3-(1H-Imidazol-1-yl)propane­nitrile

Peppel, T.; Köckerling, M.

doi:10.1107/S1600536809035685

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2480

doi:10.1107/S1600536809035685

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

Tim Peppel ^a and Martin Köckerling ^a ^*

^aUniversität Rostock, Institut für Chemie, Abteilung Anorganische Chemie/Festkörperchemie, Albert-Einstein-Strasse 3a, D-18059 Rostock, Germany
^*Correspondence e-mail: Martin.Koeckerling@uni-rostock.de

(Received 18 August 2009; accepted 3 September 2009; online 16 September 2009)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.032
wR(F²) = 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

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)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

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

Figures top

	Fig. 1. Molecular structure of 3-(1H-imidazol-1-yl)propanenitrile with atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Two neighboring C₆H₇N₃ molecules with the short N2···H(C5) contact.
	Fig. 3. Packing diagram of 3-(1H-imidazol-1-yl)propanenitrile in a view down the crystallographic b direction.

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

Crystal data top

C₆H₇N₃	D_x = 1.304 Mg m⁻³
M_r = 121.15	Melting point: 310 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2712 (3) Å	Cell parameters from 8906 reflections
b = 5.5917 (2) Å	θ = 2.7–28.3°
c = 15.4625 (5) Å	µ = 0.09 mm⁻¹
β = 100.979 (1)°	T = 173 K
V = 617.17 (4) Å³	Block, colourless
Z = 4	0.45 × 0.40 × 0.30 mm
F(000) = 256

Data collection top

Bruker–Nonius X8 Apex diffractometer	1542 independent reflections
Radiation source: fine-focus sealed tube	1456 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.946, T_max = 0.975	k = −7→7
11604 measured reflections	l = −20→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	All H-atom parameters refined
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0486P)² + 0.1206P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1542 reflections	Δρ_max = 0.27 e Å⁻³
111 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.064 (15)

Crystal data top

C₆H₇N₃	V = 617.17 (4) Å³
M_r = 121.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2712 (3) Å	µ = 0.09 mm⁻¹
b = 5.5917 (2) Å	T = 173 K
c = 15.4625 (5) Å	0.45 × 0.40 × 0.30 mm
β = 100.979 (1)°

Data collection top

Bruker–Nonius X8 Apex diffractometer	1542 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1456 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.975	R_int = 0.018
11604 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.086	All H-atom parameters refined
S = 1.04	Δρ_max = 0.27 e Å⁻³
1542 reflections	Δρ_min = −0.16 e Å⁻³
111 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
N1	0.76561 (9)	0.2518 (1)	0.30688 (4)	0.0207 (2)
C1	0.6541 (1)	0.1964 (2)	0.22892 (5)	0.0254 (2)
H1	0.579 (2)	0.053 (2)	0.2217 (7)	0.033 (3)*
N2	0.6623 (1)	0.3580 (1)	0.16800 (4)	0.0302 (2)
C2	0.7866 (1)	0.5266 (2)	0.20919 (6)	0.0281 (2)
H2	0.817 (2)	0.670 (2)	0.1771 (8)	0.037 (3)*
C3	0.8519 (1)	0.4648 (1)	0.29465 (5)	0.0249 (2)
H3	0.944 (2)	0.535 (2)	0.3408 (8)	0.035 (3)*
C4	0.7876 (1)	0.1115 (1)	0.38757 (5)	0.0239 (2)
H4A	0.919 (2)	0.109 (2)	0.4147 (7)	0.030 (3)*
H4B	0.744 (2)	−0.051 (2)	0.3700 (7)	0.031 (3)*
C5	0.6708 (1)	0.2069 (2)	0.45232 (5)	0.0254 (2)
H5A	0.683 (2)	0.100 (2)	0.5022 (8)	0.037 (3)*
H5B	0.538 (2)	0.217 (2)	0.4243 (7)	0.035 (3)*
C6	0.7298 (1)	0.4436 (2)	0.48692 (5)	0.0244 (2)
N3	0.7779 (1)	0.6275 (1)	0.51425 (5)	0.0333 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0242 (3)	0.0212 (3)	0.0176 (3)	0.0012 (2)	0.0061 (2)	0.0007 (2)
C1	0.0293 (4)	0.0279 (4)	0.0194 (4)	0.0001 (3)	0.0057 (3)	−0.0026 (3)
N2	0.0345 (4)	0.0371 (4)	0.0196 (3)	0.0033 (3)	0.0064 (3)	0.0029 (3)
C2	0.0290 (4)	0.0307 (4)	0.0271 (4)	0.0027 (3)	0.0113 (3)	0.0075 (3)
C3	0.0246 (4)	0.0249 (4)	0.0257 (4)	−0.0015 (3)	0.0065 (3)	0.0023 (3)
C4	0.0318 (4)	0.0213 (4)	0.0188 (3)	0.0026 (3)	0.0058 (3)	0.0025 (3)
C5	0.0321 (4)	0.0265 (4)	0.0190 (4)	−0.0056 (3)	0.0084 (3)	−0.0011 (3)
C6	0.0265 (4)	0.0288 (4)	0.0186 (3)	0.0011 (3)	0.0060 (3)	−0.0002 (3)
N3	0.0386 (4)	0.0303 (4)	0.0313 (4)	−0.0002 (3)	0.0078 (3)	−0.0047 (3)

Geometric parameters (Å, º) top

N1—C1	1.354 (1)	C6—N3	1.141 (1)
N1—C3	1.376 (1)	C1—H1	0.97 (1)
N1—C4	1.4565 (9)	C2—H2	0.99 (1)
C1—N2	1.315 (1)	C3—H3	0.97 (1)
N2—C2	1.376 (1)	C4—H4A	0.97 (1)
C2—C3	1.361 (1)	C4—H4B	0.99 (1)
C4—C5	1.527 (1)	C5—H5A	0.97 (1)
C5—C6	1.461 (1)	C5—H5B	0.98 (1)

C1—N1—C3	106.68 (6)	H2—C2—N2	120.9 (7)
C1—N1—C4	126.06 (7)	H3—C3—C2	132.8 (7)
C3—N1—C4	127.27 (7)	H3—C3—N1	121.4 (7)
N2—C1—N1	112.30 (7)	H4A—C4—H4B	110.4 (9)
C1—N2—C2	104.76 (7)	H4A—C4—N1	108.5 (7)
C3—C2—N2	110.64 (7)	H4B—C4—N1	106.5 (7)
C2—C3—N1	105.63 (7)	H4A—C4—C5	110.2 (7)
N1—C4—C5	112.92 (6)	H4B—C4—C5	108.2 (7)
C6—C5—C4	113.28 (7)	H5A—C5—H5B	109 (1)
N3—C6—C5	179.24 (9)	H5A—C5—C6	107.0 (7)
H1—C1—N2	126.2 (7)	H5B—C5—C6	107.9 (7)
H1—C1—N1	121.5 (7)	H5A—C5—C4	109.2 (7)
H2—C2—C3	128.4 (7)	H5B—C5—C4	110.7 (7)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₇N₃
M_r	121.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	7.2712 (3), 5.5917 (2), 15.4625 (5)
β (°)	100.979 (1)
V (Å³)	617.17 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.40 × 0.30

Data collection
Diffractometer	Bruker–Nonius X8 Apex diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.946, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	11604, 1542, 1456
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.04
No. of reflections	1542
No. of parameters	111
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.16

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), ct.exe (Köckerling, 1996).

Hydrogen-bond geometry (Å, º) top

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)

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

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.

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