1-(2-Cyano­eth­yl)-1H-imidazole-4,5-dicarbonitrile

Yu, H.; Lei, K.-W.

doi:10.1107/S1600536812036252

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2765

doi:10.1107/S1600536812036252

Open

access

1-(2-Cyanoethyl)-1H-imidazole-4,5-dicarbonitrile

Hong Yu ^a and Ke-Wei Lei ^a ^*

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: leikeweipublic@hotmail.com

(Received 6 August 2012; accepted 20 August 2012; online 25 August 2012)

In the title tricyanonitrile compound, C₈H₅N₅, the N-substituted cyanoethyl group is offset to the imidazole ring [dihedral angle = 75.41 (15)°].

Related literature

For background to the application of imidazole compounds as ligands, see: Li et al. (1955 ). For the significance of N atoms in metal complex chemistry, see: Fujita et al. (1994 ). For examples of some imidazole complexes, see: Martin & Edsall (1958 ).

Experimental

Crystal data

C₈H₅N₅
M_r = 171.17
Triclinic, $[P \overline 1]$
a = 6.4831 (6) Å
b = 6.7538 (6) Å
c = 10.4040 (11) Å
α = 77.865 (9)°
β = 84.297 (8)°
γ = 74.499 (8)°
V = 428.71 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.43 × 0.25 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.973, T_max = 0.986
3805 measured reflections
2265 independent reflections
1439 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.124
S = 1.09
2265 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalRED (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812036252/zs2228sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036252/zs2228Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812036252/zs2228Isup3.cml

checkCIF report

Comment top

Imidazole ligands have been used with remarkable success in coordination chemistry over past decades (Li et al., 1955). Some of the reasons are for this are that the N atom plays an important role in the formation of metal complexes (Fujita et al., 1994), and that imidazole complexes show conjugate acid-base properties and good complexation coordination performance in the solid state. Some examples of imidazole complexes have been reported (Martin & Edsall, 1958). Here we report on a new imidazole compound, the polycyano-substituted imidazole, the title compound C₈H₅N₅.

In the molecular structure of this compound (Fig. 1). The bond lengths and bond angles are within normal ranges. The N-bound cyanoethyl side chain is offset to the imidazole ring [torsion angles C5—N4—C4—C2 and N4—C4—C2—C1, -78.0 (2) and -61.4 (2)° respectively]. The dihedral angle between the cyanoethyl group defined by atoms N1—C1—C2—C4 and the imidazole ring is 75.41 (15)°]

Related literature top

For background to the application of imidazole compounds as ligands, see: Li et al. (1955). For the significance of N atoms in metal complex chemistry, see: Fujita et al. (1994). For examples of some imidazole complexes, see: Martin & Edsall (1958).

Experimental top

A mixture of 4,5-dicyanoimidazole (1.18 g, 10 mmol) and powdered potassium hydroxide (100 mg) (as a catalyst) in acrylonitrile (20 ml) was heated at 130 °C for 3 hr in a sealed tube, after which the solution was evaporated to dryness. The crude product obtained was recrystallized twice from acetone to give a pure blue product. Yield: 89.7%. Anal: Calcd. for C₈H₅N₅: C, 56.1; H, 2.9; N, 40.9%: Found: C, 56.15; H, 2.96; N, 40.89%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalRED (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Figure 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

1-(2-Cyanoethyl)-1H-imidazole-4,5-dicarbonitrile top

Crystal data top

C₈H₅N₅	Z = 2
M_r = 171.17	F(000) = 176
Triclinic, P1	D_x = 1.326 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4831 (6) Å	Cell parameters from 1220 reflections
b = 6.7538 (6) Å	θ = 3.2–29.0°
c = 10.4040 (11) Å	µ = 0.09 mm⁻¹
α = 77.865 (9)°	T = 293 K
β = 84.297 (8)°	Block, blue
γ = 74.499 (8)°	0.43 × 0.25 × 0.16 mm
V = 428.71 (7) Å³

Data collection top

Rigaku R-AXIS RAPID CCD diffractometer	2265 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1439 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.020
Detector resolution: 16.1623 pixels mm^-1	θ_max = 29.0°, θ_min = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→9
T_min = 0.973, T_max = 0.986	l = −13→14
3805 measured reflections

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0428P)² + 0.0566P] where P = (F_o² + 2F_c²)/3
2265 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₅N₅	γ = 74.499 (8)°
M_r = 171.17	V = 428.71 (7) Å³
Triclinic, P1	Z = 2
a = 6.4831 (6) Å	Mo Kα radiation
b = 6.7538 (6) Å	µ = 0.09 mm⁻¹
c = 10.4040 (11) Å	T = 293 K
α = 77.865 (9)°	0.43 × 0.25 × 0.16 mm
β = 84.297 (8)°

Data collection top

Rigaku R-AXIS RAPID CCD diffractometer	2265 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1439 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.986	R_int = 0.020
3805 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.09	Δρ_max = 0.13 e Å⁻³
2265 reflections	Δρ_min = −0.21 e Å⁻³
118 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
N4	0.25841 (19)	0.19385 (19)	0.19288 (12)	0.0356 (3)
N5	0.5564 (2)	0.2497 (2)	0.08299 (14)	0.0438 (4)
C8	0.5883 (2)	0.0426 (2)	0.13842 (15)	0.0367 (4)
C7	0.3704 (3)	−0.1861 (3)	0.28068 (17)	0.0462 (4)
C6	0.4074 (2)	0.0040 (2)	0.20743 (15)	0.0353 (4)
C5	0.3567 (2)	0.3342 (2)	0.11807 (16)	0.0420 (4)
H5A	0.2902	0.4759	0.0938	0.050*
N3	0.9384 (2)	−0.2328 (3)	0.10572 (16)	0.0632 (5)
C4	0.0347 (2)	0.2341 (3)	0.24210 (16)	0.0425 (4)
H4A	−0.0060	0.1025	0.2662	0.051*
H4B	−0.0557	0.3222	0.1723	0.051*
C3	0.7842 (3)	−0.1089 (3)	0.12134 (16)	0.0430 (4)
C2	−0.0044 (3)	0.3398 (3)	0.36024 (17)	0.0502 (5)
H2A	0.0338	0.4727	0.3357	0.060*
H2B	−0.1557	0.3685	0.3862	0.060*
N2	0.3452 (3)	−0.3409 (3)	0.3388 (2)	0.0740 (6)
C1	0.1183 (3)	0.2129 (3)	0.47147 (19)	0.0534 (5)
N1	0.2152 (3)	0.1117 (3)	0.55746 (19)	0.0798 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N4	0.0358 (7)	0.0354 (7)	0.0338 (7)	−0.0091 (5)	0.0008 (5)	−0.0038 (5)
N5	0.0430 (7)	0.0361 (7)	0.0470 (8)	−0.0091 (6)	0.0055 (6)	−0.0008 (6)
C8	0.0379 (8)	0.0356 (8)	0.0347 (8)	−0.0078 (6)	−0.0010 (6)	−0.0049 (7)
C7	0.0486 (10)	0.0386 (9)	0.0500 (10)	−0.0131 (8)	−0.0032 (8)	−0.0023 (8)
C6	0.0409 (8)	0.0323 (8)	0.0324 (8)	−0.0096 (6)	−0.0032 (6)	−0.0040 (6)
C5	0.0433 (9)	0.0322 (8)	0.0452 (9)	−0.0077 (7)	0.0030 (7)	−0.0004 (7)
N3	0.0538 (9)	0.0568 (10)	0.0660 (11)	0.0044 (8)	0.0037 (8)	−0.0100 (8)
C4	0.0348 (8)	0.0482 (9)	0.0436 (10)	−0.0118 (7)	0.0015 (7)	−0.0067 (8)
C3	0.0430 (9)	0.0419 (9)	0.0407 (9)	−0.0082 (7)	0.0011 (7)	−0.0053 (7)
C2	0.0505 (10)	0.0462 (10)	0.0514 (11)	−0.0108 (8)	0.0123 (8)	−0.0124 (8)
N2	0.0836 (13)	0.0471 (10)	0.0879 (14)	−0.0269 (9)	−0.0008 (10)	0.0065 (9)
C1	0.0591 (12)	0.0660 (13)	0.0442 (11)	−0.0288 (10)	0.0112 (9)	−0.0204 (10)
N1	0.0850 (14)	0.1093 (17)	0.0516 (11)	−0.0391 (12)	−0.0047 (10)	−0.0104 (11)

Geometric parameters (Å, º) top

N4—C5	1.3509 (19)	C5—H5A	0.9300
N4—C6	1.3729 (18)	N3—C3	1.142 (2)
N4—C4	1.4630 (19)	C4—C2	1.515 (2)
N5—C5	1.3172 (19)	C4—H4A	0.9700
N5—C8	1.3641 (19)	C4—H4B	0.9700
C8—C6	1.370 (2)	C2—C1	1.452 (3)
C8—C3	1.424 (2)	C2—H2A	0.9700
C7—N2	1.137 (2)	C2—H2B	0.9700
C7—C6	1.416 (2)	C1—N1	1.135 (2)

C5—N4—C6	106.18 (12)	N4—C4—C2	112.63 (13)
C5—N4—C4	126.80 (13)	N4—C4—H4A	109.1
C6—N4—C4	126.95 (13)	C2—C4—H4A	109.1
C5—N5—C8	104.35 (13)	N4—C4—H4B	109.1
N5—C8—C6	110.83 (13)	C2—C4—H4B	109.1
N5—C8—C3	122.98 (14)	H4A—C4—H4B	107.8
C6—C8—C3	126.16 (14)	N3—C3—C8	178.15 (19)
N2—C7—C6	178.5 (2)	C1—C2—C4	112.42 (15)
C8—C6—N4	105.61 (13)	C1—C2—H2A	109.1
C8—C6—C7	129.79 (15)	C4—C2—H2A	109.1
N4—C6—C7	124.59 (14)	C1—C2—H2B	109.1
N5—C5—N4	113.02 (14)	C4—C2—H2B	109.1
N5—C5—H5A	123.5	H2A—C2—H2B	107.9
N4—C5—H5A	123.5	N1—C1—C2	179.1 (2)

C5—N4—C4—C2	−78.0 (2)	C8—N5—C5—N4	0.08 (17)
C6—N4—C4—C2	105.74 (18)	C5—N5—C8—C3	178.04 (15)
C4—N4—C5—N5	−176.61 (14)	C5—N5—C8—C6	−0.40 (17)
C6—N4—C5—N5	0.25 (18)	C1—C2—C4—N4	−61.4 (2)
C4—N4—C6—C7	−3.8 (2)	N4—C6—C8—N5	0.55 (17)
C4—N4—C6—C8	176.38 (14)	N4—C6—C8—C3	−177.82 (15)
C5—N4—C6—C7	179.31 (15)	C7—C6—C8—N5	−179.22 (16)
C5—N4—C6—C8	−0.48 (16)	C7—C6—C8—C3	2.4 (3)

Experimental details

Crystal data
Chemical formula	C₈H₅N₅
M_r	171.17
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.4831 (6), 6.7538 (6), 10.4040 (11)
α, β, γ (°)	77.865 (9), 84.297 (8), 74.499 (8)
V (Å³)	428.71 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.25 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID CCD diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.973, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	3805, 2265, 1439
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.681

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.124, 1.09
No. of reflections	2265
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.21

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalRED (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund in Ningbo University, the Talent Fund of Ningbo Municipal Natural Science Foundation (No. 2010 A610187) and the Talent Fund of Ningbo University (No. Xkl09070).

References

Fujita, M., Kwon, Y. J., Washizu, S. & Ogura, K. (1994). J. Am. Chem. Soc. 116, 1151–1152. CSD CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, N. C., Chu, T. L., Fujii, C. T. & White, J. M. (1955). J. Am. Chem. Soc. 77, 859–861. CrossRef CAS Web of Science Google Scholar
Martin, R. B. & Edsall, J. T. (1958). J. Am. Chem. Soc. 80, 5033–5035. CrossRef CAS Web of Science Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalRED. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar