Bis[1-(4-chloro-benz-yl)pyridinium] bis-(1,2,5-thia-diazole-3,4-dithiol-ato)nickelate(II).

The asymmetric unit of the salt, (C(12)H(11)ClN)(2)[Ni(C(2)N(2)S(3))(2)], comprises one cation and a half of Ni(tdas)(2) (tdas = 1,2,5-thia-diazole-3,4-dithiol-ate) anion. The Ni(II) atom is located at a centre of inversion. The Ni(II) atom has a square-planar coordination with Ni-S distances of 2.2052 (4) and 2.1970 (5) Å. In crystal, weak C-H⋯S and C-H⋯Ni contacts are observed between the anions and cations.

Related literature

For background to complexes containing the [Ni(mnt)2] anion, see: Robertson & Cronin (2002 ▶); Xie et al. (2002 ▶); Ni et al. (2005 ▶); Chen et al. (2010 ▶). For details of other square-planar [Ni(tdas)2] complexes, see: Awaga et al. (1994 ▶); Yamochi et al. (2001 ▶); Okuno et al. (2003 ▶); Ni et al. (2004 ▶). For C—H⋯Ni contacts, see: Brookhart et al. (2007 ▶); Yang & Ni (2006 ▶).

Experimental

Crystal data

(C12H11ClN)2[Ni(C2N2S3)2]

M = 764.49

Monoclinic,

a = 11.3091 (10) Å

b = 12.6699 (12) Å

c = 12.2405 (11) Å

β = 116.005 (1)°

V = 1576.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.21 mm−1

T = 296 K

0.22 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.788, T max = 0.872

11011 measured reflections

2771 independent reflections

2583 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.062

S = 1.03

2771 reflections

196 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102873X/kp2343sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102873X/kp2343Isup2.hkl

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

(C12H11ClN)2[Ni(C2N2S3)2]	F(000) = 780
Mr = 764.49	Dx = 1.611 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8963 reflections
a = 11.3091 (10) Å	θ = 2.5–27.6°
b = 12.6699 (12) Å	µ = 1.21 mm−1
c = 12.2405 (11) Å	T = 296 K
β = 116.005 (1)°	Block, brown
V = 1576.3 (2) Å3	0.22 × 0.17 × 0.11 mm
Z = 2

Bruker Smart AAPEX CCD diffractometer	2771 independent reflections
Radiation source: fine-focus sealed tube	2583 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→13
Tmin = 0.788, Tmax = 0.872	k = −15→15
11011 measured reflections	l = −14→14

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0288P)2 + 0.688P] where P = (Fo2 + 2Fc2)/3
2771 reflections	(Δ/σ)max = 0.001
196 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.34 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	1.0000	0.0000	1.0000	0.03315 (10)
S1	0.92227 (4)	0.11624 (3)	0.85099 (4)	0.04375 (12)
S2	0.80993 (4)	−0.08083 (4)	0.94044 (4)	0.04587 (13)
S3	0.52625 (5)	0.07090 (6)	0.64534 (5)	0.06730 (18)
Cl1	0.81302 (6)	0.64372 (5)	1.10601 (5)	0.06886 (17)
N1	0.66806 (17)	0.13162 (15)	0.68113 (15)	0.0560 (4)
N2	0.57869 (16)	−0.02144 (15)	0.75207 (15)	0.0570 (4)
N3	0.71207 (14)	0.36476 (11)	0.59981 (13)	0.0386 (3)
C1	0.75730 (17)	0.08146 (14)	0.77589 (16)	0.0414 (4)
C2	0.70635 (18)	−0.00619 (13)	0.81645 (17)	0.0419 (4)
C3	0.8199 (2)	0.57027 (15)	0.79196 (18)	0.0511 (5)
H3	0.8155	0.6055	0.7236	0.061*
C4	0.8134 (2)	0.62703 (16)	0.88550 (19)	0.0550 (5)
H4	0.8048	0.7001	0.8807	0.066*
C5	0.81978 (17)	0.57358 (15)	0.98640 (17)	0.0470 (4)
C6	0.83425 (19)	0.46580 (16)	0.99634 (18)	0.0507 (4)
H6	0.8390	0.4309	1.0650	0.061*
C7	0.84157 (19)	0.41026 (15)	0.90237 (18)	0.0479 (4)
H7	0.8525	0.3374	0.9087	0.057*
C8	0.83301 (17)	0.46093 (15)	0.79884 (16)	0.0420 (4)
C9	0.84261 (18)	0.39821 (16)	0.69918 (17)	0.0464 (4)
H9A	0.8950	0.3356	0.7343	0.056*
H9B	0.8886	0.4401	0.6636	0.056*
C10	0.59709 (18)	0.38027 (15)	0.60462 (18)	0.0471 (4)
H10	0.5951	0.4172	0.6695	0.057*
C11	0.48229 (19)	0.34190 (18)	0.51417 (19)	0.0564 (5)
H11	0.4028	0.3531	0.5178	0.068*
C12	0.4847 (2)	0.28709 (17)	0.41842 (19)	0.0560 (5)
H12	0.4075	0.2604	0.3572	0.067*
C13	0.6037 (2)	0.27238 (17)	0.41461 (18)	0.0549 (5)
H13	0.6077	0.2358	0.3504	0.066*
C14	0.71548 (19)	0.31201 (15)	0.50599 (17)	0.0485 (4)
H14	0.7957	0.3023	0.5033	0.058*

	U11	U22	U33	U12	U13	U23
Ni1	0.03566 (17)	0.02727 (16)	0.04445 (18)	0.00239 (11)	0.02487 (14)	0.00392 (11)
S1	0.0409 (2)	0.0400 (2)	0.0576 (3)	0.00339 (18)	0.0282 (2)	0.0144 (2)
S2	0.0434 (3)	0.0386 (2)	0.0568 (3)	−0.00545 (18)	0.0230 (2)	0.00919 (19)
S3	0.0467 (3)	0.0940 (5)	0.0522 (3)	0.0000 (3)	0.0134 (2)	0.0145 (3)
Cl1	0.0629 (3)	0.0786 (4)	0.0630 (3)	0.0043 (3)	0.0258 (3)	−0.0204 (3)
N1	0.0504 (9)	0.0693 (11)	0.0502 (9)	0.0087 (8)	0.0237 (8)	0.0178 (8)
N2	0.0454 (9)	0.0700 (11)	0.0526 (10)	−0.0095 (8)	0.0188 (8)	0.0016 (8)
N3	0.0401 (8)	0.0377 (7)	0.0441 (8)	0.0038 (6)	0.0240 (7)	0.0060 (6)
C1	0.0431 (10)	0.0454 (10)	0.0435 (9)	0.0059 (7)	0.0262 (8)	0.0043 (8)
C2	0.0422 (10)	0.0437 (10)	0.0450 (10)	−0.0019 (7)	0.0238 (8)	−0.0020 (7)
C3	0.0558 (11)	0.0458 (11)	0.0493 (11)	0.0039 (9)	0.0208 (9)	0.0107 (8)
C4	0.0566 (12)	0.0397 (10)	0.0609 (12)	0.0055 (9)	0.0185 (10)	0.0014 (9)
C5	0.0345 (9)	0.0545 (11)	0.0487 (11)	0.0003 (8)	0.0152 (8)	−0.0068 (8)
C6	0.0530 (11)	0.0528 (11)	0.0511 (11)	−0.0024 (9)	0.0274 (9)	0.0048 (9)
C7	0.0536 (11)	0.0390 (9)	0.0566 (11)	−0.0019 (8)	0.0292 (9)	0.0053 (8)
C8	0.0354 (9)	0.0437 (9)	0.0477 (10)	−0.0011 (7)	0.0190 (8)	0.0034 (8)
C9	0.0388 (9)	0.0537 (11)	0.0513 (11)	0.0012 (8)	0.0239 (8)	0.0035 (8)
C10	0.0431 (10)	0.0535 (11)	0.0518 (11)	0.0087 (8)	0.0274 (9)	0.0012 (9)
C11	0.0392 (10)	0.0688 (14)	0.0630 (13)	0.0102 (9)	0.0240 (9)	0.0005 (10)
C12	0.0478 (11)	0.0634 (13)	0.0510 (11)	0.0030 (9)	0.0164 (9)	0.0025 (9)
C13	0.0597 (12)	0.0629 (13)	0.0484 (11)	0.0013 (10)	0.0294 (10)	−0.0047 (9)
C14	0.0500 (11)	0.0541 (11)	0.0549 (11)	0.0028 (9)	0.0354 (9)	−0.0002 (9)

Ni1—S2	2.1970 (5)	C4—H4	0.9300
Ni1—S2i	2.1970 (5)	C5—C6	1.374 (3)
Ni1—S1	2.2052 (4)	C6—C7	1.382 (3)
Ni1—S1i	2.2052 (4)	C6—H6	0.9300
S1—C1	1.7367 (19)	C7—C8	1.386 (3)
S2—C2	1.7351 (19)	C7—H7	0.9300
S3—N1	1.6552 (18)	C8—C9	1.499 (3)
S3—N2	1.6576 (19)	C9—H9A	0.9700
Cl1—C5	1.7428 (19)	C9—H9B	0.9700
N1—C1	1.320 (2)	C10—C11	1.374 (3)
N2—C2	1.321 (2)	C10—H10	0.9300
N3—C10	1.342 (2)	C11—C12	1.373 (3)
N3—C14	1.344 (2)	C11—H11	0.9300
N3—C9	1.505 (2)	C12—C13	1.379 (3)
C1—C2	1.436 (2)	C12—H12	0.9300
C3—C4	1.381 (3)	C13—C14	1.364 (3)
C3—C8	1.392 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.382 (3)
S2—Ni1—S2i	180.0	C5—C6—H6	120.6
S2—Ni1—S1	93.419 (17)	C7—C6—H6	120.6
S2i—Ni1—S1	86.581 (17)	C6—C7—C8	121.32 (18)
S2—Ni1—S1i	86.581 (17)	C6—C7—H7	119.3
S2i—Ni1—S1i	93.419 (17)	C8—C7—H7	119.3
S1—Ni1—S1i	180.0	C7—C8—C3	118.64 (17)
C1—S1—Ni1	102.38 (6)	C7—C8—C9	119.85 (17)
C2—S2—Ni1	102.90 (6)	C3—C8—C9	121.48 (16)
N1—S3—N2	98.58 (8)	C8—C9—N3	114.31 (14)
C1—N1—S3	106.72 (13)	C8—C9—H9A	108.7
C2—N2—S3	106.67 (14)	N3—C9—H9A	108.7
C10—N3—C14	120.12 (16)	C8—C9—H9B	108.7
C10—N3—C9	123.34 (15)	N3—C9—H9B	108.7
C14—N3—C9	116.44 (14)	H9A—C9—H9B	107.6
N1—C1—C2	114.09 (17)	N3—C10—C11	120.30 (18)
N1—C1—S1	124.97 (14)	N3—C10—H10	119.9
C2—C1—S1	120.93 (14)	C11—C10—H10	119.9
N2—C2—C1	113.95 (17)	C12—C11—C10	120.10 (18)
N2—C2—S2	125.75 (14)	C12—C11—H11	119.9
C1—C2—S2	120.30 (14)	C10—C11—H11	119.9
C4—C3—C8	120.74 (18)	C11—C12—C13	118.82 (19)
C4—C3—H3	119.6	C11—C12—H12	120.6
C8—C3—H3	119.6	C13—C12—H12	120.6
C3—C4—C5	118.99 (18)	C14—C13—C12	119.31 (19)
C3—C4—H4	120.5	C14—C13—H13	120.3
C5—C4—H4	120.5	C12—C13—H13	120.3
C6—C5—C4	121.56 (18)	N3—C14—C13	121.34 (17)
C6—C5—Cl1	118.66 (16)	N3—C14—H14	119.3
C4—C5—Cl1	119.76 (15)	C13—C14—H14	119.3
C5—C6—C7	118.73 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···S2ii	0.93	2.86	3.765 (2)	163
C11—H11···S2iii	0.93	2.80	3.715 (2)	169
C9—H9B···Ni1iv	0.97	2.90	3.818 (3)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯S2i	0.93	2.86	3.765 (2)	163
C11—H11⋯S2ii	0.93	2.80	3.715 (2)	169
C9—H9B⋯Ni1iii	0.97	2.90	3.818 (3)	159

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