Bis(2,6-dimethyl-pyridinium) tetra-bromido-zincate(II).

In the crystal structure of the title compound, (C(7)H(10)N)(2)[ZnBr(4)], the coordination geometry of the anion is approximately tetra-hedral and a twofold rotation axis passes through the Zn atom. The Zn-Br bond lengths range from 2.400 (2) to 2.408 (3) Å and the Br-Zn-Br angles range from 108.14 (6) to 115.15 (15)°. In the crystal structure, the [ZnBr(4)](2-) anion is connected to two cations through N-H⋯Br and H(2)C-H⋯Br hydrogen bonds, forming two-dimensional cation-anion-cation layers normal to the b axis. No significant Br⋯Br inter-actions [the shortest being 4.423 (4) Å] are observed in the structure.

Related literature

The title salt is isotypic with the Co-analogue, see: Ali et al. (2008 ▶). For non-covalent inter­actions and their influence on the organization and properties of materials, see: Desiraju (1997 ▶); Desiraju & Steiner (1999 ▶); Hunter (1994 ▶); Allen et al. (1997 ▶); Dolling et al. (2001 ▶); Panunto et al. (1987 ▶); Robinson et al. (2000 ▶). For the structures of related halo-metal anion salts, see: Ali & Al-Far (2007 ▶); Al-Far & Ali (2007 ▶); Al-Far & Ali (2009 ▶). For distances and angles in [ZnBr4] anions, see: Gao et al. (2007 ▶). For cation bond distances, see: Allen et al. (1987 ▶).

Experimental

Crystal data

(C7H10N)2[ZnBr4]

M = 601.33

Orthorhombic,

a = 17.237 (2) Å

b = 9.0754 (17) Å

c = 13.7302 (14) Å

V = 2147.9 (5) Å3

Z = 4

Mo Kα radiation

μ = 8.58 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker P4 diffractometer

Absorption correction: numerical (SADABS; Bruker 2001 ▶) T min = 0.183, T max = 0.279

2020 measured reflections

1987 independent reflections

1850 reflections with I > 2σ(I)

R int = 0.086

3 standard reflections every 97 reflections intensity decay: 0.01%

Refinement

R[F 2 > 2σ(F 2)] = 0.088

wR(F 2) = 0.177

S = 0.98

1980 reflections

98 parameters

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.48 e Å−3

Data collection: XSCANS (Siemens, 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/S1600536809015219/at2771sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015219/at2771Isup2.hkl

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

(C7H10N)2[ZnBr4]	F(000) = 1152
Mr = 601.33	Dx = 1.860 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 250 reflections
a = 17.237 (2) Å	θ = 3.2–18.0°
b = 9.0754 (17) Å	µ = 8.58 mm−1
c = 13.7302 (14) Å	T = 293 K
V = 2147.9 (5) Å3	Plate, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Bruker P4 diffractometer	1850 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.086
graphite	θmax = 25.5°, θmin = 2.5°
ω scans	h = −1→20
Absorption correction: numerical (SADABS; Bruker 2001)	k = −1→10
Tmin = 0.183, Tmax = 0.279	l = −1→16
2020 measured reflections	3 standard reflections every 97 reflections
1987 independent reflections	intensity decay: 0.01%

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)] = 0.088	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3
1980 reflections	(Δ/σ)max < 0.001
98 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.48 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.7 reflections were rejected based on high deviation from observed ones

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.7858 (3)	0.2500	0.0644 (10)
Br1	0.60634 (9)	0.9276 (2)	0.18715 (12)	0.0652 (6)
N1	0.3780 (7)	0.6538 (15)	0.4943 (10)	0.057 (4)
H1	0.4205	0.6422	0.4626	0.068*
Br2	0.54864 (10)	0.6305 (2)	0.37844 (13)	0.0812 (7)
C2	0.3794 (11)	0.736 (2)	0.5723 (14)	0.062 (5)
C3	0.3122 (13)	0.747 (2)	0.6241 (14)	0.087 (6)
H3	0.3123	0.8001	0.6818	0.105*
C4	0.2454 (14)	0.683 (3)	0.5953 (19)	0.105 (9)
H4	0.1999	0.6943	0.6308	0.126*
C5	0.2470 (11)	0.599 (2)	0.5103 (15)	0.093 (7)
H5	0.2025	0.5519	0.4879	0.112*
C6	0.3146 (12)	0.586 (2)	0.4611 (11)	0.065 (5)
C7	0.4534 (12)	0.819 (2)	0.5998 (14)	0.134 (9)
H7A	0.4741	0.8668	0.5431	0.200*
H7B	0.4908	0.7507	0.6250	0.200*
H7C	0.4416	0.8915	0.6485	0.200*
C8	0.3264 (10)	0.498 (2)	0.3707 (13)	0.102 (7)
H8A	0.3733	0.4416	0.3764	0.153*
H8B	0.3302	0.5628	0.3157	0.153*
H8C	0.2833	0.4323	0.3618	0.153*

	U11	U22	U33	U12	U13	U23
Zn1	0.0466 (16)	0.079 (2)	0.0675 (17)	0.000	0.0036 (16)	0.000
Br1	0.0502 (10)	0.0731 (13)	0.0722 (11)	−0.0146 (10)	0.0135 (10)	−0.0024 (12)
N1	0.041 (8)	0.073 (11)	0.057 (9)	−0.007 (8)	0.001 (8)	−0.013 (9)
Br2	0.0493 (10)	0.1111 (17)	0.0831 (12)	0.0147 (12)	0.0050 (11)	0.0377 (13)
C2	0.065 (13)	0.060 (13)	0.061 (12)	−0.004 (11)	0.009 (11)	0.010 (11)
C3	0.090 (15)	0.097 (17)	0.075 (13)	0.007 (15)	0.012 (15)	−0.012 (14)
C4	0.069 (15)	0.11 (2)	0.14 (2)	0.034 (15)	0.052 (16)	0.023 (19)
C5	0.043 (11)	0.12 (2)	0.116 (17)	0.005 (13)	0.017 (13)	0.018 (18)
C6	0.074 (13)	0.085 (15)	0.037 (10)	0.014 (13)	−0.021 (10)	0.011 (12)
C7	0.107 (18)	0.17 (2)	0.125 (18)	−0.016 (18)	−0.024 (15)	−0.080 (18)
C8	0.069 (12)	0.14 (2)	0.094 (15)	−0.031 (14)	0.008 (13)	−0.011 (16)

Zn1—Br1	2.400 (2)	C4—C5	1.39 (3)
Zn1—Br1i	2.400 (2)	C4—H4	0.9300
Zn1—Br2i	2.408 (3)	C5—C6	1.35 (2)
Zn1—Br2	2.408 (3)	C5—H5	0.9300
N1—C2	1.31 (2)	C6—C8	1.49 (2)
N1—C6	1.333 (19)	C7—H7A	0.9600
N1—H1	0.8600	C7—H7B	0.9600
C2—C3	1.36 (2)	C7—H7C	0.9600
C2—C7	1.53 (2)	C8—H8A	0.9600
C3—C4	1.35 (3)	C8—H8B	0.9600
C3—H3	0.9300	C8—H8C	0.9600
Br1—Zn1—Br1i	115.15 (15)	C6—C5—C4	119 (2)
Br1—Zn1—Br2i	108.45 (6)	C6—C5—H5	120.6
Br1i—Zn1—Br2i	108.14 (6)	C4—C5—H5	120.6
Br1—Zn1—Br2	108.14 (6)	N1—C6—C5	119.8 (17)
Br1i—Zn1—Br2	108.45 (6)	N1—C6—C8	114.9 (17)
Br2i—Zn1—Br2	108.35 (16)	C5—C6—C8	125 (2)
C2—N1—C6	124.1 (15)	C2—C7—H7A	109.5
C2—N1—H1	118.0	C2—C7—H7B	109.5
C6—N1—H1	118.0	H7A—C7—H7B	109.5
N1—C2—C3	116.7 (18)	C2—C7—H7C	109.5
N1—C2—C7	120.0 (16)	H7A—C7—H7C	109.5
C3—C2—C7	123 (2)	H7B—C7—H7C	109.5
C4—C3—C2	123 (2)	C6—C8—H8A	109.5
C4—C3—H3	118.5	C6—C8—H8B	109.5
C2—C3—H3	118.5	H8A—C8—H8B	109.5
C3—C4—C5	118 (2)	C6—C8—H8C	109.5
C3—C4—H4	121.2	H8A—C8—H8C	109.5
C5—C4—H4	121.2	H8B—C8—H8C	109.5
C6—N1—C2—C3	3(2)	C3—C4—C5—C6	0(3)
C6—N1—C2—C7	−175.0 (17)	C2—N1—C6—C5	−2(3)
N1—C2—C3—C4	−4(3)	C2—N1—C6—C8	179.9 (15)
C7—C2—C3—C4	175 (2)	C4—C5—C6—N1	0(3)
C2—C3—C4—C5	2(3)	C4—C5—C6—C8	178.4 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br2	0.86	2.49	3.351 (12)	175
C7—H7C···Br1ii	0.96	2.91	3.861 (18)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br2	0.86	2.49	3.351 (12)	175
C7—H7C⋯Br1ii	0.96	2.91	3.861 (18)	171

Symmetry code: (ii) .