1-Carb­oxy­methyl-3-octylimidazolium bromide

Al-Mohammed, N.N.; Alias, Y.; Abdullah, Z.; Khaledi, H.

doi:10.1107/S1600536811022094

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1701

doi:10.1107/S1600536811022094

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1-Carboxymethyl-3-octylimidazolium bromide

Nassir N. Al-Mohammed,^a Yatimah Alias,^a Zanariah Abdullah ^a and Hamid Khaledi ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 26 May 2011; accepted 7 June 2011; online 18 June 2011)

In the title compound, C₁₃H₂₃N₂O₂⁺·Br⁻, the octyl chain has an all-trans conformation. In the crystal, the cations are linked by C—H⋯O bonds into a zigzag chain along the b axis. The bromide anions further link the chains via C—H⋯Br interactions into a two-dimensional array parallel to the ab plane. An O—H⋯Br interaction is also observed.

Related literature

For related structures, see: Wei et al. (2009 ); Chen et al. (2009 ).

Experimental

Crystal data

C₁₃H₂₃N₂O²⁺·Br⁻
M_r = 319.24
Monoclinic, P 2₁ /c
a = 7.6745 (2) Å
b = 4.6176 (1) Å
c = 41.8663 (9) Å
β = 92.167 (1)°
V = 1482.59 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.77 mm⁻¹
T = 100 K
0.21 × 0.19 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.594, T_max = 0.851
10905 measured reflections
2761 independent reflections
2678 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.095
S = 1.43
2761 reflections
167 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.25 e Å⁻³
Δρ_min = −2.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6B⋯Br1ⁱ	0.99	2.89	3.772 (4)	148
C5—H5⋯Br1ⁱⁱ	0.95	2.91	3.681 (4)	139
C4—H4⋯O2ⁱⁱⁱ	0.95	2.25	3.151 (5)	158
C3—H3⋯Br1ⁱ	0.95	2.82	3.593 (4)	139
C2—H2B⋯Br1^iv	0.99	2.90	3.676 (4)	136
C2—H2A⋯O2^v	0.99	2.44	3.328 (5)	150
O1—H1⋯Br1	0.84 (2)	2.33 (2)	3.153 (3)	168 (4)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) x, y+1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536811022094/is2721sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022094/is2721Isup2.hkl

checkCIF report

Comment top

The imidazolium ring is N-bound to a long alkyl chain, namely an octyl chain, and a carboxymethyl group. The alkyl chain adopts an all-trans conformation, as observed in similar structures (Wei et al., 2009; Chen et al., 2009). The carboxy group and the imidazolium ring subtend an N1—C2—C1 angle of 110.7 (3)°. In the crystal, the cationic moieties are bonded via C—H···O interactions (Table 1) into infinite chains along the b axis. The bromide anions link the cationic chains through C—H···Br interactions into layers parallel to the ab plane (Fig. 2).

Related literature top

For related structures, see: Wei et al. (2009); Chen et al. (2009).

Experimental top

A solution of bromoacetic acid (1 g, 7.2 mmol) and octylimidazole (1.29 g, 7.2 mmol) in dry 1,4-dioxane (10 ml) was stirred under nitrogen atmosphere at 70 °C for 7 hr. The solution was then poured into dichloromethane (25 ml) and extracted with distilled water (50 ml). The aqueous solution was evaporated under vacuum to give a viscous oil which crystallized from THF to yield the colorless crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Packing view looking down the crystallographic b axis.

1-Carboxymethyl-3-octylimidazolium bromide top

Crystal data top

C₁₃H₂₃N₂O²⁺·Br⁻	F(000) = 664
M_r = 319.24	D_x = 1.430 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9093 reflections
a = 7.6745 (2) Å	θ = 2.7–30.4°
b = 4.6176 (1) Å	µ = 2.77 mm⁻¹
c = 41.8663 (9) Å	T = 100 K
β = 92.167 (1)°	Plate, colorless
V = 1482.59 (6) Å³	0.21 × 0.19 × 0.06 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2761 independent reflections
Radiation source: fine-focus sealed tube	2678 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.594, T_max = 0.851	k = −5→5
10905 measured reflections	l = −50→50

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.43	w = 1/[σ²(F_o²) + (0.P)² + 5.6415P] where P = (F_o² + 2F_c²)/3
2761 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 1.25 e Å⁻³
1 restraint	Δρ_min = −2.19 e Å⁻³

Crystal data top

C₁₃H₂₃N₂O²⁺·Br⁻	V = 1482.59 (6) Å³
M_r = 319.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6745 (2) Å	µ = 2.77 mm⁻¹
b = 4.6176 (1) Å	T = 100 K
c = 41.8663 (9) Å	0.21 × 0.19 × 0.06 mm
β = 92.167 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2761 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2678 reflections with I > 2σ(I)
T_min = 0.594, T_max = 0.851	R_int = 0.023
10905 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.43	Δρ_max = 1.25 e Å⁻³
2761 reflections	Δρ_min = −2.19 e Å⁻³
167 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	0.10811 (5)	0.60448 (9)	0.158623 (9)	0.01633 (12)
O1	0.1327 (4)	0.9207 (7)	0.22540 (7)	0.0206 (6)
H1	0.140 (6)	0.823 (9)	0.2087 (7)	0.025*
O2	0.3056 (4)	0.5633 (7)	0.24528 (7)	0.0223 (7)
N1	0.3042 (4)	0.7879 (7)	0.30550 (7)	0.0135 (7)
N2	0.3636 (4)	0.4977 (8)	0.34476 (7)	0.0141 (7)
C1	0.2224 (5)	0.7809 (9)	0.24846 (9)	0.0145 (8)
C2	0.2071 (6)	0.9390 (9)	0.27999 (9)	0.0179 (9)
H2A	0.2530	1.1383	0.2780	0.021*
H2B	0.0829	0.9524	0.2853	0.021*
C3	0.2346 (5)	0.6121 (9)	0.32676 (9)	0.0144 (8)
H3	0.1137	0.5747	0.3287	0.017*
C4	0.4832 (5)	0.7869 (10)	0.31017 (10)	0.0191 (9)
H4	0.5648	0.8927	0.2983	0.023*
C5	0.5201 (5)	0.6074 (10)	0.33479 (9)	0.0191 (9)
H5	0.6328	0.5640	0.3437	0.023*
C6	0.3422 (5)	0.3118 (9)	0.37260 (9)	0.0168 (9)
H6A	0.4475	0.1900	0.3759	0.020*
H6B	0.2413	0.1816	0.3686	0.020*
C7	0.3137 (5)	0.4881 (9)	0.40246 (9)	0.0163 (8)
H7A	0.2055	0.6032	0.3994	0.020*
H7B	0.4120	0.6248	0.4059	0.020*
C8	0.2994 (5)	0.2982 (9)	0.43200 (9)	0.0172 (8)
H8A	0.4069	0.1809	0.4348	0.021*
H8B	0.2002	0.1632	0.4286	0.021*
C9	0.2731 (5)	0.4719 (9)	0.46238 (9)	0.0158 (8)
H9A	0.3717	0.6083	0.4656	0.019*
H9B	0.1651	0.5879	0.4596	0.019*
C10	0.2602 (6)	0.2852 (10)	0.49212 (10)	0.0195 (9)
H10A	0.3684	0.1697	0.4949	0.023*
H10B	0.1618	0.1484	0.4889	0.023*
C11	0.2332 (5)	0.4592 (9)	0.52259 (9)	0.0162 (9)
H11A	0.3315	0.5965	0.5258	0.019*
H11B	0.1250	0.5744	0.5198	0.019*
C12	0.2207 (6)	0.2733 (10)	0.55249 (9)	0.0196 (9)
H12A	0.3290	0.1586	0.5554	0.023*
H12B	0.1225	0.1359	0.5494	0.023*
C13	0.1934 (6)	0.4506 (10)	0.58268 (9)	0.0215 (10)
H13A	0.2926	0.5814	0.5864	0.032*
H13B	0.1840	0.3199	0.6010	0.032*
H13C	0.0860	0.5643	0.5800	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0160 (2)	0.0183 (2)	0.01477 (19)	0.00006 (18)	0.00112 (13)	−0.00132 (18)
O1	0.0278 (15)	0.0187 (17)	0.0153 (14)	0.0039 (14)	0.0000 (12)	0.0001 (13)
O2	0.0315 (16)	0.0190 (18)	0.0164 (14)	0.0086 (14)	0.0024 (12)	−0.0021 (13)
N1	0.0177 (16)	0.0132 (17)	0.0098 (15)	−0.0009 (14)	0.0026 (13)	−0.0002 (13)
N2	0.0145 (16)	0.0162 (17)	0.0118 (16)	−0.0005 (14)	0.0018 (13)	0.0000 (13)
C1	0.0155 (19)	0.015 (2)	0.0131 (19)	−0.0032 (17)	0.0029 (15)	0.0017 (16)
C2	0.027 (2)	0.010 (2)	0.0162 (19)	0.0048 (18)	0.0005 (16)	0.0010 (16)
C3	0.0160 (18)	0.0128 (19)	0.0144 (18)	−0.0016 (17)	0.0004 (14)	−0.0021 (17)
C4	0.0145 (19)	0.025 (2)	0.018 (2)	−0.0043 (18)	0.0032 (16)	−0.0028 (18)
C5	0.0131 (18)	0.026 (2)	0.018 (2)	0.0021 (19)	0.0008 (15)	−0.0008 (19)
C6	0.021 (2)	0.010 (2)	0.019 (2)	−0.0004 (17)	−0.0022 (16)	0.0039 (16)
C7	0.0177 (19)	0.016 (2)	0.0150 (19)	0.0011 (17)	0.0002 (15)	0.0010 (16)
C8	0.0175 (19)	0.015 (2)	0.019 (2)	0.0016 (17)	0.0007 (16)	0.0014 (17)
C9	0.0159 (19)	0.015 (2)	0.0166 (19)	0.0021 (16)	−0.0006 (15)	0.0014 (16)
C10	0.020 (2)	0.020 (2)	0.019 (2)	0.0037 (18)	0.0011 (16)	−0.0003 (18)
C11	0.0158 (19)	0.014 (2)	0.019 (2)	0.0012 (16)	0.0013 (16)	0.0010 (17)
C12	0.021 (2)	0.021 (2)	0.017 (2)	0.0009 (18)	0.0031 (16)	0.0011 (18)
C13	0.025 (2)	0.024 (3)	0.016 (2)	0.0012 (19)	0.0033 (16)	−0.0001 (18)

Geometric parameters (Å, º) top

O1—C1	1.332 (5)	C7—H7A	0.9900
O1—H1	0.837 (19)	C7—H7B	0.9900
O2—C1	1.200 (5)	C8—C9	1.524 (5)
N1—C3	1.331 (5)	C8—H8A	0.9900
N1—C4	1.381 (5)	C8—H8B	0.9900
N1—C2	1.457 (5)	C9—C10	1.521 (6)
N2—C3	1.331 (5)	C9—H9A	0.9900
N2—C5	1.382 (5)	C9—H9B	0.9900
N2—C6	1.462 (5)	C10—C11	1.528 (6)
C1—C2	1.517 (5)	C10—H10A	0.9900
C2—H2A	0.9900	C10—H10B	0.9900
C2—H2B	0.9900	C11—C12	1.524 (6)
C3—H3	0.9500	C11—H11A	0.9900
C4—C5	1.344 (6)	C11—H11B	0.9900
C4—H4	0.9500	C12—C13	1.527 (6)
C5—H5	0.9500	C12—H12A	0.9900
C6—C7	1.515 (6)	C12—H12B	0.9900
C6—H6A	0.9900	C13—H13A	0.9800
C6—H6B	0.9900	C13—H13B	0.9800
C7—C8	1.523 (5)	C13—H13C	0.9800

C1—O1—H1	107 (3)	C7—C8—C9	113.0 (3)
C3—N1—C4	109.0 (3)	C7—C8—H8A	109.0
C3—N1—C2	125.1 (3)	C9—C8—H8A	109.0
C4—N1—C2	125.7 (3)	C7—C8—H8B	109.0
C3—N2—C5	108.6 (3)	C9—C8—H8B	109.0
C3—N2—C6	125.5 (3)	H8A—C8—H8B	107.8
C5—N2—C6	125.5 (3)	C10—C9—C8	113.6 (3)
O2—C1—O1	126.0 (4)	C10—C9—H9A	108.9
O2—C1—C2	123.9 (4)	C8—C9—H9A	108.9
O1—C1—C2	110.0 (3)	C10—C9—H9B	108.9
N1—C2—C1	110.7 (3)	C8—C9—H9B	108.9
N1—C2—H2A	109.5	H9A—C9—H9B	107.7
C1—C2—H2A	109.5	C9—C10—C11	113.6 (4)
N1—C2—H2B	109.5	C9—C10—H10A	108.8
C1—C2—H2B	109.5	C11—C10—H10A	108.8
H2A—C2—H2B	108.1	C9—C10—H10B	108.8
N2—C3—N1	108.2 (3)	C11—C10—H10B	108.8
N2—C3—H3	125.9	H10A—C10—H10B	107.7
N1—C3—H3	125.9	C12—C11—C10	113.9 (3)
C5—C4—N1	106.9 (4)	C12—C11—H11A	108.8
C5—C4—H4	126.6	C10—C11—H11A	108.8
N1—C4—H4	126.6	C12—C11—H11B	108.8
C4—C5—N2	107.3 (3)	C10—C11—H11B	108.8
C4—C5—H5	126.3	H11A—C11—H11B	107.7
N2—C5—H5	126.3	C11—C12—C13	113.1 (4)
N2—C6—C7	111.5 (3)	C11—C12—H12A	109.0
N2—C6—H6A	109.3	C13—C12—H12A	109.0
C7—C6—H6A	109.3	C11—C12—H12B	109.0
N2—C6—H6B	109.3	C13—C12—H12B	109.0
C7—C6—H6B	109.3	H12A—C12—H12B	107.8
H6A—C6—H6B	108.0	C12—C13—H13A	109.5
C6—C7—C8	112.2 (3)	C12—C13—H13B	109.5
C6—C7—H7A	109.2	H13A—C13—H13B	109.5
C8—C7—H7A	109.2	C12—C13—H13C	109.5
C6—C7—H7B	109.2	H13A—C13—H13C	109.5
C8—C7—H7B	109.2	H13B—C13—H13C	109.5
H7A—C7—H7B	107.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···Br1ⁱ	0.99	2.89	3.772 (4)	148
C5—H5···Br1ⁱⁱ	0.95	2.91	3.681 (4)	139
C4—H4···O2ⁱⁱⁱ	0.95	2.25	3.151 (5)	158
C3—H3···Br1ⁱ	0.95	2.82	3.593 (4)	139
C2—H2B···Br1^iv	0.99	2.90	3.676 (4)	136
C2—H2A···O2^v	0.99	2.44	3.328 (5)	150
O1—H1···Br1	0.84 (2)	2.33 (2)	3.153 (3)	168 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₃H₂₃N₂O²⁺·Br⁻
M_r	319.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.6745 (2), 4.6176 (1), 41.8663 (9)
β (°)	92.167 (1)
V (Å³)	1482.59 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.77
Crystal size (mm)	0.21 × 0.19 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.594, 0.851
No. of measured, independent and observed [I > 2σ(I)] reflections	10905, 2761, 2678
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.095, 1.43
No. of reflections	2761
No. of parameters	167
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.25, −2.19

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···Br1ⁱ	0.99	2.89	3.772 (4)	148
C5—H5···Br1ⁱⁱ	0.95	2.91	3.681 (4)	139
C4—H4···O2ⁱⁱⁱ	0.95	2.25	3.151 (5)	158
C3—H3···Br1ⁱ	0.95	2.82	3.593 (4)	139
C2—H2B···Br1^iv	0.99	2.90	3.676 (4)	136
C2—H2A···O2^v	0.99	2.44	3.328 (5)	150
O1—H1···Br1	0.837 (19)	2.33 (2)	3.153 (3)	168 (4)

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

Acknowledgements

The authors thank the University of Malaya for funding this study (FRGS grant No. FP001/2010 A).

References

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