Bis(2-amino-4-methyl-pyridinium) tetra-chloridocuprate(II).

The asymmetric unit of the title compound, (C(6)H(9)N(2))(2)[CuCl(4)], consists of one cation and one half-anion, bis-ected by a twofold rotation axis through the metal center. The anion exhibits a geometry that is inter-mediate between a T(d) and D(4h) arrangement about the Cu atom. The crystal structure contains chains of cations alternating with stacks of anions. The cationic groups inter-act via offset face-to-face π-π stacking, forming chains running along the c axis. The anion stacks are parallel to the cation chains, with no significant inter- nor intra-stack Cl⋯Cl inter-actions. There are several anion-cation hydrogen-bonding inter-actions of the (N-H)(pyridine)⋯Cl and (N-H)(amino)⋯Cl types, connecting the chains of cations to the stacks of anions. Both the N-H⋯Cl and π-π stacking inter-actions [centroid-centroid distances 3.61 (8) and 3.92 (2) Å] contribute to the formation of a three-dimensional supra-molecular architecture.

Related literature

For related literature on organic–inorganic hybrids, see: Al-Far, Ali & Haddad (2008 ▶); Ali & Al-Far (2007 ▶, 2008 ▶); Coffey et al. (2000 ▶). For bond-length and angle data, see: Raithby et al. (2000 ▶); Allen et al. (1987 ▶).

Experimental

Crystal data

(C6H9N2)2[CuCl4]

M = 423.65

Monoclinic,

a = 11.313 (3) Å

b = 12.272 (3) Å

c = 14.264 (4) Å

β = 113.201 (17)°

V = 1820.2 (9) Å3

Z = 4

Mo Kα radiation

μ = 1.78 mm−1

T = 293 (2) K

0.35 × 0.06 × 0.06 mm

Data collection

Siemens P4 diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.874, T max = 0.898

2039 measured reflections

1590 independent reflections

841 reflections with I > 2σ(I)

R int = 0.058

3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.145

S = 0.99

1590 reflections

97 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.37 e Å−3

Data collection: XSCANS (Bruker, 1996 ▶); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808041652/bg2228sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041652/bg2228Isup2.hkl

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

(C6H9N2)2[CuCl4]	F(000) = 860
Mr = 423.65	Dx = 1.546 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 290 reflections
a = 11.313 (3) Å	θ = 2.5–27.3°
b = 12.272 (3) Å	µ = 1.78 mm−1
c = 14.264 (4) Å	T = 293 K
β = 113.201 (17)°	Parallelepiped, yellow
V = 1820.2 (9) Å3	0.35 × 0.06 × 0.06 mm
Z = 4

Siemens P4 diffractometer	841 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.058
graphite	θmax = 25.0°, θmin = 2.6°
ω scans	h = −1→13
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −14→1
Tmin = 0.874, Tmax = 0.898	l = −16→16
2039 measured reflections	3 standard reflections every 97 reflections
1590 independent reflections	intensity decay: none

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0577P)2] where P = (Fo2 + 2Fc2)/3
1590 reflections	(Δ/σ)max < 0.001
97 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.37 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
Cu1	0.5000	0.00098 (10)	0.7500	0.0539 (4)
Cl1	0.64416 (17)	−0.12430 (14)	0.74530 (17)	0.0716 (7)
N1	0.9282 (5)	0.0108 (5)	0.8601 (4)	0.0552 (15)
H1A	0.8473	0.0000	0.8432	0.066*
Cl2	0.35031 (15)	0.12618 (14)	0.66064 (15)	0.0632 (6)
C2	1.0055 (6)	−0.0772 (6)	0.8719 (5)	0.0487 (18)
N2	0.9548 (6)	−0.1746 (5)	0.8554 (5)	0.0736 (19)
H2A	0.8732	−0.1825	0.8372	0.088*
H2B	1.0030	−0.2309	0.8626	0.088*
C3	1.1373 (6)	−0.0577 (6)	0.9018 (5)	0.0551 (19)
H3A	1.1933	−0.1161	0.9116	0.066*
C4	1.1850 (7)	0.0474 (7)	0.9168 (5)	0.0584 (19)
C5	1.0969 (9)	0.1339 (6)	0.9006 (6)	0.072 (2)
H5A	1.1258	0.2057	0.9089	0.087*
C6	0.9713 (9)	0.1124 (6)	0.8733 (6)	0.071 (2)
H6A	0.9138	0.1697	0.8636	0.085*
C7	1.3250 (7)	0.0704 (8)	0.9462 (7)	0.095 (3)
H7A	1.3691	0.0038	0.9454	0.143*
H7B	1.3604	0.1013	1.0134	0.143*
H7C	1.3352	0.1209	0.8985	0.143*

	U11	U22	U33	U12	U13	U23
Cu1	0.0460 (7)	0.0348 (6)	0.0783 (9)	0.000	0.0215 (6)	0.000
Cl1	0.0511 (11)	0.0382 (10)	0.1332 (19)	−0.0006 (8)	0.0444 (11)	−0.0103 (11)
N1	0.049 (3)	0.052 (4)	0.064 (4)	0.006 (3)	0.022 (3)	−0.005 (3)
Cl2	0.0447 (10)	0.0374 (10)	0.0867 (14)	−0.0050 (8)	0.0037 (8)	0.0074 (9)
C2	0.050 (4)	0.046 (4)	0.049 (4)	0.004 (4)	0.020 (3)	0.000 (3)
N2	0.059 (4)	0.043 (4)	0.121 (6)	−0.008 (3)	0.038 (4)	−0.007 (4)
C3	0.057 (5)	0.049 (5)	0.062 (5)	0.007 (4)	0.027 (4)	−0.002 (4)
C4	0.063 (5)	0.058 (5)	0.055 (5)	−0.007 (4)	0.023 (4)	0.002 (4)
C5	0.097 (7)	0.041 (5)	0.080 (6)	−0.006 (5)	0.035 (5)	−0.003 (4)
C6	0.073 (6)	0.049 (5)	0.085 (6)	0.008 (5)	0.026 (5)	−0.004 (5)
C7	0.078 (6)	0.104 (8)	0.109 (7)	−0.038 (6)	0.044 (6)	−0.031 (6)

Cu1—Cl1i	2.2615 (19)	C3—C4	1.381 (9)
Cu1—Cl1	2.2614 (19)	C3—H3A	0.9300
Cu1—Cl2i	2.2698 (19)	C4—C5	1.412 (10)
Cu1—Cl2	2.2698 (19)	C4—C7	1.496 (10)
N1—C6	1.326 (9)	C5—C6	1.343 (11)
N1—C2	1.358 (8)	C5—H5A	0.9300
N1—H1A	0.8600	C6—H6A	0.9300
C2—N2	1.307 (8)	C7—H7A	0.9600
C2—C3	1.400 (9)	C7—H7B	0.9600
N2—H2A	0.8600	C7—H7C	0.9600
N2—H2B	0.8600
Cl1i—Cu1—Cl1	94.33 (10)	C2—C3—H3A	119.6
Cl1i—Cu1—Cl2i	146.17 (8)	C3—C4—C5	118.0 (7)
Cl1—Cu1—Cl2i	95.15 (7)	C3—C4—C7	121.7 (7)
Cl1i—Cu1—Cl2	95.15 (6)	C5—C4—C7	120.3 (8)
Cl1—Cu1—Cl2	146.17 (8)	C6—C5—C4	119.8 (8)
Cl2i—Cu1—Cl2	94.80 (10)	C6—C5—H5A	120.1
C6—N1—C2	123.2 (7)	C4—C5—H5A	120.1
C6—N1—H1A	118.4	N1—C6—C5	120.9 (8)
C2—N1—H1A	118.4	N1—C6—H6A	119.5
N2—C2—N1	119.3 (6)	C5—C6—H6A	119.5
N2—C2—C3	123.4 (7)	C4—C7—H7A	109.5
N1—C2—C3	117.3 (7)	C4—C7—H7B	109.5
C2—N2—H2A	120.0	H7A—C7—H7B	109.5
C2—N2—H2B	120.0	C4—C7—H7C	109.5
H2A—N2—H2B	120.0	H7A—C7—H7C	109.5
C4—C3—C2	120.8 (7)	H7B—C7—H7C	109.5
C4—C3—H3A	119.6
C6—N1—C2—N2	−178.6 (7)	C2—C3—C4—C7	−178.4 (7)
C6—N1—C2—C3	1.5 (10)	C3—C4—C5—C6	1.2 (11)
N2—C2—C3—C4	179.1 (7)	C7—C4—C5—C6	179.3 (8)
N1—C2—C3—C4	−1.0 (10)	C2—N1—C6—C5	−0.6 (12)
C2—C3—C4—C5	−0.3 (11)	C4—C5—C6—N1	−0.8 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.86	2.65	3.407 (6)	147
N1—H1A···Cl2i	0.86	2.70	3.360 (6)	134
N2—H2A···Cl1	0.86	2.50	3.294 (6)	153
N2—H2B···Cl2ii	0.86	2.53	3.359 (6)	164

Cu1—Cl1	2.2614 (19)
Cu1—Cl2	2.2698 (19)

Cl1i—Cu1—Cl1	94.33 (10)
Cl1—Cu1—Cl2	146.17 (8)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.86	2.65	3.407 (6)	147
N1—H1A⋯Cl2i	0.86	2.70	3.360 (6)	134
N2—H2A⋯Cl1	0.86	2.50	3.294 (6)	153
N2—H2B⋯Cl2ii	0.86	2.53	3.359 (6)	164

Symmetry codes: (i) ; (ii) .