Bis(4,4'-sulfanediyldipyridinium) tetra-chloridonickelate(II) dichloride.

In the title compound, (C10H10N2S)2[NiCl4]Cl2, the Ni(2+) cation is tetra-hedrally coordinated by four chloride anions. Two 4,4'-sulfanediyldipyridinium cations and two non-coordinating chloride anions are connected via N-H⋯Cl hydrogen-bonding inter-actions into 20-membered rings, in the middle of which are situated the [NiCl4](2-) complex anions. These rings are stacked in the b-axis direction. The Ni(2+) cation is located on a twofold rotation axis, whereas the chloride anions and the 4,4'-sulfanediyldipyridinium cations occupy general positions.

Related literature

For background information on this project, see: Boeckmann & Näther (2010 ▶, 2011 ▶); Wöhlert et al. (2011 ▶). For the crystal structure of 4,4′-thio­dipyridine, see: Vaganova et al. (2004 ▶).

Experimental

Crystal data

(C10H10N2S)2[NiCl4]Cl2

M = 651.93

Monoclinic,

a = 19.0497 (9) Å

b = 8.0534 (5) Å

c = 17.7883 (11) Å

β = 92.368 (6)°

V = 2726.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.47 mm−1

T = 200 K

0.32 × 0.13 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T min = 0.789, T max = 0.899

10707 measured reflections

3162 independent reflections

2308 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.084

S = 0.99

3162 reflections

151 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.43 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2011 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812050623/wm2703sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050623/wm2703Isup2.hkl

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

(C10H10N2S)2[NiCl4]Cl2	F(000) = 1320
Mr = 651.93	Dx = 1.588 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 10707 reflections
a = 19.0497 (9) Å	θ = 2.3–27.9°
b = 8.0534 (5) Å	µ = 1.47 mm−1
c = 17.7883 (11) Å	T = 200 K
β = 92.368 (6)°	Needle, blue
V = 2726.7 (3) Å3	0.32 × 0.13 × 0.07 mm
Z = 4

Stoe IPDS-1 diffractometer	3162 independent reflections
Radiation source: fine-focus sealed tube	2308 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Phi scans	θmax = 27.9°, θmin = 2.3°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −23→22
Tmin = 0.789, Tmax = 0.899	k = −10→10
10707 measured reflections	l = −23→23

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)] = 0.037	H-atom parameters constrained
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0463P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.001
3162 reflections	Δρmax = 0.47 e Å−3
151 parameters	Δρmin = −0.43 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (3)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.5000	0.66427 (5)	0.7500	0.02527 (13)
Cl1	0.59273 (4)	0.81985 (9)	0.71816 (4)	0.0465 (2)
Cl2	0.55194 (4)	0.49082 (8)	0.83619 (3)	0.03563 (17)
Cl3	0.75812 (4)	0.08791 (10)	0.90585 (4)	0.04236 (19)
N1	0.73877 (13)	0.1738 (3)	0.73764 (14)	0.0425 (6)
H1N1	0.7637	0.1582	0.7798	0.051*
C1	0.76591 (16)	0.1281 (4)	0.67229 (18)	0.0424 (7)
H1	0.8121	0.0839	0.6718	0.051*
C2	0.72674 (14)	0.1451 (3)	0.60598 (16)	0.0366 (6)
H2	0.7444	0.1073	0.5598	0.044*
C3	0.66077 (14)	0.2189 (3)	0.60792 (14)	0.0305 (5)
C4	0.63496 (14)	0.2699 (3)	0.67604 (14)	0.0319 (5)
H4	0.5905	0.3227	0.6779	0.038*
C5	0.67510 (14)	0.2424 (3)	0.74071 (15)	0.0351 (6)
H5	0.6575	0.2724	0.7880	0.042*
S1	0.61640 (4)	0.26112 (10)	0.52047 (4)	0.03808 (18)
N2	0.38935 (13)	0.1530 (3)	0.55137 (14)	0.0394 (5)
H1N2	0.3443	0.1351	0.5570	0.047*
C6	0.40903 (15)	0.2520 (4)	0.49540 (15)	0.0383 (6)
H6	0.3746	0.2986	0.4615	0.046*
C7	0.47845 (14)	0.2859 (3)	0.48701 (14)	0.0313 (5)
H7	0.4926	0.3573	0.4479	0.038*
C8	0.52829 (13)	0.2148 (3)	0.53643 (13)	0.0262 (5)
C9	0.50641 (14)	0.1074 (3)	0.59261 (14)	0.0284 (5)
H9	0.5398	0.0541	0.6257	0.034*
C10	0.43635 (15)	0.0807 (3)	0.59898 (15)	0.0357 (6)
H10	0.4206	0.0100	0.6376	0.043*

	U11	U22	U33	U12	U13	U23
Ni1	0.0281 (3)	0.0202 (2)	0.0271 (2)	0.000	−0.00296 (16)	0.000
Cl1	0.0355 (4)	0.0461 (4)	0.0574 (4)	−0.0070 (3)	−0.0039 (3)	0.0256 (3)
Cl2	0.0370 (4)	0.0359 (3)	0.0341 (3)	0.0052 (3)	0.0038 (2)	0.0137 (3)
Cl3	0.0275 (4)	0.0549 (4)	0.0440 (4)	0.0065 (3)	−0.0057 (3)	−0.0111 (3)
N1	0.0347 (15)	0.0451 (13)	0.0462 (14)	0.0034 (11)	−0.0153 (10)	−0.0021 (11)
C1	0.0290 (17)	0.0392 (16)	0.0586 (19)	0.0058 (11)	−0.0034 (12)	0.0004 (13)
C2	0.0266 (15)	0.0371 (15)	0.0462 (15)	0.0021 (11)	0.0050 (10)	−0.0019 (12)
C3	0.0248 (14)	0.0302 (12)	0.0365 (13)	−0.0030 (9)	−0.0002 (9)	0.0021 (10)
C4	0.0256 (14)	0.0339 (13)	0.0359 (13)	0.0016 (10)	−0.0006 (9)	−0.0040 (10)
C5	0.0351 (16)	0.0326 (13)	0.0372 (14)	0.0001 (11)	−0.0035 (10)	−0.0023 (11)
S1	0.0278 (4)	0.0548 (4)	0.0316 (3)	−0.0045 (3)	0.0014 (2)	0.0041 (3)
N2	0.0240 (13)	0.0422 (13)	0.0520 (14)	−0.0035 (10)	−0.0005 (9)	−0.0154 (11)
C6	0.0339 (16)	0.0375 (14)	0.0421 (15)	0.0076 (12)	−0.0139 (11)	−0.0110 (12)
C7	0.0360 (16)	0.0305 (13)	0.0269 (12)	0.0033 (10)	−0.0051 (9)	−0.0018 (9)
C8	0.0265 (13)	0.0239 (11)	0.0280 (11)	0.0017 (9)	−0.0005 (9)	−0.0082 (9)
C9	0.0282 (14)	0.0236 (11)	0.0330 (12)	0.0000 (9)	−0.0039 (9)	−0.0021 (9)
C10	0.0384 (17)	0.0292 (13)	0.0397 (14)	−0.0060 (11)	0.0038 (11)	−0.0047 (11)

Ni1—Cl1	2.2569 (7)	C4—H4	0.9500
Ni1—Cl1i	2.2569 (7)	C5—H5	0.9500
Ni1—Cl2i	2.2706 (7)	S1—C8	1.754 (3)
Ni1—Cl2	2.2706 (6)	N2—C10	1.340 (4)
N1—C5	1.336 (4)	N2—C6	1.341 (4)
N1—C1	1.343 (4)	N2—H1N2	0.8800
N1—H1N1	0.8800	C6—C7	1.365 (4)
C1—C2	1.376 (4)	C6—H6	0.9500
C1—H1	0.9500	C7—C8	1.391 (3)
C2—C3	1.392 (4)	C7—H7	0.9500
C2—H2	0.9500	C8—C9	1.398 (3)
C3—C4	1.389 (4)	C9—C10	1.361 (4)
C3—S1	1.772 (3)	C9—H9	0.9500
C4—C5	1.373 (4)	C10—H10	0.9500
Cl1—Ni1—Cl1i	112.56 (5)	N1—C5—H5	119.7
Cl1—Ni1—Cl2i	119.73 (3)	C4—C5—H5	119.7
Cl1i—Ni1—Cl2i	100.79 (2)	C8—S1—C3	104.00 (12)
Cl1—Ni1—Cl2	100.79 (2)	C10—N2—C6	121.9 (3)
Cl1i—Ni1—Cl2	119.73 (3)	C10—N2—H1N2	119.1
Cl2i—Ni1—Cl2	104.07 (4)	C6—N2—H1N2	119.1
C5—N1—C1	122.1 (2)	N2—C6—C7	120.1 (2)
C5—N1—H1N1	119.0	N2—C6—H6	119.9
C1—N1—H1N1	119.0	C7—C6—H6	119.9
N1—C1—C2	120.0 (3)	C6—C7—C8	119.2 (3)
N1—C1—H1	120.0	C6—C7—H7	120.4
C2—C1—H1	120.0	C8—C7—H7	120.4
C1—C2—C3	118.7 (3)	C7—C8—C9	119.4 (2)
C1—C2—H2	120.7	C7—C8—S1	116.3 (2)
C3—C2—H2	120.7	C9—C8—S1	124.26 (19)
C4—C3—C2	120.0 (2)	C10—C9—C8	118.6 (2)
C4—C3—S1	122.4 (2)	C10—C9—H9	120.7
C2—C3—S1	117.3 (2)	C8—C9—H9	120.7
C5—C4—C3	118.6 (3)	N2—C10—C9	120.7 (3)
C5—C4—H4	120.7	N2—C10—H10	119.7
C3—C4—H4	120.7	C9—C10—H10	119.7
N1—C5—C4	120.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···Cl3i	0.88	2.12	2.987 (3)	168
N1—H1N1···Cl3	0.88	2.32	3.078 (3)	144

Table 1

Selected bond lengths (Å)

Ni1—Cl1	2.2569 (7)
Ni1—Cl2	2.2706 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯Cl3i	0.88	2.12	2.987 (3)	168
N1—H1N1⋯Cl3	0.88	2.32	3.078 (3)	144

Symmetry code: (i) .