1,1′-(Ethane-1,2-di­yl)dipyridinium bis­(1,2-di­cyano­ethene-1,2-di­thiol­ato-κ2S,S′)cuprate(II)

Hu, B.-X.; Zhou, C.-X.; Liu, Y.-M.; Chen, L.-Z.; Wang, F.-M.

doi:10.1107/S1600536813012439

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page m312

doi:10.1107/S1600536813012439

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1,1′-(Ethane-1,2-diyl)dipyridinium bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)cuprate(II)

Bing-Xiang Hu,^a Chang-Xiao Zhou,^a Yang-Mei Liu,^b Li-Zhuang Chen ^a and Fang-Ming Wang ^a ^*

^aSchool of Biology and Chemistry Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, People's Republic of China, and ^bNational Food Packaging Products Quality Supervision and Inspection Center, Jiangsu Provincial Supervising and Testing Research Institute for Products Quality, Nanjing 210007, People's Republic of China
^*Correspondence e-mail: wangfmzj@hotmail.com

(Received 27 April 2013; accepted 7 May 2013; online 11 May 2013)

In the title ion-pair complex, (C₁₂H₁₄N₂)[Cu(C₄N₂S₂)₂], the complex anion exhibits a highly twisted coordination environment around the tetracoordinated Cu^II atom. The dihedral angles between the 1,2-dicyanoethene-1,2-dithiolato ligands and between the two pyridine rings in the cation are 37.49 (3) and 29.18 (10)°, respectively. Weak C—H⋯N and C—H⋯S hydrogen bonds link the cations and anions into a three-dimensional network.

Related literature

For background to crystalline molecular materials and coordination polymer networks, see: Brammer (2004 ); Robin & Fromm (2006 ). For 1,2-dithiolene–metal complexes, see: Duan et al. (2010 ); Ni et al. (2005 ). For related structures, see: Ren et al. (2006 ); Wang et al. (2012 ).

Experimental

Crystal data

(C₁₂H₁₄N₂)[Cu(C₄N₂S₂)₂]
M_r = 530.20
Triclinic, $[P \overline 1]$
a = 7.7598 (10) Å
b = 12.3811 (15) Å
c = 12.6572 (16) Å
α = 77.676 (2)°
β = 72.791 (2)°
γ = 84.122 (2)°
V = 1133.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.35 mm⁻¹
T = 291 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.730, T_max = 0.815
5682 measured reflections
3921 independent reflections
3217 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.083
S = 1.00
3921 reflections
280 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯N2ⁱ	0.93	2.61	3.356 (4)	137
C14—H14A⋯N4ⁱⁱ	0.97	2.60	3.341 (4)	133
C14—H14B⋯N1ⁱⁱⁱ	0.97	2.60	3.479 (4)	151
C15—H15B⋯S1	0.97	2.83	3.769 (3)	163
C16—H16A⋯N2^iv	0.93	2.56	3.368 (4)	146
C17—H17A⋯S2^iv	0.93	2.82	3.743 (3)	171
C19—H19A⋯N3^v	0.93	2.56	3.235 (4)	129
C20—H20A⋯N1ⁱⁱⁱ	0.93	2.52	3.422 (4)	164
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z; (iv) -x+1, -y+1, -z+1; (v) x-1, y+1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813012439/hy2624sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012439/hy2624Isup2.hkl

checkCIF report

Comment top

During the past few years, the molecular-based materials are widely studied due to their novel applications in the areas of materials science, medicines, biology and so on (Brammer, 2004; Robin & Fromm, 2006). Among these materials, maleonitriledithiolate (mnt) transition metal complexes are a typical kind of bis(1,2-dithiolene) complexes used as building blocks, because they possess an extended electronically delocalized core comprising a central metal, four S atoms and C═C units (Duan et al., 2010; Ni et al., 2005). Studies showed that weak inter- or intramolecular interactions in the complexes could influence on their properties (Ren et al., 2006; Wang et al., 2012).

In order to know how the cations affects the stacking mode of [Cu(mnt)₂]^2- anion, herein, we present a new ion-pair complex. As shown in Fig. 1, it consists of one ethane-1,2-dipydinium (PyEtPy)²⁺ cation and a [Cu(mnt)₂]^2- dianion in the asymmetric unit. The [Cu(mnt)₂]^2- anion exhibits highly twisted coordination environment around the tetracoordinated Cu^II atom. The dihedral angle between the two mnt ligands is 37.49 (3)°, which is the largest value in this kind complexes. The dihedral angle between two pyridyl planes in the organic cation is 29.18 (10)°. It is seen from Table 1 and Fig. 2 that the crystal structure is stabilized by weak C—H···N and C—H···S hydrogen bonds, which link the cations and anions into a three-dimensional network.

Related literature top

For background to crystalline molecular materials and coordination polymer networks, see: Brammer (2004); Robin & Fromm (2006). For 1,2-dithiolene–metal complexes, see: Duan et al. (2010); Ni et al. (2005). For related structures, see: Ren et al. (2006); Wang et al. (2012).

Experimental top

The synthesis route of the title compound is similar to reference (Wang et al., 2012). It was prepared by a direct reaction of CuCl₂ (0.171g, 1.0 mmol), Na₂(mnt) (0.372g, 2.0 mmol) and ethane-1,2-dipydinium bromide (0.344g, 1.0 mmol) in a mixed solution of ethanol and H₂O (v/v 1:1; 20 ml). After filtration, brown-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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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. The packing diagram of the title compound as viewed along the a axis. Dashed lines denote hydrogen bonds.

1,1'-(Ethane-1,2-diyl)dipyridinium bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')cuprate(II) top

Crystal data top

(C₁₂H₁₄N₂)[Cu(C₄N₂S₂)₂]	Z = 2
M_r = 530.20	F(000) = 538
Triclinic, P1	D_x = 1.553 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7598 (10) Å	Cell parameters from 2653 reflections
b = 12.3811 (15) Å	θ = 2.2–28.0°
c = 12.6572 (16) Å	µ = 1.35 mm⁻¹
α = 77.676 (2)°	T = 291 K
β = 72.791 (2)°	Block, brown-red
γ = 84.122 (2)°	0.25 × 0.20 × 0.15 mm
V = 1133.8 (2) Å³

Data collection top

Bruker APEX CCD diffractometer	3921 independent reflections
Radiation source: sealed tube	3217 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→8
T_min = 0.730, T_max = 0.815	k = −14→12
5682 measured reflections	l = −15→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) = 0.083	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0333P)²] where P = (F_o² + 2F_c²)/3
3921 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.39 e Å⁻³
1 restraint	Δρ_min = −0.26 e Å⁻³

Crystal data top

(C₁₂H₁₄N₂)[Cu(C₄N₂S₂)₂]	γ = 84.122 (2)°
M_r = 530.20	V = 1133.8 (2) Å³
Triclinic, P1	Z = 2
a = 7.7598 (10) Å	Mo Kα radiation
b = 12.3811 (15) Å	µ = 1.35 mm⁻¹
c = 12.6572 (16) Å	T = 291 K
α = 77.676 (2)°	0.25 × 0.20 × 0.15 mm
β = 72.791 (2)°

Data collection top

Bruker APEX CCD diffractometer	3921 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3217 reflections with I > 2σ(I)
T_min = 0.730, T_max = 0.815	R_int = 0.054
5682 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.083	H-atom parameters constrained
S = 1.00	Δρ_max = 0.39 e Å⁻³
3921 reflections	Δρ_min = −0.26 e Å⁻³
280 parameters

Special details top

Experimental. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.9701 (0.0047) x + 5.1850 (0.0148) y + 7.5933 (0.0151) z = 5.1170 (0.0027)

* -0.0036 (0.0020) N5 * 0.0025 (0.0022) C9 * 0.0020 (0.0024) C10 * -0.0053 (0.0025) C11 * 0.0043 (0.0025) C12 * 0.0001 (0.0022) C13

Rms deviation of fitted atoms = 0.0034

7.3331 (0.0038) x + 4.3436 (0.0161) y + 1.7102 (0.0200) z = 4.6388 (0.0108)

Angle to previous plane (with approximate e.s.d.) = 29.18 (10)

* 0.0013 (0.0022) N6 * -0.0036 (0.0025) C16 * 0.0015 (0.0028) C17 * 0.0027 (0.0028) C18 * -0.0049 (0.0027) C19 * 0.0029 (0.0024) C20

Rms deviation of fitted atoms = 0.0031

6.9588 (0.0022) x + 3.8087 (0.0081) y - 0.7118 (0.0088) z = 7.0678 (0.0051)

Angle to previous plane (with approximate e.s.d.) = 10.99 (12)

* -0.0330 (0.0015) S1 * -0.0111 (0.0015) S2 * 0.0353 (0.0026) C1 * 0.0220 (0.0028) C4 * 0.0292 (0.0027) C2 * 0.0074 (0.0032) C3 * -0.0259 (0.0020) N1 * -0.0239 (0.0024) N2

Rms deviation of fitted atoms = 0.0252

7.2222 (0.0021) x + 4.6573 (0.0073) y + 6.9013 (0.0071) z = 8.7279 (0.0018)

Angle to previous plane (with approximate e.s.d.) = 36.27 (4)

* 0.0321 (0.0014) S3 * 0.0067 (0.0014) S4 * -0.0293 (0.0025) C5 * -0.0251 (0.0025) C7 * 0.0012 (0.0029) C8 * -0.0242 (0.0028) C6 * 0.0188 (0.0021) N3 * 0.0197 (0.0021) N4

Rms deviation of fitted atoms = 0.0220

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
C1	0.7697 (4)	0.4815 (2)	0.1224 (2)	0.0391 (7)
C2	0.7087 (4)	0.5794 (2)	0.0580 (2)	0.0438 (7)
C3	0.7285 (5)	0.5782 (3)	0.2764 (3)	0.0534 (9)
C4	0.7788 (4)	0.4812 (2)	0.2281 (2)	0.0399 (7)
C5	1.0203 (4)	−0.0026 (2)	0.1945 (2)	0.0381 (7)
C6	1.1186 (5)	−0.0989 (2)	0.1573 (2)	0.0471 (8)
C7	0.9214 (4)	−0.0103 (2)	0.3037 (2)	0.0383 (7)
C8	0.9143 (5)	−0.1115 (2)	0.3834 (3)	0.0476 (8)
C9	0.4956 (4)	0.0999 (2)	0.1511 (2)	0.0473 (8)
H9A	0.5115	0.1626	0.0943	0.057*
C10	0.5896 (5)	0.0029 (3)	0.1309 (3)	0.0597 (10)
H10A	0.6695	−0.0002	0.0604	0.072*
C11	0.5661 (5)	−0.0882 (3)	0.2138 (3)	0.0638 (10)
H11A	0.6283	−0.1545	0.2005	0.077*
C12	0.4494 (5)	−0.0818 (3)	0.3178 (3)	0.0622 (10)
H12A	0.4333	−0.1435	0.3759	0.075*
C13	0.3573 (5)	0.0154 (2)	0.3354 (3)	0.0511 (8)
H13A	0.2774	0.0200	0.4056	0.061*
C14	0.2858 (4)	0.2108 (2)	0.2732 (3)	0.0413 (7)
H14A	0.1753	0.1975	0.3341	0.050*
H14B	0.2547	0.2506	0.2061	0.050*
C15	0.4079 (4)	0.2779 (2)	0.3040 (3)	0.0453 (8)
H15A	0.4296	0.2404	0.3747	0.054*
H15B	0.5232	0.2838	0.2464	0.054*
C16	0.2857 (5)	0.4217 (2)	0.4142 (3)	0.0525 (9)
H16A	0.2996	0.3717	0.4776	0.063*
C17	0.2222 (5)	0.5267 (3)	0.4229 (3)	0.0678 (11)
H17A	0.1934	0.5488	0.4921	0.081*
C18	0.2010 (5)	0.5992 (3)	0.3304 (3)	0.0662 (11)
H18A	0.1578	0.6712	0.3359	0.079*
C19	0.2430 (5)	0.5663 (3)	0.2295 (3)	0.0593 (10)
H19A	0.2276	0.6150	0.1657	0.071*
C20	0.3078 (4)	0.4609 (2)	0.2238 (3)	0.0506 (8)
H20A	0.3384	0.4378	0.1551	0.061*
Cu1	0.88151 (5)	0.23822 (3)	0.20268 (3)	0.03682 (13)
N1	0.6543 (4)	0.6544 (2)	0.0053 (2)	0.0597 (8)
N2	0.6877 (5)	0.6526 (2)	0.3190 (3)	0.0809 (11)
N3	1.2014 (5)	−0.1729 (2)	0.1268 (2)	0.0733 (10)
N4	0.9043 (5)	−0.1908 (2)	0.4499 (2)	0.0708 (9)
N5	0.3814 (3)	0.10412 (17)	0.25224 (19)	0.0362 (6)
N6	0.3283 (3)	0.39007 (18)	0.31502 (19)	0.0375 (6)
S1	0.81723 (12)	0.36536 (6)	0.06140 (6)	0.0456 (2)
S2	0.84617 (12)	0.36517 (6)	0.31245 (6)	0.0456 (2)
S3	1.04488 (12)	0.11853 (6)	0.09586 (6)	0.0457 (2)
S4	0.80239 (11)	0.10227 (6)	0.35693 (6)	0.0459 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0419 (18)	0.0328 (15)	0.0380 (17)	0.0020 (13)	−0.0092 (14)	−0.0017 (13)
C2	0.051 (2)	0.0408 (17)	0.0368 (17)	−0.0010 (15)	−0.0112 (15)	−0.0036 (14)
C3	0.079 (3)	0.0398 (18)	0.049 (2)	0.0081 (17)	−0.0337 (19)	−0.0061 (16)
C4	0.0478 (19)	0.0299 (15)	0.0422 (18)	0.0034 (13)	−0.0154 (15)	−0.0060 (13)
C5	0.0471 (19)	0.0306 (15)	0.0361 (17)	0.0025 (13)	−0.0127 (14)	−0.0060 (12)
C6	0.067 (2)	0.0352 (17)	0.0350 (17)	0.0019 (15)	−0.0125 (16)	−0.0032 (14)
C7	0.0486 (19)	0.0275 (14)	0.0375 (17)	−0.0017 (13)	−0.0135 (14)	−0.0018 (12)
C8	0.063 (2)	0.0393 (18)	0.0370 (18)	−0.0026 (15)	−0.0067 (16)	−0.0102 (15)
C9	0.063 (2)	0.0375 (17)	0.0339 (17)	0.0012 (15)	−0.0050 (16)	−0.0033 (13)
C10	0.065 (2)	0.054 (2)	0.050 (2)	0.0092 (18)	0.0008 (18)	−0.0185 (18)
C11	0.076 (3)	0.0374 (19)	0.082 (3)	0.0137 (18)	−0.026 (2)	−0.0213 (19)
C12	0.090 (3)	0.0356 (18)	0.059 (2)	0.0010 (18)	−0.027 (2)	0.0027 (16)
C13	0.069 (2)	0.0411 (18)	0.0373 (18)	−0.0007 (16)	−0.0114 (17)	−0.0022 (14)
C14	0.0418 (18)	0.0342 (15)	0.0461 (18)	0.0081 (13)	−0.0112 (15)	−0.0103 (13)
C15	0.0436 (19)	0.0362 (16)	0.056 (2)	0.0069 (14)	−0.0153 (16)	−0.0110 (14)
C16	0.079 (3)	0.0449 (19)	0.0355 (18)	−0.0065 (17)	−0.0199 (17)	−0.0051 (14)
C17	0.108 (3)	0.050 (2)	0.042 (2)	0.002 (2)	−0.010 (2)	−0.0206 (17)
C18	0.093 (3)	0.0376 (19)	0.065 (3)	0.0082 (19)	−0.017 (2)	−0.0171 (18)
C19	0.086 (3)	0.0396 (19)	0.052 (2)	0.0044 (18)	−0.026 (2)	−0.0020 (16)
C20	0.071 (2)	0.0458 (18)	0.0339 (18)	−0.0015 (16)	−0.0114 (16)	−0.0099 (14)
Cu1	0.0427 (2)	0.0313 (2)	0.0346 (2)	0.00331 (15)	−0.01034 (17)	−0.00546 (15)
N1	0.071 (2)	0.0499 (17)	0.0505 (18)	0.0040 (15)	−0.0195 (16)	0.0059 (14)
N2	0.139 (3)	0.0435 (18)	0.074 (2)	0.0230 (19)	−0.053 (2)	−0.0209 (17)
N3	0.108 (3)	0.0440 (17)	0.058 (2)	0.0173 (17)	−0.0132 (19)	−0.0122 (15)
N4	0.108 (3)	0.0420 (17)	0.0482 (18)	−0.0037 (17)	−0.0094 (18)	0.0032 (15)
N5	0.0413 (15)	0.0309 (12)	0.0347 (14)	0.0027 (11)	−0.0111 (12)	−0.0043 (10)
N6	0.0417 (15)	0.0319 (13)	0.0377 (14)	0.0017 (11)	−0.0096 (12)	−0.0075 (11)
S1	0.0638 (6)	0.0395 (4)	0.0309 (4)	0.0057 (4)	−0.0127 (4)	−0.0057 (3)
S2	0.0669 (6)	0.0341 (4)	0.0418 (5)	0.0090 (4)	−0.0272 (4)	−0.0091 (3)
S3	0.0639 (6)	0.0335 (4)	0.0312 (4)	0.0070 (4)	−0.0053 (4)	−0.0034 (3)
S4	0.0571 (5)	0.0370 (4)	0.0342 (4)	0.0031 (4)	−0.0018 (4)	−0.0046 (3)

Geometric parameters (Å, º) top

C1—C4	1.360 (4)	C13—H13A	0.9300
C1—C2	1.431 (4)	C14—N5	1.482 (3)
C1—S1	1.730 (3)	C14—C15	1.503 (4)
C2—N1	1.143 (3)	C14—H14A	0.9700
C3—N2	1.136 (4)	C14—H14B	0.9700
C3—C4	1.430 (4)	C15—N6	1.479 (3)
C4—S2	1.732 (3)	C15—H15A	0.9700
C5—C7	1.357 (4)	C15—H15B	0.9700
C5—C6	1.437 (4)	C16—N6	1.333 (3)
C5—S3	1.721 (3)	C16—C17	1.357 (4)
C6—N3	1.134 (3)	C16—H16A	0.9300
C7—C8	1.425 (4)	C17—C18	1.356 (4)
C7—S4	1.738 (3)	C17—H17A	0.9300
C8—N4	1.141 (4)	C18—C19	1.361 (4)
C9—N5	1.332 (4)	C18—H18A	0.9300
C9—C10	1.371 (4)	C19—C20	1.358 (4)
C9—H9A	0.9300	C19—H19A	0.9300
C10—C11	1.353 (5)	C20—N6	1.332 (4)
C10—H10A	0.9300	C20—H20A	0.9300
C11—C12	1.373 (5)	Cu1—S3	2.2554 (8)
C11—H11A	0.9300	Cu1—S1	2.2561 (8)
C12—C13	1.361 (4)	Cu1—S2	2.2571 (8)
C12—H12A	0.9300	Cu1—S4	2.2630 (8)
C13—N5	1.335 (4)

C4—C1—C2	120.1 (2)	N6—C15—C14	111.5 (2)
C4—C1—S1	123.3 (2)	N6—C15—H15A	109.3
C2—C1—S1	116.5 (2)	C14—C15—H15A	109.3
N1—C2—C1	176.5 (3)	N6—C15—H15B	109.3
N2—C3—C4	177.2 (3)	C14—C15—H15B	109.3
C1—C4—C3	120.8 (2)	H15A—C15—H15B	108.0
C1—C4—S2	122.9 (2)	N6—C16—C17	120.2 (3)
C3—C4—S2	116.3 (2)	N6—C16—H16A	119.9
C7—C5—C6	119.5 (2)	C17—C16—H16A	119.9
C7—C5—S3	124.0 (2)	C18—C17—C16	119.7 (3)
C6—C5—S3	116.5 (2)	C18—C17—H17A	120.1
N3—C6—C5	177.7 (4)	C16—C17—H17A	120.1
C5—C7—C8	121.6 (2)	C17—C18—C19	119.9 (3)
C5—C7—S4	122.7 (2)	C17—C18—H18A	120.1
C8—C7—S4	115.7 (2)	C19—C18—H18A	120.1
N4—C8—C7	177.6 (3)	C20—C19—C18	118.7 (3)
N5—C9—C10	119.9 (3)	C20—C19—H19A	120.6
N5—C9—H9A	120.0	C18—C19—H19A	120.6
C10—C9—H9A	120.0	N6—C20—C19	121.1 (3)
C11—C10—C9	119.9 (3)	N6—C20—H20A	119.4
C11—C10—H10A	120.1	C19—C20—H20A	119.4
C9—C10—H10A	120.1	S3—Cu1—S1	97.08 (3)
C10—C11—C12	119.3 (3)	S3—Cu1—S2	153.90 (4)
C10—C11—H11A	120.4	S1—Cu1—S2	92.15 (3)
C12—C11—H11A	120.4	S3—Cu1—S4	92.28 (3)
C13—C12—C11	119.6 (3)	S1—Cu1—S4	152.11 (4)
C13—C12—H12A	120.2	S2—Cu1—S4	90.80 (3)
C11—C12—H12A	120.2	C9—N5—C13	121.1 (2)
N5—C13—C12	120.2 (3)	C9—N5—C14	119.0 (2)
N5—C13—H13A	119.9	C13—N5—C14	119.9 (2)
C12—C13—H13A	119.9	C20—N6—C16	120.3 (2)
N5—C14—C15	108.6 (2)	C20—N6—C15	119.3 (2)
N5—C14—H14A	110.0	C16—N6—C15	120.2 (2)
C15—C14—H14A	110.0	C1—S1—Cu1	100.72 (10)
N5—C14—H14B	110.0	C4—S2—Cu1	100.81 (9)
C15—C14—H14B	110.0	C5—S3—Cu1	100.54 (9)
H14A—C14—H14B	108.4	C7—S4—Cu1	100.40 (10)

C2—C1—C4—C3	−0.3 (5)	C17—C16—N6—C20	−0.4 (5)
S1—C1—C4—C3	−176.6 (3)	C17—C16—N6—C15	176.2 (3)
C2—C1—C4—S2	178.5 (2)	C14—C15—N6—C20	−67.1 (4)
S1—C1—C4—S2	2.1 (4)	C14—C15—N6—C16	116.2 (3)
C6—C5—C7—C8	0.8 (5)	C4—C1—S1—Cu1	1.0 (3)
S3—C5—C7—C8	−176.3 (2)	C2—C1—S1—Cu1	−175.5 (2)
C6—C5—C7—S4	178.5 (2)	S3—Cu1—S1—C1	−158.09 (11)
S3—C5—C7—S4	1.4 (4)	S2—Cu1—S1—C1	−2.55 (11)
N5—C9—C10—C11	0.0 (5)	S4—Cu1—S1—C1	93.23 (12)
C9—C10—C11—C12	−0.8 (5)	C1—C4—S2—Cu1	−3.9 (3)
C10—C11—C12—C13	1.0 (6)	C3—C4—S2—Cu1	174.9 (2)
C11—C12—C13—N5	−0.5 (5)	S3—Cu1—S2—C4	114.23 (12)
N5—C14—C15—N6	174.3 (2)	S1—Cu1—S2—C4	3.32 (11)
N6—C16—C17—C18	0.4 (6)	S4—Cu1—S2—C4	−148.94 (11)
C16—C17—C18—C19	0.2 (6)	C7—C5—S3—Cu1	1.0 (3)
C17—C18—C19—C20	−0.8 (6)	C6—C5—S3—Cu1	−176.2 (2)
C18—C19—C20—N6	0.8 (6)	S1—Cu1—S3—C5	−155.81 (11)
C10—C9—N5—C13	0.5 (5)	S2—Cu1—S3—C5	94.35 (12)
C10—C9—N5—C14	178.0 (3)	S4—Cu1—S3—C5	−2.14 (11)
C12—C13—N5—C9	−0.3 (5)	C5—C7—S4—Cu1	−2.9 (3)
C12—C13—N5—C14	−177.7 (3)	C8—C7—S4—Cu1	174.9 (2)
C15—C14—N5—C9	−83.5 (3)	S3—Cu1—S4—C7	2.65 (11)
C15—C14—N5—C13	94.0 (3)	S1—Cu1—S4—C7	112.46 (11)
C19—C20—N6—C16	−0.2 (5)	S2—Cu1—S4—C7	−151.43 (10)
C19—C20—N6—C15	−176.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···N2ⁱ	0.93	2.61	3.356 (4)	137
C14—H14A···N4ⁱⁱ	0.97	2.60	3.341 (4)	133
C14—H14B···N1ⁱⁱⁱ	0.97	2.60	3.479 (4)	151
C15—H15B···S1	0.97	2.83	3.769 (3)	163
C16—H16A···N2^iv	0.93	2.56	3.368 (4)	146
C17—H17A···S2^iv	0.93	2.82	3.743 (3)	171
C19—H19A···N3^v	0.93	2.56	3.235 (4)	129
C20—H20A···N1ⁱⁱⁱ	0.93	2.52	3.422 (4)	164

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

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₄N₂)[Cu(C₄N₂S₂)₂]
M_r	530.20
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	7.7598 (10), 12.3811 (15), 12.6572 (16)
α, β, γ (°)	77.676 (2), 72.791 (2), 84.122 (2)
V (Å³)	1133.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.35
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.730, 0.815
No. of measured, independent and observed [I > 2σ(I)] reflections	5682, 3921, 3217
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.083, 1.00
No. of reflections	3921
No. of parameters	280
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.26

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···N2ⁱ	0.93	2.61	3.356 (4)	137
C14—H14A···N4ⁱⁱ	0.97	2.60	3.341 (4)	133
C14—H14B···N1ⁱⁱⁱ	0.97	2.60	3.479 (4)	151
C15—H15B···S1	0.97	2.83	3.769 (3)	163
C16—H16A···N2^iv	0.93	2.56	3.368 (4)	146
C17—H17A···S2^iv	0.93	2.82	3.743 (3)	171
C19—H19A···N3^v	0.93	2.56	3.235 (4)	129
C20—H20A···N1ⁱⁱⁱ	0.93	2.52	3.422 (4)	164

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China for Young Scholars (grant No. 21201087), the Natural Science Foundation of Jiangsu Provincial Department of Education (grant No. 11KJB150004), the Science and Technology Project of the State General Administration of Quality Supervision, Inspection and Quarantine, People's Republic of China (grant Nos. 2011QK121 and 2011QK122) and a start-up grant from Jiangsu University of Science and Technology.

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