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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1159.
Published online 2009 April 30. doi:  10.1107/S1600536809014950
PMCID: PMC2977825

1-Hexadecyl-3-methyl­imidazolium bromide monohydrate

Abstract

In the crystal structure of the title compound, C20H39N2 +·Br·H2O, the 1-hexa­decyl-3-methyl­imidazolium cations are stacked along the b axis, forming channels parallel to [100] which are occupied by the bromide anions and water mol­ecules. The crystal is stabilized by O—H(...)Br, C—H(...)O and C—H(...)Br hydrogen-bonding inter­actions, generating a two-dimensional network.

Related literature

For the applications of imidazolium compounds, see: Downard et al. (2004 [triangle]); Wasserscheid & Keim (2000 [triangle]). For the structure of free imidazole, see: Craven et al. (1977 [triangle]).

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Object name is e-65-o1159-scheme1.jpg

Experimental

Crystal data

  • C20H39N2 +·Br·H2O
  • M r = 405.46
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1159-efi1.jpg
  • a = 5.4989 (5) Å
  • b = 7.8507 (9) Å
  • c = 27.330 (3) Å
  • α = 94.080 (1)°
  • β = 91.492 (1)°
  • γ = 101.929 (2)°
  • V = 1150.4 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.80 mm−1
  • T = 293 K
  • 0.38 × 0.23 × 0.12 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.549, T max = 0.813
  • 5929 measured reflections
  • 3995 independent reflections
  • 3058 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.057
  • wR(F 2) = 0.148
  • S = 1.04
  • 3995 reflections
  • 219 parameters
  • H-atom parameters constrained
  • Δρmax = 0.58 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014950/rz2309sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014950/rz2309Isup2.hkl

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

Acknowledgments

The authors acknowledge the financial support of the National Natural Science Foundation of China (20673050) and the Shandong Province Science Foundation (2006B05).

supplementary crystallographic information

Comment

Various ionic liquids based on imidazolium cations such as 1-alkyl-3-methylimidazolium have been extensively investigated over the last several years (Wasserscheid & Keim, 2000), in particular with respect to their applications as liquid crystals (Downard et al., 2004). As a contribution to the chemistry of ionic liquids, we report here the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1), consists of a 1-hexadecyl-3-methylimidazolium cation, a bromide anion and a water molecule. The C1—N1—C3 bond angle of 108.0 (3)° is similar to those in free imidazole (Craven et al., 1977). The relative orientation of the imidazolium ring with respect to the aliphatic chain can be described by the value of -126.4 (4)° of the C1—N1—C4—C5 torsion angle. The N1—C4 bond length is 1.472 (5) Å. In the crystal, the cations are stacked along the b axis forming channels parallel to the [1 0 0] direction that are occupied by the bromide anions and water molecules (Fig. 2). Adjacent anions and water molecules are linked by O—H···Br hydrogen bonds, and are connected into a two-dimensional network with the cations through C—H···O and C—H···Br hydrogen interactions (Table 1).

Experimental

1-Methylimidazole (0.14 mol) and 1-bromohexadecyl (0.15 mol) were added to a stirred solution of dichloromethane (30 ml) and stirred at 350 K for 48 h under nitrogen atmosphere. The resulting clear solution was evaporated under vacuum. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution over a period of two weeks (yield 83%, m.p.339.15k). Anal. Calcd (%) for C20H41Br1N2O1 (Mr = 405.46): C, 59.19; H, 10.11; N, 6.90. Found (%): C, 59.47; H, 9.98; N, 7.02.

Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms with O—H = 0.85 Å, C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, with atom labelling scheme and 50% probability displacement ellipsoids.
Fig. 2.
Crystal packing of the title compound, showing the two-dimensional network structure formed by O—H···Br, C—H···O and C—H···Br hydrogen bonds (dashed lines). ...

Crystal data

C20H39N2+·Br·H2OZ = 2
Mr = 405.46F(000) = 436
Triclinic, P1Dx = 1.170 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.4989 (5) ÅCell parameters from 2080 reflections
b = 7.8507 (9) Åθ = 2.7–26.1°
c = 27.330 (3) ŵ = 1.80 mm1
α = 94.080 (1)°T = 293 K
β = 91.492 (1)°Block, colourless
γ = 101.929 (2)°0.38 × 0.23 × 0.12 mm
V = 1150.4 (2) Å3

Data collection

Bruker SMART CCD area-detector diffractometer3995 independent reflections
Radiation source: fine-focus sealed tube3058 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −6→6
Tmin = 0.549, Tmax = 0.813k = −9→9
5929 measured reflectionsl = −26→32

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0658P)2 + 1.4252P] where P = (Fo2 + 2Fc2)/3
3995 reflections(Δ/σ)max < 0.001
219 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = −0.31 e Å3

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

xyzUiso*/Ueq
Br10.32508 (9)0.81313 (7)0.096948 (19)0.0561 (2)
N11.3915 (6)0.5675 (4)0.88874 (12)0.0368 (8)
N21.5673 (6)0.7181 (4)0.95356 (12)0.0362 (8)
O10.9084 (8)0.0620 (5)0.1247 (2)0.1026 (16)
H1C0.76350.00070.11790.123*
H1D1.0139−0.00040.11780.123*
C11.5917 (8)0.6802 (5)0.90640 (15)0.0396 (10)
H11.72830.72570.88850.047*
C21.3422 (8)0.6274 (6)0.96668 (16)0.0435 (10)
H21.27670.63120.99770.052*
C31.2336 (8)0.5322 (6)0.92639 (16)0.0425 (10)
H31.07930.45590.92430.051*
C41.3519 (8)0.4847 (6)0.83835 (15)0.0444 (10)
H4A1.34880.36100.83930.053*
H4B1.49160.53410.81920.053*
C51.1161 (8)0.5065 (6)0.81304 (15)0.0398 (10)
H5A1.11310.62970.81360.048*
H5B0.97460.44940.83050.048*
C61.0949 (8)0.4291 (6)0.76032 (15)0.0432 (10)
H6A1.23770.48700.74330.052*
H6B1.10240.30670.76030.052*
C70.8610 (8)0.4429 (6)0.73170 (15)0.0425 (10)
H7A0.71780.38230.74810.051*
H7B0.85110.56490.73220.051*
C80.8469 (8)0.3686 (6)0.67886 (15)0.0431 (10)
H8A0.85700.24660.67850.052*
H8B0.99100.42890.66270.052*
C90.6135 (8)0.3815 (6)0.64922 (15)0.0441 (10)
H9A0.46910.32140.66540.053*
H9B0.60360.50350.64940.053*
C100.6022 (8)0.3061 (6)0.59670 (16)0.0439 (10)
H10A0.61180.18410.59660.053*
H10B0.74710.36590.58060.053*
C110.3715 (8)0.3186 (6)0.56681 (15)0.0444 (11)
H11A0.22650.25890.58290.053*
H11B0.36190.44060.56690.053*
C120.3604 (8)0.2429 (6)0.51412 (16)0.0453 (11)
H12A0.36990.12090.51410.054*
H12B0.50540.30260.49810.054*
C130.1286 (8)0.2556 (6)0.48404 (16)0.0450 (10)
H13A−0.01660.19590.50000.054*
H13B0.11910.37760.48400.054*
C140.1186 (8)0.1793 (6)0.43125 (16)0.0449 (11)
H14A0.12730.05720.43130.054*
H14B0.26420.23860.41530.054*
C15−0.1115 (8)0.1925 (6)0.40110 (16)0.0449 (10)
H15A−0.25710.13350.41710.054*
H15B−0.12000.31470.40100.054*
C16−0.1225 (8)0.1161 (6)0.34835 (16)0.0446 (10)
H16A−0.1132−0.00590.34840.054*
H16B0.02270.17550.33230.054*
C17−0.3534 (8)0.1286 (6)0.31826 (16)0.0458 (11)
H17A−0.49850.06900.33430.055*
H17B−0.36290.25060.31830.055*
C18−0.3646 (10)0.0529 (7)0.26567 (17)0.0546 (12)
H18A−0.21860.11140.24970.066*
H18B−0.3577−0.06960.26560.066*
C19−0.5916 (11)0.0679 (8)0.2361 (2)0.0707 (16)
H19A−0.73760.00810.25110.106*
H19B−0.58490.01640.20340.106*
H19C−0.59780.18880.23490.106*
C201.7530 (9)0.8399 (6)0.98616 (18)0.0546 (12)
H20A1.91720.83510.97590.082*
H20B1.73610.80741.01930.082*
H20C1.72660.95650.98450.082*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0480 (3)0.0590 (3)0.0595 (3)0.0071 (2)−0.0019 (2)0.0057 (2)
N10.0361 (19)0.0398 (19)0.0343 (19)0.0086 (15)−0.0046 (15)0.0022 (15)
N20.0325 (18)0.0348 (18)0.039 (2)0.0021 (14)−0.0084 (15)0.0031 (15)
O10.059 (3)0.064 (3)0.178 (5)0.002 (2)0.025 (3)−0.010 (3)
C10.031 (2)0.046 (2)0.041 (3)0.0034 (19)0.0004 (18)0.012 (2)
C20.041 (3)0.054 (3)0.034 (2)0.007 (2)0.0003 (19)0.007 (2)
C30.032 (2)0.050 (3)0.040 (3)−0.0032 (19)−0.0039 (19)0.008 (2)
C40.044 (3)0.053 (3)0.038 (2)0.016 (2)−0.0076 (19)−0.004 (2)
C50.040 (2)0.043 (2)0.037 (2)0.0110 (19)−0.0005 (18)0.0025 (18)
C60.040 (2)0.050 (3)0.041 (3)0.017 (2)−0.0044 (19)−0.005 (2)
C70.038 (2)0.053 (3)0.039 (2)0.015 (2)−0.0019 (19)−0.002 (2)
C80.038 (2)0.055 (3)0.039 (2)0.018 (2)−0.0041 (19)−0.004 (2)
C90.040 (2)0.055 (3)0.040 (3)0.019 (2)−0.0052 (19)−0.002 (2)
C100.040 (2)0.053 (3)0.041 (3)0.017 (2)−0.0034 (19)−0.003 (2)
C110.042 (3)0.055 (3)0.040 (3)0.021 (2)−0.002 (2)−0.002 (2)
C120.041 (2)0.055 (3)0.043 (3)0.017 (2)−0.0002 (19)−0.002 (2)
C130.044 (3)0.053 (3)0.041 (3)0.017 (2)−0.002 (2)0.001 (2)
C140.040 (2)0.055 (3)0.042 (3)0.018 (2)−0.003 (2)0.000 (2)
C150.043 (3)0.054 (3)0.041 (3)0.020 (2)−0.003 (2)0.003 (2)
C160.041 (2)0.053 (3)0.042 (3)0.017 (2)−0.004 (2)−0.001 (2)
C170.045 (3)0.046 (3)0.046 (3)0.013 (2)−0.005 (2)−0.002 (2)
C180.058 (3)0.063 (3)0.044 (3)0.018 (2)−0.004 (2)−0.003 (2)
C190.073 (4)0.088 (4)0.049 (3)0.020 (3)−0.019 (3)−0.007 (3)
C200.046 (3)0.052 (3)0.055 (3)−0.010 (2)−0.015 (2)0.000 (2)

Geometric parameters (Å, °)

N1—C11.318 (5)C10—H10B0.9700
N1—C31.370 (5)C11—C121.513 (6)
N1—C41.472 (5)C11—H11A0.9700
N2—C11.319 (5)C11—H11B0.9700
N2—C21.365 (5)C12—C131.523 (6)
N2—C201.476 (5)C12—H12A0.9700
O1—H1C0.8500C12—H12B0.9700
O1—H1D0.8500C13—C141.517 (6)
C1—H10.9300C13—H13A0.9700
C2—C31.339 (6)C13—H13B0.9700
C2—H20.9300C14—C151.517 (6)
C3—H30.9300C14—H14A0.9700
C4—C51.500 (6)C14—H14B0.9700
C4—H4A0.9700C15—C161.517 (6)
C4—H4B0.9700C15—H15A0.9700
C5—C61.515 (6)C15—H15B0.9700
C5—H5A0.9700C16—C171.519 (6)
C5—H5B0.9700C16—H16A0.9700
C6—C71.515 (6)C16—H16B0.9700
C6—H6A0.9700C17—C181.511 (6)
C6—H6B0.9700C17—H17A0.9700
C7—C81.512 (6)C17—H17B0.9700
C7—H7A0.9700C18—C191.499 (7)
C7—H7B0.9700C18—H18A0.9700
C8—C91.525 (6)C18—H18B0.9700
C8—H8A0.9700C19—H19A0.9600
C8—H8B0.9700C19—H19B0.9600
C9—C101.508 (6)C19—H19C0.9600
C9—H9A0.9700C20—H20A0.9600
C9—H9B0.9700C20—H20B0.9600
C10—C111.515 (6)C20—H20C0.9600
C10—H10A0.9700
C1—N1—C3108.0 (3)C12—C11—H11A108.5
C1—N1—C4126.0 (4)C10—C11—H11A108.5
C3—N1—C4125.9 (4)C12—C11—H11B108.5
C1—N2—C2108.6 (3)C10—C11—H11B108.5
C1—N2—C20125.2 (4)H11A—C11—H11B107.5
C2—N2—C20126.2 (4)C11—C12—C13115.0 (4)
H1C—O1—H1D108.4C11—C12—H12A108.5
N1—C1—N2109.0 (4)C13—C12—H12A108.5
N1—C1—H1125.5C11—C12—H12B108.5
N2—C1—H1125.5C13—C12—H12B108.5
C3—C2—N2106.9 (4)H12A—C12—H12B107.5
C3—C2—H2126.6C14—C13—C12114.7 (4)
N2—C2—H2126.6C14—C13—H13A108.6
C2—C3—N1107.5 (4)C12—C13—H13A108.6
C2—C3—H3126.2C14—C13—H13B108.6
N1—C3—H3126.2C12—C13—H13B108.6
N1—C4—C5113.8 (3)H13A—C13—H13B107.6
N1—C4—H4A108.8C13—C14—C15114.8 (4)
C5—C4—H4A108.8C13—C14—H14A108.6
N1—C4—H4B108.8C15—C14—H14A108.6
C5—C4—H4B108.8C13—C14—H14B108.6
H4A—C4—H4B107.7C15—C14—H14B108.6
C4—C5—C6111.2 (3)H14A—C14—H14B107.5
C4—C5—H5A109.4C16—C15—C14115.0 (4)
C6—C5—H5A109.4C16—C15—H15A108.5
C4—C5—H5B109.4C14—C15—H15A108.5
C6—C5—H5B109.4C16—C15—H15B108.5
H5A—C5—H5B108.0C14—C15—H15B108.5
C7—C6—C5115.3 (3)H15A—C15—H15B107.5
C7—C6—H6A108.5C15—C16—C17115.0 (4)
C5—C6—H6A108.5C15—C16—H16A108.5
C7—C6—H6B108.5C17—C16—H16A108.5
C5—C6—H6B108.5C15—C16—H16B108.5
H6A—C6—H6B107.5C17—C16—H16B108.5
C8—C7—C6114.3 (3)H16A—C16—H16B107.5
C8—C7—H7A108.7C18—C17—C16115.1 (4)
C6—C7—H7A108.7C18—C17—H17A108.5
C8—C7—H7B108.7C16—C17—H17A108.5
C6—C7—H7B108.7C18—C17—H17B108.5
H7A—C7—H7B107.6C16—C17—H17B108.5
C7—C8—C9115.2 (3)H17A—C17—H17B107.5
C7—C8—H8A108.5C19—C18—C17114.7 (4)
C9—C8—H8A108.5C19—C18—H18A108.6
C7—C8—H8B108.5C17—C18—H18A108.6
C9—C8—H8B108.5C19—C18—H18B108.6
H8A—C8—H8B107.5C17—C18—H18B108.6
C10—C9—C8114.5 (3)H18A—C18—H18B107.6
C10—C9—H9A108.6C18—C19—H19A109.5
C8—C9—H9A108.6C18—C19—H19B109.5
C10—C9—H9B108.6H19A—C19—H19B109.5
C8—C9—H9B108.6C18—C19—H19C109.5
H9A—C9—H9B107.6H19A—C19—H19C109.5
C9—C10—C11115.0 (3)H19B—C19—H19C109.5
C9—C10—H10A108.5N2—C20—H20A109.5
C11—C10—H10A108.5N2—C20—H20B109.5
C9—C10—H10B108.5H20A—C20—H20B109.5
C11—C10—H10B108.5N2—C20—H20C109.5
H10A—C10—H10B107.5H20A—C20—H20C109.5
C12—C11—C10114.9 (3)H20B—C20—H20C109.5
C3—N1—C1—N2−0.2 (5)C5—C6—C7—C8178.6 (4)
C4—N1—C1—N2−176.2 (4)C6—C7—C8—C9−179.8 (4)
C2—N2—C1—N1−0.5 (5)C7—C8—C9—C10−179.8 (4)
C20—N2—C1—N1−179.9 (4)C8—C9—C10—C11−179.8 (4)
C1—N2—C2—C30.9 (5)C9—C10—C11—C12−180.0 (4)
C20—N2—C2—C3−179.7 (4)C10—C11—C12—C13−180.0 (4)
N2—C2—C3—N1−1.0 (5)C11—C12—C13—C14−180.0 (4)
C1—N1—C3—C20.7 (5)C12—C13—C14—C15−179.7 (4)
C4—N1—C3—C2176.7 (4)C13—C14—C15—C16−179.9 (4)
C1—N1—C4—C5−126.4 (4)C14—C15—C16—C17179.7 (4)
C3—N1—C4—C558.3 (6)C15—C16—C17—C18179.9 (4)
N1—C4—C5—C6176.2 (4)C16—C17—C18—C19−179.3 (4)
C4—C5—C6—C7179.4 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1C···Br1i0.852.583.429 (4)180
O1—H1D···Br1ii0.852.523.373 (4)180
C3—H3···Br1iii0.932.753.661 (4)167
C1—H1···O1iv0.932.383.231 (6)153

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2309).

References

  • Craven, B. M., McMullan, R. K., Bell, J. D. & Freeman, H. C. (1977). Acta Cryst. B33, 2585–2589.
  • Downard, A., Earle, M. J., Hardacre, C., McMath, S. E. J., Nieuwenhuyzen, M. & Teat, S. J. (2004). Chem. Mater.16, 43–48.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Wasserscheid, P. & Keim, W. (2000). Angew. Chem. Int. Ed.39, 3772–3789. [PubMed]

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