1-Bromo-methyl-1,4-diazo-niabicyclo-[2.2.2]octane tetra-chloridozincate.

The reaction of 1-bromo-methyl-1,4-diazo-niabicyclo-[2.2.2]octane bromide, zinc chloride and hydro-chloric acid in water yields the title compound, (C(7)H(15)BrN(2))[ZnCl(4)]. In the crystal, the components are linked by N-H⋯Cl hydrogen bonds. The Zn(II) atom has an approximately tetra-hedral coordination geometry.

Related literature

For applications of ferroelectric materials, see: Fu et al. (2009 ▶); Ye et al. (2009 ▶); Zhang et al. (2009 ▶). 1,4-diazo­niabicyclo­[2.2.2]octane (DABCO) salts with inorganic tetra­hedral anions exhibit exceptional properties, see: Szafrański et al. (2002 ▶). Furthermore, DABCO can undergo substitution with dibromo­methane to obtain 1-bromo­methyl-DABCO bromide, see: Finke et al. (2010 ▶).

Experimental

Crystal data

(C7H15BrN2)[ZnCl4]

M = 414.30

Monoclinic,

a = 10.253 (2) Å

b = 12.214 (2) Å

c = 11.147 (2) Å

β = 90.97 (3)°

V = 1395.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 5.36 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.342, T max = 0.356

14183 measured reflections

3201 independent reflections

2698 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.099

S = 1.12

3201 reflections

136 parameters

H-atom parameters constrained

Δρmax = 1.12 e Å−3

Δρmin = −0.92 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811032430/qm2022sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032430/qm2022Isup2.hkl

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

(C7H15BrN2)[ZnCl4]	F(000) = 816
Mr = 414.30	Dx = 1.972 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12777 reflections
a = 10.253 (2) Å	θ = 3.2–27.5°
b = 12.214 (2) Å	µ = 5.36 mm−1
c = 11.147 (2) Å	T = 293 K
β = 90.97 (3)°	Prism, colorless
V = 1395.7 (4) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Rigaku SCXmini diffractometer	3201 independent reflections
Radiation source: fine-focus sealed tube	2698 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
Tmin = 0.342, Tmax = 0.356	l = −14→14
14183 measured 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0381P)2 + 2.7437P] where P = (Fo2 + 2Fc2)/3
3201 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 1.12 e Å−3
0 restraints	Δρmin = −0.92 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
Zn1	0.22858 (4)	0.07443 (4)	0.21406 (4)	0.02816 (13)
Br1	0.60658 (5)	0.19087 (4)	0.46852 (4)	0.04538 (15)
Cl1	0.06383 (9)	0.14865 (9)	0.09911 (9)	0.0345 (2)
Cl2	0.41010 (10)	0.13065 (10)	0.11498 (9)	0.0379 (2)
Cl3	0.21448 (13)	−0.10851 (8)	0.23132 (11)	0.0455 (3)
Cl4	0.22216 (16)	0.14841 (9)	0.40008 (9)	0.0534 (4)
N1	0.7521 (3)	0.0408 (2)	0.3236 (3)	0.0220 (6)
C5	0.7422 (4)	0.1103 (3)	0.2117 (3)	0.0294 (8)
H5A	0.8157	0.1601	0.2089	0.035*
H5B	0.6628	0.1534	0.2130	0.035*
N2	0.7501 (3)	−0.0797 (3)	0.1395 (3)	0.0299 (7)
H2C	0.7495	−0.1232	0.0732	0.036*
C2	0.6364 (4)	−0.1081 (4)	0.2143 (4)	0.0383 (10)
H2A	0.6409	−0.1847	0.2371	0.046*
H2B	0.5562	−0.0967	0.1686	0.046*
C4	0.8766 (4)	−0.0259 (4)	0.3192 (4)	0.0313 (9)
H4A	0.8840	−0.0717	0.3900	0.038*
H4B	0.9514	0.0228	0.3181	0.038*
C6	0.7411 (4)	0.0367 (3)	0.1011 (3)	0.0316 (9)
H6A	0.6614	0.0482	0.0548	0.038*
H6B	0.8143	0.0548	0.0508	0.038*
C3	0.8752 (4)	−0.0969 (4)	0.2076 (4)	0.0371 (10)
H3A	0.9483	−0.0780	0.1576	0.045*
H3B	0.8836	−0.1733	0.2302	0.045*
C1	0.6368 (4)	−0.0367 (3)	0.3260 (4)	0.0315 (9)
H1A	0.5564	0.0049	0.3290	0.038*
H1B	0.6425	−0.0824	0.3971	0.038*
C7	0.7626 (4)	0.1111 (4)	0.4357 (3)	0.0341 (9)
H7A	0.8338	0.1626	0.4267	0.041*
H7B	0.7835	0.0645	0.5038	0.041*

	U11	U22	U33	U12	U13	U23
Zn1	0.0349 (3)	0.0251 (2)	0.0246 (2)	−0.00060 (18)	0.00461 (18)	0.00046 (18)
Br1	0.0530 (3)	0.0438 (3)	0.0399 (3)	0.0122 (2)	0.0152 (2)	−0.0048 (2)
Cl1	0.0290 (5)	0.0422 (6)	0.0323 (5)	−0.0009 (4)	0.0019 (4)	0.0055 (4)
Cl2	0.0273 (5)	0.0515 (6)	0.0351 (5)	−0.0061 (4)	0.0039 (4)	−0.0019 (5)
Cl3	0.0708 (8)	0.0177 (5)	0.0478 (6)	0.0032 (5)	−0.0015 (6)	0.0023 (4)
Cl4	0.1096 (11)	0.0293 (5)	0.0214 (5)	0.0050 (6)	0.0062 (6)	0.0014 (4)
N1	0.0254 (15)	0.0230 (15)	0.0178 (14)	0.0006 (12)	0.0041 (12)	0.0003 (12)
C5	0.041 (2)	0.0245 (19)	0.0231 (19)	−0.0007 (16)	0.0025 (17)	0.0050 (15)
N2	0.0380 (19)	0.0261 (17)	0.0258 (16)	0.0002 (14)	0.0020 (14)	−0.0046 (13)
C2	0.041 (2)	0.031 (2)	0.043 (2)	−0.0126 (19)	0.008 (2)	−0.0026 (19)
C4	0.030 (2)	0.036 (2)	0.028 (2)	0.0072 (17)	0.0029 (16)	−0.0013 (17)
C6	0.045 (2)	0.029 (2)	0.0209 (19)	0.0009 (18)	0.0001 (17)	−0.0003 (16)
C3	0.038 (2)	0.034 (2)	0.039 (2)	0.0142 (18)	−0.0051 (19)	−0.0089 (19)
C1	0.030 (2)	0.034 (2)	0.031 (2)	−0.0063 (17)	0.0062 (16)	0.0022 (17)
C7	0.040 (2)	0.040 (2)	0.0229 (19)	0.0052 (18)	0.0022 (17)	−0.0085 (17)

Zn1—Cl3	2.2475 (12)	N2—H2C	0.9100
Zn1—Cl4	2.2639 (12)	C2—C1	1.521 (6)
Zn1—Cl2	2.2858 (12)	C2—H2A	0.9700
Zn1—Cl1	2.2899 (12)	C2—H2B	0.9700
Br1—C7	1.913 (4)	C4—C3	1.516 (5)
N1—C5	1.511 (5)	C4—H4A	0.9700
N1—C1	1.515 (5)	C4—H4B	0.9700
N1—C4	1.516 (5)	C6—H6A	0.9700
N1—C7	1.519 (5)	C6—H6B	0.9700
C5—C6	1.525 (5)	C3—H3A	0.9700
C5—H5A	0.9700	C3—H3B	0.9700
C5—H5B	0.9700	C1—H1A	0.9700
N2—C2	1.486 (5)	C1—H1B	0.9700
N2—C6	1.487 (5)	C7—H7A	0.9700
N2—C3	1.494 (5)	C7—H7B	0.9700
Cl3—Zn1—Cl4	108.39 (5)	N1—C4—C3	109.8 (3)
Cl3—Zn1—Cl2	113.21 (5)	N1—C4—H4A	109.7
Cl4—Zn1—Cl2	111.05 (5)	C3—C4—H4A	109.7
Cl3—Zn1—Cl1	113.17 (5)	N1—C4—H4B	109.7
Cl4—Zn1—Cl1	108.78 (5)	C3—C4—H4B	109.7
Cl2—Zn1—Cl1	102.10 (4)	H4A—C4—H4B	108.2
C5—N1—C1	108.9 (3)	N2—C6—C5	109.3 (3)
C5—N1—C4	108.7 (3)	N2—C6—H6A	109.8
C1—N1—C4	108.8 (3)	C5—C6—H6A	109.8
C5—N1—C7	111.4 (3)	N2—C6—H6B	109.8
C1—N1—C7	112.5 (3)	C5—C6—H6B	109.8
C4—N1—C7	106.5 (3)	H6A—C6—H6B	108.3
N1—C5—C6	109.6 (3)	N2—C3—C4	109.4 (3)
N1—C5—H5A	109.7	N2—C3—H3A	109.8
C6—C5—H5A	109.7	C4—C3—H3A	109.8
N1—C5—H5B	109.7	N2—C3—H3B	109.8
C6—C5—H5B	109.7	C4—C3—H3B	109.8
H5A—C5—H5B	108.2	H3A—C3—H3B	108.2
C2—N2—C6	109.8 (3)	N1—C1—C2	109.6 (3)
C2—N2—C3	110.9 (3)	N1—C1—H1A	109.8
C6—N2—C3	109.2 (3)	C2—C1—H1A	109.8
C2—N2—H2C	108.9	N1—C1—H1B	109.8
C6—N2—H2C	108.9	C2—C1—H1B	109.8
C3—N2—H2C	108.9	H1A—C1—H1B	108.2
N2—C2—C1	109.5 (3)	N1—C7—Br1	113.4 (3)
N2—C2—H2A	109.8	N1—C7—H7A	108.9
C1—C2—H2A	109.8	Br1—C7—H7A	108.9
N2—C2—H2B	109.8	N1—C7—H7B	108.9
C1—C2—H2B	109.8	Br1—C7—H7B	108.9
H2A—C2—H2B	108.2	H7A—C7—H7B	107.7

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl2i	0.91	2.64	3.313 (4)	131.
N2—H2C···Cl1i	0.91	2.75	3.405 (4)	130.
N2—H2C···Cl4ii	0.91	2.82	3.363 (3)	120.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯Cl2i	0.91	2.64	3.313 (4)	131
N2—H2C⋯Cl1i	0.91	2.75	3.405 (4)	130
N2—H2C⋯Cl4ii	0.91	2.82	3.363 (3)	120

Symmetry codes: (i) ; (ii) .