1-Bromo­methyl-1,4-diazo­niabicyclo­[2.2.2]octane tetra­chloridozincate

Shi, P.P.

doi:10.1107/S1600536811032430

metal-organic compounds

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Volume 67| Part 9| September 2011| Page m1297

doi:10.1107/S1600536811032430

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1-Bromomethyl-1,4-diazoniabicyclo[2.2.2]octane tetrachloridozincate

Ping Ping Shi ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: shipingping1990@126.com

(Received 9 August 2011; accepted 10 August 2011; online 27 August 2011)

The reaction of 1-bromomethyl-1,4-diazoniabicyclo[2.2.2]octane bromide, zinc chloride and hydrochloric acid in water yields the title compound, (C₇H₁₅BrN₂)[ZnCl₄]. In the crystal, the components are linked by N—H⋯Cl hydrogen bonds. The Zn^II atom has an approximately tetrahedral 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_r = 414.30
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.041
wR(F²) = 0.099
S = 1.12
3201 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.92 e Å⁻³

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) -x+1, -y, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811032430/qm2022sup1.cif

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

checkCIF report

Comment top

Ferroelectric materials have so many potential applications in memory storage that they attract much attention(Fu et al., 2009; Ye et al., 2009; Zhang et al., 2009). In order to find more dielectric or ferroelectric materials, many novel compounds have been synthesized. Thereinto 1,4-diazoniabicyclo[2.2.2]octane (DABCO) salts with inorganic tetrahedral anions exhibit exceptional properties (Szafrański et al.,2002). Furthermore, DABCO can undergo substitution with dibromomethane to obtain 1-Bromomethyl-DABCO bromide (Finke et al.,2010).

Therefore, we report the single-crystal structure of the title copound which consists of a 1-Bromomethyl-1,4-diazoniabicyclo[2.2.2]octane-1,4-diium cation and a tetrachloridozincate dianion(Fig.1).In the ctystal structure,as showed in the packing diagram(Fig.2), the protonated N2 atom of DABCO derivant interacts via a trifurcated hydrogen bond with three Cl atoms of the two neighbouring anions.

However, within the measured temperature range from 190 K to near its melting point(m.p. > 473 K), the dielectric constant of the title compound is basically temperature-independant, suggesting that this material should be not a real ferroelectric.

Related literature top

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 top

The mixture solution of 1,4-diazoniabicyclo[2.2.2]octane (20 mmol,2.24 g) and dibromomethane (20 mmol,3.48 g) in acetone was stirred for three hours. A white precipite of 1-Bromomethyl-1,4-diazoniabicyclo[2.2.2]octane-1-ium bromide(1) was synthesized. At room temperature,by slow evaporation of a hydrochloric acid solution containing 1 (20 mmol,5.72 g) and zinc chloride (20 mmol,2.72 g),colorless crystals of the title copound suitable for X-ray analysis were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecule structure of the title compound,with atom lables and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound,showing molecules connected by N—H···Cl hydrogen bonds (dash lines).

1-Bromomethyl-1,4-diazoniabicyclo[2.2.2]octane tetrachloridozincate top

Crystal data top

(C₇H₁₅BrN₂)[ZnCl₄]	F(000) = 816
M_r = 414.30	D_x = 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

Data collection top

Rigaku SCXmini diffractometer	3201 independent reflections
Radiation source: fine-focus sealed tube	2698 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.342, T_max = 0.356	l = −14→14
14183 measured reflections

Refinement top

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(F_o²) + (0.0381P)² + 2.7437P] where P = (F_o² + 2F_c²)/3
3201 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 1.12 e Å⁻³
0 restraints	Δρ_min = −0.92 e Å⁻³

Crystal data top

(C₇H₁₅BrN₂)[ZnCl₄]	V = 1395.7 (4) Å³
M_r = 414.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.253 (2) Å	µ = 5.36 mm⁻¹
b = 12.214 (2) Å	T = 293 K
c = 11.147 (2) Å	0.20 × 0.20 × 0.20 mm
β = 90.97 (3)°

Data collection top

Rigaku SCXmini diffractometer	3201 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2698 reflections with I > 2σ(I)
T_min = 0.342, T_max = 0.356	R_int = 0.040
14183 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.12	Δρ_max = 1.12 e Å⁻³
3201 reflections	Δρ_min = −0.92 e Å⁻³
136 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y, −z; (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	(C₇H₁₅BrN₂)[ZnCl₄]
M_r	414.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.253 (2), 12.214 (2), 11.147 (2)
β (°)	90.97 (3)
V (Å³)	1395.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.36
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.342, 0.356
No. of measured, independent and observed [I > 2σ(I)] reflections	14183, 3201, 2698
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.099, 1.12
No. of reflections	3201
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.12, −0.92

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Cl2ⁱ	0.91	2.64	3.313 (4)	131.4
N2—H2C···Cl1ⁱ	0.91	2.75	3.405 (4)	129.6
N2—H2C···Cl4ⁱⁱ	0.91	2.82	3.363 (3)	119.5

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors are grateful to the starter fund of Southeast University for financial support to purchase the X-ray diffractometer.

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