	0.0553 (13)	0.0505 (12)	−0.0052 (10)	−0.0133 (10)	−0.0118 (10)
C7	0.0439 (14)	0.0775 (19)	0.095 (2)	−0.0151 (12)	−0.0167 (13)	−0.0157 (16)
C8	0.0681 (19)	0.099 (2)	0.095 (2)	−0.0250 (17)	−0.0201 (17)	−0.006 (2)
C9	0.082 (2)	0.150 (4)	0.098 (3)	−0.045 (3)	−0.019 (2)	−0.018 (3)
C10	0.077 (2)	0.165 (4)	0.102 (3)	−0.036 (3)	−0.007 (2)	−0.052 (3)
C11	0.0607 (18)	0.113 (3)	0.129 (3)	−0.0204 (17)	−0.0139 (19)	−0.057 (3)
C12	0.0415 (13)	0.0823 (19)	0.096 (2)	−0.0117 (12)	−0.0158 (13)	−0.0276 (16)
C13	0.131 (3)	0.077 (2)	0.090 (2)	0.0043 (19)	−0.047 (2)	−0.0267 (18)
C14	0.095 (2)	0.0486 (14)	0.0756 (17)	0.0042 (13)	−0.0351 (16)	−0.0201 (13)
C15	0.113 (3)	0.0626 (17)	0.0636 (16)	−0.0043 (16)	−0.0130 (16)	−0.0199 (13)
C16	0.0724 (18)	0.0616 (16)	0.0770 (18)	−0.0079 (13)	−0.0066 (14)	−0.0209 (14)
C17	0.0669 (15)	0.0398 (12)	0.0625 (14)	0.0040 (10)	−0.0202 (12)	−0.0113 (10)
C18	0.0655 (15)	0.0529 (14)	0.0629 (14)	0.0007 (11)	−0.0178 (12)	−0.0137 (11)
C19	0.0727 (17)	0.0596 (15)	0.0846 (19)	−0.0003 (13)	−0.0283 (15)	−0.0213 (14)
C20	0.0626 (15)	0.0515 (14)	0.0749 (16)	0.0057 (11)	−0.0262 (13)	−0.0145 (12)
C21	0.0633 (15)	0.0659 (16)	0.0537 (14)	−0.0124 (12)	−0.0227 (11)	−0.0084 (12)
C22	0.0615 (15)	0.0786 (18)	0.0563 (14)	−0.0147 (13)	−0.0149 (12)	−0.0226 (14)
C23	0.0522 (14)	0.0626 (15)	0.0682 (15)	−0.0056 (11)	−0.0131 (11)	−0.0265 (13)
C24	0.0393 (11)	0.0540 (13)	0.0609 (13)	−0.0056 (9)	−0.0159 (10)	−0.0168 (11)
C25	0.0479 (12)	0.0544 (13)	0.0508 (12)	−0.0033 (10)	−0.0187 (10)	−0.0132 (10)
C26	0.114 (3)	0.114 (3)	0.0588 (16)	−0.019 (2)	−0.0142 (16)	−0.0323 (17)
C27	0.0556 (14)	0.0527 (13)	0.0729 (15)	0.0009 (10)	−0.0198 (12)	−0.0130 (12)
N1	0.186 (4)	0.134 (3)	0.112 (2)	−0.004 (3)	−0.083 (3)	−0.044 (2)
N2	0.0505 (11)	0.0507 (11)	0.0562 (11)	−0.0044 (8)	−0.0207 (9)	−0.0109 (9)

Geometric parameters (Å, º) top

Ni1—S1	2.1459 (6)	C13—C14	1.443 (4)
Ni1—S1ⁱ	2.1459 (6)	C14—C15	1.380 (4)
Ni1—S2	2.1560 (6)	C14—C19	1.392 (4)
Ni1—S2ⁱ	2.1560 (6)	C15—C16	1.379 (4)
Ni2—S3ⁱⁱ	2.1451 (7)	C15—H15	0.9300
Ni2—S3	2.1451 (7)	C16—C17	1.388 (4)
Ni2—S4ⁱⁱ	2.1569 (8)	C16—H16	0.9300
Ni2—S4	2.1569 (8)	C17—C18	1.385 (3)
S1—C1	1.741 (3)	C17—C20	1.506 (3)
S2—C6	1.747 (2)	C18—C19	1.372 (3)
S3—C7	1.735 (3)	C18—H18	0.9300
S4—C12	1.739 (3)	C19—H19	0.9300
C1—C6	1.399 (3)	C20—N2	1.491 (3)
C1—C2	1.400 (3)	C20—H20A	0.9700
C2—C3	1.366 (4)	C20—H20B	0.9700
C2—H2	0.9300	C21—N2	1.349 (3)
C3—C4	1.395 (4)	C21—C22	1.370 (4)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.368 (4)	C22—C23	1.373 (4)
C4—H4	0.9300	C22—C26	1.518 (4)
C5—C6	1.397 (4)	C23—C24	1.388 (3)
C5—H5	0.9300	C23—H23	0.9300
C7—C8	1.395 (4)	C24—C25	1.374 (3)
C7—C12	1.407 (4)	C24—C27	1.496 (3)
C8—C9	1.356 (5)	C25—N2	1.341 (3)
C8—H8	0.9300	C25—H25	0.9300
C9—C10	1.377 (6)	C26—H26A	0.9600
C9—H9	0.9300	C26—H26B	0.9600
C10—C11	1.379 (5)	C26—H26C	0.9600
C10—H10	0.9300	C27—H27A	0.9600
C11—C12	1.414 (4)	C27—H27B	0.9600
C11—H11	0.9300	C27—H27C	0.9600
C13—N1	1.133 (4)

S1—Ni1—S1ⁱ	180.00 (3)	C15—C14—C13	119.2 (3)
S1—Ni1—S2	92.04 (2)	C19—C14—C13	120.8 (3)
S1ⁱ—Ni1—S2	87.97 (2)	C16—C15—C14	119.9 (3)
S1—Ni1—S2ⁱ	87.97 (2)	C16—C15—H15	120.0
S1ⁱ—Ni1—S2ⁱ	92.03 (2)	C14—C15—H15	120.0
S2—Ni1—S2ⁱ	180.0	C15—C16—C17	120.5 (3)
S3ⁱⁱ—Ni2—S3	180.00 (4)	C15—C16—H16	119.8
S3ⁱⁱ—Ni2—S4ⁱⁱ	91.75 (3)	C17—C16—H16	119.8
S3—Ni2—S4ⁱⁱ	88.25 (3)	C18—C17—C16	119.0 (2)
S3ⁱⁱ—Ni2—S4	88.25 (3)	C18—C17—C20	120.1 (2)
S3—Ni2—S4	91.75 (3)	C16—C17—C20	120.9 (2)
S4ⁱⁱ—Ni2—S4	180.00 (2)	C19—C18—C17	121.1 (2)
C1—S1—Ni1	104.89 (8)	C19—C18—H18	119.5
C6—S2—Ni1	104.81 (8)	C17—C18—H18	119.5
C7—S3—Ni2	105.49 (11)	C18—C19—C14	119.5 (3)
C12—S4—Ni2	104.82 (11)	C18—C19—H19	120.3
C6—C1—C2	119.0 (2)	C14—C19—H19	120.3
C6—C1—S1	119.51 (18)	N2—C20—C17	112.08 (18)
C2—C1—S1	121.47 (19)	N2—C20—H20A	109.2
C3—C2—C1	120.5 (3)	C17—C20—H20A	109.2
C3—C2—H2	119.7	N2—C20—H20B	109.2
C1—C2—H2	119.7	C17—C20—H20B	109.2
C2—C3—C4	120.5 (3)	H20A—C20—H20B	107.9
C2—C3—H3	119.8	N2—C21—C22	120.2 (2)
C4—C3—H3	119.8	N2—C21—H21	119.9
C5—C4—C3	119.7 (3)	C22—C21—H21	119.9
C5—C4—H4	120.1	C21—C22—C23	118.4 (2)
C3—C4—H4	120.1	C21—C22—C26	119.2 (3)
C4—C5—C6	120.7 (2)	C23—C22—C26	122.3 (3)
C4—C5—H5	119.7	C22—C23—C24	122.0 (2)
C6—C5—H5	119.7	C22—C23—H23	119.0
C5—C6—C1	119.5 (2)	C24—C23—H23	119.0
C5—C6—S2	121.75 (19)	C25—C24—C23	116.6 (2)
C1—C6—S2	118.69 (19)	C25—C24—C27	120.6 (2)
C8—C7—C12	119.3 (3)	C23—C24—C27	122.8 (2)
C8—C7—S3	122.0 (3)	N2—C25—C24	121.7 (2)
C12—C7—S3	118.7 (2)	N2—C25—H25	119.1
C9—C8—C7	121.0 (4)	C24—C25—H25	119.1
C9—C8—H8	119.5	C22—C26—H26A	109.5
C7—C8—H8	119.5	C22—C26—H26B	109.5
C8—C9—C10	120.2 (4)	H26A—C26—H26B	109.5
C8—C9—H9	119.9	C22—C26—H26C	109.5
C10—C9—H9	119.9	H26A—C26—H26C	109.5
C9—C10—C11	121.3 (4)	H26B—C26—H26C	109.5
C9—C10—H10	119.4	C24—C27—H27A	109.5
C11—C10—H10	119.4	C24—C27—H27B	109.5
C10—C11—C12	119.1 (4)	H27A—C27—H27B	109.5
C10—C11—H11	120.4	C24—C27—H27C	109.5
C12—C11—H11	120.4	H27A—C27—H27C	109.5
C7—C12—C11	119.0 (3)	H27B—C27—H27C	109.5
C7—C12—S4	119.2 (2)	C25—N2—C21	121.1 (2)
C11—C12—S4	121.8 (3)	C25—N2—C20	119.51 (19)
N1—C13—C14	178.7 (4)	C21—N2—C20	119.3 (2)
C15—C14—C19	120.0 (2)

S2—Ni1—S1—C1	2.24 (8)	C8—C7—C12—S4	−179.55 (19)
S2ⁱ—Ni1—S1—C1	−177.76 (8)	S3—C7—C12—S4	0.3 (3)
S1—Ni1—S2—C6	−1.49 (8)	C10—C11—C12—C7	0.6 (4)
S1ⁱ—Ni1—S2—C6	178.51 (8)	C10—C11—C12—S4	−179.1 (2)
S4ⁱⁱ—Ni2—S3—C7	−177.93 (9)	Ni2—S4—C12—C7	1.4 (2)
S4—Ni2—S3—C7	2.07 (9)	Ni2—S4—C12—C11	−179.0 (2)
S3ⁱⁱ—Ni2—S4—C12	178.07 (8)	C19—C14—C15—C16	−1.4 (4)
S3—Ni2—S4—C12	−1.93 (8)	C13—C14—C15—C16	177.7 (3)
Ni1—S1—C1—C6	−2.8 (2)	C14—C15—C16—C17	0.3 (4)
Ni1—S1—C1—C2	178.49 (18)	C15—C16—C17—C18	0.7 (4)
C6—C1—C2—C3	−0.9 (4)	C15—C16—C17—C20	−178.4 (2)
S1—C1—C2—C3	177.8 (2)	C16—C17—C18—C19	−0.5 (4)
C1—C2—C3—C4	−0.4 (4)	C20—C17—C18—C19	178.6 (2)
C2—C3—C4—C5	0.5 (5)	C17—C18—C19—C14	−0.6 (4)
C3—C4—C5—C6	0.7 (4)	C15—C14—C19—C18	1.5 (4)
C4—C5—C6—C1	−2.0 (4)	C13—C14—C19—C18	−177.5 (3)
C4—C5—C6—S2	179.6 (2)	C18—C17—C20—N2	−72.8 (3)
C2—C1—C6—C5	2.1 (3)	C16—C17—C20—N2	106.3 (3)
S1—C1—C6—C5	−176.67 (18)	N2—C21—C22—C23	−0.1 (3)
C2—C1—C6—S2	−179.45 (18)	N2—C21—C22—C26	179.2 (2)
S1—C1—C6—S2	1.8 (3)	C21—C22—C23—C24	−0.3 (3)
Ni1—S2—C6—C5	178.62 (18)	C26—C22—C23—C24	−179.7 (2)
Ni1—S2—C6—C1	0.16 (19)	C22—C23—C24—C25	0.3 (3)
Ni2—S3—C7—C8	178.04 (19)	C22—C23—C24—C27	179.3 (2)
Ni2—S3—C7—C12	−1.8 (2)	C23—C24—C25—N2	0.2 (3)
C12—C7—C8—C9	−1.4 (4)	C27—C24—C25—N2	−178.85 (19)
S3—C7—C8—C9	178.8 (2)	C24—C25—N2—C21	−0.7 (3)
C7—C8—C9—C10	0.6 (5)	C24—C25—N2—C20	−177.0 (2)
C8—C9—C10—C11	0.8 (6)	C22—C21—N2—C25	0.6 (3)
C9—C10—C11—C12	−1.4 (5)	C22—C21—N2—C20	176.9 (2)
C8—C7—C12—C11	0.8 (4)	C17—C20—N2—C25	−44.8 (3)
S3—C7—C12—C11	−179.4 (2)	C17—C20—N2—C21	138.9 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	(C₁₅H₁₅N₂)[Ni(C₆H₄S₂)₂]
M_r	562.42
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.1517 (7), 12.8190 (13), 15.3294 (16)
α, β, γ (°)	69.774 (1), 77.740 (1), 87.721 (1)
V (Å³)	1287.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.36 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.694, 0.749
No. of measured, independent and observed [I > 2σ(I)] reflections	6530, 4530, 3728
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.02
No. of reflections	4530
No. of parameters	312
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.39

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 20971004), the Key Project of Chinese Ministry of Education (No. 210102) and the Natural Science Foundation of Anhui Province (No. 11040606M45).

References

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