Bis(3-methyl-pyridinium) tetra-chlorido-cuprate(II).

The title compound, (C(6)H(8)N)(2)[CuCl(4)], is composed of two 3-methyl-pyridinium cation and one tetra-chloridocuprate(II) anion. The geometry around the copper(II) ion is that of a distorted tetra-hedron. In the crystal structure, the anions and cations are linked by three different N-H⋯Cl hydrogen bonds. In addition, the crystal structure exhibits aromatic π-π inter-actions between the pyridinium rings of two discrete units [centroid-centroid distance = 3.704 (2) Å].

Related literature

For general background on the influence of crystal-packing forces on the geometry of the tetrahalogenidocuprate(II) species, see: Schneider et al. (2007 ▶); Parent et al. (2007 ▶); Haddad et al. (2006 ▶); Marzotto et al. (2001 ▶); Choi et al. (2002 ▶); Awwadi et al. (2007 ▶). For the electronic spectrum in DMF solution, see Lee et al. (2002 ▶). For related literature, see: Lee et al. (2008 ▶).

Experimental

Crystal data

(C6H8N)2[CuCl4]

M = 393.61

Monoclinic,

a = 9.0438 (3) Å

b = 13.0530 (4) Å

c = 13.7391 (5) Å

β = 103.541 (2)°

V = 1576.80 (9) Å3

Z = 4

Mo Kα radiation

μ = 2.05 mm−1

T = 123 K

0.25 × 0.24 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.603, T max = 0.62

16009 measured reflections

3899 independent reflections

3429 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.062

S = 1.04

3899 reflections

182 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.35 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007818/lx2094sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007818/lx2094Isup2.hkl

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

(C6H8N)2[CuCl4]	F(000) = 796
Mr = 393.61	Dx = 1.658 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7316 reflections
a = 9.0438 (3) Å	θ = 2.8–28.3°
b = 13.0530 (4) Å	µ = 2.05 mm−1
c = 13.7391 (5) Å	T = 123 K
β = 103.541 (2)°	Block, orange
V = 1576.80 (9) Å3	0.25 × 0.24 × 0.23 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3429 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2002)	θmax = 28.3°, θmin = 2.2°
Tmin = 0.603, Tmax = 0.62	h = −11→12
16009 measured reflections	k = −17→17
3899 independent reflections	l = −17→18

Refinement on F2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.024	w = 1/[σ2(Fo2) + (0.0228P)2 + 0.7012P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.062	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.36 e Å−3
3899 reflections	Δρmin = −0.35 e Å−3
182 parameters

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.

	x	y	z	Uiso*/Ueq
Cu	0.55797 (2)	0.545725 (15)	0.703075 (14)	0.01588 (6)
Cl1	0.65531 (4)	0.43858 (3)	0.60513 (3)	0.02068 (9)
Cl2	0.75323 (4)	0.65743 (3)	0.73115 (3)	0.02099 (9)
Cl3	0.36357 (4)	0.65699 (3)	0.68081 (3)	0.01929 (9)
Cl4	0.46771 (5)	0.42349 (3)	0.78922 (3)	0.02114 (9)
N1	0.44305 (15)	0.24760 (11)	0.59904 (10)	0.0181 (3)
H1	0.486 (2)	0.2980 (17)	0.6238 (15)	0.031 (6)*
C1	0.46256 (17)	0.21958 (12)	0.50880 (11)	0.0172 (3)
H1A	0.5226	0.2594	0.4771	0.021*
C2	0.39398 (17)	0.13197 (12)	0.46271 (11)	0.0175 (3)
C3	0.30426 (18)	0.07611 (13)	0.51325 (12)	0.0207 (3)
H3	0.2563	0.0168	0.4843	0.025*
C4	0.28506 (18)	0.10739 (13)	0.60617 (12)	0.0214 (3)
H4	0.2243	0.0698	0.6392	0.026*
C5	0.35733 (18)	0.19485 (13)	0.64851 (12)	0.0198 (3)
H5	0.3467	0.217	0.7108	0.024*
C6	0.4135 (2)	0.10069 (14)	0.36131 (12)	0.0244 (4)
H6A	0.3316	0.1282	0.3106	0.037*
H6B	0.413	0.0273	0.3567	0.037*
H6C	0.5086	0.1266	0.3519	0.037*
N2	0.85716 (15)	0.61542 (11)	0.52789 (10)	0.0188 (3)
H2	0.820 (3)	0.5984 (19)	0.5735 (17)	0.044 (7)*
C7	0.94635 (17)	0.69916 (13)	0.54089 (11)	0.0182 (3)
H7	0.9581	0.7377	0.5992	0.022*
C8	1.02028 (17)	0.72809 (12)	0.46826 (11)	0.0178 (3)
C9	0.99762 (18)	0.66842 (13)	0.38198 (12)	0.0197 (3)
H9	1.0457	0.6861	0.3315	0.024*
C10	0.90430 (19)	0.58299 (13)	0.37064 (12)	0.0223 (3)
H10	0.8895	0.5436	0.3128	0.027*
C11	0.83398 (19)	0.55690 (13)	0.44509 (12)	0.0214 (3)
H11	0.7712	0.4997	0.4386	0.026*
C12	1.1178 (2)	0.82208 (13)	0.48099 (13)	0.0253 (4)
H12A	1.0547	0.8815	0.4636	0.038*
H12B	1.1875	0.8177	0.4381	0.038*
H12C	1.1738	0.8273	0.5494	0.038*

	U11	U22	U33	U12	U13	U23
Cu	0.01598 (11)	0.01411 (10)	0.01823 (11)	−0.00095 (7)	0.00540 (8)	−0.00009 (7)
Cl1	0.0225 (2)	0.01704 (18)	0.0254 (2)	−0.00297 (15)	0.01148 (16)	−0.00423 (14)
Cl2	0.02040 (19)	0.02015 (19)	0.02291 (19)	−0.00627 (15)	0.00604 (15)	−0.00435 (15)
Cl3	0.02013 (19)	0.01763 (18)	0.02150 (19)	0.00232 (14)	0.00768 (15)	0.00053 (14)
Cl4	0.0242 (2)	0.01839 (19)	0.02248 (19)	−0.00029 (15)	0.00882 (15)	0.00461 (14)
N1	0.0172 (6)	0.0156 (7)	0.0202 (7)	−0.0019 (5)	0.0016 (5)	−0.0005 (5)
C1	0.0163 (7)	0.0172 (7)	0.0186 (7)	0.0000 (6)	0.0048 (6)	0.0028 (6)
C2	0.0168 (7)	0.0177 (7)	0.0174 (7)	0.0020 (6)	0.0028 (6)	0.0017 (6)
C3	0.0197 (8)	0.0171 (8)	0.0243 (8)	−0.0027 (6)	0.0029 (6)	0.0012 (6)
C4	0.0189 (8)	0.0215 (8)	0.0245 (8)	−0.0009 (6)	0.0066 (6)	0.0061 (7)
C5	0.0184 (7)	0.0233 (8)	0.0177 (7)	0.0030 (6)	0.0042 (6)	0.0025 (6)
C6	0.0300 (9)	0.0238 (9)	0.0192 (8)	0.0011 (7)	0.0053 (7)	−0.0024 (7)
N2	0.0180 (7)	0.0204 (7)	0.0185 (7)	−0.0002 (5)	0.0056 (5)	0.0027 (5)
C7	0.0186 (8)	0.0183 (8)	0.0173 (7)	0.0003 (6)	0.0034 (6)	−0.0004 (6)
C8	0.0157 (7)	0.0185 (8)	0.0191 (7)	0.0030 (6)	0.0039 (6)	0.0029 (6)
C9	0.0206 (8)	0.0228 (8)	0.0162 (7)	0.0069 (6)	0.0056 (6)	0.0042 (6)
C10	0.0254 (8)	0.0225 (8)	0.0172 (7)	0.0039 (7)	0.0015 (6)	−0.0035 (6)
C11	0.0196 (8)	0.0186 (8)	0.0238 (8)	−0.0006 (6)	0.0005 (6)	0.0001 (6)
C12	0.0263 (9)	0.0237 (9)	0.0272 (9)	−0.0058 (7)	0.0089 (7)	0.0020 (7)

Cu—Cl3	2.2455 (4)	C6—H6B	0.96
Cu—Cl4	2.2506 (4)	C6—H6C	0.96
Cu—Cl2	2.2526 (4)	N2—C7	1.345 (2)
Cu—Cl1	2.2576 (4)	N2—C11	1.345 (2)
N1—C5	1.336 (2)	N2—H2	0.81 (2)
N1—C1	1.343 (2)	C7—C8	1.378 (2)
N1—H1	0.80 (2)	C7—H7	0.93
C1—C2	1.382 (2)	C8—C9	1.393 (2)
C1—H1A	0.93	C8—C12	1.497 (2)
C2—C3	1.391 (2)	C9—C10	1.385 (2)
C2—C6	1.501 (2)	C9—H9	0.93
C3—C4	1.389 (2)	C10—C11	1.368 (2)
C3—H3	0.93	C10—H10	0.93
C4—C5	1.375 (2)	C11—H11	0.93
C4—H4	0.93	C12—H12A	0.96
C5—H5	0.93	C12—H12B	0.96
C6—H6A	0.96	C12—H12C	0.96
Cl3—Cu—Cl4	99.283 (16)	C2—C6—H6C	109.5
Cl3—Cu—Cl2	99.327 (17)	H6A—C6—H6C	109.5
Cl4—Cu—Cl2	137.322 (16)	H6B—C6—H6C	109.5
Cl3—Cu—Cl1	136.189 (16)	C7—N2—C11	122.92 (15)
Cl4—Cu—Cl1	96.568 (17)	C7—N2—H2	117.7 (17)
Cl2—Cu—Cl1	95.946 (16)	C11—N2—H2	119.3 (17)
C5—N1—C1	123.14 (15)	N2—C7—C8	120.27 (15)
C5—N1—H1	119.2 (15)	N2—C7—H7	119.9
C1—N1—H1	117.7 (15)	C8—C7—H7	119.9
N1—C1—C2	120.43 (15)	C7—C8—C9	117.62 (15)
N1—C1—H1A	119.8	C7—C8—C12	120.84 (15)
C2—C1—H1A	119.8	C9—C8—C12	121.53 (15)
C1—C2—C3	117.17 (15)	C10—C9—C8	120.68 (15)
C1—C2—C6	120.83 (15)	C10—C9—H9	119.7
C3—C2—C6	121.98 (15)	C8—C9—H9	119.7
C4—C3—C2	121.16 (15)	C11—C10—C9	119.60 (15)
C4—C3—H3	119.4	C11—C10—H10	120.2
C2—C3—H3	119.4	C9—C10—H10	120.2
C5—C4—C3	118.91 (16)	N2—C11—C10	118.90 (16)
C5—C4—H4	120.5	N2—C11—H11	120.5
C3—C4—H4	120.5	C10—C11—H11	120.5
N1—C5—C4	119.19 (16)	C8—C12—H12A	109.5
N1—C5—H5	120.4	C8—C12—H12B	109.5
C4—C5—H5	120.4	H12A—C12—H12B	109.5
C2—C6—H6A	109.5	C8—C12—H12C	109.5
C2—C6—H6B	109.5	H12A—C12—H12C	109.5
H6A—C6—H6B	109.5	H12B—C12—H12C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.80 (2)	2.44 (2)	3.136 (2)	146 (2)
N2—H2···Cl1	0.81 (2)	2.66 (2)	3.270 (2)	134 (2)
N2—H2···Cl2	0.81 (2)	2.50 (2)	3.196 (2)	145 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.80 (2)	2.44 (2)	3.136 (2)	146 (2)
N2—H2⋯Cl1	0.81 (2)	2.66 (2)	3.270 (2)	134 (2)
N2—H2⋯Cl2	0.81 (2)	2.50 (2)	3.196 (2)	145 (2)