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organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

2-Amino-5-(4-chlorophenyl)-1-methylimidazole

Victor B. Rybakov,* Eugene V. Babaev and Eugene N. Belykh
Chemistry Department, Moscow State University, 119899 Moscow, Russia Correspondence e-mail: rybakov@biocryst.phys.msu.su

The asymmetric unit of the title compound, C10H10ClN3, contains four independent molecules, two of which are related by a pseudo-inversion centre. Intermolecular N HŅŅŅN and N HŅŅŅCl interactions are present in the crystal.

Received 10 October 2001 Accepted 3 January 2002 Online 11 January 2002

Comment
According to the Cambridge Structural Database (Allen & Kennard, 1993) and to the best of our knowledge, the X-ray structure of the title compound, (I), has not been determined previously. The present analysis showed that four independent molecules are present in the asymmetric unit (molecules A, B, C and D). The planar phenyl ring (C6 C11) is twisted about the C5 C6 bond with respect to the planar imidazole moiety (N1 C5) by 22.8 (1), 29.8 (1), 28.9 (1) and 29.3 (1) for molecules A D, respectively. The main structural features of these four molecules are essentially identical, as shown in Table 1.

Key indicators Single-crystal X-ray study T = 293 K Ú Mean ' (CÁC) = 0.004 A R factor = 0.051 wR factor = 0.133 Data-to-parameter ratio = 12.9 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

# 2002 International Union of Crystallography Printed in Great Britain Á all rights reserved

There are four endocyclic C N bonds of the imidazole ring and one exocyclic C N bond involving an amino group. As might be expected, the shortest C N bond is the endocyclic Ú C2 N3 double bond [mean 1.319 (3) A], whereas the other C N bond lengths follow the order C2 N1 [mean 1.359 (3)] < C2 N13 [mean 1.367 (3)] < C4 N3 [mean 1.377 (3)] < Ú C5 N1 [mean 1.402 (3) A]. A reason why the C2 N1 and C2 N13 single bonds are shorter than the other C N bonds is the possibility of conjugation between the lone pairs of atoms N1 and N13 and the C2 N3 double bond. Although amino imino tautomerism is possible for aminoheterocycles, X-ray data con?rm the amine form of the present structure. A system of intermolecular N HŅŅŅN and N HŅŅŅCl contacts is formed in the crystal (Table 2). The hydrogen bonds N13C H10CŅŅŅN3Ciii (molecule C) and N13D H10DŅŅŅN3Div (molecule D) [symmetry codes: (iii) 1Đx,1Đy, 1Đz; (iv) 1Đx, 2Đy, 2Đz] link molecules C or D in the crystal into centrosymmetric dimers, whereas molecules A and B are linked by similar N HŅŅŅN bonds to form a pseudocentrosymmetric dimer (Fig. 1). Moreover, molecules C and D form endless chains, as shown in Fig. 2 and Table 2. Molecules
DOI: 10.1107/S1600536802000284 Acta Cryst. (2002). E58, o126 o128

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Table 1
Ú Selected geometric parameters (A, ).
Cl1AāC9A N1AāC2A N1AāC5A N1AāC12A C2AāN3A C2AāN13A N3AāC4A C4AāC5A C5AāC6A C6AāC11A C6AāC7A C7AāC8A C8AāC9A C9AāC10A C10AāC11A Cl1BāC9B N1BāC2B N1BāC5B N1BāC12B C2BāN3B C2BāN13B N3BāC4B C4BāC5B C5BāC6B C6BāC11B C6BāC7B C7BāC8B C8BāC9B C9BāC10B C10BāC11B C2AāN1AāC5A C2AāN1AāC12A C5AāN1AāC12A N3AāC2AāN1A N3AāC2AāN13A N1AāC2AāN13A C2AāN3AāC4A C5AāC4AāN3A C4AāC5AāN1A C4AāC5AāC6A N1AāC5AāC6A C11AāC6AāC7A C11AāC6AāC5A C7AāC6AāC5A C8AāC7AāC6A C7AāC8AāC9A C10AāC9AāC8A C10AāC9AāCl1A C8AāC9AāCl1A C9AāC10AāC11A C10AāC11AāC6A C2BāN1BāC5B C2BāN1BāC12B C5BāN1BāC12B N3BāC2BāN1B N3BāC2BāN13B N1BāC2BāN13B C2BāN3BāC4B C5BāC4BāN3B C4BāC5BāN1B C4BāC5BāC6B N1BāC5BāC6B C11BāC6BāC7B C11BāC6BāC5B C7BāC6BāC5B C8BāC7BāC6B C7BāC8BāC9B C8BāC9BāC10B C8BāC9BāCl1B C10BāC9BāCl1B C11BāC10BāC9B C10BāC11BāC6B 1.740 1.360 1.400 1.461 1.323 1.367 1.375 1.360 1.447 1.398 1.398 1.373 1.374 1.374 1.384 1.737 1.360 1.402 1.450 1.319 1.371 1.376 1.363 1.457 1.395 1.399 1.378 1.379 1.384 1.383 (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (4) (4) (4) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (4) (4) (4) Cl1CāC9C N1CāC2C N1CāC5C N1CāC12C C2CāN3C C2CāN13C N3CāC4C C4CāC5C C5CāC6C C6CāC11C C6CāC7C C7CāC8C C8CāC9C C9CāC10C C10CāC11C Cl1DāC9D N1DāC2D N1DāC5D N1DāC12D C2DāN3D C2DāN13D N3DāC4D C4DāC5D C5DāC6D C6DāC11D C6DāC7D C7DāC8D C8DāC9D C9DāC10D C10DāC11D C2CāN1CāC5C C2CāN1CāC12C C5CāN1CāC12C N3CāC2CāN1C N3CāC2CāN13C N1CāC2CāN13C C2CāN3CāC4C C5CāC4CāN3C C4CāC5CāN1C C4CāC5CāC6C N1CāC5CāC6C C11CāC6CāC7C C11CāC6CāC5C C7CāC6CāC5C C8CāC7CāC6C C7CāC8CāC9C C8CāC9CāC10C C8CāC9CāCl1C C10CāC9CāCl1C C11CāC10CāC9C C10CāC11CāC6C C2DāN1DāC5D C2DāN1DāC12D C5DāN1DāC12D N3DāC2DāN1D N3DāC2DāN13D N1DāC2DāN13D C2DāN3DāC4D C5DāC4DāN3D C4DāC5DāN1D C4DāC5DāC6D N1DāC5DāC6D C11DāC6DāC7D C11DāC6DāC5D C7DāC6DāC5D C8DāC7DāC6D C7DāC8DāC9D C8DāC9DāC10D C8DāC9DāCl1D C10DāC9DāCl1D C11DāC10DāC9D C10DāC11DāC6D 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 740 356 404 455 316 366 382 358 454 396 407 375 375 388 380 738 359 402 454 317 365 376 360 457 397 401 373 380 384 380 (2) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (4) (3) (3) (2) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (3) (4)

View of the pseudocentrosymmetric dimer of molecules A and B with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 1

A and B display similar packing, forming endless chains with long HŅŅŅCl contacts, as shown in Table 2.

Experimental
The title compound was prepared according to the procedure of Babaev & Belykh (2001). A single crystal of (I) was obtained while attempting to perform alkylation of the title compound with ethyl bromide. In a single experiment, 0.2 g of 2 amino 1 methyl 5 (4 chlorophenyl)imidazole was re?uxed with excess EtBr in 10 ml MeCN for 3 h. After cooling the reaction mixture, the precipitated crystals were of the unchanged aminoimidazole. Crystal data
C10H10ClN3 Mr = 207.66 Triclinic, P1 Ú a = 10.552 (5) A Ú b = 12.833 (5) A Ú c = 15.432 (11) A = 95.53 (2) = 106.57 (2) = 97.02 (2) Ú V = 1969.0 (18) A3 Z=8 Dx = 1.401 Mg m 3 Mo K radiation Cell parameters from 25 re?ections = 16.0 17.0 " = 0.35 mm 1 T = 293 (2) K Prism, colourless 0.3 Ō 0.3 Ō 0.3 mm max = 27.0 h = 13 3 12 k = 16 3 16 l = 0 3 19 2 standard re?ections every 200 re?ections frequency: 120 min intensity decay: none w = 1/[' 2(Fo2) + (0.0575P)2 + 0.5308P] where P = (Fo2 + 2Fc2)/3 (Ņ/' )max = 0.047 Ú Ņ&max = 0.27 e A 3 Ú Ņ&min = 0.41 e A 3

Data collection
Enraf Nonius CAD-4 diffractometer 3 scans Absorption correction: none 8918 measured re?ections 8591 independent re?ections 5153 re?ections with I > 2' (I) Rint = 0.017

Re?nement
Re?nement on F 2 R[F 2 > 2' (F 2)] = 0.051 wR(F 2) = 0.133 S = 1.01 8591 re?ections 666 parameters All H-atom parameters re?ned

107.06 (19) 122.8 (2) 128.7 (2) 112.2 (2) 125.0 (2) 122.7 (2) 104.3 (2) 112.4 (2) 104.1 (2) 129.6 (2) 126.2 (2) 116.0 (2) 124.2 (2) 119.7 (2) 122.7 (2) 119.2 (2) 120.8 (2) 118.8 (2) 120.4 (2) 119.2 (3) 122.1 (2) 106.56 (19) 124.0 (2) 129.3 (2) 112.7 (2) 124.9 (2) 122.3 (2) 104.3 (2) 112.0 (2) 104.4 (2) 129.5 (2) 126.0 (2) 117.0 (2) 123.9 (2) 119.1 (2) 122.0 (2) 119.2 (2) 120.8 (2) 120.02 (19) 119.2 (2) 119.2 (2) 121.8 (2)

106.64 (19) 123.5 (2) 128.4 (2) 112.7 (2) 124.5 (2) 122.8 (2) 104.3 (2) 111.9 (2) 104.4 (2) 129.6 (2) 125.5 (2) 117.1 (2) 123.7 (2) 119.1 (2) 121.6 (2) 119.6 (2) 120.8 (2) 120.09 (19) 119.14 (19) 119.2 (2) 121.7 (2) 106.24 (19) 123.7 (2) 127.9 (2) 112.8 (2) 124.9 (2) 122.2 (2) 104.4 (2) 111.8 (2) 104.8 (2) 129.4 (2) 125.4 (2) 117.2 (2) 123.2 (2) 119.5 (2) 121.8 (2) 119.4 (2) 120.6 (2) 119.71 (19) 119.7 (2) 119.4 (2) 121.5 (2)

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Table 2
Ú Hydrogen bonding geometry (A, ).
DāHŅŅ ŅA N13 N13 N13 N13 N13 N13 N13 N13 CāH10CŅŅ ŅN3Ci DāH10DŅŅ ŅN3Dii AāH9AŅŅŅN3Biii BāH9BŅŅ ŅN3Aiv CāH9CŅŅ ŅCl1Ciii DāH9DŅŅŅCl1Diii AāH10AŅŅ ŅCl1Aiii BāH10BŅŅ ŅCl1Biv
xY 1

DāH 0.85 0.85 0.89 0.89 0.81 0.82 0.78 0.82 (3) (3) (3) (3) (4) (3) (3) (3)

HŅŅ ŅA 2.11 2.11 2.09 2.11 2.90 2.91 3.21 3.11
z; (ii) 1

DŅŅ ŅA 2.955 2.949 2.979 2.998 3.646 3.650 3.696 3.729
yY 2

DāHŅŅŅA 173 175 176 176 154 152 122 134 (3) (3) (2) (3) (3) (3) (3) (3)

(3) (3) (3) (3) (4) (4) (3) (3)
xY 2

(3) (3) (4) (3) (3) (3) (3) (3)

Symmetry codes: (i) 1 x 1Y yY z.

yY 1

z; (iii) 1 xY yY z; (iv)

All H atoms were re?ned isotropically; the C H distances were in Ú the range 0.78 (3) 1.04 (3) A. Data collection: CAD 4 Software (Enraf Nonius, 1989); cell re?nement: CAD 4 Software; data reduction: WinGX98 (Farrugia, 1998) and XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re?ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP 3 (Farrugia, 1998) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figure 2

Part of the structure showing the formation of endless chains involving N HŅŅ ŅCl hydrogen bonds. For the sake of clarity, H atoms not participating in the hydrogen bonding have been omitted, and no labels have been shown apart from those of the Cl atoms to differentiate the two chains formed by molecules C and D.

References
Allen, F. H. & Kennard, O. (1993). Chem. Des. Autom. News, 8, 1, 31 37. Babaev, E. V. & Belykh, E. N. (2001). Unpublished work. Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Enraf Nonius (1989). CAD-4 Software. Version 5.0. Enraf Nonius, Delft, The Netherlands. Farrugia, L. J. (1998). ORTEP-3 for Windows and WinGX98. University of Glasgow, Scotland. Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Ø Gottingen, Germany.

We acknowledge the support of the Russian Foundation for Basic Research in payment of the licence for using the Cambridge Structural Database (project No. 99-07-90133).

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