1-(3,4-Dichloro­benz­yl)pyridinium bis­(2-sulfanyl­idene-1,3-dithiole-4,5-dithiol­ato-κ2S,S′)nickelate(III)

Liu, G.-X.

doi:10.1107/S160053681104267X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1570

doi:10.1107/S160053681104267X

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1-(3,4-Dichlorobenzyl)pyridinium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-κ²S,S′)nickelate(III)

Guang-Xiang Liu ^a ^*

^aSchool of Biochemical and Environmental Engineering, Nanjing Xiaozhuang University, Nanjing 211171, People's Republic of China
^*Correspondence e-mail: njuliugx@gmail.com

(Received 8 October 2011; accepted 14 October 2011; online 22 October 2011)

The title compound, (C₁₂H₁₀Cl₂N)[Ni(C₃S₅)₂], is an ion-pair complex consisting of 1-(3,4-dichlorobenzyl)pyridinium cations and [Ni(dmit)₂] anions (dmit = 2-sulfanylidene-1,3-dithiole-4,5-dithiolate). In the anion, the Ni^III ion exhibits a square-planar coordination involving four S atoms from two dmit ligands. In the crystal, weak S⋯S [3.368 (2) and 3.482 (3) Å], Ni⋯S [3.680 (2) Å] and Cl⋯S [3.491 (2) Å] interactions and C—H⋯S hydrogen bonds lead to a three-dimensional supramolecular network.

Related literature

For general background to the network topologies and applications of bis(dithiolate)–metal complexes, see: Cassoux (1999 ). For the synthesis, structures and properties of related complexes containing dmit ligands, see: Akutagawa & Nakamura (2000 ); Liu et al. (2010 ); Li et al. (2006 ); Zang et al. (2006 , 2009 ). For the synthesis of a starting material, see: Wang et al. (1998 ).

Experimental

Crystal data

(C₁₂H₁₀Cl₂N)[Ni(C₃S₅)₂]
M_r = 690.48
Triclinic, $[P \overline 1]$
a = 9.3711 (11) Å
b = 11.7210 (14) Å
c = 11.9640 (14) Å
α = 82.814 (1)°
β = 88.854 (1)°
γ = 76.644 (1)°
V = 1268.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.81 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.692, T_max = 0.761
9520 measured reflections
4692 independent reflections
4083 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.082
S = 1.04
4692 reflections
290 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯S10ⁱ	0.93	2.82	3.622 (3)	145
C18—H18⋯S1ⁱⁱ	0.93	2.79	3.708 (3)	168
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z.

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/S160053681104267X/rz2651sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104267X/rz2651Isup2.hkl

checkCIF report

Comment top

Extensive research has been focused on the synthesis and characterization of bis(dithiolate)-metal complexes and their analogues, due to their properties and potential applications as conducting, magnetic and non-linear optical (NLO) materials (Cassoux, 1999). 2-Thioxo-1,3-dithiole-4,5-dithiolate (dmit) metal complexes are in fact excellent building blocks employed for the construction of molecular magnetic materials (Li et al., 2006; Liu et al., 2010; Zang et al., 2006, 2009) apart from their well known electric conductivity as molecular conductors (Akutagawa & Nakamura, 2000). Herein the crystal structure of the title compound, a new ion-pair complex, is reported.

The title compound comprises [Ni(dmit)₂]^- anions and 1-(3,4-dichlorobenzyl)pyridinium cations (Fig. 1). The Ni ion adopts a square-planar geometry coordinated by four S atoms from two dmit ligands, with Ni—S bond lengths ranging from 2.1518 (7) to 2.1714 (7) Å. The [Ni(dmit)₂]^- anions are in a parallel arrangement, with S···S interactions ranging from 3.474 (3) to 3.547 (3) Å. Two neighbouring anions are parallel in a face-to-face fashion with the shortest Ni···S distance of 3.680 (2) Å (Ni1—S2ⁱ) [symmetry code: (i) -x, -y, -z], indicating the existence of the Ni···S interactions. Adjacent [Ni(dmit)₂]^- anions are associated together through such Ni···S interactions resulting in a dimer. The dimers are linked together through S9···S3ⁱⁱ and S9···S5ⁱⁱ [symmetry code: (ii) x, 1 + y, z] interactions forming a one-dimensional chain structure, as depicted in Fig. 2. The (C₁₂H₁₀Cl₂N)⁺ cation has a Λ-shaped conformation, and the dihedral angles formed by the C12/C13/N1 plane with the benzene and pyridinium rings are 85.29 (2) and 77.84 (2)°, respectively. Cations and the anions are linked by S···Cl interactions and C—H···S hydrogen bonds to generate a three-dimensional supramolecular structure (Fig. 3).

Related literature top

For general background to the network topologies and applications of bis(dithiolate)–metal complexes, see: Cassoux (1999). For the synthesis, structures and properties of related complexes containing dmit ligands, see: Akutagawa & Nakamura (2000); Liu et al. (2010); Li et al. (2006); Zang et al. (2006, 2009). For the synthesis of a starting material, see: Wang et al. (1998).

Experimental top

4,5-Di(thiobenzoyl)-1,3-dithiole-2-thione (812 mg, 2 mmol; Wang et al., 1998) was suspended in methanol (10 ml). Sodium methoxide in methanol (prepared form 184 mg of sodium in 10 ml of methanol) was added to the above mixture under argon atmosphere at room temperature from 30 min to give a dark red solution. To this solution, NiCl~2~.6H~2Õ (238 mg, 1 mmol) was added. After 30 min, a solution of I~2~ (127 mg, 1 mmol) and NaI (150 mg, 1 mmol) in methanol (20 ml) was added (the monoanionic [Ni(dmit)~2~]^-^ are obtained from the dianionic [Ni(dmit)~2~]^2-^ by I~3~^-^ oxidation). After another 10 min, a solution of 1-(3,4-dichlorobenzyl)pyridinium bromide [(DiClPy)Br] (317 mg, 1 mmol) in methanol (20 ml) was added to the reaction mixture. The solution was stirred for 30 min and cooled in a refrigerator overnight. The resultant dark green crystalline solid was collected by filtration, and purified by recrystallization using a mixed solution of acetonitrile and benzene (1:1 v/v).

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 cation and anion in [DiClPy][Ni(dmit)~2~], showing thermal ellipsoids drawn at the 30% probability level. Hydrogen atoms have been omitted for clarity.
	Fig. 2. The one-dimensional chain structure of [Ni(dmit)~2~]- anions through S···S and Ni···S contacts. Dashed lines indicate weak interactions.
	Fig. 3. Packing of [DiClPy][Ni(dmit)~2~] viewed along the b axis.

1-(3,4-Dichlorobenzyl)pyridinium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato- κ²S,S')nickelate(III) top

Crystal data top

(C₁₂H₁₀Cl₂N)[Ni(C₃S₅)₂]	Z = 2
M_r = 690.48	F(000) = 694
Triclinic, P1	D_x = 1.808 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3711 (11) Å	Cell parameters from 5426 reflections
b = 11.7210 (14) Å	θ = 2.2–27.4°
c = 11.9640 (14) Å	µ = 1.81 mm⁻¹
α = 82.814 (1)°	T = 293 K
β = 88.854 (1)°	Block, black
γ = 76.644 (1)°	0.22 × 0.20 × 0.16 mm
V = 1268.5 (3) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4692 independent reflections
Radiation source: sealed tube	4083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 25.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.692, T_max = 0.761	k = −14→14
9520 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.037P)² + 0.5172P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4692 reflections	Δρ_max = 0.38 e Å⁻³
290 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0118 (8)

Crystal data top

(C₁₂H₁₀Cl₂N)[Ni(C₃S₅)₂]	γ = 76.644 (1)°
M_r = 690.48	V = 1268.5 (3) Å³
Triclinic, P1	Z = 2
a = 9.3711 (11) Å	Mo Kα radiation
b = 11.7210 (14) Å	µ = 1.81 mm⁻¹
c = 11.9640 (14) Å	T = 293 K
α = 82.814 (1)°	0.22 × 0.20 × 0.16 mm
β = 88.854 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4692 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4083 reflections with I > 2σ(I)
T_min = 0.692, T_max = 0.761	R_int = 0.028
9520 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.04	Δρ_max = 0.38 e Å⁻³
4692 reflections	Δρ_min = −0.34 e Å⁻³
290 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	0.17029 (3)	0.03411 (2)	0.11584 (2)	0.03211 (11)
S1	0.32210 (7)	−0.05513 (5)	−0.00222 (5)	0.03971 (16)
S2	0.05550 (7)	−0.10606 (5)	0.14274 (5)	0.04056 (16)
S3	0.09306 (7)	−0.33353 (5)	0.04221 (5)	0.03969 (16)
S4	0.34360 (8)	−0.29296 (6)	−0.08879 (6)	0.04871 (18)
S5	0.24451 (11)	−0.51768 (7)	−0.09332 (7)	0.0698 (3)
S6	0.28357 (7)	0.17691 (5)	0.09083 (6)	0.03971 (16)
S7	0.01554 (7)	0.11932 (5)	0.23353 (6)	0.04310 (17)
S8	−0.00090 (8)	0.34602 (6)	0.33578 (6)	0.04481 (17)
S9	0.23172 (7)	0.40488 (5)	0.19675 (6)	0.03994 (16)
S10	0.09387 (8)	0.56899 (6)	0.35872 (6)	0.04947 (19)
C1	0.2605 (3)	−0.1815 (2)	−0.00797 (19)	0.0345 (5)
C2	0.1445 (3)	−0.20223 (19)	0.05421 (19)	0.0325 (5)
C3	0.2283 (3)	−0.3877 (2)	−0.0501 (2)	0.0436 (6)
C4	0.1888 (3)	0.27107 (19)	0.1800 (2)	0.0333 (5)
C5	0.0760 (3)	0.2457 (2)	0.2430 (2)	0.0355 (5)
C6	0.1081 (3)	0.4452 (2)	0.3007 (2)	0.0363 (5)
C7	0.6079 (3)	0.9937 (2)	0.3192 (2)	0.0501 (7)
H7	0.5323	1.0062	0.2667	0.060*
C8	0.6073 (3)	1.0755 (2)	0.3933 (2)	0.0485 (6)
C9	0.7202 (3)	1.0565 (2)	0.4706 (2)	0.0498 (7)
C10	0.8302 (3)	0.9562 (3)	0.4754 (3)	0.0578 (8)
H10	0.9047	0.9426	0.5290	0.069*
C11	0.8304 (3)	0.8754 (2)	0.4010 (2)	0.0512 (7)
H11	0.9062	0.8080	0.4036	0.061*
C12	0.7197 (3)	0.8940 (2)	0.3231 (2)	0.0445 (6)
C13	0.7260 (4)	0.8061 (3)	0.2393 (2)	0.0553 (8)
H13A	0.6883	0.8484	0.1671	0.066*
H13B	0.8274	0.7663	0.2292	0.066*
C14	0.6972 (3)	0.6255 (2)	0.3536 (2)	0.0453 (6)
H14	0.7872	0.6219	0.3868	0.054*
C15	0.6241 (3)	0.5380 (2)	0.3842 (2)	0.0483 (6)
H15	0.6653	0.4742	0.4371	0.058*
C16	0.4906 (3)	0.5447 (3)	0.3368 (2)	0.0522 (7)
H16	0.4399	0.4858	0.3569	0.063*
C17	0.4328 (3)	0.6394 (3)	0.2594 (3)	0.0576 (8)
H17	0.3413	0.6460	0.2272	0.069*
C18	0.5084 (3)	0.7237 (2)	0.2294 (2)	0.0532 (7)
H18	0.4691	0.7873	0.1760	0.064*
Cl1	0.72732 (13)	1.15957 (9)	0.56077 (8)	0.0904 (3)
Cl2	0.46624 (11)	1.19991 (8)	0.38728 (9)	0.0858 (3)
N1	0.6396 (2)	0.71609 (18)	0.27623 (16)	0.0396 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.03753 (19)	0.02357 (17)	0.03463 (18)	−0.00516 (12)	0.00213 (13)	−0.00512 (12)
S1	0.0444 (4)	0.0296 (3)	0.0457 (4)	−0.0097 (3)	0.0117 (3)	−0.0064 (3)
S2	0.0457 (4)	0.0316 (3)	0.0478 (4)	−0.0123 (3)	0.0151 (3)	−0.0138 (3)
S3	0.0490 (4)	0.0300 (3)	0.0430 (4)	−0.0122 (3)	0.0052 (3)	−0.0103 (3)
S4	0.0604 (4)	0.0377 (4)	0.0490 (4)	−0.0094 (3)	0.0197 (3)	−0.0155 (3)
S5	0.1137 (7)	0.0433 (4)	0.0602 (5)	−0.0236 (4)	0.0240 (5)	−0.0297 (4)
S6	0.0433 (4)	0.0307 (3)	0.0478 (4)	−0.0105 (3)	0.0124 (3)	−0.0134 (3)
S7	0.0522 (4)	0.0326 (3)	0.0487 (4)	−0.0155 (3)	0.0160 (3)	−0.0123 (3)
S8	0.0539 (4)	0.0346 (3)	0.0484 (4)	−0.0112 (3)	0.0161 (3)	−0.0153 (3)
S9	0.0424 (4)	0.0286 (3)	0.0513 (4)	−0.0096 (3)	0.0080 (3)	−0.0127 (3)
S10	0.0481 (4)	0.0387 (4)	0.0655 (5)	−0.0078 (3)	0.0055 (3)	−0.0265 (3)
C1	0.0414 (13)	0.0279 (11)	0.0322 (12)	−0.0032 (10)	0.0038 (10)	−0.0049 (9)
C2	0.0395 (13)	0.0240 (11)	0.0327 (12)	−0.0041 (9)	−0.0026 (10)	−0.0041 (9)
C3	0.0615 (17)	0.0322 (13)	0.0366 (13)	−0.0067 (12)	0.0040 (12)	−0.0107 (10)
C4	0.0379 (13)	0.0244 (11)	0.0369 (12)	−0.0051 (9)	−0.0010 (10)	−0.0045 (9)
C5	0.0416 (13)	0.0273 (11)	0.0365 (13)	−0.0036 (10)	0.0017 (10)	−0.0085 (10)
C6	0.0377 (13)	0.0286 (12)	0.0406 (13)	−0.0012 (10)	−0.0040 (10)	−0.0084 (10)
C7	0.0596 (17)	0.0500 (16)	0.0416 (15)	−0.0162 (14)	−0.0084 (13)	−0.0006 (12)
C8	0.0566 (17)	0.0423 (15)	0.0439 (15)	−0.0076 (13)	0.0006 (13)	−0.0019 (12)
C9	0.0634 (18)	0.0460 (15)	0.0425 (15)	−0.0130 (13)	0.0014 (13)	−0.0142 (12)
C10	0.0571 (18)	0.0591 (18)	0.0574 (18)	−0.0101 (14)	−0.0133 (14)	−0.0115 (15)
C11	0.0505 (16)	0.0456 (15)	0.0566 (17)	−0.0074 (13)	0.0037 (13)	−0.0099 (13)
C12	0.0595 (17)	0.0406 (14)	0.0381 (14)	−0.0205 (13)	0.0094 (12)	−0.0071 (11)
C13	0.083 (2)	0.0518 (16)	0.0410 (15)	−0.0342 (16)	0.0201 (14)	−0.0110 (12)
C14	0.0390 (14)	0.0527 (16)	0.0428 (15)	−0.0092 (12)	−0.0013 (11)	−0.0024 (12)
C15	0.0506 (16)	0.0469 (15)	0.0432 (15)	−0.0080 (12)	0.0037 (12)	0.0039 (12)
C16	0.0549 (17)	0.0564 (17)	0.0527 (17)	−0.0257 (14)	0.0091 (14)	−0.0125 (14)
C17	0.0458 (16)	0.069 (2)	0.0609 (19)	−0.0165 (15)	−0.0098 (14)	−0.0116 (16)
C18	0.0634 (19)	0.0434 (15)	0.0472 (16)	−0.0029 (13)	−0.0158 (14)	0.0007 (12)
Cl1	0.1180 (8)	0.0762 (6)	0.0815 (6)	−0.0117 (5)	−0.0170 (6)	−0.0447 (5)
Cl2	0.0858 (6)	0.0596 (5)	0.0972 (7)	0.0171 (5)	−0.0164 (5)	−0.0142 (5)
N1	0.0488 (12)	0.0408 (12)	0.0321 (11)	−0.0139 (10)	0.0058 (9)	−0.0106 (9)

Geometric parameters (Å, º) top

Ni1—S2	2.1518 (7)	C8—C9	1.380 (4)
Ni1—S7	2.1643 (7)	C8—Cl2	1.722 (3)
Ni1—S6	2.1681 (7)	C9—C10	1.369 (4)
Ni1—S1	2.1714 (7)	C9—Cl1	1.731 (3)
S1—C1	1.719 (2)	C10—C11	1.378 (4)
S2—C2	1.708 (2)	C10—H10	0.9300
S3—C3	1.725 (3)	C11—C12	1.370 (4)
S3—C2	1.739 (2)	C11—H11	0.9300
S4—C3	1.738 (3)	C12—C13	1.515 (4)
S4—C1	1.750 (2)	C13—N1	1.493 (3)
S5—C3	1.642 (2)	C13—H13A	0.9700
S6—C4	1.717 (2)	C13—H13B	0.9700
S7—C5	1.721 (2)	C14—N1	1.336 (3)
S8—C6	1.727 (2)	C14—C15	1.369 (4)
S8—C5	1.742 (2)	C14—H14	0.9300
S9—C6	1.717 (3)	C15—C16	1.365 (4)
S9—C4	1.742 (2)	C15—H15	0.9300
S10—C6	1.662 (2)	C16—C17	1.368 (4)
C1—C2	1.356 (3)	C16—H16	0.9300
C4—C5	1.353 (3)	C17—C18	1.353 (4)
C7—C12	1.374 (4)	C17—H17	0.9300
C7—C8	1.383 (4)	C18—N1	1.340 (3)
C7—H7	0.9300	C18—H18	0.9300

S2—Ni1—S7	85.25 (3)	C7—C8—Cl2	119.6 (2)
S2—Ni1—S6	179.02 (3)	C10—C9—C8	120.1 (3)
S7—Ni1—S6	93.77 (2)	C10—C9—Cl1	119.0 (2)
S2—Ni1—S1	93.18 (3)	C8—C9—Cl1	120.9 (2)
S7—Ni1—S1	178.41 (3)	C9—C10—C11	120.0 (3)
S6—Ni1—S1	87.80 (3)	C9—C10—H10	120.0
C1—S1—Ni1	101.80 (8)	C11—C10—H10	120.0
C2—S2—Ni1	102.21 (8)	C12—C11—C10	120.3 (3)
C3—S3—C2	97.20 (12)	C12—C11—H11	119.8
C3—S4—C1	97.08 (12)	C10—C11—H11	119.8
C4—S6—Ni1	101.19 (8)	C11—C12—C7	119.8 (2)
C5—S7—Ni1	101.47 (9)	C11—C12—C13	119.1 (3)
C6—S8—C5	97.19 (11)	C7—C12—C13	121.0 (3)
C6—S9—C4	97.89 (11)	N1—C13—C12	112.5 (2)
C2—C1—S1	120.90 (18)	N1—C13—H13A	109.1
C2—C1—S4	115.57 (18)	C12—C13—H13A	109.1
S1—C1—S4	123.50 (14)	N1—C13—H13B	109.1
C1—C2—S2	121.87 (17)	C12—C13—H13B	109.1
C1—C2—S3	116.76 (18)	H13A—C13—H13B	107.8
S2—C2—S3	121.35 (14)	N1—C14—C15	120.3 (2)
S5—C3—S3	121.91 (17)	N1—C14—H14	119.9
S5—C3—S4	124.71 (17)	C15—C14—H14	119.9
S3—C3—S4	113.37 (13)	C16—C15—C14	119.7 (3)
C5—C4—S6	122.13 (17)	C16—C15—H15	120.1
C5—C4—S9	115.30 (17)	C14—C15—H15	120.1
S6—C4—S9	122.56 (14)	C15—C16—C17	118.9 (3)
C4—C5—S7	121.35 (18)	C15—C16—H16	120.6
C4—C5—S8	116.38 (17)	C17—C16—H16	120.6
S7—C5—S8	122.25 (15)	C18—C17—C16	120.1 (3)
S10—C6—S9	122.86 (15)	C18—C17—H17	119.9
S10—C6—S8	124.01 (15)	C16—C17—H17	119.9
S9—C6—S8	113.12 (13)	N1—C18—C17	120.5 (3)
C12—C7—C8	120.3 (3)	N1—C18—H18	119.7
C12—C7—H7	119.9	C17—C18—H18	119.7
C8—C7—H7	119.9	C14—N1—C18	120.5 (2)
C9—C8—C7	119.5 (3)	C14—N1—C13	119.1 (2)
C9—C8—Cl2	120.9 (2)	C18—N1—C13	120.4 (2)

S2—Ni1—S1—C1	1.40 (9)	Ni1—S7—C5—S8	−175.28 (13)
S6—Ni1—S1—C1	−178.64 (8)	C6—S8—C5—C4	1.5 (2)
S7—Ni1—S2—C2	177.99 (8)	C6—S8—C5—S7	−179.86 (15)
S1—Ni1—S2—C2	−1.80 (8)	C4—S9—C6—S10	178.91 (15)
S7—Ni1—S6—C4	1.33 (8)	C4—S9—C6—S8	−2.37 (15)
S1—Ni1—S6—C4	−178.88 (8)	C5—S8—C6—S10	179.61 (16)
S2—Ni1—S7—C5	177.64 (9)	C5—S8—C6—S9	0.91 (15)
S6—Ni1—S7—C5	−2.31 (9)	C12—C7—C8—C9	0.4 (4)
Ni1—S1—C1—C2	−0.6 (2)	C12—C7—C8—Cl2	−180.0 (2)
Ni1—S1—C1—S4	−178.50 (13)	C7—C8—C9—C10	−1.4 (4)
C3—S4—C1—C2	0.5 (2)	Cl2—C8—C9—C10	178.9 (2)
C3—S4—C1—S1	178.56 (16)	C7—C8—C9—Cl1	177.3 (2)
S1—C1—C2—S2	−1.1 (3)	Cl2—C8—C9—Cl1	−2.3 (4)
S4—C1—C2—S2	177.06 (12)	C8—C9—C10—C11	1.7 (5)
S1—C1—C2—S3	−179.55 (12)	Cl1—C9—C10—C11	−177.0 (2)
S4—C1—C2—S3	−1.4 (3)	C9—C10—C11—C12	−1.1 (5)
Ni1—S2—C2—C1	2.0 (2)	C10—C11—C12—C7	0.0 (4)
Ni1—S2—C2—S3	−179.53 (11)	C10—C11—C12—C13	177.6 (3)
C3—S3—C2—C1	1.6 (2)	C8—C7—C12—C11	0.3 (4)
C3—S3—C2—S2	−176.89 (15)	C8—C7—C12—C13	−177.2 (2)
C2—S3—C3—S5	177.82 (17)	C11—C12—C13—N1	95.9 (3)
C2—S3—C3—S4	−1.20 (17)	C7—C12—C13—N1	−86.5 (3)
C1—S4—C3—S5	−178.40 (18)	N1—C14—C15—C16	−1.2 (4)
C1—S4—C3—S3	0.59 (17)	C14—C15—C16—C17	0.0 (4)
Ni1—S6—C4—C5	0.4 (2)	C15—C16—C17—C18	1.0 (5)
Ni1—S6—C4—S9	179.73 (12)	C16—C17—C18—N1	−0.9 (5)
C6—S9—C4—C5	3.5 (2)	C15—C14—N1—C18	1.4 (4)
C6—S9—C4—S6	−175.90 (15)	C15—C14—N1—C13	−176.2 (2)
S6—C4—C5—S7	−2.6 (3)	C17—C18—N1—C14	−0.4 (4)
S9—C4—C5—S7	177.97 (12)	C17—C18—N1—C13	177.2 (3)
S6—C4—C5—S8	176.01 (13)	C12—C13—N1—C14	−78.8 (3)
S9—C4—C5—S8	−3.4 (3)	C12—C13—N1—C18	103.7 (3)
Ni1—S7—C5—C4	3.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···S10ⁱ	0.93	2.82	3.622 (3)	145
C18—H18···S1ⁱⁱ	0.93	2.79	3.708 (3)	168

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

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₀Cl₂N)[Ni(C₃S₅)₂]
M_r	690.48
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.3711 (11), 11.7210 (14), 11.9640 (14)
α, β, γ (°)	82.814 (1), 88.854 (1), 76.644 (1)
V (Å³)	1268.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.81
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.692, 0.761
No. of measured, independent and observed [I > 2σ(I)] reflections	9520, 4692, 4083
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.082, 1.04
No. of reflections	4692
No. of parameters	290
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.34

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
C14—H14···S10ⁱ	0.93	2.82	3.622 (3)	145
C18—H18···S1ⁱⁱ	0.93	2.79	3.708 (3)	168

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

Acknowledgements

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

References

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