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

The structure of the title salt, (C(6)H(8)N)(2)[CuCl(3.4)Br(0.6)], consists of two 3-methyl-pyridinium cations and a distorted tetra-hedral [CuCl(3.4)Br(0.6)](2-) dianion. Substitutional disorder with Br is exhibited for three of the Cl atoms of the anion, giving a mixed chloride/bromide cuprate(II) anion. In the crystal, inter-molecular N-H⋯Cl hydrogen bonds link two cations to one anion, forming a three-ion aggregate. These are connected into a supra-molecular chain along the b axis via π-π inter-actions between the pyridinium rings [centroid-centroid distance = 3.743 (3) Å].

Related literature

For general background to the geometry of the tetra­halidocuprate(II) species, see: Solomon et al. (1992 ▶); Kim et al. (2001 ▶); Panja et al. (2005 ▶); Sengottvelan et al. (2009 ▶). For its magnetic properties, see: Lee et al. (2004 ▶); Turnbull et al. (2005 ▶); Shapiro et al. (2007 ▶). CuBr4 2− ions usually show less distortion from the ideal tetra­hedral geometry compared with CuCl4 2− ions, see: Edwards et al. (2011 ▶); AlDaman & Haddad (2011 ▶).

Experimental

Crystal data

(C6H8N)2[CuBr0.60Cl3.40]

M = 420.28

Monoclinic,

a = 9.0617 (18) Å

b = 13.259 (3) Å

c = 14.060 (3) Å

β = 102.47 (3)°

V = 1649.4 (6) Å3

Z = 4

Mo Kα radiation

μ = 3.32 mm−1

T = 295 K

0.19 × 0.15 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.560, T max = 0.610

17556 measured reflections

4094 independent reflections

2621 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.089

S = 1.03

4094 reflections

209 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.41 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811019076/tk2745sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811019076/tk2745Isup2.hkl

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

(C6H8N)2[CuBr0.60Cl3.40]	F(000) = 839.2
Mr = 420.28	Dx = 1.693 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3355 reflections
a = 9.0617 (18) Å	θ = 2.8–23.7°
b = 13.259 (3) Å	µ = 3.32 mm−1
c = 14.060 (3) Å	T = 295 K
β = 102.47 (3)°	Block, brown
V = 1649.4 (6) Å3	0.19 × 0.15 × 0.15 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2621 reflections with I > 2σ(I)
graphite	Rint = 0.039
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→12
Tmin = 0.560, Tmax = 0.610	k = −17→17
17556 measured reflections	l = −18→18
4094 independent reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0389P)2 + 0.0822P] where P = (Fo2 + 2Fc2)/3
4094 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Cu1	0.55622 (4)	0.54229 (2)	0.70365 (2)	0.04278 (13)
Cl2	0.3635 (8)	0.6509 (5)	0.6823 (4)	0.0600 (16)	0.8
Br2	0.3543 (11)	0.6580 (8)	0.6803 (5)	0.0397 (14)	0.2
Cl3	0.7542 (4)	0.6516 (3)	0.7331 (2)	0.0967 (10)	0.8
Br3	0.7538 (3)	0.6533 (2)	0.73299 (19)	0.0289 (6)	0.2
Cl4	0.4607 (10)	0.4267 (9)	0.7907 (6)	0.0538 (15)	0.8
Br4	0.4680 (16)	0.4110 (15)	0.7913 (9)	0.0511 (18)	0.2
Cl5	0.65337 (8)	0.43724 (5)	0.60629 (6)	0.0550 (2)
N1	0.4441 (3)	0.2452 (2)	0.59512 (19)	0.0492 (6)
H1	0.485 (3)	0.291 (2)	0.621 (2)	0.044 (9)*
C2	0.4632 (3)	0.2199 (2)	0.5066 (2)	0.0457 (7)
H2	0.5221	0.26	0.4752	0.055*
C3	0.3953 (3)	0.1343 (2)	0.4620 (2)	0.0451 (7)
C4	0.3078 (3)	0.0789 (2)	0.5126 (2)	0.0526 (8)
H4	0.2593	0.0211	0.4842	0.063*
C5	0.2909 (3)	0.1070 (2)	0.6036 (2)	0.0565 (8)
H5	0.2323	0.0686	0.6367	0.068*
C6	0.3615 (3)	0.1921 (2)	0.6445 (2)	0.0516 (7)
H6	0.3519	0.2128	0.7061	0.062*
C7	0.4157 (4)	0.1058 (2)	0.3622 (2)	0.0674 (9)
H7A	0.5116	0.1301	0.3534	0.101*
H7B	0.3362	0.1354	0.3139	0.101*
H7C	0.4122	0.0338	0.3556	0.101*
N8	0.8582 (3)	0.61568 (19)	0.52884 (19)	0.0494 (6)
H8	0.820 (4)	0.599 (3)	0.574 (2)	0.082 (12)*
C9	0.9467 (3)	0.6976 (2)	0.54021 (19)	0.0461 (7)
H9	0.9599	0.735	0.5974	0.055*
C10	1.0178 (3)	0.7265 (2)	0.46804 (19)	0.0446 (7)
C11	0.9936 (3)	0.6688 (2)	0.3849 (2)	0.0522 (7)
H11	1.0407	0.6864	0.3347	0.063*
C12	0.9011 (4)	0.5857 (2)	0.3745 (2)	0.0587 (8)
H12	0.885	0.5478	0.3176	0.07*
C13	0.8329 (3)	0.5591 (2)	0.4483 (2)	0.0559 (8)
H13	0.7703	0.5028	0.4427	0.067*
C14	1.1163 (4)	0.8186 (2)	0.4800 (2)	0.0691 (9)
H14A	1.0553	0.877	0.4589	0.104*
H14B	1.1911	0.8115	0.4414	0.104*
H14C	1.1654	0.8262	0.5472	0.104*

	U11	U22	U33	U12	U13	U23
Cu1	0.0438 (2)	0.0394 (2)	0.0472 (2)	−0.00244 (15)	0.01439 (16)	−0.00025 (15)
Cl2	0.060 (2)	0.051 (2)	0.073 (3)	0.0085 (14)	0.0232 (16)	−0.0012 (14)
Br2	0.046 (2)	0.040 (2)	0.036 (3)	0.0049 (18)	0.0167 (17)	0.0047 (16)
Cl3	0.097 (2)	0.091 (2)	0.104 (2)	−0.0196 (18)	0.0272 (18)	−0.0123 (19)
Br3	0.0263 (13)	0.0305 (15)	0.0315 (14)	−0.0156 (11)	0.0099 (11)	−0.0118 (12)
Cl4	0.0612 (13)	0.041 (3)	0.0660 (18)	0.0059 (13)	0.0280 (14)	0.0153 (12)
Br4	0.066 (3)	0.036 (4)	0.052 (2)	0.000 (2)	0.014 (2)	0.0125 (17)
Cl5	0.0605 (5)	0.0437 (4)	0.0693 (5)	−0.0081 (3)	0.0328 (4)	−0.0127 (4)
N1	0.0478 (15)	0.0433 (15)	0.0527 (16)	−0.0041 (13)	0.0029 (12)	−0.0027 (13)
C2	0.0449 (16)	0.0437 (16)	0.0494 (17)	−0.0037 (13)	0.0120 (13)	0.0060 (14)
C3	0.0444 (16)	0.0417 (16)	0.0473 (16)	0.0046 (13)	0.0054 (13)	0.0060 (13)
C4	0.0505 (18)	0.0368 (15)	0.066 (2)	−0.0078 (13)	0.0032 (15)	0.0033 (14)
C5	0.0518 (19)	0.0563 (19)	0.064 (2)	−0.0032 (15)	0.0180 (16)	0.0121 (16)
C6	0.0502 (18)	0.062 (2)	0.0449 (17)	0.0057 (15)	0.0141 (14)	0.0085 (15)
C7	0.087 (3)	0.060 (2)	0.054 (2)	0.0054 (18)	0.0111 (18)	−0.0029 (16)
N8	0.0457 (15)	0.0545 (16)	0.0509 (16)	0.0018 (12)	0.0167 (12)	0.0088 (13)
C9	0.0473 (17)	0.0496 (17)	0.0421 (16)	0.0010 (14)	0.0110 (13)	−0.0021 (13)
C10	0.0412 (15)	0.0520 (17)	0.0415 (16)	0.0037 (13)	0.0110 (12)	0.0065 (13)
C11	0.0509 (18)	0.064 (2)	0.0436 (17)	0.0096 (16)	0.0136 (14)	0.0052 (15)
C12	0.067 (2)	0.060 (2)	0.0457 (17)	0.0075 (17)	0.0055 (16)	−0.0093 (15)
C13	0.0502 (18)	0.0478 (18)	0.065 (2)	−0.0019 (14)	0.0025 (16)	−0.0008 (16)
C14	0.069 (2)	0.070 (2)	0.072 (2)	−0.0139 (18)	0.0230 (18)	0.0057 (18)

Cu1—Cl2	2.232 (8)	C7—H7A	0.96
Cu1—Cl4	2.248 (10)	C7—H7B	0.96
Cu1—Cl5	2.2604 (8)	C7—H7C	0.96
Cu1—Cl3	2.273 (3)	N8—C13	1.336 (4)
Cu1—Br3	2.286 (2)	N8—C9	1.339 (4)
Cu1—Br2	2.356 (12)	N8—H8	0.82 (3)
Cu1—Br4	2.369 (17)	C9—C10	1.369 (3)
N1—C6	1.328 (4)	C9—H9	0.93
N1—C2	1.336 (4)	C10—C11	1.374 (4)
N1—H1	0.76 (3)	C10—C14	1.500 (4)
C2—C3	1.376 (4)	C11—C12	1.373 (4)
C2—H2	0.93	C11—H11	0.93
C3—C4	1.385 (4)	C12—C13	1.363 (4)
C3—C7	1.502 (4)	C12—H12	0.93
C4—C5	1.373 (4)	C13—H13	0.93
C4—H4	0.93	C14—H14A	0.96
C5—C6	1.362 (4)	C14—H14B	0.96
C5—H5	0.93	C14—H14C	0.96
C6—H6	0.93
Cl2—Cu1—Cl4	97.5 (3)	C4—C5—H5	120.6
Cl2—Cu1—Cl5	135.34 (14)	N1—C6—C5	119.0 (3)
Cl4—Cu1—Cl5	99.0 (3)	N1—C6—H6	120.5
Cl2—Cu1—Cl3	100.2 (2)	C5—C6—H6	120.5
Cl4—Cu1—Cl3	135.8 (2)	C3—C7—H7A	109.5
Cl5—Cu1—Cl3	96.18 (8)	C3—C7—H7B	109.5
Cl2—Cu1—Br3	99.70 (18)	H7A—C7—H7B	109.5
Cl4—Cu1—Br3	136.0 (2)	C3—C7—H7C	109.5
Cl5—Cu1—Br3	96.53 (7)	H7A—C7—H7C	109.5
Cl3—Cu1—Br3	0.49 (16)	H7B—C7—H7C	109.5
Cl2—Cu1—Br2	0.6 (3)	C13—N8—C9	123.1 (3)
Cl4—Cu1—Br2	98.1 (3)	C13—N8—H8	119 (2)
Cl5—Cu1—Br2	135.17 (16)	C9—N8—H8	117 (2)
Cl3—Cu1—Br2	99.7 (2)	N8—C9—C10	120.3 (3)
Br3—Cu1—Br2	99.2 (2)	N8—C9—H9	119.9
Cl2—Cu1—Br4	101.6 (5)	C10—C9—H9	119.9
Cl4—Cu1—Br4	4.5 (7)	C9—C10—C11	117.4 (3)
Cl5—Cu1—Br4	94.7 (4)	C9—C10—C14	120.6 (3)
Cl3—Cu1—Br4	135.7 (3)	C11—C10—C14	122.0 (3)
Br3—Cu1—Br4	135.9 (3)	C12—C11—C10	121.2 (3)
Br2—Cu1—Br4	102.2 (5)	C12—C11—H11	119.4
C6—N1—C2	123.7 (3)	C10—C11—H11	119.4
C6—N1—H1	116 (2)	C13—C12—C11	119.6 (3)
C2—N1—H1	120 (2)	C13—C12—H12	120.2
N1—C2—C3	119.8 (3)	C11—C12—H12	120.2
N1—C2—H2	120.1	N8—C13—C12	118.4 (3)
C3—C2—H2	120.1	N8—C13—H13	120.8
C2—C3—C4	116.9 (3)	C12—C13—H13	120.8
C2—C3—C7	120.0 (3)	C10—C14—H14A	109.5
C4—C3—C7	123.1 (3)	C10—C14—H14B	109.5
C5—C4—C3	121.7 (3)	H14A—C14—H14B	109.5
C5—C4—H4	119.1	C10—C14—H14C	109.5
C3—C4—H4	119.1	H14A—C14—H14C	109.5
C6—C5—C4	118.8 (3)	H14B—C14—H14C	109.5
C6—C5—H5	120.6

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl5	0.76 (3)	2.50 (3)	3.158 (3)	145 (3)
N8—H8···Cl3	0.82 (3)	2.53 (3)	3.245 (4)	147 (3)
N8—H8···Cl5	0.82 (3)	2.72 (3)	3.332 (3)	133 (3)

Cu1—Cl2	2.232 (8)
Cu1—Cl4	2.248 (10)
Cu1—Cl5	2.2604 (8)
Cu1—Cl3	2.273 (3)

Cl2—Cu1—Cl4	97.5 (3)
Cl2—Cu1—Cl5	135.34 (14)
Cl4—Cu1—Cl5	99.0 (3)
Cl2—Cu1—Cl3	100.2 (2)
Cl4—Cu1—Cl3	135.8 (2)
Cl5—Cu1—Cl3	96.18 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl5	0.76 (3)	2.50 (3)	3.158 (3)	145 (3)
N8—H8⋯Cl3	0.82 (3)	2.53 (3)	3.245 (4)	147 (3)
N8—H8⋯Cl5	0.82 (3)	2.72 (3)	3.332 (3)	133 (3)