3-(1H-Imidazol-1-yl)propane­nitrile

Tim Peppel; Martin Köckerling

doi:10.1107/S1600536809035685

. 2009 Sep 16;65(Pt 10):o2480. doi: 10.1107/S1600536809035685

3-(1H-Imidazol-1-yl)propanenitrile

Tim Peppel ^a, Martin Köckerling ^a,^*

PMCID: PMC2970166 PMID: 21577931

Abstract

The title compound, C₆H₇N₃, has an ethylene group connecting an imidazole ring and a –CN group. These groups are in a staggered conformation. The shortest intermolecular contact is found between the imidazole N atom and a –CH₂– group of a neighboring molecule.

Related literature

For background and applications of ionic liquids, see: Hayashi et al. (2006 ▶); Kozlova et al. (2009a ▶,b ▶); Lombardo et al. (2007 ▶); Macaev et al. (2007 ▶); Sawa & Okamura (1969 ▶); Scheers et al. (2008 ▶); Visser et al. (2001 ▶); Wang et al. (2003 ▶); Wasserscheid & Keim (2000 ▶); Xu et al. (2007 ▶); Yamauchi & Masui (1976 ▶); Yang et al. (2006 ▶).

Experimental

Crystal data

C₆H₇N₃
M _r = 121.15
Monoclinic,
a = 7.2712 (3) Å
b = 5.5917 (2) Å
c = 15.4625 (5) Å
β = 100.979 (1)°
V = 617.17 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.45 × 0.40 × 0.30 mm

Data collection

Bruker–Nonius X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.946, T _max = 0.975
11604 measured reflections
1542 independent reflections
1456 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.086
S = 1.04
1542 reflections
111 parameters
All H-atom parameters refined
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (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: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: ct.exe (Köckerling, 1996 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035685/om2269sup1.cif

e-65-o2480-sup1.cif^{(13.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035685/om2269Isup2.hkl

e-65-o2480-Isup2.hkl^{(76KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯N2ⁱ	0.97 (1)	2.66 (1)	3.366 (1)	135.7 (9)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank Professor Dr Helmut Reinke (University of Rostock/Germany, Institute of Chemistry) for maintaining the X-ray equipment. Support from the DFG (priority program SPP 1191-Ionic Liquids, KO-1616/4-1 and 1616/4-2) is gratefully acknowledged.

supplementary crystallographic information

Comment

Ionic Liquids (ILs) are more and more attracting remarkable attention as new solvents and reaction media for organic and inorganic synthesis and catalysis in order to replace volatile organic solvents (Wasserscheid & Keim, 2000). Imidazolium based ILs have emerged as leading candidates since they have very low vapor pressures, are moisture and air stable, and are highly solvating for both molecular and ionic species. Furthermore, ILs are finding use in separation processes (Visser et al., 2001), in battery applications (Scheers et al., 2008), as electrolytes in solar cells (Wang et al., 2003), or as part of metal catalysts and magnetic liquids (Lombardo et al., 2007; Hayashi et al., 2006; Kozlova et al., 2009a; Kozlova et al., 2009b). Ionic Liquids and imidazole compounds incorporating nitrile functionalities have shown applications in heterocyclic and terpene chemistry (Macaev et al., 2007; Yamauchi & Masui, 1976), in Michael addition or aza-Michael reactions (Xu et al., 2007; Yang et al., 2006).

In this context we present the molecular and single-crystal structure of 3-(1H-imidazol-1-yl)propanenitrile, an important precursor of nitrile functionalized ILs. Although all other sources report this compound to be a liquid at room temperature, there is one single indication in the literature that it is a solid melting at 33–35 °C (Sawa & Okamura, 1969). A freshly distilled sample crystallizes spontaneously within days, forming big block-shaped colourless crystals, which are barely deliquescent and melting at 37 °C.

All the bond lengths are within the expected ranges. The molecular structure of the title compound is shown in Figure 1. The C6–N3 bond length of 1.141 (1) Å indicates the triple-bond nitrile character. This nitrile group is connected through an ethylene group with the planar imidazolyl ring. The ethylene group has a staggered conformation with an N1–C4–C5–C6 torsion angle of -65.43 (9)°.

The shortest intermolecular contacts are found between one of the H atoms bonded at C5 and the N2 atom of the symmetry equivalent neighboring molecule. The H5A···N2^# distance measures 2.66 (1) Å, the corresponding C5···N2^# distance 3.366 (1) Å, and the C5–H5a···N2^# angle 135.6° (symmetry code #: x, 1/2-y, z+1/2). Therefore the contact can be considered as a weak hydrogen bond. Figure 2 shows the orientation of two molecules, which are attached through this weak hydrogen bond.

In the crystal the molecules are arranged in rows, such that this weak hydrogen bond is oriented approximately parallel to the crystallographic c direction. Due to the c glide plane, every second row, stacked along a is shifted by c/2. The packing diagram, Figure 3, shows this assembly.

Experimental

1H-Imidazole (50.0 g, 0.7 mol) and acrylonitrile (117.0 g, 2.2 mol) were refluxed in 150 ml of ethanol overnight. Excess acrylonitrile and the solvent were evaporated and the residue was distilled in vacuum, yielding a colourless supercooled liquid, which crystallized at room temperature after several days. Yield: 75.0 g (84%), mp 37 °C.