3,3′-Bis(3-meth­oxy­benz­yl)-1,1′-(ethane-1,2-diyl)­diimidazolium dibromide dihydrate

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

doi:10.1107/S1600536811050240

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3464

https://doi.org/10.1107/S1600536811050240

Open

access

3,3′-Bis(3-methoxybenzyl)-1,1′-(ethane-1,2-diyl)diimidazolium dibromide dihydrate

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

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

(Received 10 November 2011; accepted 22 November 2011; online 30 November 2011)

In the title compound, C₂₄H₂₈N₄O₂²⁺·2Br⁻·2H₂O, the diimidazolium cation is located on an inversion center. The imidazole and the benzene rings make a dihedral angle of 68.08 (04)°. In the crystal, O—H⋯Br, C—H⋯O and C—H⋯Br hydrogen bonds link the diimidazolium cations, the bromide anions and the water molecules into a two-dimensional network.

Related literature

For the non-hydrated crystal structure of the title compound, see: Lee & Lu (2008 ). For preparation of the title compound, see: Lee et al. (2004 ).

Experimental

Crystal data

C₂₄H₂₈N₄O₂²⁺·2Br⁻·2H₂O
M_r = 600.36
Monoclinic, P 2₁ /c
a = 8.5879 (3) Å
b = 13.7822 (6) Å
c = 11.0964 (5) Å
β = 107.277 (2)°
V = 1254.11 (9) Å³
Z = 2
Mo Kα radiation
μ = 3.27 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 = 0.495, T_max = 0.561
9596 measured reflections
2986 independent reflections
2560 reflections with I > 2σ
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.059
S = 1.04
2986 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H12⋯Br1ⁱ	0.74	2.63	3.3419 (13)	161.9
O2—H13⋯Br1	0.89	2.52	3.3362 (14)	153.2
C11—H1⋯O2ⁱⁱ	0.91	2.45	3.295 (2)	154.5
C1—H6⋯Br1ⁱⁱ	0.94	2.86	3.6743 (16)	145.5
C5—H4⋯O2ⁱⁱ	0.95	2.60	3.402 (2)	142.6
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS96 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); 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/S1600536811050240/pv2485sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050240/pv2485Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811050240/pv2485Isup3.cml

checkCIF report

Comment top

The non-hydrated crystal structure of the same imidazolium bromide, has been published previously (Lee & Lu, 2008). The title compound is a dihydrated salt. The structure of the title compound (Fig. 1) is similar to the non-hydrated structure, wherein the bis(imidazolium) dication is also located on an inversion center with the two imidazole rings being parallel to each other. The imidazole and the benzene rings in the title compound make a dihedral angle of 68.08 (04)°, which is much smaller than 77.25 (16)° reported in the non-hydrated structure. Intermolecular hydrogen bonds of the type O—H···Br, C—H···O and C—H···Br link the imidazolium cations, bromide anions and water solvent molecules, forming a two-dimensional hydrogen-bonded network (Fig. 2 and Table 1).

Related literature top

For the non-hydrated crystal structure of the title compound, see: Lee & Lu (2008). For preparation of the title compound, see: 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 wet DMF solution of the compound at room temperature.

Structure description top

For the non-hydrated crystal structure of the title compound, see: Lee & Lu (2008). For preparation of the title compound, see: 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: SHELXSL96 (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 dipicted by circles of an arbitrary radius. The unlabelled atoms of the imidazolium cation are related to the labelled ones by symmetry operation: 2 - x, -y, 1 - z; for the anion, the symmetry operation for Br1 is x, 1/2 - y, -1/2 + z.
	Fig. 2. Unit cell packing of the title compound showing hydrogen bonding interactions.

3,3'-Bis(3-methoxybenzyl)-1,1'-(ethane-1,2-diyl)diimidazolium dibromide dihydrate top

Crystal data top

C₂₄H₂₈N₄O₂²⁺·2Br⁻·2H₂O	F(000) = 612
M_r = 600.36	D_x = 1.590 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4076 reflections
a = 8.5879 (3) Å	θ = 2.4–27.8°
b = 13.7822 (6) Å	µ = 3.27 mm⁻¹
c = 11.0964 (5) Å	T = 150 K
β = 107.277 (2)°	Block, white
V = 1254.11 (9) Å³	0.25 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEXII diffractometer	2986 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 27.9°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −11→11
T_min = 0.495, T_max = 0.561	k = −18→17
9596 measured reflections	l = −10→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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0332P)² + 0.2216P] where P = (F_o² + 2F_c²)/3
2986 reflections	(Δ/σ)_max = 0.004
154 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₄H₂₈N₄O₂²⁺·2Br⁻·2H₂O	V = 1254.11 (9) Å³
M_r = 600.36	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5879 (3) Å	µ = 3.27 mm⁻¹
b = 13.7822 (6) Å	T = 150 K
c = 11.0964 (5) Å	0.25 × 0.20 × 0.20 mm
β = 107.277 (2)°

Data collection top

Bruker SMART APEXII diffractometer	2986 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2560 reflections with I > 2σ
T_min = 0.495, T_max = 0.561	R_int = 0.020
9596 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.04	Δρ_max = 0.34 e Å⁻³
2986 reflections	Δρ_min = −0.26 e Å⁻³
154 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	0.359161 (19)	0.146752 (12)	0.490121 (15)	0.02394 (7)
C1	0.92203 (19)	0.14465 (11)	0.31701 (14)	0.0160 (3)
C11	0.9179 (2)	0.13818 (11)	−0.03275 (15)	0.0177 (3)
C5	0.8031 (2)	0.23349 (11)	0.11436 (14)	0.0184 (3)
C3	0.6531 (2)	0.14528 (12)	0.24893 (16)	0.0209 (3)
C7	0.6246 (2)	0.14644 (12)	−0.07555 (16)	0.0222 (3)
C6	0.7804 (2)	0.17085 (11)	−0.00127 (14)	0.0168 (3)
C10	0.8960 (2)	0.08036 (12)	−0.13955 (14)	0.0193 (3)
C4	0.96949 (19)	0.04905 (12)	0.51517 (14)	0.0180 (3)
C8	0.6059 (2)	0.08805 (13)	−0.18098 (15)	0.0236 (4)
C2	0.69825 (19)	0.09468 (12)	0.35762 (15)	0.0204 (3)
C9	0.7400 (2)	0.05481 (12)	−0.21304 (14)	0.0225 (4)
N1	0.86714 (16)	0.09507 (9)	0.39930 (11)	0.0157 (3)
N2	0.79482 (16)	0.17629 (10)	0.22518 (12)	0.0154 (3)
O1	1.02188 (14)	0.04640 (9)	−0.18024 (11)	0.0257 (3)
O2	0.21749 (17)	0.23175 (12)	0.19624 (13)	0.0436 (4)
C12	1.1839 (2)	0.07413 (14)	−0.10897 (17)	0.0264 (4)
H12A	1.2623	0.0455	−0.1472	0.040*
H12B	1.2066	0.0509	−0.0220	0.040*
H12C	1.1934	0.1450	−0.1089	0.040*
H1	1.0194	0.1540	0.0159	0.020*
H3	0.5023	0.0720	−0.2314	0.021*
H2	0.5349	0.1704	−0.0595	0.026*
H5	0.7189	0.2815	0.1019	0.015*
H4	0.9057	0.2648	0.1384	0.016*
H6	1.0329	0.1567	0.3255	0.017*
H7	0.5462	0.1622	0.1957	0.029*
H8	1.0586	0.0915	0.5535	0.025*
H9	0.9081	0.0408	0.5698	0.023*
H12	0.2685	0.2563	0.1623	0.059*
H13	0.2877	0.2129	0.2690	0.062*
H15	0.7253	0.0152	−0.2863	0.031*
H16	0.6386	0.0624	0.4035	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02082 (10)	0.02866 (11)	0.02254 (10)	−0.00226 (7)	0.00672 (7)	0.00185 (7)
C1	0.0177 (7)	0.0153 (8)	0.0149 (7)	0.0004 (6)	0.0048 (6)	−0.0012 (6)
C11	0.0196 (8)	0.0171 (8)	0.0155 (7)	−0.0023 (6)	0.0040 (6)	0.0015 (6)
C5	0.0249 (8)	0.0143 (8)	0.0164 (7)	0.0018 (7)	0.0068 (6)	0.0018 (6)
C3	0.0155 (7)	0.0257 (9)	0.0216 (8)	0.0017 (7)	0.0058 (6)	−0.0015 (7)
C7	0.0215 (8)	0.0244 (9)	0.0199 (8)	0.0040 (7)	0.0047 (7)	0.0021 (7)
C6	0.0216 (8)	0.0133 (8)	0.0148 (7)	0.0015 (6)	0.0042 (6)	0.0021 (6)
C10	0.0261 (8)	0.0171 (8)	0.0170 (7)	0.0003 (7)	0.0102 (7)	0.0027 (6)
C4	0.0223 (8)	0.0192 (8)	0.0129 (7)	0.0012 (7)	0.0058 (6)	0.0009 (6)
C8	0.0218 (8)	0.0267 (9)	0.0188 (8)	−0.0036 (7)	0.0005 (6)	0.0009 (7)
C2	0.0178 (8)	0.0220 (9)	0.0239 (8)	−0.0009 (7)	0.0101 (7)	−0.0004 (7)
C9	0.0317 (9)	0.0204 (9)	0.0153 (7)	−0.0060 (7)	0.0069 (7)	−0.0026 (6)
N1	0.0182 (6)	0.0145 (7)	0.0156 (6)	0.0010 (5)	0.0068 (5)	0.0001 (5)
N2	0.0172 (6)	0.0141 (6)	0.0157 (6)	0.0009 (5)	0.0063 (5)	−0.0006 (5)
O1	0.0270 (6)	0.0312 (7)	0.0227 (6)	−0.0013 (5)	0.0129 (5)	−0.0059 (5)
O2	0.0347 (8)	0.0646 (11)	0.0281 (7)	−0.0162 (7)	0.0040 (6)	0.0061 (7)
C12	0.0248 (9)	0.0262 (9)	0.0319 (9)	−0.0004 (7)	0.0142 (7)	−0.0004 (7)

Geometric parameters (Å, º) top

C1—N2	1.327 (2)	C10—C9	1.391 (2)
C1—N1	1.3337 (19)	C4—N1	1.4686 (19)
C1—H6	0.9430	C4—C4ⁱ	1.523 (3)
C11—C10	1.394 (2)	C4—H8	0.9571
C11—C6	1.401 (2)	C4—H9	0.9209
C11—H1	0.9051	C8—C9	1.381 (2)
C5—N2	1.4800 (19)	C8—H3	0.9264
C5—C6	1.510 (2)	C2—N1	1.385 (2)
C5—H5	0.9596	C2—H16	0.9355
C5—H4	0.9459	C9—H15	0.9552
C3—C2	1.347 (2)	O1—C12	1.433 (2)
C3—N2	1.387 (2)	O2—H12	0.7395
C3—H7	0.9616	O2—H13	0.8910
C7—C6	1.388 (2)	C12—H12A	0.9800
C7—C8	1.389 (2)	C12—H12B	0.9800
C7—H2	0.9033	C12—H12C	0.9800
C10—O1	1.3720 (19)

N2—C1—N1	108.44 (13)	N1—C4—H9	108.6
N2—C1—H6	126.5	C4ⁱ—C4—H9	109.7
N1—C1—H6	125.0	H8—C4—H9	108.8
C10—C11—C6	118.97 (15)	C9—C8—C7	120.81 (15)
C10—C11—H1	120.5	C9—C8—H3	119.4
C6—C11—H1	120.5	C7—C8—H3	119.8
N2—C5—C6	112.06 (13)	C3—C2—N1	106.92 (13)
N2—C5—H5	105.5	C3—C2—H16	132.5
C6—C5—H5	111.7	N1—C2—H16	120.6
N2—C5—H4	106.2	C8—C9—C10	119.78 (15)
C6—C5—H4	112.0	C8—C9—H15	119.9
H5—C5—H4	109.0	C10—C9—H15	120.3
C2—C3—N2	107.13 (14)	C1—N1—C2	108.74 (13)
C2—C3—H7	130.1	C1—N1—C4	125.41 (13)
N2—C3—H7	122.7	C2—N1—C4	125.85 (13)
C6—C7—C8	119.38 (15)	C1—N2—C3	108.76 (13)
C6—C7—H2	121.5	C1—N2—C5	125.55 (13)
C8—C7—H2	119.0	C3—N2—C5	125.68 (13)
C7—C6—C11	120.59 (15)	C10—O1—C12	117.28 (12)
C7—C6—C5	120.07 (14)	H12—O2—H13	104.6
C11—C6—C5	119.34 (15)	O1—C12—H12A	109.5
O1—C10—C9	115.89 (14)	O1—C12—H12B	109.5
O1—C10—C11	123.64 (15)	H12A—C12—H12B	109.5
C9—C10—C11	120.47 (15)	O1—C12—H12C	109.5
N1—C4—C4ⁱ	110.22 (15)	H12A—C12—H12C	109.5
N1—C4—H8	108.5	H12B—C12—H12C	109.5
C4ⁱ—C4—H8	111.0

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H12···Br1ⁱⁱ	0.74	2.63	3.3419 (13)	161.9
O2—H13···Br1	0.89	2.52	3.3362 (14)	153.2
C11—H1···O2ⁱⁱⁱ	0.91	2.45	3.295 (2)	154.5
C1—H6···Br1ⁱⁱⁱ	0.94	2.86	3.6743 (16)	145.5
C5—H4···O2ⁱⁱⁱ	0.95	2.60	3.402 (2)	142.6

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

Experimental details

Crystal data
Chemical formula	C₂₄H₂₈N₄O₂²⁺·2Br⁻·2H₂O
M_r	600.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	8.5879 (3), 13.7822 (6), 11.0964 (5)
β (°)	107.277 (2)
V (Å³)	1254.11 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.27
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	0.495, 0.561
No. of measured, independent and observed (I > 2σ) reflections	9596, 2986, 2560
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.059, 1.04
No. of reflections	2986
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXSL96 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H12···Br1ⁱ	0.74	2.63	3.3419 (13)	161.9
O2—H13···Br1	0.89	2.52	3.3362 (14)	153.2
C11—H1···O2ⁱⁱ	0.91	2.45	3.295 (2)	154.5
C1—H6···Br1ⁱⁱ	0.94	2.86	3.6743 (16)	145.5
C5—H4···O2ⁱⁱ	0.95	2.60	3.402 (2)	142.6

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

Acknowledgements

We thank the National Science Council of Taiwan for financial support of this work.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lee, H. M. & Lu, C.-Y. (2008). Acta Cryst. E64, o2086. Web of Science CrossRef IUCr Journals Google Scholar
Lee, H. M., Lu, C. Y., Chen, C. Y., Chen, W. L., Lin, H. C., Chiu, P. L. & Cheng, P. Y. (2004). Tetrahedron, 60, 5807–5825. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3464

https://doi.org/10.1107/S1600536811050240

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3,3′-Bis(3-meth­­oxy­benz­yl)-1,1′-(ethane-1,2-diyl)­diimidazolium dibromide dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3,3′-Bis(3-methoxybenzyl)-1,1′-(ethane-1,2-diyl)diimidazolium dibromide dihydrate