Bis-(2-amino-6-methyl-pyridinium) tetra-bromido-cuprate(II).

In the crystal structure of the title compound, (C(6)H(9)N(2))(2)[CuBr(4)], the geometry around the Cu atom is inter-mediate between tetra-hedral (T(d)) and square planar (D(4h)). Each [CuBr(4)](2-) anion is connected non-symmetrically to four surrounding cations through N-H⋯X (pyridine and amine proton) hydrogen bonds, forming chains of the ladder-type running parallel to the crystallographic b axis. These layers are further connected by means of offset face-to-face inter-actions (parallel to the a axis), giving a three-dimensional network. Cation π-π stacking [centroid separations of 3.69 (9) and 3.71 (1) Å] and Br⋯aryl inter-actions [3.72 (2) and 4.04 (6) Å] are present in the crystal structure. There are no inter-molecular Br⋯Br inter-actions.

Related literature

For related literature, see: Al-Far & Ali (2007a ▶,b ▶); Ali & Al-Far (2007 ▶, 2008 ▶); Allen et al. (1987 ▶, 1997 ▶); Desiraju & Steiner (1999 ▶); Dolling et al. (2001 ▶); Haddad et al. (2006 ▶); Hunter (1994 ▶); Panunto et al. (1987 ▶); Raithby et al. (2000 ▶); Robinson et al. (2000 ▶); Luque et al. (2001 ▶).

Experimental

Crystal data

(C6H9N2)2[CuBr4]

M = 601.45

Triclinic,

a = 7.9238 (9) Å

b = 8.2521 (11) Å

c = 15.2916 (18) Å

α = 78.472 (11)°

β = 82.839 (10)°

γ = 89.947 (14)°

V = 971.8 (2) Å3

Z = 2

Mo Kα radiation

μ = 9.35 mm−1

T = 293 (2) K

0.20 × 0.15 × 0.10 mm

Data collection

Bruker P4 diffractometer

Absorption correction: ψ scan (XSCANS; Bruker, 1996 ▶)T min = 0.199, T max = 0.392

4381 measured reflections

3567 independent reflections

2018 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.153

S = 1.00

3567 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −0.65 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, global. DOI: 10.1107/S1600536808010647/at2561sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010647/at2561Isup2.hkl

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

(C6H9N2)2[CuBr4]	Z = 2
Mr = 601.45	F000 = 574
Triclinic, P1	Dx = 2.056 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.9238 (9) Å	Cell parameters from 298 reflections
b = 8.2521 (11) Å	θ = 2.2–27.5º
c = 15.2916 (18) Å	µ = 9.35 mm−1
α = 78.472 (11)º	T = 293 (2) K
β = 82.839 (10)º	Block, blue
γ = 89.947 (14)º	0.20 × 0.15 × 0.10 mm
V = 971.8 (2) Å3

Bruker P4 diffractometer	3567 independent reflections
Radiation source: fine-focus sealed tube	2018 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.053
Detector resolution: 3 pixels mm-1	θmax = 25.5º
T = 293(2) K	θmin = 2.5º
ω scans	h = −9→1
Absorption correction: ψ scan(PROGRAM; REF (YEAR)	k = −9→9
Tmin = 0.199, Tmax = 0.392	l = −18→18
4381 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058	H-atom parameters constrained
wR(F2) = 0.153	w = 1/[σ2(Fo2) + (0.0724P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
3567 reflections	Δρmax = 0.57 e Å−3
190 parameters	Δρmin = −0.65 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
Br1	0.18757 (14)	0.94944 (11)	0.69574 (7)	0.0597 (3)
Cu1	0.32354 (14)	0.69646 (13)	0.74711 (8)	0.0442 (3)
N1	0.6876 (10)	1.0718 (9)	1.0416 (6)	0.052 (2)
H1	0.6292	1.1120	1.0832	0.062*
Br2	0.08231 (15)	0.54289 (13)	0.82710 (9)	0.0745 (4)
N2	0.6864 (13)	0.8282 (10)	1.1440 (6)	0.074 (3)
H2A	0.6268	0.8750	1.1825	0.089*
H2B	0.7143	0.7266	1.1591	0.089*
C2	0.7347 (13)	0.9116 (12)	1.0624 (7)	0.052 (3)
Br3	0.56567 (13)	0.80573 (15)	0.79499 (8)	0.0679 (4)
C3	0.8257 (13)	0.8462 (13)	0.9938 (8)	0.060 (3)
H3	0.8594	0.7368	1.0049	0.072*
Br4	0.45192 (14)	0.50445 (13)	0.66438 (8)	0.0650 (4)
C4	0.8653 (14)	0.9439 (17)	0.9100 (8)	0.073 (4)
H4	0.9239	0.9006	0.8636	0.087*
C5	0.8171 (15)	1.1093 (15)	0.8947 (7)	0.070 (3)
H5	0.8487	1.1761	0.8384	0.084*
C6	0.7270 (14)	1.1742 (12)	0.9585 (7)	0.058 (3)
C7	0.6683 (17)	1.3493 (13)	0.9503 (9)	0.089 (4)
H7C	0.7028	1.4097	0.8902	0.134*
H7B	0.7180	1.4007	0.9923	0.134*
H7A	0.5465	1.3491	0.9630	0.134*
N8	0.0896 (10)	0.7845 (9)	0.5235 (5)	0.049 (2)
H8	0.1279	0.8242	0.5653	0.059*
C9	−0.0722 (12)	0.7230 (11)	0.5402 (7)	0.049 (2)
N9	−0.1600 (12)	0.7226 (11)	0.6204 (7)	0.080 (3)
H9A	−0.1137	0.7608	0.6603	0.095*
H9B	−0.2629	0.6841	0.6322	0.095*
C10	−0.1360 (13)	0.6650 (11)	0.4711 (8)	0.057 (3)
H10	−0.2473	0.6239	0.4788	0.068*
C11	−0.0343 (14)	0.6690 (12)	0.3923 (8)	0.057 (3)
H11	−0.0771	0.6302	0.3461	0.069*
C12	0.1301 (15)	0.7289 (12)	0.3794 (7)	0.062 (3)
H12	0.1968	0.7290	0.3249	0.074*
C13	0.1985 (13)	0.7888 (11)	0.4451 (7)	0.052 (3)
C14	0.3706 (14)	0.8601 (14)	0.4410 (8)	0.075 (3)
H14A	0.3823	0.8923	0.4969	0.112*
H14B	0.3878	0.9553	0.3929	0.112*
H14C	0.4538	0.7792	0.4306	0.112*

	U11	U22	U33	U12	U13	U23
Br1	0.0758 (8)	0.0456 (6)	0.0583 (7)	0.0137 (5)	−0.0121 (6)	−0.0101 (5)
Cu1	0.0410 (7)	0.0451 (6)	0.0453 (7)	0.0029 (5)	0.0001 (5)	−0.0096 (5)
N1	0.049 (5)	0.058 (5)	0.050 (6)	−0.003 (4)	0.005 (4)	−0.023 (4)
Br2	0.0557 (7)	0.0607 (7)	0.0916 (10)	−0.0022 (5)	0.0223 (7)	0.0021 (6)
N2	0.116 (9)	0.060 (5)	0.045 (6)	0.010 (5)	−0.009 (6)	−0.003 (5)
C2	0.067 (7)	0.050 (6)	0.046 (7)	0.015 (5)	−0.013 (6)	−0.018 (5)
Br3	0.0443 (6)	0.1028 (9)	0.0670 (8)	−0.0010 (6)	−0.0037 (6)	−0.0441 (7)
C3	0.052 (7)	0.067 (7)	0.071 (9)	0.000 (5)	−0.013 (6)	−0.034 (7)
Br4	0.0553 (7)	0.0640 (7)	0.0793 (9)	0.0006 (5)	0.0101 (6)	−0.0345 (6)
C4	0.050 (7)	0.125 (11)	0.061 (9)	0.010 (7)	−0.010 (6)	−0.060 (8)
C5	0.076 (8)	0.100 (9)	0.035 (7)	0.001 (7)	−0.010 (6)	−0.013 (6)
C6	0.063 (7)	0.063 (6)	0.044 (7)	−0.002 (5)	−0.010 (6)	−0.003 (5)
C7	0.091 (10)	0.069 (8)	0.098 (11)	0.009 (7)	0.000 (8)	0.001 (7)
N8	0.050 (5)	0.055 (5)	0.045 (5)	0.008 (4)	−0.009 (4)	−0.014 (4)
C9	0.037 (6)	0.049 (5)	0.059 (7)	0.009 (4)	−0.002 (5)	−0.010 (5)
N9	0.058 (6)	0.108 (8)	0.080 (8)	−0.007 (5)	0.009 (6)	−0.048 (6)
C10	0.048 (6)	0.053 (6)	0.069 (8)	0.010 (5)	−0.020 (6)	−0.001 (6)
C11	0.057 (7)	0.070 (7)	0.049 (7)	0.007 (6)	−0.022 (6)	−0.011 (5)
C12	0.079 (9)	0.070 (7)	0.035 (6)	0.017 (6)	−0.005 (6)	−0.005 (5)
C13	0.055 (6)	0.042 (5)	0.053 (7)	0.003 (5)	0.002 (6)	0.001 (5)
C14	0.050 (7)	0.091 (8)	0.075 (9)	−0.006 (6)	0.008 (6)	−0.006 (7)

Br1—Cu1	2.3848 (14)	C7—H7B	0.9600
Cu1—Br2	2.3575 (16)	C7—H7A	0.9600
Cu1—Br4	2.3713 (14)	N8—C9	1.355 (12)
Cu1—Br3	2.3765 (16)	N8—C13	1.382 (12)
N1—C2	1.360 (11)	N8—H8	0.8600
N1—C6	1.377 (13)	C9—N9	1.331 (13)
N1—H1	0.8600	C9—C10	1.391 (14)
N2—C2	1.310 (13)	N9—H9A	0.8600
N2—H2A	0.8600	N9—H9B	0.8600
N2—H2B	0.8600	C10—C11	1.359 (14)
C2—C3	1.396 (13)	C10—H10	0.9300
C3—C4	1.371 (16)	C11—C12	1.370 (15)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.399 (15)	C12—C13	1.371 (14)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.335 (14)	C13—C14	1.475 (14)
C5—H5	0.9300	C14—H14A	0.9600
C6—C7	1.504 (13)	C14—H14B	0.9600
C7—H7C	0.9600	C14—H14C	0.9600
Br2—Cu1—Br4	101.27 (6)	C6—C7—H7A	109.5
Br2—Cu1—Br3	132.23 (7)	H7C—C7—H7A	109.5
Br4—Cu1—Br3	100.99 (6)	H7B—C7—H7A	109.5
Br2—Cu1—Br1	98.36 (6)	C9—N8—C13	125.5 (9)
Br4—Cu1—Br1	129.74 (7)	C9—N8—H8	117.2
Br3—Cu1—Br1	98.93 (6)	C13—N8—H8	117.2
C2—N1—C6	124.6 (8)	N9—C9—N8	118.6 (10)
C2—N1—H1	117.7	N9—C9—C10	124.3 (10)
C6—N1—H1	117.7	N8—C9—C10	117.1 (9)
C2—N2—H2A	120.0	C9—N9—H9A	120.0
C2—N2—H2B	120.0	C9—N9—H9B	120.0
H2A—N2—H2B	120.0	H9A—N9—H9B	120.0
N2—C2—N1	117.9 (9)	C11—C10—C9	119.4 (10)
N2—C2—C3	124.8 (9)	C11—C10—H10	120.3
N1—C2—C3	117.3 (10)	C9—C10—H10	120.3
C4—C3—C2	119.8 (10)	C10—C11—C12	121.3 (10)
C4—C3—H3	120.1	C10—C11—H11	119.4
C2—C3—H3	120.1	C12—C11—H11	119.4
C3—C4—C5	119.5 (10)	C11—C12—C13	121.6 (10)
C3—C4—H4	120.3	C11—C12—H12	119.2
C5—C4—H4	120.3	C13—C12—H12	119.2
C6—C5—C4	122.0 (11)	C12—C13—N8	115.1 (10)
C6—C5—H5	119.0	C12—C13—C14	128.1 (11)
C4—C5—H5	119.0	N8—C13—C14	116.8 (10)
C5—C6—N1	116.8 (10)	C13—C14—H14A	109.5
C5—C6—C7	126.9 (11)	C13—C14—H14B	109.5
N1—C6—C7	116.3 (9)	H14A—C14—H14B	109.5
C6—C7—H7C	109.5	C13—C14—H14C	109.5
C6—C7—H7B	109.5	H14A—C14—H14C	109.5
H7C—C7—H7B	109.5	H14B—C14—H14C	109.5
C6—N1—C2—N2	−179.2 (10)	C13—N8—C9—N9	177.8 (9)
C6—N1—C2—C3	−1.6 (15)	C13—N8—C9—C10	−2.5 (13)
N2—C2—C3—C4	178.1 (11)	N9—C9—C10—C11	−179.0 (10)
N1—C2—C3—C4	0.7 (15)	N8—C9—C10—C11	1.4 (13)
C2—C3—C4—C5	1.4 (16)	C9—C10—C11—C12	0.1 (15)
C3—C4—C5—C6	−2.8 (17)	C10—C11—C12—C13	−0.6 (16)
C4—C5—C6—N1	1.9 (17)	C11—C12—C13—N8	−0.3 (14)
C4—C5—C6—C7	179.9 (11)	C11—C12—C13—C14	−178.6 (10)
C2—N1—C6—C5	0.3 (16)	C9—N8—C13—C12	2.0 (14)
C2—N1—C6—C7	−177.9 (9)	C9—N8—C13—C14	−179.5 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br3i	0.86	2.47	3.324 (7)	172
N8—H8···Br1	0.86	2.52	3.367 (8)	170
N9—H9B···Br4ii	0.86	2.64	3.487 (10)	168
N2—H2B···Br2iii	0.86	2.73	3.547 (9)	158

Br1—Cu1	2.3848 (14)
Cu1—Br2	2.3575 (16)
Cu1—Br4	2.3713 (14)
Cu1—Br3	2.3765 (16)

Br2—Cu1—Br4	101.27 (6)
Br2—Cu1—Br3	132.23 (7)
Br4—Cu1—Br3	100.99 (6)
Br2—Cu1—Br1	98.36 (6)
Br4—Cu1—Br1	129.74 (7)
Br3—Cu1—Br1	98.93 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br3i	0.86	2.47	3.324 (7)	172
N8—H8⋯Br1	0.86	2.52	3.367 (8)	170
N9—H9B⋯Br4ii	0.86	2.64	3.487 (10)	168
N2—H2B⋯Br2iii	0.86	2.73	3.547 (9)	158

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