Bis(2,4,6-trimethyl-pyridinium) tetra-bromidozincate.

In the title compound, (C(8)H(12)N)(2)[ZnBr(4)], the coordination geometry of the anion is approximately tetra-hedral. The Zn-Br bond lengths range from 2.3901 (19) to 2.449 (2) Å and the Br-Zn-Br angles range from 107.09 (8) to 112.48 (8)°. In the crystal, each [ZnBr(4)](2-) anion is connected to four cations through two N-H⋯Br and two C-H⋯Br hydrogen bonds, forming two-dimensional ⋯(cation)(2)⋯anion⋯(cation(2))⋯ sheets parallel to the bc plane. Within each sheet, the anions are arranged in stacks with no significant inter-anion Br⋯Br inter-actions [the shortest being > 4.3 Å], while the cations are in chains, with weak π-π stacking inter-actions [centroid-centroid distance = 3.991 Å] between cations inter-acting with the same anion.

Related literature

For background information, see: Ali & Al-Far (2009 ▶). For bond lengths and angles in the [ZnBr4]2− anion, see: Ali & Al-Far (2009 ▶); Peng & Li (2011 ▶). For another structure containing the 2,4,6-trimethyl­pyridinium cation, see: Abbasi et al. (2011 ▶).

Experimental

Crystal data

(C8H12N)2[ZnBr4]

M = 629.36

Triclinic,

a = 7.3627 (8) Å

b = 9.0310 (8) Å

c = 9.1854 (9) Å

α = 101.741 (8)°

β = 110.778 (10)°

γ = 96.321 (8)°

V = 547.89 (9) Å3

Z = 1

Mo Kα radiation

μ = 8.41 mm−1

T = 293 K

0.35 × 0.25 × 0.20 mm

Data collection

Oxford Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.413, T max = 1.000

3637 measured reflections

2730 independent reflections

2399 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.140

S = 1.02

2730 reflections

214 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.75 e Å−3

Δρmin = −0.77 e Å−3

Absolute structure: Flack (1983 ▶), 797 Friedel pairs

Flack parameter: −0.02 (2)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812040925/pv2593sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812040925/pv2593Isup2.hkl

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

(C8H12N)2[ZnBr4]	Z = 1
Mr = 629.36	F(000) = 304
Triclinic, P1	Dx = 1.908 Mg m−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3627 (8) Å	Cell parameters from 1674 reflections
b = 9.0310 (8) Å	θ = 2.9–29.1°
c = 9.1854 (9) Å	µ = 8.41 mm−1
α = 101.741 (8)°	T = 293 K
β = 110.778 (10)°	Chunk, colourless
γ = 96.321 (8)°	0.35 × 0.25 × 0.2 mm
V = 547.89 (9) Å3

Oxford Xcalibur Eos diffractometer	2730 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2399 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.0534 pixels mm-1	θmax = 25.0°, θmin = 2.9°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→7
Tmin = 0.413, Tmax = 1.000	l = −10→10
3637 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)] = 0.054	H-atom parameters constrained
wR(F2) = 0.140	w = 1/[σ2(Fo2) + (0.0933P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2730 reflections	Δρmax = 0.75 e Å−3
214 parameters	Δρmin = −0.77 e Å−3
3 restraints	Absolute structure: Flack (1983), 797 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.02 (2)

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
Zn1	0.9260 (2)	0.39402 (17)	0.49611 (17)	0.0439 (3)
Br4	0.9532 (2)	0.27784 (15)	0.24750 (16)	0.0629 (4)
Br3	0.59389 (18)	0.45209 (17)	0.43497 (16)	0.0576 (4)
Br2	0.9650 (2)	0.22617 (15)	0.67076 (16)	0.0609 (4)
Br1	1.16750 (19)	0.63427 (15)	0.62829 (16)	0.0617 (4)
N2	0.6828 (15)	0.6293 (11)	0.8284 (12)	0.046 (2)
H2A	0.6588	0.5839	0.7298	0.055*
C10	0.7852 (19)	0.8528 (16)	1.0355 (17)	0.053 (3)
H10A	0.8271	0.9595	1.0719	0.063*
C13	0.6550 (18)	0.5429 (14)	0.9227 (15)	0.047 (3)
C9	0.7459 (19)	0.7828 (15)	0.8773 (18)	0.052 (3)
C12	0.7024 (18)	0.6132 (16)	1.0853 (15)	0.053 (3)
H12A	0.6917	0.5538	1.1546	0.064*
C11	0.7654 (18)	0.7721 (14)	1.1426 (16)	0.045 (3)
N1	0.2717 (18)	−0.1748 (16)	0.0480 (15)	0.065 (3)
H1A	0.2518	−0.2148	−0.0511	0.078*
C4	0.2765 (16)	−0.1995 (15)	0.3001 (15)	0.046 (3)
H4A	0.2619	−0.2619	0.3658	0.056*
C2	0.3449 (17)	0.0429 (13)	0.2619 (15)	0.045 (3)
H2B	0.3782	0.1497	0.3019	0.054*
C5	0.2520 (17)	−0.2679 (15)	0.1393 (14)	0.045 (3)
C3	0.3220 (18)	−0.0405 (15)	0.3603 (15)	0.047 (3)
C1	0.323 (2)	−0.0168 (17)	0.1074 (18)	0.058 (3)
C15	0.804 (2)	0.848 (2)	1.3147 (17)	0.067 (4)
H15A	0.9121	0.8130	1.3848	0.100*
H15B	0.6876	0.8221	1.3356	0.100*
H15C	0.8381	0.9580	1.3338	0.100*
C7	0.350 (2)	0.038 (2)	0.5270 (19)	0.062 (4)
H7A	0.4814	0.0996	0.5823	0.093*
H7B	0.3321	−0.0378	0.5830	0.093*
H7C	0.2547	0.1030	0.5239	0.093*
C14	0.774 (3)	0.864 (2)	0.758 (2)	0.083 (5)
H14A	0.8654	0.8205	0.7171	0.125*
H14B	0.8253	0.9715	0.8091	0.125*
H14C	0.6487	0.8504	0.6700	0.125*
C8	0.202 (2)	−0.4391 (14)	0.0714 (18)	0.057 (3)
H8A	0.1790	−0.4631	−0.0411	0.086*
H8B	0.0841	−0.4806	0.0842	0.086*
H8C	0.3094	−0.4835	0.1277	0.086*
C16	0.585 (3)	0.3720 (16)	0.851 (2)	0.064 (4)
H16A	0.6220	0.3414	0.7604	0.097*
H16B	0.4432	0.3467	0.8150	0.097*
H16C	0.6444	0.3188	0.9303	0.097*
C6	0.353 (4)	0.090 (3)	0.010 (3)	0.120 (9)
H6A	0.2549	0.1531	−0.0043	0.179*
H6B	0.3405	0.0304	−0.0941	0.179*
H6C	0.4828	0.1540	0.0641	0.179*

	U11	U22	U33	U12	U13	U23
Zn1	0.0515 (8)	0.0429 (7)	0.0372 (7)	0.0055 (6)	0.0178 (6)	0.0109 (5)
Br4	0.0890 (11)	0.0564 (9)	0.0506 (8)	0.0112 (7)	0.0382 (8)	0.0105 (6)
Br3	0.0525 (8)	0.0733 (9)	0.0461 (7)	0.0155 (7)	0.0172 (6)	0.0155 (6)
Br2	0.0802 (10)	0.0601 (8)	0.0521 (8)	0.0160 (7)	0.0292 (7)	0.0279 (7)
Br1	0.0650 (9)	0.0521 (8)	0.0573 (9)	−0.0076 (6)	0.0207 (7)	0.0073 (6)
N2	0.055 (6)	0.047 (6)	0.029 (5)	−0.006 (5)	0.012 (4)	0.012 (4)
C10	0.042 (6)	0.048 (7)	0.061 (9)	0.009 (5)	0.013 (6)	0.009 (6)
C13	0.047 (7)	0.037 (6)	0.053 (7)	0.002 (5)	0.019 (6)	0.007 (6)
C9	0.051 (7)	0.047 (8)	0.059 (8)	0.007 (6)	0.020 (6)	0.018 (6)
C12	0.049 (7)	0.070 (9)	0.041 (7)	0.016 (7)	0.017 (6)	0.015 (6)
C11	0.036 (6)	0.051 (8)	0.047 (7)	0.009 (5)	0.016 (5)	0.008 (6)
N1	0.059 (7)	0.094 (10)	0.044 (6)	0.012 (6)	0.020 (5)	0.021 (6)
C4	0.041 (6)	0.062 (8)	0.040 (6)	0.017 (6)	0.016 (5)	0.018 (6)
C2	0.047 (7)	0.029 (6)	0.051 (8)	0.003 (5)	0.011 (6)	0.010 (5)
C5	0.035 (6)	0.069 (8)	0.030 (6)	0.011 (5)	0.010 (5)	0.013 (6)
C3	0.045 (7)	0.058 (8)	0.037 (6)	0.015 (6)	0.014 (5)	0.007 (6)
C1	0.051 (8)	0.064 (9)	0.058 (9)	0.007 (6)	0.014 (6)	0.031 (7)
C15	0.064 (9)	0.082 (11)	0.037 (8)	0.007 (8)	0.018 (7)	−0.014 (7)
C7	0.066 (10)	0.074 (10)	0.048 (8)	0.020 (8)	0.027 (7)	0.009 (7)
C14	0.109 (14)	0.086 (12)	0.073 (12)	0.029 (10)	0.035 (10)	0.057 (10)
C8	0.070 (9)	0.037 (7)	0.061 (9)	0.006 (6)	0.024 (7)	0.009 (6)
C16	0.087 (11)	0.049 (8)	0.065 (10)	0.000 (7)	0.039 (8)	0.021 (7)
C6	0.120 (17)	0.15 (2)	0.119 (19)	0.027 (15)	0.047 (15)	0.101 (17)

Zn1—Br2	2.3901 (19)	C2—C1	1.356 (19)
Zn1—Br4	2.398 (2)	C2—H2B	0.9300
Zn1—Br1	2.4270 (19)	C5—C8	1.494 (18)
Zn1—Br3	2.449 (2)	C3—C7	1.480 (19)
N2—C13	1.329 (16)	C1—C6	1.49 (2)
N2—C9	1.340 (16)	C15—H15A	0.9600
N2—H2A	0.8600	C15—H15B	0.9600
C10—C9	1.37 (2)	C15—H15C	0.9600
C10—C11	1.38 (2)	C7—H7A	0.9600
C10—H10A	0.9300	C7—H7B	0.9600
C13—C12	1.397 (18)	C7—H7C	0.9600
C13—C16	1.501 (18)	C14—H14A	0.9600
C9—C14	1.50 (2)	C14—H14B	0.9600
C12—C11	1.387 (18)	C14—H14C	0.9600
C12—H12A	0.9300	C8—H8A	0.9600
C11—C15	1.498 (18)	C8—H8B	0.9600
N1—C5	1.333 (18)	C8—H8C	0.9600
N1—C1	1.377 (19)	C16—H16A	0.9600
N1—H1A	0.8600	C16—H16B	0.9600
C4—C3	1.385 (17)	C16—H16C	0.9600
C4—C5	1.418 (17)	C6—H6A	0.9600
C4—H4A	0.9300	C6—H6B	0.9600
C2—C3	1.331 (18)	C6—H6C	0.9600
Br2—Zn1—Br4	112.48 (8)	C2—C1—N1	117.5 (12)
Br2—Zn1—Br1	110.92 (8)	C2—C1—C6	119.3 (16)
Br4—Zn1—Br1	109.19 (7)	N1—C1—C6	123.1 (16)
Br2—Zn1—Br3	107.09 (8)	C11—C15—H15A	109.5
Br4—Zn1—Br3	108.55 (8)	C11—C15—H15B	109.5
Br1—Zn1—Br3	108.49 (8)	H15A—C15—H15B	109.5
C13—N2—C9	124.2 (11)	C11—C15—H15C	109.5
C13—N2—H2A	117.9	H15A—C15—H15C	109.5
C9—N2—H2A	117.9	H15B—C15—H15C	109.5
C9—C10—C11	122.8 (12)	C3—C7—H7A	109.5
C9—C10—H10A	118.6	C3—C7—H7B	109.5
C11—C10—H10A	118.6	H7A—C7—H7B	109.5
N2—C13—C12	118.9 (11)	C3—C7—H7C	109.5
N2—C13—C16	118.0 (11)	H7A—C7—H7C	109.5
C12—C13—C16	123.1 (12)	H7B—C7—H7C	109.5
N2—C9—C10	116.9 (12)	C9—C14—H14A	109.5
N2—C9—C14	117.8 (13)	C9—C14—H14B	109.5
C10—C9—C14	125.2 (14)	H14A—C14—H14B	109.5
C11—C12—C13	119.6 (12)	C9—C14—H14C	109.5
C11—C12—H12A	120.2	H14A—C14—H14C	109.5
C13—C12—H12A	120.2	H14B—C14—H14C	109.5
C10—C11—C12	117.4 (12)	C5—C8—H8A	109.5
C10—C11—C15	123.1 (12)	C5—C8—H8B	109.5
C12—C11—C15	119.5 (13)	H8A—C8—H8B	109.5
C5—N1—C1	122.0 (12)	C5—C8—H8C	109.5
C5—N1—H1A	119.0	H8A—C8—H8C	109.5
C1—N1—H1A	119.0	H8B—C8—H8C	109.5
C3—C4—C5	120.7 (12)	C13—C16—H16A	109.5
C3—C4—H4A	119.7	C13—C16—H16B	109.5
C5—C4—H4A	119.7	H16A—C16—H16B	109.5
C3—C2—C1	124.6 (12)	C13—C16—H16C	109.5
C3—C2—H2B	117.7	H16A—C16—H16C	109.5
C1—C2—H2B	117.7	H16B—C16—H16C	109.5
N1—C5—C4	118.0 (12)	C1—C6—H6A	109.5
N1—C5—C8	120.4 (12)	C1—C6—H6B	109.5
C4—C5—C8	121.6 (12)	H6A—C6—H6B	109.5
C2—C3—C4	117.0 (11)	C1—C6—H6C	109.5
C2—C3—C7	119.7 (12)	H6A—C6—H6C	109.5
C4—C3—C7	123.3 (13)	H6B—C6—H6C	109.5
C9—N2—C13—C12	−3.1 (18)	C1—N1—C5—C4	2.9 (19)
C9—N2—C13—C16	−179.7 (13)	C1—N1—C5—C8	−178.3 (13)
C13—N2—C9—C10	0.6 (19)	C3—C4—C5—N1	−0.8 (17)
C13—N2—C9—C14	178.8 (13)	C3—C4—C5—C8	−179.6 (12)
C11—C10—C9—N2	1 (2)	C1—C2—C3—C4	1.3 (19)
C11—C10—C9—C14	−177.0 (14)	C1—C2—C3—C7	179.9 (13)
N2—C13—C12—C11	3.9 (18)	C5—C4—C3—C2	−1.3 (17)
C16—C13—C12—C11	−179.7 (13)	C5—C4—C3—C7	−179.8 (12)
C9—C10—C11—C12	−0.1 (19)	C3—C2—C1—N1	1 (2)
C9—C10—C11—C15	−178.8 (13)	C3—C2—C1—C6	−180.0 (15)
C13—C12—C11—C10	−2.4 (17)	C5—N1—C1—C2	−3 (2)
C13—C12—C11—C15	176.3 (12)	C5—N1—C1—C6	177.8 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1i	0.86	2.79	3.647 (13)	175
N2—H2A···Br3	0.86	2.57	3.433 (10)	179
C2—H2B···Br3	0.93	2.79	3.685 (11)	162
C10—H10A···Br4ii	0.93	2.86	3.776 (13)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1i	0.86	2.79	3.647 (13)	175
N2—H2A⋯Br3	0.86	2.57	3.433 (10)	179
C2—H2B⋯Br3	0.93	2.79	3.685 (11)	162
C10—H10A⋯Br4ii	0.93	2.86	3.776 (13)	168

Symmetry codes: (i) ; (ii) .