Bis[1-(4-cyano-benz-yl)pyrazinium] bis-(1,2-dicyano-ethene-1,2-dithiol-ato)nickelate(II).

The asymmetric unit of the title complex, (C(12)H(10)N(3))(2)[Ni(C(4)N(2)S(2))(2)], consists of one 1-(4-cyano-benz-yl)pyrazinium cation and one half of an [Ni(mnt)(2)](2-) dianion (mnt(2-) is 1,2-dicyano-ethene-1,2-dithiol-ate). The Ni(2+) ion is located on an inversion center and is coordinated by four S atoms from two mnt(2-) ligands, exhibiting a square-planar coordination geometry. The cation adopts a conformation where both the pyrazine ring and the benzene ring are twisted with respect to the C-C-N reference plane by 16.5 (2) and 69.8 (1)°, respectively.

Related literature

For general background to square-planar bis-1,2-dithiol­ato complexes of transition metals showing potential application as magnetic or conducting materials and other properties, see: Bigoli et al. (2002 ▶); Duan et al. (2010 ▶); Pei et al. (2011 ▶). For the synthesis, see: Davison & Holm (1967 ▶).

Experimental

Crystal data

(C12H10N3)2[Ni(C4N2S2)2]

M = 731.53

Monoclinic,

a = 7.115 (3) Å

b = 13.623 (6) Å

c = 17.186 (8) Å

β = 101.671 (5)°

V = 1631.4 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.89 mm−1

T = 298 K

0.30 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002) ▶ T min = 0.807, T max = 0.875

8060 measured reflections

2871 independent reflections

2586 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.074

S = 1.06

2871 reflections

214 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022550/im2295sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022550/im2295Isup2.hkl

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

(C12H10N3)2[Ni(C4N2S2)2]	F(000) = 748
Mr = 731.53	Dx = 1.489 Mg m−3
Monoclinic, P21/n	Melting point: 456 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.115 (3) Å	Cell parameters from 8060 reflections
b = 13.623 (6) Å	θ = 2.4–25.0°
c = 17.186 (8) Å	µ = 0.89 mm−1
β = 101.671 (5)°	T = 298 K
V = 1631.4 (13) Å3	Block, red
Z = 2	0.30 × 0.20 × 0.15 mm

Bruker SMART APEX CCD diffractometer	2871 independent reflections
Radiation source: fine-focus sealed tube	2586 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→4
Tmin = 0.807, Tmax = 0.875	k = −16→15
8060 measured reflections	l = −20→20

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0431P)2 + 0.3009P] where P = (Fo2 + 2Fc2)/3
2871 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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
Ni1	0.0000	0.0000	0.0000	0.04070 (11)
C1	0.0668 (2)	0.13286 (12)	0.14603 (9)	0.0452 (4)
C2	0.2425 (2)	0.09233 (12)	0.14864 (10)	0.0464 (4)
C3	0.4020 (3)	0.11475 (13)	0.21086 (11)	0.0566 (4)
C4	0.0334 (2)	0.19910 (13)	0.20637 (10)	0.0508 (4)
C5	0.3059 (2)	0.61780 (13)	−0.03334 (11)	0.0515 (4)
C6	0.4014 (3)	0.67295 (15)	−0.08013 (11)	0.0608 (5)
H6A	0.3440	0.6865	−0.1326	0.073*
C7	0.5826 (3)	0.70790 (15)	−0.04870 (11)	0.0594 (5)
H7A	0.6473	0.7448	−0.0805	0.071*
C8	0.6697 (2)	0.68900 (12)	0.02927 (10)	0.0473 (4)
C9	0.5730 (2)	0.63300 (13)	0.07578 (10)	0.0513 (4)
H9A	0.6311	0.6190	0.1281	0.062*
C10	0.3910 (3)	0.59771 (13)	0.04520 (11)	0.0550 (4)
H10A	0.3260	0.5608	0.0769	0.066*
C11	0.1164 (3)	0.58128 (16)	−0.06742 (13)	0.0670 (5)
C12	0.8708 (2)	0.72452 (14)	0.06029 (11)	0.0541 (4)
H12A	0.9486	0.6693	0.0833	0.065*
H12B	0.9232	0.7484	0.0159	0.065*
C13	0.7384 (3)	0.85735 (13)	0.13272 (12)	0.0558 (4)
H13A	0.6171	0.8476	0.1014	0.067*
C14	0.7677 (3)	0.92685 (15)	0.19170 (13)	0.0672 (5)
H14A	0.6632	0.9643	0.1989	0.081*
C15	1.0821 (3)	0.89226 (14)	0.22341 (12)	0.0658 (5)
H15A	1.2038	0.9037	0.2539	0.079*
C16	1.0618 (3)	0.82300 (14)	0.16465 (11)	0.0573 (5)
H16A	1.1684	0.7893	0.1549	0.069*
N1	0.0083 (2)	0.25233 (14)	0.25432 (10)	0.0707 (5)
N2	0.5329 (3)	0.13221 (16)	0.25944 (11)	0.0842 (6)
N3	−0.0327 (3)	0.55373 (19)	−0.09570 (13)	0.0963 (7)
N4	0.88726 (18)	0.80422 (10)	0.12132 (8)	0.0455 (3)
N5	0.9357 (3)	0.94368 (12)	0.23882 (10)	0.0677 (4)
S1	−0.12375 (6)	0.10653 (3)	0.06901 (3)	0.05089 (13)
S2	0.28315 (7)	0.01308 (3)	0.07488 (3)	0.05495 (14)

	U11	U22	U33	U12	U13	U23
Ni1	0.04532 (18)	0.03877 (17)	0.03648 (17)	−0.00199 (11)	0.00463 (12)	−0.00037 (10)
C1	0.0529 (9)	0.0417 (8)	0.0406 (8)	−0.0064 (7)	0.0085 (7)	−0.0019 (7)
C2	0.0511 (9)	0.0440 (8)	0.0423 (8)	−0.0041 (7)	0.0051 (7)	−0.0038 (7)
C3	0.0564 (11)	0.0559 (10)	0.0541 (10)	0.0060 (8)	0.0036 (9)	−0.0140 (8)
C4	0.0470 (9)	0.0544 (10)	0.0508 (9)	−0.0046 (7)	0.0094 (8)	−0.0047 (8)
C5	0.0449 (9)	0.0502 (9)	0.0585 (10)	0.0017 (7)	0.0079 (8)	−0.0081 (8)
C6	0.0608 (11)	0.0711 (12)	0.0473 (10)	0.0045 (9)	0.0033 (8)	0.0033 (9)
C7	0.0599 (11)	0.0661 (11)	0.0531 (10)	−0.0045 (9)	0.0135 (8)	0.0121 (9)
C8	0.0461 (9)	0.0454 (9)	0.0512 (9)	−0.0015 (7)	0.0118 (7)	0.0002 (7)
C9	0.0520 (10)	0.0547 (10)	0.0463 (9)	−0.0037 (8)	0.0074 (7)	0.0036 (7)
C10	0.0533 (10)	0.0555 (10)	0.0577 (10)	−0.0076 (8)	0.0147 (8)	0.0039 (8)
C11	0.0542 (12)	0.0750 (13)	0.0690 (13)	−0.0025 (10)	0.0059 (10)	−0.0086 (10)
C12	0.0479 (9)	0.0575 (10)	0.0587 (10)	−0.0046 (8)	0.0153 (8)	−0.0027 (8)
C13	0.0464 (9)	0.0524 (10)	0.0664 (11)	−0.0008 (8)	0.0066 (8)	0.0011 (8)
C14	0.0634 (12)	0.0577 (11)	0.0791 (14)	0.0017 (9)	0.0111 (10)	−0.0062 (10)
C15	0.0651 (12)	0.0559 (11)	0.0669 (12)	−0.0098 (9)	−0.0091 (10)	0.0106 (9)
C16	0.0455 (9)	0.0546 (10)	0.0673 (11)	−0.0028 (8)	0.0006 (8)	0.0099 (9)
N1	0.0665 (11)	0.0800 (12)	0.0676 (11)	0.0002 (9)	0.0182 (8)	−0.0250 (9)
N2	0.0671 (11)	0.0967 (14)	0.0773 (12)	0.0143 (10)	−0.0129 (10)	−0.0363 (11)
N3	0.0612 (12)	0.1261 (19)	0.0940 (15)	−0.0216 (12)	−0.0021 (11)	−0.0063 (14)
N4	0.0427 (7)	0.0434 (7)	0.0499 (8)	−0.0049 (6)	0.0080 (6)	0.0103 (6)
N5	0.0823 (12)	0.0551 (9)	0.0618 (10)	−0.0071 (9)	0.0051 (9)	0.0015 (8)
S1	0.0477 (2)	0.0538 (3)	0.0488 (2)	0.00206 (18)	0.00416 (18)	−0.00887 (18)
S2	0.0479 (3)	0.0615 (3)	0.0517 (3)	0.00499 (19)	0.0009 (2)	−0.01617 (19)

Ni1—S2	2.1674 (9)	C8—C12	1.502 (2)
Ni1—S2i	2.1674 (9)	C9—C10	1.382 (2)
Ni1—S1	2.1704 (7)	C9—H9A	0.9300
Ni1—S1i	2.1704 (7)	C10—H10A	0.9300
C1—C2	1.359 (2)	C11—N3	1.138 (3)
C1—C4	1.430 (2)	C12—N4	1.498 (2)
C1—S1	1.7302 (17)	C12—H12A	0.9700
C2—C3	1.426 (2)	C12—H12B	0.9700
C2—S2	1.7334 (18)	C13—N4	1.330 (2)
C3—N2	1.143 (2)	C13—C14	1.372 (3)
C4—N1	1.139 (2)	C13—H13A	0.9300
C5—C6	1.376 (3)	C14—N5	1.322 (3)
C5—C10	1.390 (3)	C14—H14A	0.9300
C5—C11	1.445 (3)	C15—N5	1.325 (3)
C6—C7	1.378 (3)	C15—C16	1.368 (3)
C6—H6A	0.9300	C15—H15A	0.9300
C7—C8	1.382 (2)	C16—N4	1.337 (2)
C7—H7A	0.9300	C16—H16A	0.9300
C8—C9	1.384 (2)
S2—Ni1—S2i	180.00 (2)	C9—C10—C5	119.44 (17)
S2—Ni1—S1	92.96 (3)	C9—C10—H10A	120.3
S2i—Ni1—S1	87.04 (3)	C5—C10—H10A	120.3
S2—Ni1—S1i	87.04 (3)	N3—C11—C5	178.5 (3)
S2i—Ni1—S1i	92.96 (3)	N4—C12—C8	114.59 (14)
S1—Ni1—S1i	180.00 (2)	N4—C12—H12A	108.6
C2—C1—C4	121.29 (15)	C8—C12—H12A	108.6
C2—C1—S1	120.95 (13)	N4—C12—H12B	108.6
C4—C1—S1	117.76 (13)	C8—C12—H12B	108.6
C1—C2—C3	121.67 (15)	H12A—C12—H12B	107.6
C1—C2—S2	121.17 (12)	N4—C13—C14	118.57 (17)
C3—C2—S2	117.14 (13)	N4—C13—H13A	120.7
N2—C3—C2	178.3 (2)	C14—C13—H13A	120.7
N1—C4—C1	179.3 (2)	N5—C14—C13	123.76 (19)
C6—C5—C10	120.33 (16)	N5—C14—H14A	118.1
C6—C5—C11	118.78 (17)	C13—C14—H14A	118.1
C10—C5—C11	120.88 (17)	N5—C15—C16	122.83 (19)
C5—C6—C7	119.54 (17)	N5—C15—H15A	118.6
C5—C6—H6A	120.2	C16—C15—H15A	118.6
C7—C6—H6A	120.2	N4—C16—C15	119.37 (18)
C6—C7—C8	121.07 (17)	N4—C16—H16A	120.3
C6—C7—H7A	119.5	C15—C16—H16A	120.3
C8—C7—H7A	119.5	C13—N4—C16	119.44 (16)
C7—C8—C9	119.00 (16)	C13—N4—C12	123.08 (14)
C7—C8—C12	119.48 (16)	C16—N4—C12	117.47 (15)
C9—C8—C12	121.42 (16)	C14—N5—C15	115.85 (18)
C10—C9—C8	120.61 (16)	C1—S1—Ni1	102.41 (7)
C10—C9—H9A	119.7	C2—S2—Ni1	102.28 (6)
C8—C9—H9A	119.7