Bis[4-(di-methyl-amino)-pyridinium] tetra-chlorido-cuprate(II).

The asymmetric unit of the title salt, (C7H11N2)2[CuCl4], comprises half a tetrahedral tetra-chlorido-cuprate anion, being located on a twofold axis, and a protonated 4-(di-methyl-amino)-pyridine cation. The geometry around the Cu(II) ion is highly distorted with the range of Cl-Cu-Cl angles being 94.94 (1)-141.03 (1)°. The crystal structure is stabilized by N-H⋯Cl and C-H⋯Cl hydrogen bonds. In the three-dimensional network, cations and anions pack in the lattice so as to generate chains of [CuCl4](2-) anions separated by two orientations of cation layers, which are inter-locked through π-π stacking contacts between pairs of pyridine rings, with centroid-centroid distances of 3.7874 (7) Å.

Related literature

For general background to organic-inorganic systems, see: Bouacida (2008 ▶). For related 4-di­methyl­amino­pyridinium metal(II) chloride salts, see: Khadri et al. (2013 ▶). For the geometry of four-coordinated tetra­halocuprate(II) ions, see: Awwadi et al. (2007 ▶); Choi et al. (2002 ▶); Diaz et al. (1999 ▶); Haddad et al. (2006 ▶); Harlow et al. (1975 ▶); Marzotto et al. (2001 ▶); Parent et al. (2007 ▶).

Experimental

Crystal data

(C7H11N2)2[CuCl4]

M = 451.71

Monoclinic,

a = 12.3750 (8) Å

b = 12.1901 (8) Å

c = 14.1713 (9) Å

β = 115.023 (1)°

V = 1937.1 (2) Å3

Z = 4

Mo Kα radiation

μ = 1.68 mm−1

T = 150 K

0.13 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T min = 0.675, T max = 0.747

12787 measured reflections

3895 independent reflections

3389 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.059

S = 1.05

3895 reflections

107 parameters

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2011 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813028006/bq2389sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028006/bq2389Isup2.hkl

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

(C7H11N2)2[CuCl4]	F(000) = 924
Mr = 451.71	Dx = 1.549 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6282 reflections
a = 12.3750 (8) Å	θ = 2.5–34.7°
b = 12.1901 (8) Å	µ = 1.68 mm−1
c = 14.1713 (9) Å	T = 150 K
β = 115.023 (1)°	Cube, yellow
V = 1937.1 (2) Å3	0.13 × 0.12 × 0.10 mm
Z = 4

Bruker APEXII CCD diffractometer	3895 independent reflections
Radiation source: sealed tube	3389 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 34.7°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −19→19
Tmin = 0.675, Tmax = 0.747	k = −18→18
12787 measured reflections	l = −22→22

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0283P)2 + 0.9756P] where P = (Fo2 + 2Fc2)/3
3895 reflections	(Δ/σ)max = 0.001
107 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
N1	0.43961 (8)	0.14134 (8)	−0.05308 (7)	0.0225 (2)
N2	0.24689 (8)	0.09752 (8)	0.12016 (7)	0.0250 (3)
C1	0.37610 (8)	0.12756 (8)	0.00275 (7)	0.0179 (2)
C2	0.39370 (8)	0.19580 (8)	0.08966 (7)	0.0202 (2)
C3	0.32794 (9)	0.17919 (9)	0.14518 (8)	0.0229 (3)
C4	0.22731 (9)	0.03122 (9)	0.03815 (9)	0.0259 (3)
C5	0.28831 (9)	0.04393 (8)	−0.02169 (8)	0.0222 (2)
C11	0.53277 (10)	0.22510 (10)	−0.02403 (9)	0.0286 (3)
C12	0.41514 (11)	0.07546 (10)	−0.14600 (9)	0.0280 (3)
Cu1	0.00000	0.05740 (1)	0.25000	0.0173 (1)
Cl1	0.07732 (2)	−0.06512 (2)	0.17693 (2)	0.0251 (1)
Cl2	0.15211 (2)	0.17785 (2)	0.29261 (2)	0.0211 (1)
H2	0.20730	0.08760	0.15680	0.0300*
H2A	0.45010	0.25170	0.10860	0.0240*
H3	0.33920	0.22490	0.20110	0.0270*
H4	0.17090	−0.02440	0.02220	0.0310*
H5	0.27260	−0.00200	−0.07840	0.0270*
H11A	0.49760	0.29640	−0.02970	0.0430*
H11B	0.57180	0.22070	−0.06980	0.0430*
H11C	0.59000	0.21310	0.04640	0.0430*
H12A	0.42520	−0.00080	−0.12750	0.0420*
H12B	0.46940	0.09570	−0.17540	0.0420*
H12C	0.33470	0.08820	−0.19620	0.0420*

	U11	U22	U33	U12	U13	U23
N1	0.0217 (4)	0.0262 (4)	0.0203 (4)	−0.0016 (3)	0.0097 (3)	0.0010 (3)
N2	0.0215 (4)	0.0318 (5)	0.0241 (4)	−0.0019 (3)	0.0120 (3)	0.0016 (3)
C1	0.0164 (4)	0.0182 (4)	0.0172 (4)	0.0003 (3)	0.0052 (3)	0.0015 (3)
C2	0.0200 (4)	0.0194 (4)	0.0192 (4)	−0.0025 (3)	0.0063 (3)	−0.0007 (3)
C3	0.0226 (4)	0.0250 (5)	0.0200 (4)	0.0010 (3)	0.0079 (3)	−0.0012 (3)
C4	0.0217 (4)	0.0265 (5)	0.0276 (5)	−0.0067 (4)	0.0087 (4)	−0.0001 (4)
C5	0.0210 (4)	0.0215 (4)	0.0217 (4)	−0.0036 (3)	0.0067 (3)	−0.0032 (3)
C11	0.0245 (5)	0.0341 (6)	0.0282 (5)	−0.0058 (4)	0.0122 (4)	0.0049 (4)
C12	0.0320 (5)	0.0322 (6)	0.0216 (4)	0.0056 (4)	0.0132 (4)	0.0010 (4)
Cu1	0.0164 (1)	0.0169 (1)	0.0192 (1)	0.0000	0.0082 (1)	0.0000
Cl1	0.0269 (1)	0.0203 (1)	0.0353 (1)	−0.0061 (1)	0.0200 (1)	−0.0087 (1)
Cl2	0.0205 (1)	0.0197 (1)	0.0232 (1)	−0.0035 (1)	0.0095 (1)	−0.0029 (1)

Cu1—Cl1i	2.2487 (3)	C2—C3	1.3653 (16)
Cu1—Cl2i	2.2588 (3)	C4—C5	1.3618 (17)
Cu1—Cl1	2.2487 (3)	C2—H2A	0.9300
Cu1—Cl2	2.2588 (3)	C3—H3	0.9300
N1—C1	1.3409 (15)	C4—H4	0.9300
N1—C12	1.4606 (15)	C5—H5	0.9300
N1—C11	1.4627 (16)	C11—H11A	0.9600
N2—C3	1.3498 (15)	C11—H11B	0.9600
N2—C4	1.3507 (15)	C11—H11C	0.9600
N2—H2	0.8600	C12—H12B	0.9600
C1—C2	1.4246 (13)	C12—H12C	0.9600
C1—C5	1.4217 (15)	C12—H12A	0.9600
Cl1i—Cu1—Cl2i	94.94 (1)	C3—C2—H2A	120.00
Cl1—Cu1—Cl2i	141.03 (1)	C2—C3—H3	119.00
Cl1—Cu1—Cl2	94.94 (1)	N2—C3—H3	120.00
Cl1—Cu1—Cl1i	96.76 (1)	N2—C4—H4	119.00
Cl1i—Cu1—Cl2	141.03 (1)	C5—C4—H4	119.00
Cl2—Cu1—Cl2i	98.91 (1)	C1—C5—H5	120.00
C1—N1—C12	120.89 (10)	C4—C5—H5	120.00
C1—N1—C11	120.68 (9)	H11A—C11—H11B	109.00
C11—N1—C12	118.41 (10)	H11A—C11—H11C	110.00
C3—N2—C4	120.68 (10)	N1—C11—H11A	109.00
C4—N2—H2	120.00	N1—C11—H11B	109.00
C3—N2—H2	120.00	N1—C11—H11C	109.00
C2—C1—C5	116.81 (9)	H11B—C11—H11C	109.00
N1—C1—C2	121.57 (9)	H12B—C12—H12C	109.00
N1—C1—C5	121.62 (9)	N1—C12—H12A	109.00
C1—C2—C3	120.08 (9)	N1—C12—H12B	109.00
N2—C3—C2	121.05 (10)	N1—C12—H12C	109.00
N2—C4—C5	121.52 (11)	H12A—C12—H12B	109.00
C1—C5—C4	119.84 (9)	H12A—C12—H12C	109.00
C1—C2—H2A	120.00
C11—N1—C1—C2	2.21 (15)	N1—C1—C2—C3	−179.66 (10)
C11—N1—C1—C5	−177.56 (10)	C5—C1—C2—C3	0.11 (14)
C12—N1—C1—C2	−175.95 (10)	N1—C1—C5—C4	178.72 (10)
C12—N1—C1—C5	4.28 (16)	C2—C1—C5—C4	−1.06 (15)
C4—N2—C3—C2	−1.18 (16)	C1—C2—C3—N2	1.00 (16)
C3—N2—C4—C5	0.20 (17)	N2—C4—C5—C1	0.93 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1	0.86	2.55	3.2264 (11)	136
N2—H2···Cl2	0.86	2.55	3.2760 (10)	143
C2—H2A···Cl1ii	0.93	2.67	3.5790 (11)	167
C5—H5···Cl2iii	0.93	2.80	3.6501 (11)	152
C11—H11B···Cl2iv	0.96	2.82	3.6850 (13)	150

Table 1

Selected bond lengths (Å)

Cu1—Cl1	2.2487 (3)
Cu1—Cl2	2.2588 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1	0.86	2.55	3.2264 (11)	136
N2—H2⋯Cl2	0.86	2.55	3.2760 (10)	143
C2—H2A⋯Cl1i	0.93	2.67	3.5790 (11)	167
C5—H5⋯Cl2ii	0.93	2.80	3.6501 (11)	152
C11—H11B⋯Cl2iii	0.96	2.82	3.6850 (13)	150

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