1,1'-(Ethane-1,2-di-yl)dipyridinium bis-(1,2-di-cyano-ethene-1,2-di-thiol-ato-κ(2) S,S')cuprate(II).

In the title ion-pair complex, (C12H14N2)[Cu(C4N2S2)2], the complex anion exhibits a highly twisted coordination environment around the tetra-coordinated Cu(II) atom. The dihedral angles between the 1,2-di-cyano-ethene-1,2-di-thiol-ato 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 = 530.20

Triclinic,

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[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.083

S = 1.00

3921 reflections

280 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.26 e Å−3

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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813012439/hy2624sup1.cif

Click here for additional data file.

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C12H14N2)[Cu(C4N2S2)2]	Z = 2
Mr = 530.20	F(000) = 538
Triclinic, P1	Dx = 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

Bruker APEX CCD diffractometer	3921 independent reflections
Radiation source: sealed tube	3217 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
φ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→8
Tmin = 0.730, Tmax = 0.815	k = −14→12
5682 measured reflections	l = −15→15

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(Fo2) + (0.0333P)2] where P = (Fo2 + 2Fc2)/3
3921 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.39 e Å−3
1 restraint	Δρmin = −0.26 e Å−3

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) C13Rms deviation of fitted atoms = 0.00347.3331 (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) C20Rms deviation of fitted atoms = 0.00316.9588 (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) N2Rms deviation of fitted atoms = 0.02527.2222 (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) N4Rms 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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···N2iv	0.93	2.56	3.368 (4)	146
C17—H17A···S2iv	0.93	2.82	3.743 (3)	171
C19—H19A···N3v	0.93	2.56	3.235 (4)	129
C20—H20A···N1iii	0.93	2.52	3.422 (4)	164

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⋯N2iv	0.93	2.56	3.368 (4)	146
C17—H17A⋯S2iv	0.93	2.82	3.743 (3)	171
C19—H19A⋯N3v	0.93	2.56	3.235 (4)	129
C20—H20A⋯N1iii	0.93	2.52	3.422 (4)	164

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .