Acta Cryst. (2011). E67, o1890 [ doi:10.1107/S1600536811025700 ]
The crystal packing of the title compound, C6H11N2O+·I-, can be described as intercalated layers lying parallel to (010), with the iodide ions located between the cations. A weak intramolecular C-H
O hydrogen bond occurs within the cation. In the crystal, intermolecular O-HI hydrogen bonds result in the formation of a three-dimensional network and reinforce the cohesion of the ionic structure.
The title compound I was synthesized by treating 1eq of (1-methyl-1H-imidazol-2-yl)methanol by 3 eq of methyl iodide in refluxing THF during two days. The solid is filtered off and washed with boiling THF. Suitable crystals of I were obtained by crystallization from a CH3CN/THF solution.
All non-H atoms were refined with anisotropic atomic displacement parameters. All H atoms were localized on Fourier maps but introduced in calculated positions and treated as riding on their parent C or O atom. (with C—H = 0.95Å 0.98Å 0.99 Å, O—H = 84 Å and Uiso(H) =1.2 or 1.5(carrier atom)).
Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./hg5062fig1thm.gif)
| Fig. 1. (Farrugia, 1997) the structure of the title compound with the atomic labelling scheme.Displacement are drawn at the 50% probability level. |
![[Figure 2]](./hg5062fig2thm.gif)
| Fig. 2. (Brandenburg & Berndt, 2001) A diagram of the layered crystal packing of (I) viewed down the a axis. |
![[Figure 3]](./hg5062fig3thm.gif)
| Fig. 3. (Brandenburg & Berndt, 2001)Part of crystal packing of (I) showing hydrogen bond [C—H···O, O—H···I] as dashed line. |
| C6H11N2O+·I− | F(000) = 488 |
| Mr = 254.07 | Dx = 1.888 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1935 reflections |
| a = 7.3428 (3) Å | θ = 2.4–27.4° |
| b = 7.2186 (3) Å | µ = 3.53 mm−1 |
| c = 16.8870 (8) Å | T = 150 K |
| β = 93.093 (2)° | Prism, colourless |
| V = 893.79 (7) Å3 | 0.3 × 0.13 × 0.01 mm |
| Z = 4 |
| Bruker APEXII diffractometer | 1463 reflections with I > 2σ(I) |
| graphite | Rint = 0.019 |
| CCD rotation images, thin slices scans | θmax = 27.4°, θmin = 3.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −5→9 |
| Tmin = 0.718, Tmax = 0.965 | k = −6→9 |
| 4200 measured reflections | l = −21→21 |
| 2035 independent reflections |
| 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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.063 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0289P)2 + 0.3175P] where P = (Fo2 + 2Fc2)/3 |
| 2035 reflections | (Δ/σ)max = 0.001 |
| 94 parameters | Δρmax = 0.66 e Å−3 |
| 0 restraints | Δρmin = −0.54 e Å−3 |
| C6H11N2O+·I− | V = 893.79 (7) Å3 |
| Mr = 254.07 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 7.3428 (3) Å | µ = 3.53 mm−1 |
| b = 7.2186 (3) Å | T = 150 K |
| c = 16.8870 (8) Å | 0.3 × 0.13 × 0.01 mm |
| β = 93.093 (2)° |
| Bruker APEXII diffractometer | 2035 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1463 reflections with I > 2σ(I) |
| Tmin = 0.718, Tmax = 0.965 | Rint = 0.019 |
| 4200 measured reflections | θmax = 27.4° |
| R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
| wR(F2) = 0.063 | Δρmax = 0.66 e Å−3 |
| S = 1.03 | Δρmin = −0.54 e Å−3 |
| 2035 reflections | Absolute structure: ? |
| 94 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| I1 | 0.80624 (2) | 0.74882 (2) | 0.413580 (10) | 0.02430 (8) | |
| C1 | 0.6996 (5) | 0.2724 (3) | 0.20049 (17) | 0.0284 (6) | |
| H1A | 0.8326 | 0.2864 | 0.2033 | 0.043* | |
| H1B | 0.6438 | 0.3775 | 0.1716 | 0.043* | |
| H1C | 0.6663 | 0.157 | 0.1728 | 0.043* | |
| N2 | 0.6343 (3) | 0.2668 (2) | 0.28084 (14) | 0.0204 (5) | |
| C3 | 0.4551 (4) | 0.2855 (3) | 0.29967 (18) | 0.0251 (6) | |
| H3 | 0.3528 | 0.3011 | 0.2634 | 0.03* | |
| C4 | 0.4528 (4) | 0.2773 (3) | 0.37988 (17) | 0.0232 (6) | |
| H4 | 0.3482 | 0.2865 | 0.4104 | 0.028* | |
| N5 | 0.6304 (3) | 0.2533 (2) | 0.40871 (13) | 0.0195 (5) | |
| C6 | 0.6882 (4) | 0.2431 (3) | 0.49319 (18) | 0.0271 (6) | |
| H6A | 0.7534 | 0.1265 | 0.5038 | 0.041* | |
| H6B | 0.5807 | 0.2483 | 0.5251 | 0.041* | |
| H6C | 0.7689 | 0.3475 | 0.5071 | 0.041* | |
| C7 | 0.7404 (4) | 0.2472 (3) | 0.34775 (16) | 0.0192 (5) | |
| C8 | 0.9437 (4) | 0.2288 (3) | 0.35238 (19) | 0.0254 (6) | |
| H8A | 0.9867 | 0.2055 | 0.4081 | 0.03* | |
| H8B | 0.9789 | 0.1212 | 0.3202 | 0.03* | |
| O9 | 1.0295 (3) | 0.3905 (2) | 0.32453 (12) | 0.0305 (4) | |
| H9 | 0.9902 | 0.4838 | 0.348 | 0.046* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I1 | 0.01963 (12) | 0.02953 (13) | 0.02391 (12) | 0.00057 (7) | 0.00275 (8) | −0.00027 (6) |
| C1 | 0.0296 (16) | 0.0386 (16) | 0.0173 (14) | −0.0004 (12) | 0.0043 (12) | −0.0005 (11) |
| N2 | 0.0192 (11) | 0.0243 (11) | 0.0179 (11) | 0.0006 (8) | 0.0020 (9) | −0.0003 (8) |
| C3 | 0.0170 (14) | 0.0308 (15) | 0.0277 (15) | 0.0020 (11) | 0.0027 (11) | 0.0000 (11) |
| C4 | 0.0147 (13) | 0.0310 (14) | 0.0242 (14) | 0.0011 (10) | 0.0029 (11) | 0.0007 (10) |
| N5 | 0.0154 (11) | 0.0256 (11) | 0.0176 (11) | 0.0004 (8) | 0.0017 (9) | −0.0005 (8) |
| C6 | 0.0209 (14) | 0.0408 (17) | 0.0196 (14) | 0.0001 (11) | 0.0011 (11) | 0.0017 (10) |
| C7 | 0.0161 (12) | 0.0217 (13) | 0.0200 (13) | −0.0007 (10) | 0.0026 (10) | 0.0003 (9) |
| C8 | 0.0172 (14) | 0.0315 (15) | 0.0276 (15) | 0.0006 (11) | 0.0026 (12) | 0.0005 (11) |
| O9 | 0.0217 (10) | 0.0301 (10) | 0.0410 (11) | −0.0052 (9) | 0.0133 (8) | −0.0041 (9) |
| C1—N2 | 1.464 (4) | N5—C7 | 1.343 (3) |
| C1—H1A | 0.98 | N5—C6 | 1.468 (4) |
| C1—H1B | 0.98 | C6—H6A | 0.98 |
| C1—H1C | 0.98 | C6—H6B | 0.98 |
| N2—C7 | 1.345 (3) | C6—H6C | 0.98 |
| N2—C3 | 1.376 (4) | C7—C8 | 1.497 (4) |
| C3—C4 | 1.357 (4) | C8—O9 | 1.419 (3) |
| C3—H3 | 0.95 | C8—H8A | 0.99 |
| C4—N5 | 1.379 (4) | C8—H8B | 0.99 |
| C4—H4 | 0.95 | O9—H9 | 0.84 |
| N2—C1—H1A | 109.5 | C4—N5—C6 | 124.6 (2) |
| N2—C1—H1B | 109.5 | N5—C6—H6A | 109.5 |
| H1A—C1—H1B | 109.5 | N5—C6—H6B | 109.5 |
| N2—C1—H1C | 109.5 | H6A—C6—H6B | 109.5 |
| H1A—C1—H1C | 109.5 | N5—C6—H6C | 109.5 |
| H1B—C1—H1C | 109.5 | H6A—C6—H6C | 109.5 |
| C7—N2—C3 | 109.5 (2) | H6B—C6—H6C | 109.5 |
| C7—N2—C1 | 125.3 (3) | N5—C7—N2 | 107.2 (3) |
| C3—N2—C1 | 125.2 (3) | N5—C7—C8 | 127.0 (3) |
| C4—C3—N2 | 106.9 (3) | N2—C7—C8 | 125.7 (3) |
| C4—C3—H3 | 126.6 | O9—C8—C7 | 111.6 (2) |
| N2—C3—H3 | 126.6 | O9—C8—H8A | 109.3 |
| C3—C4—N5 | 107.2 (3) | C7—C8—H8A | 109.3 |
| C3—C4—H4 | 126.4 | O9—C8—H8B | 109.3 |
| N5—C4—H4 | 126.4 | C7—C8—H8B | 109.3 |
| C7—N5—C4 | 109.3 (2) | H8A—C8—H8B | 108 |
| C7—N5—C6 | 126.1 (3) | C8—O9—H9 | 109.5 |
| C7—N2—C3—C4 | 0.1 (3) | C6—N5—C7—C8 | 0.1 (3) |
| C1—N2—C3—C4 | −178.4 (2) | C3—N2—C7—N5 | 0.0 (2) |
| N2—C3—C4—N5 | −0.2 (3) | C1—N2—C7—N5 | 178.48 (18) |
| C3—C4—N5—C7 | 0.2 (2) | C3—N2—C7—C8 | −178.1 (2) |
| C3—C4—N5—C6 | 178.15 (19) | C1—N2—C7—C8 | 0.3 (3) |
| C4—N5—C7—N2 | −0.1 (2) | N5—C7—C8—O9 | −113.9 (3) |
| C6—N5—C7—N2 | −178.06 (18) | N2—C7—C8—O9 | 63.8 (3) |
| C4—N5—C7—C8 | 178.0 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O9—H9···I1 | 0.84 | 2.62 | 3.4504 (18) | 169 |
| C1—H1A···O9 | 0.98 | 2.55 | 3.230 (4) | 126 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O9—H9···I1 | 0.84 | 2.62 | 3.4504 (18) | 169 |
| C1—H1A···O9 | 0.98 | 2.55 | 3.230 (4) | 126 |
We are grateful to all personal of the PHYSYNOR laboratory, Université Mentouri-Constantine, Algeria, for their assistance. Thanks are due to the MESRS (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique - Algérie) for financial support.
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The development of cleaner technologies is a major emphasis in green chemistry. Among the several aspects of green chemistry, the reduction/replacement of volatile organic solvents from the reaction medium is of utmost importance. The use of a large excess of conventional volatile solvents required to conduct a chemical reaction creates ecological and economic concerns. The search for a nonvolatile and recyclable alternative is thus holding a key role in this field of research. The use of fused organic salts, consisting of ions, is now emerging as a possible alternative. A proper choice of cations and anions is required to achieve ionic salts that are liquids at room temperature and are appropriately termed room temperature ionic liquids (RTILs) (Welton, 1999; Kubisa 2004; Corma & Garcia 2003; Sheldon, 2001; Wasserscheid & Kerm, 2000). The ionic liquids based on 1,3-dialkylimidazolium are becoming more important for several synthetic applications (Varma & Namboodiri 2001).
In this work, we report synthesis and the structure determination of an ionic compound obtained from the quaternization reaction of 1-methyl-2-hydroxymethylimidazole using methyl iodide (I).
The molecular geometry and the atom-numbering scheme of (I) are shown in Fig. 1. The asymetric unit of title molecule, C6H11N2O+, I-, contains a 2-hydroxymethyl-1,3-dimethylimidazolium cation and iodide anion.
The crystal packing can be described as intercalated layers parallel to the (010) plane, wich iodide ions are located between cations (Fig. 2). It is stabilized by weak intra and intermolecular hydrogen bonds [O—H···I and C—H···O] (Fig. 3). These interaction bonds link the molecules within the layers and also link the layers together, forming a three dimensional network and reinforcing the cohesion of the ionic structure. Hydrogen-bonding parameters are listed in table 1.