3,3′-Dibenzyl-1,1′-ethyl­enediimidazolium dibromide

Lee, H.M.; Cheng, P.-Y.

doi:10.1107/S1600536810031934

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2308

https://doi.org/10.1107/S1600536810031934

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3,3′-Dibenzyl-1,1′-ethylenediimidazolium dibromide

Hon Man Lee ^a ^* and Pi-Yun Cheng ^a

^aNational Changhua University of Education, Department of Chemistry, Changhua, Taiwan 50058
^*Correspondence e-mail: leehm@cc.ncue.edu.tw

(Received 5 August 2010; accepted 9 August 2010; online 18 August 2010)

In the title compound, C₂₂H₂₄N₄²⁺·2Br⁻, the imidazolium dication is located on a crystallographic inversion center. The imidazole and benzene rings make a dihedral angle of 73.1 (9)°. In the crystal, non-classical intermolecular C—H⋯Br hydrogen bonds link the ion pairs into a two-dimensional network.

Related literature

For related structures of bis(imidazolium) salts, see: Baker et al. (2002 ); Lee et al. (2004 , 2007 , 2008 ); Jin et al. (2007 ); Lee & Lu (2008 ); Paulose et al. (2008 ) and of methylene-linked bis(imidazolium) salts, see: Cheng et al. (2006 ); Lee & Chiu (2004 ); Lee et al. (2004).

Experimental

Crystal data

C₂₂H₂₄N₄²⁺·2Br⁻
M_r = 504.27
Monoclinic, P 2₁ /c
a = 16.4674 (8) Å
b = 5.2099 (2) Å
c = 12.3736 (6) Å
β = 96.495 (3)°
V = 1054.76 (8) Å³
Z = 2
Mo Kα radiation
μ = 3.86 mm⁻¹
T = 150 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.446, T_max = 0.513
10232 measured reflections
2542 independent reflections
1915 reflections with I > 2σ
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.074
S = 1.03
2542 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Br1ⁱ	0.95	2.86	3.663 (2)	143
C3—H3⋯Br1ⁱⁱ	0.95	2.77	3.683 (2)	162
C4—H4B⋯Br1ⁱ	0.99	2.83	3.661 (3)	142
Symmetry codes: (i) x, y-1, z; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: DIAMOND (Brandenburg, 2006 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810031934/om2353sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031934/om2353Isup2.hkl

checkCIF report

Comment top

The title compound is a precursor to the formation of bidentate N-heterocyclic carbene ligand (Lee et al. 2004). It can be easily prepared by the reaction of 1,2-dibromoethane and 1-benzylimidazole in tetrahydrofuran (Lee et al. 2004).

The dication is located on a crystallographic inversion center. The non-classical intermolecular hydrogen bonds of the type C—H···Br link the imidazolium dications and bromide anions into a two dimensional hydrogen bonded network.

Ethylene-linked bis(imidazolium) salts similar to the title compound were reported by us (Lee et al., 2004; Lee et al. 2007; Lee & Lu (2008); Lee et al. 2008) and others (Baker et al. 2002; Jin et al. 2007; Paulose et al. 2008). We also published crystal structures of relevant methylene-linked bis(imidazolium) salts (Lee et al., 2004; Lee & Chiu, 2004; Cheng et al. 2006).

Related literature top

For related structures of bis(imidazolium) salts, see: Baker et al. (2002); Lee et al. (2004, 2007, 2008); Jin et al. (2007); Lee & Lu (2008); Paulose et al. (2008) and of methylene-linked bis(imidazolium) salts, see: Cheng et al. (2006); Lee & Chiu (2004); Lee et al. (2004).

Experimental top

The compound was prepared according to the literature procedure (Lee et al., 2004). Suitable crystals were obtained by slow diffusion of diethyl ether into a DMF solution of the compound at room temperature.

Structure description top

For related structures of bis(imidazolium) salts, see: Baker et al. (2002); Lee et al. (2004, 2007, 2008); Jin et al. (2007); Lee & Lu (2008); Paulose et al. (2008) and of methylene-linked bis(imidazolium) salts, see: Cheng et al. (2006); Lee & Chiu (2004); Lee et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: DIAMOND (Brandenburg, 2006).

Figures top

	Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids for the non-hydrogen atoms. The H atoms are depicted by circles of an arbitrary radius. The unlabelled atoms of the imidazolium cation and the bromide anion are related to the labelled ones by 1 - x, -y, 1 - z.
	Fig. 2. A view of the crystal packing along the b axis. Hydrogen bonds are shown as dashed lines.

3,3'-Dibenzyl-1,1'-ethylenediimidazolium dibromide top

Crystal data top

C₂₂H₂₄N₄²⁺·2Br⁻	F(000) = 508
M_r = 504.27	D_x = 1.588 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2242 reflections
a = 16.4674 (8) Å	θ = 2.5–24.5°
b = 5.2099 (2) Å	µ = 3.86 mm⁻¹
c = 12.3736 (6) Å	T = 150 K
β = 96.495 (3)°	Block, colorless
V = 1054.76 (8) Å³	0.25 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEXII diffractometer	2542 independent reflections
Radiation source: fine-focus sealed tube	1915 reflections with I > 2σ
Graphite monochromator	R_int = 0.047
ω scans	θ_max = 28.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −21→21
T_min = 0.446, T_max = 0.513	k = −6→6
10232 measured reflections	l = −16→14

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0338P)² + 0.006P] where P = (F_o² + 2F_c²)/3
2542 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₂₂H₂₄N₄²⁺·2Br⁻	V = 1054.76 (8) Å³
M_r = 504.27	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.4674 (8) Å	µ = 3.86 mm⁻¹
b = 5.2099 (2) Å	T = 150 K
c = 12.3736 (6) Å	0.25 × 0.20 × 0.20 mm
β = 96.495 (3)°

Data collection top

Bruker SMART APEXII diffractometer	2542 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1915 reflections with I > 2σ
T_min = 0.446, T_max = 0.513	R_int = 0.047
10232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	Δρ_max = 0.49 e Å⁻³
2542 reflections	Δρ_min = −0.46 e Å⁻³
127 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
Br1	0.326856 (16)	0.58076 (5)	0.570787 (19)	0.02456 (10)
C1	0.34814 (15)	0.0860 (5)	0.37001 (19)	0.0191 (5)
H1	0.3171	−0.0415	0.4018	0.023*
C2	0.45155 (15)	0.3145 (5)	0.32355 (19)	0.0186 (5)
H2	0.5056	0.3725	0.3176	0.022*
C3	0.38199 (15)	0.4239 (5)	0.27857 (19)	0.0196 (5)
H3	0.3777	0.5737	0.2345	0.024*
C4	0.48543 (14)	−0.0683 (4)	0.44729 (18)	0.0173 (5)
H4A	0.5327	−0.1128	0.4082	0.021*
H4B	0.4569	−0.2290	0.4628	0.021*
C5	0.23178 (16)	0.3432 (5)	0.2752 (2)	0.0300 (7)
H5A	0.2227	0.3566	0.1949	0.036*
H5B	0.2199	0.5131	0.3056	0.036*
C6	0.17344 (15)	0.1494 (5)	0.3122 (2)	0.0230 (6)
C7	0.15780 (16)	0.1430 (6)	0.4197 (2)	0.0324 (7)
H7	0.1842	0.2621	0.4701	0.039*
C8	0.10409 (18)	−0.0349 (6)	0.4545 (3)	0.0381 (8)
H8	0.0944	−0.0402	0.5287	0.046*
C9	0.06422 (16)	−0.2064 (6)	0.3799 (3)	0.0380 (8)
H9	0.0271	−0.3289	0.4031	0.046*
C10	0.07858 (17)	−0.1982 (6)	0.2731 (3)	0.0350 (7)
H10	0.0508	−0.3134	0.2221	0.042*
C11	0.13354 (16)	−0.0224 (5)	0.2392 (2)	0.0281 (6)
H11	0.1439	−0.0199	0.1652	0.034*
N1	0.42965 (12)	0.1019 (4)	0.37997 (15)	0.0166 (4)
N2	0.31810 (11)	0.2793 (4)	0.30799 (15)	0.0178 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03007 (16)	0.02334 (15)	0.02017 (15)	−0.00608 (12)	0.00241 (10)	−0.00064 (12)
C1	0.0225 (13)	0.0160 (13)	0.0189 (12)	−0.0020 (10)	0.0028 (10)	0.0006 (11)
C2	0.0212 (14)	0.0178 (12)	0.0172 (12)	−0.0042 (10)	0.0035 (10)	−0.0002 (10)
C3	0.0263 (14)	0.0179 (13)	0.0148 (12)	−0.0014 (11)	0.0030 (10)	0.0003 (11)
C4	0.0188 (12)	0.0161 (12)	0.0162 (12)	0.0047 (10)	−0.0014 (9)	0.0011 (10)
C5	0.0204 (14)	0.0286 (15)	0.0395 (17)	0.0048 (11)	−0.0040 (12)	0.0103 (12)
C6	0.0147 (13)	0.0236 (14)	0.0298 (15)	0.0041 (10)	−0.0025 (11)	0.0049 (11)
C7	0.0248 (16)	0.0372 (17)	0.0338 (17)	−0.0022 (11)	−0.0022 (13)	−0.0028 (13)
C8	0.0304 (17)	0.053 (2)	0.0318 (17)	0.0014 (14)	0.0078 (13)	0.0109 (15)
C9	0.0200 (15)	0.0320 (17)	0.062 (2)	−0.0003 (12)	0.0056 (14)	0.0132 (16)
C10	0.0263 (16)	0.0279 (16)	0.050 (2)	0.0014 (12)	0.0011 (14)	−0.0091 (14)
C11	0.0241 (15)	0.0290 (15)	0.0310 (16)	0.0058 (11)	0.0023 (12)	−0.0036 (12)
N1	0.0205 (11)	0.0154 (10)	0.0135 (10)	0.0004 (8)	0.0012 (8)	0.0004 (8)
N2	0.0193 (11)	0.0155 (11)	0.0179 (11)	0.0009 (8)	−0.0008 (8)	0.0020 (9)

Geometric parameters (Å, º) top

C1—N2	1.328 (3)	C5—H5A	0.9900
C1—N1	1.336 (3)	C5—H5B	0.9900
C1—H1	0.9500	C6—C7	1.384 (4)
C2—C3	1.343 (3)	C6—C11	1.384 (4)
C2—N1	1.379 (3)	C7—C8	1.383 (4)
C2—H2	0.9500	C7—H7	0.9500
C3—N2	1.376 (3)	C8—C9	1.394 (4)
C3—H3	0.9500	C8—H8	0.9500
C4—N1	1.467 (3)	C9—C10	1.369 (4)
C4—C4ⁱ	1.515 (4)	C9—H9	0.9500
C4—H4A	0.9900	C10—C11	1.386 (4)
C4—H4B	0.9900	C10—H10	0.9500
C5—N2	1.472 (3)	C11—H11	0.9500
C5—C6	1.501 (4)

N2—C1—N1	108.1 (2)	C11—C6—C5	120.6 (3)
N2—C1—H1	125.9	C6—C7—C8	120.7 (3)
N1—C1—H1	125.9	C6—C7—H7	119.7
C3—C2—N1	106.9 (2)	C8—C7—H7	119.7
C3—C2—H2	126.5	C7—C8—C9	119.6 (3)
N1—C2—H2	126.5	C7—C8—H8	120.2
C2—C3—N2	107.5 (2)	C9—C8—H8	120.2
C2—C3—H3	126.3	C10—C9—C8	119.9 (3)
N2—C3—H3	126.3	C10—C9—H9	120.0
N1—C4—C4ⁱ	108.8 (2)	C8—C9—H9	120.0
N1—C4—H4A	109.9	C9—C10—C11	120.2 (3)
C4ⁱ—C4—H4A	109.9	C9—C10—H10	119.9
N1—C4—H4B	109.9	C11—C10—H10	119.9
C4ⁱ—C4—H4B	109.9	C6—C11—C10	120.6 (3)
H4A—C4—H4B	108.3	C6—C11—H11	119.7
N2—C5—C6	113.3 (2)	C10—C11—H11	119.7
N2—C5—H5A	108.9	C1—N1—C2	108.7 (2)
C6—C5—H5A	108.9	C1—N1—C4	125.0 (2)
N2—C5—H5B	108.9	C2—N1—C4	126.2 (2)
C6—C5—H5B	108.9	C1—N2—C3	108.8 (2)
H5A—C5—H5B	107.7	C1—N2—C5	128.0 (2)
C7—C6—C11	119.1 (3)	C3—N2—C5	123.1 (2)
C7—C6—C5	120.3 (2)

N1—C2—C3—N2	0.3 (3)	N2—C1—N1—C4	176.4 (2)
N2—C5—C6—C7	76.1 (3)	C3—C2—N1—C1	−0.7 (3)
N2—C5—C6—C11	−105.0 (3)	C3—C2—N1—C4	−176.2 (2)
C11—C6—C7—C8	1.0 (4)	C4ⁱ—C4—N1—C1	−100.5 (3)
C5—C6—C7—C8	180.0 (3)	C4ⁱ—C4—N1—C2	74.3 (3)
C6—C7—C8—C9	−1.2 (4)	N1—C1—N2—C3	−0.7 (3)
C7—C8—C9—C10	0.2 (4)	N1—C1—N2—C5	−179.3 (2)
C8—C9—C10—C11	1.0 (4)	C2—C3—N2—C1	0.2 (3)
C7—C6—C11—C10	0.1 (4)	C2—C3—N2—C5	178.9 (2)
C5—C6—C11—C10	−178.8 (2)	C6—C5—N2—C1	−4.6 (4)
C9—C10—C11—C6	−1.1 (4)	C6—C5—N2—C3	176.9 (2)
N2—C1—N1—C2	0.9 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1ⁱⁱ	0.95	2.86	3.663 (2)	143
C3—H3···Br1ⁱⁱⁱ	0.95	2.77	3.683 (2)	162
C4—H4B···Br1ⁱⁱ	0.99	2.83	3.661 (3)	142

Symmetry codes: (ii) x, y−1, z; (iii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₄N₄²⁺·2Br⁻
M_r	504.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	16.4674 (8), 5.2099 (2), 12.3736 (6)
β (°)	96.495 (3)
V (Å³)	1054.76 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.86
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.446, 0.513
No. of measured, independent and observed (I > 2σ) reflections	10232, 2542, 1915
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.074, 1.03
No. of reflections	2542
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.46

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1ⁱ	0.95	2.86	3.663 (2)	142.6
C3—H3···Br1ⁱⁱ	0.95	2.77	3.683 (2)	162.0
C4—H4B···Br1ⁱ	0.99	2.83	3.661 (3)	142.2

Symmetry codes: (i) x, y−1, z; (ii) x, −y+3/2, z−1/2.

Acknowledgements

We are grateful to the National Science Council of Taiwan for financial support of this work.

References

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