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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o218.
Published online 2009 December 19. doi:  10.1107/S1600536809053306
PMCID: PMC2980248

1-Benzyl-3-methyl­imidazolium chloride 0.25-hydrate

Abstract

The asymmetric unit of the title compound, C11H13N2 +·Cl, contains two independent ion pairs and and half a solvent water mol­ecule (m site symmetry for the O atom). The imidazole ring is oriented at dihedral angles of 66.61 (3) and 89.17 (3)° with respect to the aromatic ring in the two cations. In the crystal, O—H(...)(O,Cl) hydrogen bonds and π–π stacking inter­actions between the imidazole ring of one mol­ecule and the aromatic ring of another [perpendicular distance = 3.4 (4) Å] link the mol­ecules.

Related literature

For general background to ionic liquids, see: Fukaya et al. (2006 [triangle]); Ranu et al. (2005 [triangle]); Chen et al. (2005 [triangle]); Blanchard et al. (2001 [triangle]); Zhang et al. (2006 [triangle]); Katayanagi et al. (2004 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o218-scheme1.jpg

Experimental

Crystal data

  • C11H13N2 +·Cl·0.25H2O
  • M r = 213.19
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o218-efi1.jpg
  • a = 11.452 (2) Å
  • b = 11.410 (2) Å
  • c = 34.867 (7) Å
  • V = 4555.8 (16) Å3
  • Z = 16
  • Mo Kα radiation
  • μ = 0.30 mm−1
  • T = 113 K
  • 0.22 × 0.20 × 0.16 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 [triangle]) T min = 0.937, T max = 0.953
  • 30046 measured reflections
  • 4022 independent reflections
  • 3619 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.119
  • S = 1.08
  • 4022 reflections
  • 268 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: CrystalClear (Rigaku, 2000 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053306/bq2176sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053306/bq2176Isup2.hkl

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

Acknowledgments

We thank the China Postdoctoral Science Foundation (No. 20080440684), the Tianjin Municipal Natural Science Foundation (No. 09JCZDJC22700) and the Hebei Province Natural Science Foundation (No. E2009000081) for financial support.

supplementary crystallographic information

Comment

Ionic liquids (ILs) are a class of compounds composed of organic cations and organic or inorganic anions and have attracted significant attention due to their beneficial properties and their low impact on environment. Many investigations have been dedicated to their use as new media for synthetic chemistry (Fukaya et al., 2006), catalysts for organic synthesis (Ranu et al., 2005; Chen et al., 2005), extractants for separation science (Blanchard et al., 2001) and electrolytes for electrochemistry (Zhang et al., 2006) as well as other areas due to their peculiar physical properties such as a wide liquid range, non-volatility, chemical stability and large windows of electrochemistry. Because it is technically difficult for ionic liquid to grow single crystal and to select suitable sample for single crystal x-ray diffraction at low temperature, so far a few crystal structures have been determined by x-ray diffraction (Katayanagi et al., 2004). We have synthesized a numer of ionic liquids. The title compound is one of the products, and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. The imidazole ring is oriented with respect to the aromatic ring at a dihedral angle of 89.17 (3)° and 66.61 (3)°, respectively. The hydrogen bond are formed between one Cl and H2O (Table 1). In the crystal structure, π-π packing between the imidazole ring of one molecule and the aromatic ring of the other [perpendicular distance = 3.4 (4)Å] link the molecules. The packing diagram of the O-H···Cl bonds is shown in Fig. 2.

Experimental

For the preparation of the title compound, N-methylimidazole (8.2 g, 0.1 mol) was dissolved in dry acetonitrile (30 ml). Benzyl chloride (12.7 g, 0.1 mol) was added to this solution, the reaction was stirred under reflux for 7 h. The reaction mixture was extracted with ethyl acetate. After concentration, the residue was purified by recrystallization from chloroform (yield; 19.4 g, 93%, m.p. 251 K). Spectroscopic analysis: IR (KBr, ν, cm-1): 3415, 3085, 2927, 1634, 1571, 1455, 1160, 824, 722. Analysis required for C22H27Cl2N4O0.5: C 61.97; H 6.38; N 13.14%. Found: C 61.92; H 6.40; N 13.10%.

Refinement

H atoms of water were located in a different Fourier map and the atomic coordinates allowed to refine freely. Other H atoms were positioned geometrically and refined as riding (C-H = 0.93-0.96Å) and allowed to ride on their parent atoms, with Uiso(H) =1.2Ueq(parent) or 1.5Ueq(parent).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The packing diagram of (I).

Crystal data

C11H13N2+·Cl·0.25(H2O)Dx = 1.243 Mg m3
Mr = 213.19Melting point: 251 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 6089 reflections
a = 11.452 (2) Åθ = 2.1–27.9°
b = 11.410 (2) ŵ = 0.30 mm1
c = 34.867 (7) ÅT = 113 K
V = 4555.8 (16) Å3Block, colorless
Z = 160.22 × 0.20 × 0.16 mm
F(000) = 1800

Data collection

Rigaku Saturn diffractometer4022 independent reflections
Radiation source: rotating anode3619 reflections with I > 2σ(I)
confocalRint = 0.041
ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)h = −13→13
Tmin = 0.937, Tmax = 0.953k = −13→11
30046 measured reflectionsl = −41→39

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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0667P)2 + 2.0145P] where P = (Fo2 + 2Fc2)/3
4022 reflections(Δ/σ)max = 0.001
268 parametersΔρmax = 0.30 e Å3
3 restraintsΔρmin = −0.28 e Å3

Special details

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)

xyzUiso*/UeqOcc. (<1)
Cl10.47805 (4)1.03154 (4)0.348689 (12)0.02641 (15)
Cl20.55772 (5)0.75655 (5)0.519211 (14)0.03879 (17)
N10.76243 (14)0.70800 (14)0.42512 (4)0.0275 (4)
N20.77675 (14)0.78892 (14)0.36959 (4)0.0279 (4)
N30.30575 (13)0.63833 (13)0.43738 (4)0.0242 (3)
N40.27524 (13)0.73929 (13)0.38612 (4)0.0230 (3)
C10.7808 (2)0.6275 (2)0.45759 (6)0.0454 (6)
H1A0.77980.54810.44850.068*
H1B0.71960.63820.47610.068*
H1C0.85490.64370.46930.068*
C20.81984 (17)0.70586 (17)0.39202 (5)0.0290 (4)
H20.88010.65470.38570.035*
C30.68949 (18)0.84657 (18)0.38902 (6)0.0315 (5)
H30.64460.90850.37990.038*
C40.68136 (17)0.79632 (18)0.42386 (6)0.0312 (5)
H40.63030.81750.44340.037*
C50.8163 (2)0.8133 (2)0.33005 (6)0.0432 (6)
H5A0.89460.78250.32670.052*
H5B0.81970.89750.32630.052*
C60.73773 (18)0.76060 (18)0.30011 (5)0.0284 (4)
C70.76298 (19)0.6509 (2)0.28553 (6)0.0393 (5)
H70.82740.60970.29460.047*
C80.6929 (2)0.6021 (2)0.25757 (7)0.0520 (7)
H80.71010.52800.24800.062*
C90.5978 (2)0.6625 (2)0.24371 (6)0.0494 (7)
H90.55190.63020.22440.059*
C100.5710 (2)0.7711 (2)0.25864 (7)0.0474 (6)
H100.50610.81160.24960.057*
C110.6401 (2)0.82016 (19)0.28689 (6)0.0374 (5)
H110.62110.89310.29700.045*
C120.2976 (2)0.54811 (19)0.46704 (6)0.0358 (5)
H12A0.26470.58140.48990.054*
H12B0.37420.51820.47260.054*
H12C0.24870.48540.45820.054*
C130.24416 (16)0.64328 (16)0.40510 (5)0.0239 (4)
H130.18880.58880.39720.029*
C140.35863 (16)0.79782 (16)0.40711 (5)0.0271 (4)
H140.39520.86770.40040.032*
C150.37723 (16)0.73477 (17)0.43921 (5)0.0272 (4)
H150.42880.75310.45890.033*
C160.22392 (18)0.77900 (18)0.34989 (5)0.0291 (4)
H16A0.18320.71410.33790.035*
H16B0.28590.80360.33270.035*
C170.13971 (17)0.87942 (16)0.35559 (5)0.0251 (4)
C180.12909 (19)0.96458 (18)0.32750 (6)0.0350 (5)
H180.17550.96050.30570.042*
C190.0500 (2)1.05586 (19)0.33155 (7)0.0457 (6)
H190.04321.11200.31230.055*
C20−0.0183 (2)1.0634 (2)0.36397 (8)0.0463 (6)
H20−0.07101.12490.36680.056*
C21−0.00839 (19)0.9798 (2)0.39217 (7)0.0389 (5)
H21−0.05410.98520.41410.047*
C220.06960 (17)0.88692 (17)0.38806 (5)0.0282 (4)
H220.07480.82990.40700.034*
O10.4899 (3)0.9725 (3)0.46644 (11)0.0506 (9)0.50
H1D0.504 (5)0.998 (4)0.4438 (6)0.061*0.50
H1E0.474 (5)1.026 (3)0.4830 (9)0.061*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0257 (3)0.0269 (3)0.0266 (2)0.00190 (18)0.00007 (17)0.00296 (17)
Cl20.0373 (3)0.0435 (3)0.0356 (3)0.0013 (2)−0.0102 (2)0.0026 (2)
N10.0301 (9)0.0269 (9)0.0255 (8)−0.0025 (7)−0.0035 (6)0.0001 (6)
N20.0274 (9)0.0304 (9)0.0259 (8)−0.0078 (7)−0.0030 (6)−0.0001 (7)
N30.0244 (8)0.0234 (8)0.0249 (8)0.0034 (6)0.0008 (6)0.0020 (6)
N40.0228 (8)0.0213 (8)0.0249 (8)0.0025 (6)−0.0010 (6)−0.0013 (6)
C10.0541 (15)0.0445 (14)0.0377 (11)−0.0041 (11)−0.0141 (10)0.0141 (10)
C20.0242 (10)0.0304 (11)0.0325 (10)0.0018 (8)−0.0028 (8)−0.0064 (8)
C30.0285 (10)0.0271 (10)0.0387 (11)0.0012 (8)−0.0084 (8)−0.0028 (8)
C40.0241 (10)0.0355 (11)0.0339 (10)0.0015 (8)0.0009 (8)−0.0080 (9)
C50.0435 (13)0.0593 (15)0.0270 (10)−0.0251 (12)0.0001 (9)0.0043 (10)
C60.0309 (11)0.0318 (10)0.0225 (9)−0.0094 (8)0.0019 (8)0.0029 (8)
C70.0292 (11)0.0429 (13)0.0457 (12)0.0009 (10)0.0079 (9)−0.0036 (10)
C80.0530 (15)0.0537 (15)0.0493 (14)−0.0125 (13)0.0188 (12)−0.0275 (12)
C90.0505 (15)0.0755 (18)0.0221 (10)−0.0270 (14)0.0028 (10)−0.0111 (11)
C100.0398 (13)0.0664 (17)0.0360 (12)−0.0086 (12)−0.0101 (10)0.0171 (12)
C110.0461 (13)0.0303 (11)0.0359 (11)−0.0011 (10)0.0002 (10)0.0042 (9)
C120.0386 (12)0.0356 (12)0.0330 (10)0.0047 (9)0.0031 (9)0.0123 (9)
C130.0224 (9)0.0213 (9)0.0279 (9)−0.0004 (7)0.0001 (7)−0.0006 (7)
C140.0227 (9)0.0226 (9)0.0359 (10)−0.0027 (8)−0.0021 (8)−0.0016 (8)
C150.0231 (10)0.0285 (10)0.0301 (10)−0.0001 (8)−0.0035 (8)−0.0041 (8)
C160.0346 (11)0.0323 (11)0.0204 (9)0.0038 (9)0.0000 (8)0.0003 (8)
C170.0264 (10)0.0223 (9)0.0267 (9)−0.0013 (8)−0.0067 (7)0.0000 (7)
C180.0414 (12)0.0306 (11)0.0329 (10)−0.0063 (9)−0.0096 (9)0.0080 (8)
C190.0552 (15)0.0241 (11)0.0580 (15)−0.0024 (10)−0.0319 (12)0.0087 (10)
C200.0380 (13)0.0302 (12)0.0708 (17)0.0085 (10)−0.0283 (12)−0.0149 (12)
C210.0266 (11)0.0421 (13)0.0479 (13)0.0042 (9)−0.0087 (9)−0.0178 (11)
C220.0274 (10)0.0285 (10)0.0287 (9)−0.0012 (8)−0.0045 (8)−0.0019 (8)
O10.055 (2)0.041 (2)0.056 (2)−0.0050 (17)0.0031 (18)−0.0113 (16)

Geometric parameters (Å, °)

N1—C21.328 (2)C9—C101.379 (4)
N1—C41.371 (3)C9—H90.9300
N1—C11.473 (2)C10—C111.382 (3)
N2—C21.324 (3)C10—H100.9300
N2—C31.375 (3)C11—H110.9300
N2—C51.478 (2)C12—H12A0.9600
N3—C131.329 (2)C12—H12B0.9600
N3—C151.373 (2)C12—H12C0.9600
N3—C121.462 (2)C13—H130.9300
N4—C131.328 (2)C14—C151.348 (3)
N4—C141.376 (2)C14—H140.9300
N4—C161.465 (2)C15—H150.9300
C1—H1A0.9600C16—C171.511 (3)
C1—H1B0.9600C16—H16A0.9700
C1—H1C0.9600C16—H16B0.9700
C2—H20.9300C17—C181.385 (3)
C3—C41.347 (3)C17—C221.391 (3)
C3—H30.9300C18—C191.387 (3)
C4—H40.9300C18—H180.9300
C5—C61.504 (3)C19—C201.378 (4)
C5—H5A0.9700C19—H190.9300
C5—H5B0.9700C20—C211.375 (4)
C6—C71.382 (3)C20—H200.9300
C6—C111.387 (3)C21—C221.393 (3)
C7—C81.380 (3)C21—H210.9300
C7—H70.9300C22—H220.9300
C8—C91.376 (4)O1—H1D0.860 (10)
C8—H80.9300O1—H1E0.857 (10)
C2—N1—C4108.72 (16)C9—C10—H10119.8
C2—N1—C1125.85 (18)C11—C10—H10119.8
C4—N1—C1125.42 (18)C10—C11—C6120.0 (2)
C2—N2—C3108.79 (16)C10—C11—H11120.0
C2—N2—C5124.87 (19)C6—C11—H11120.0
C3—N2—C5126.34 (18)N3—C12—H12A109.5
C13—N3—C15108.77 (15)N3—C12—H12B109.5
C13—N3—C12126.51 (17)H12A—C12—H12B109.5
C15—N3—C12124.70 (16)N3—C12—H12C109.5
C13—N4—C14108.73 (15)H12A—C12—H12C109.5
C13—N4—C16125.25 (16)H12B—C12—H12C109.5
C14—N4—C16125.93 (16)N4—C13—N3108.34 (16)
N1—C1—H1A109.5N4—C13—H13125.8
N1—C1—H1B109.5N3—C13—H13125.8
H1A—C1—H1B109.5C15—C14—N4107.00 (17)
N1—C1—H1C109.5C15—C14—H14126.5
H1A—C1—H1C109.5N4—C14—H14126.5
H1B—C1—H1C109.5C14—C15—N3107.15 (16)
N2—C2—N1108.40 (17)C14—C15—H15126.4
N2—C2—H2125.8N3—C15—H15126.4
N1—C2—H2125.8N4—C16—C17112.14 (15)
C4—C3—N2106.93 (18)N4—C16—H16A109.2
C4—C3—H3126.5C17—C16—H16A109.2
N2—C3—H3126.5N4—C16—H16B109.2
C3—C4—N1107.16 (17)C17—C16—H16B109.2
C3—C4—H4126.4H16A—C16—H16B107.9
N1—C4—H4126.4C18—C17—C22118.81 (19)
N2—C5—C6112.86 (17)C18—C17—C16119.67 (18)
N2—C5—H5A109.0C22—C17—C16121.50 (17)
C6—C5—H5A109.0C17—C18—C19120.8 (2)
N2—C5—H5B109.0C17—C18—H18119.6
C6—C5—H5B109.0C19—C18—H18119.6
H5A—C5—H5B107.8C20—C19—C18120.1 (2)
C7—C6—C11119.36 (19)C20—C19—H19120.0
C7—C6—C5119.5 (2)C18—C19—H19120.0
C11—C6—C5121.1 (2)C21—C20—C19119.8 (2)
C8—C7—C6120.2 (2)C21—C20—H20120.1
C8—C7—H7119.9C19—C20—H20120.1
C6—C7—H7119.9C20—C21—C22120.5 (2)
C9—C8—C7120.5 (2)C20—C21—H21119.8
C9—C8—H8119.8C22—C21—H21119.8
C7—C8—H8119.8C17—C22—C21120.04 (19)
C8—C9—C10119.5 (2)C17—C22—H22120.0
C8—C9—H9120.2C21—C22—H22120.0
C10—C9—H9120.2H1D—O1—H1E114.7 (19)
C9—C10—C11120.4 (2)
C3—N2—C2—N10.4 (2)C14—N4—C13—N3−0.5 (2)
C5—N2—C2—N1−178.98 (17)C16—N4—C13—N3−177.32 (16)
C4—N1—C2—N2−0.8 (2)C15—N3—C13—N40.7 (2)
C1—N1—C2—N2177.98 (18)C12—N3—C13—N4178.88 (17)
C2—N2—C3—C40.2 (2)C13—N4—C14—C150.1 (2)
C5—N2—C3—C4179.59 (18)C16—N4—C14—C15176.88 (16)
N2—C3—C4—N1−0.7 (2)N4—C14—C15—N30.4 (2)
C2—N1—C4—C31.0 (2)C13—N3—C15—C14−0.7 (2)
C1—N1—C4—C3−177.85 (18)C12—N3—C15—C14−178.89 (17)
C2—N2—C5—C699.5 (2)C13—N4—C16—C17103.1 (2)
C3—N2—C5—C6−79.8 (3)C14—N4—C16—C17−73.2 (2)
N2—C5—C6—C7−93.2 (2)N4—C16—C17—C18147.06 (18)
N2—C5—C6—C1186.7 (3)N4—C16—C17—C22−34.8 (3)
C11—C6—C7—C81.2 (3)C22—C17—C18—C190.0 (3)
C5—C6—C7—C8−178.9 (2)C16—C17—C18—C19178.16 (19)
C6—C7—C8—C90.5 (3)C17—C18—C19—C200.7 (3)
C7—C8—C9—C10−1.6 (4)C18—C19—C20—C21−0.4 (3)
C8—C9—C10—C111.1 (3)C19—C20—C21—C22−0.5 (3)
C9—C10—C11—C60.7 (3)C18—C17—C22—C21−0.9 (3)
C7—C6—C11—C10−1.8 (3)C16—C17—C22—C21−179.04 (18)
C5—C6—C11—C10178.28 (19)C20—C21—C22—C171.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1E···O1i0.86 (1)1.81 (4)2.434 (7)128 (4)
O1—H1E···Cl2i0.86 (1)2.51 (3)3.179 (3)135 (4)

Symmetry codes: (i) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2176).

References

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