Bis(4-chloro-pyridinium) tetra-chlorido-nickelate(II).

In the title compound, (C(5)H(5)ClN)(2)[NiCl(4)], the dianion lies on a twofold rotation axis. Two cations are linked to each anion by classical N-H⋯Cl hydrogen bonds, and short Cl⋯Cl contacts and Cl⋯π stacking inter-actions [with distances of 3.376 (2) and 3.684 (2) Å, respectively] extend this pattern into a chain. The [NiCl(4)](2-) anion shows significant deviation from ideal tetra-hedral geometry.

Related literature

For related literature, see: Espallargas et al. (2006 ▶); Luque et al. (2001 ▶); Willett et al. (2003 ▶).

Experimental

Crystal data

(C5H5ClN)2[NiCl4]

M = 429.61

Monoclinic,

a = 16.513 (2) Å

b = 7.2862 (11) Å

c = 13.948 (2) Å

β = 100.526 (3)°

V = 1650.0 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.13 mm−1

T = 298 (2) K

0.36 × 0.28 × 0.26 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.46, T max = 0.57

5779 measured reflections

2049 independent reflections

1820 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.123

S = 1.07

2049 reflections

87 parameters

H-atom parameters constrained

Δρmax = 0.80 e Å−3

Δρmin = −0.98 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001360/at2533sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001360/at2533Isup2.hkl

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

(C5H5ClN)2[NiCl4]	F(000) = 856
Mr = 429.61	Dx = 1.729 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5779 reflections
a = 16.513 (2) Å	θ = 2.5–28.3°
b = 7.2862 (11) Å	µ = 2.13 mm−1
c = 13.948 (2) Å	T = 298 K
β = 100.526 (3)°	Block, light green
V = 1650.0 (4) Å3	0.36 × 0.28 × 0.26 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	2049 independent reflections
Radiation source: fine-focus sealed tube	1820 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→22
Tmin = 0.46, Tmax = 0.57	k = −9→9
5779 measured reflections	l = −16→18

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0592P)2 + 3.4552P] where P = (Fo2 + 2Fc2)/3
2049 reflections	(Δ/σ)max < 0.001
87 parameters	Δρmax = 0.80 e Å−3
0 restraints	Δρmin = −0.98 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	0.5000	0.04605 (7)	0.7500	0.03657 (17)
Cl1	0.23687 (6)	0.54295 (11)	0.57163 (7)	0.0551 (2)
N1	0.4043 (2)	0.3152 (4)	0.3908 (3)	0.0575 (8)
H1	0.4372	0.2717	0.3553	0.069*
C6	0.3310 (2)	0.3788 (5)	0.3468 (3)	0.0561 (8)
H6A	0.3162	0.3745	0.2792	0.067*
C5	0.2776 (2)	0.4503 (4)	0.4014 (3)	0.0488 (7)
H5A	0.2262	0.4942	0.3719	0.059*
C4	0.30238 (19)	0.4555 (4)	0.5012 (2)	0.0425 (6)
C3	0.3784 (2)	0.3868 (5)	0.5454 (3)	0.0557 (8)
H3A	0.3947	0.3887	0.6129	0.067*
C2	0.4285 (2)	0.3161 (5)	0.4867 (3)	0.0604 (9)
H2A	0.4798	0.2685	0.5141	0.072*
Cl2	0.42552 (5)	−0.15941 (15)	0.64578 (9)	0.0716 (3)
Cl3	0.59081 (7)	0.21312 (15)	0.68764 (8)	0.0692 (3)

	U11	U22	U33	U12	U13	U23
Ni1	0.0316 (3)	0.0336 (3)	0.0470 (3)	0.000	0.0137 (2)	0.000
Cl1	0.0570 (5)	0.0507 (5)	0.0633 (5)	0.0008 (4)	0.0259 (4)	−0.0050 (3)
N1	0.0537 (17)	0.0489 (15)	0.077 (2)	0.0035 (13)	0.0319 (16)	−0.0008 (14)
C6	0.063 (2)	0.0528 (18)	0.0570 (18)	0.0012 (17)	0.0217 (16)	0.0033 (15)
C5	0.0463 (17)	0.0456 (16)	0.0560 (18)	0.0044 (13)	0.0130 (14)	0.0072 (13)
C4	0.0402 (15)	0.0360 (14)	0.0538 (16)	−0.0028 (11)	0.0146 (13)	−0.0009 (12)
C3	0.0510 (19)	0.0515 (18)	0.062 (2)	0.0024 (15)	0.0026 (16)	0.0000 (16)
C2	0.0416 (17)	0.0540 (19)	0.085 (3)	0.0063 (15)	0.0112 (17)	−0.0002 (18)
Cl2	0.0384 (4)	0.0777 (6)	0.0951 (7)	0.0017 (4)	0.0026 (4)	−0.0373 (6)
Cl3	0.0636 (6)	0.0751 (6)	0.0769 (6)	−0.0151 (5)	0.0337 (5)	0.0112 (5)

Ni1—Cl3	2.2280 (9)	C6—C5	1.368 (5)
Ni1—Cl3i	2.2280 (9)	C6—H6A	0.9300
Ni1—Cl2	2.2833 (10)	C5—C4	1.379 (5)
Ni1—Cl2i	2.2833 (10)	C5—H5A	0.9300
Cl1—C4	1.712 (3)	C4—C3	1.387 (5)
N1—C2	1.324 (5)	C3—C2	1.368 (5)
N1—C6	1.336 (5)	C3—H3A	0.9300
N1—H1	0.8600	C2—H2A	0.9300
Cl3—Ni1—Cl3i	113.76 (6)	C6—C5—C4	118.0 (3)
Cl3—Ni1—Cl2	115.62 (4)	C6—C5—H5A	121.0
Cl3i—Ni1—Cl2	106.51 (4)	C4—C5—H5A	121.0
Cl3—Ni1—Cl2i	106.51 (4)	C5—C4—C3	121.1 (3)
Cl3i—Ni1—Cl2i	115.62 (4)	C5—C4—Cl1	119.2 (3)
Cl2—Ni1—Cl2i	98.06 (6)	C3—C4—Cl1	119.6 (3)
C2—N1—C6	122.9 (3)	C2—C3—C4	117.8 (3)
C2—N1—H1	118.5	C2—C3—H3A	121.1
C6—N1—H1	118.5	C4—C3—H3A	121.1
N1—C6—C5	119.9 (3)	N1—C2—C3	120.2 (3)
N1—C6—H6A	120.1	N1—C2—H2A	119.9
C5—C6—H6A	120.1	C3—C2—H2A	119.9

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl3	0.93	2.79	3.586 (4)	145.
N1—H1···Cl2ii	0.86	2.41	3.158 (3)	145.
C5—H5A···Cl2iii	0.93	2.75	3.633 (4)	159.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Cl3	0.93	2.79	3.586 (4)	145
N1—H1⋯Cl2i	0.86	2.41	3.158 (3)	145
C5—H5A⋯Cl2ii	0.93	2.75	3.633 (4)	159

Symmetry codes: (i) ; (ii) .