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organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

N-(4-Bromophenacyl)-4,6-dimethyl-2-oxo1,2-dihydropyridine-2-carbonitrile

Dmitry V. Albov,* Eugenia I. Turubanova, Victor B. Rybakov, Eugene V. Babaev and Leonid A. Aslanov
Department of Chemistry, Moscow State University, 119992 Moscow, Russian Federation Correspondence e-mail: albov@biocryst.phys.msu.su

The title compound, C16H13BrN2O2, was synthesized and characterized by 1H NMR and X-ray diffraction techniques.

Received 8 June 2004 Accepted 11 June 2004 Online 26 June 2004

Comment
We have described earlier the crystal structure of 4,6-dimethyl-2-oxo-1,2-dihydro-pyridin-3-carbonitrile, (1) (Rybakov et al., 2004). We report here the crystal structure of the product of its phenacylation, namely N-(4-bromophenacyl)4,6-dimethyl-2-oxo-1,2-dihydropyridine-2-carbonitrile, (2).

Key indicators Single-crystal X-ray study T = 293 K é Mean ' (CąC) = 0.004 A R factor = 0.039 wR factor = 0.107 Data-to-parameter ratio = 15.7 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

In the pyridine ring of (2), the single and double bonds alternate, though allowing some degree of conjugation. This é ring is planar to within 0.0128 (18) A (Fig. 1). Atoms attached to the pyridine moiety (O2, C31, C41 and C61) lie in its plane. The benzene ring is planar to within é 0.006 (2) A and atom Br1 lies in that plane. The torsion angle C14 C9 C8 O8 is 6.4 (5) and the dihedral angle between the benzene and pyridine rings is 85.59 (9) .

Experimental
Potassium hydroxide (5.6 g, 0.1 mol) and ethanol (100 ml) were placed in a ¯ask. Compound (1) (13.4 g, 0.1 mol) was added in small quantities with rotation of the ¯ask. This mixture was stirred for 20 min and the ethanol was evaporated. To the resulting solid, DMF (200 ml) and phenacyl bromide (0.1 mol) were added. The mixture was stirred for 2 h with heating (323 K), cooled and poured into cold water. The resulting precipitate was Žltered off and dried in air. To separate the mixture of two isomers [N isomer (2) and O isomer (2a)], the precipitate was placed on a Shott Žlter and washed several times with chloroform. Thus, we partly isolated isomer (2). The Žltrate contained both isomers and these were separated on a chro matographic column (eluant chloroform) (total yield 13.9 g, 42%; m.p. 498 499 K). 1H NMR (DMSO d6): 2.32 (s, 3 H, 6 CH3), 2.40 (s, 3H, 4 CH3), 5.62 (s, 2H, CH2), 6.32 (s, 1H, 5 CH), 7.35 7.37, 8.19 8.21 (dd, 4H, Ar). Crystal data
C16H13BrN2O2 Mr = 345.19 Monoclinic, P21 ac é a = 9.5667 (16) A é b = 7.3784 (12) A é c = 20.850 (4) A = 95.34 (1) é V = 1465.4 (4) A3 Z=4 Dx = 1.565 Mg m 3 Cu K radiation Cell parameters from 25 re¯ections = 33 35 " = 3.88 mm 1 T = 293 (2) K Prism, orange 0.15 á 0.15 á 0.15 mm DOI: 10.1107/S1600536804014175 Acta Cryst. (2004). E60, o1222ąo1223

# 2004 International Union of Crystallography Printed in Great Britain ą all rights reserved

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C16H13BrN2O2


organic papers
Data collection
Enraf Nonius CAD-4 diffractometer Non-proŽled 3/2 scans Absorption correction: none 3007 measured re¯ections 3007 independent re¯ections 2444 re¯ections with I > 2' (I) max = 74.9 h = 11 3 11 k=039 l = 0 3 26 1 standard re¯ection every 200 re¯ections intensity decay: 1% w = 1/[' 2(Fo2) + (0.0542P)2 + 0.9586P] where P = (Fo2 + 2Fc2)/3 (ā/' )max = 0.001 é ā&max = 0.34 e A 3 é ā&min = 0.39 e A 3 Extinction correction: none

ReŽnement
ReŽnement on F 2 R[F 2 > 2' (F 2)] = 0.039 wR(F 2) = 0.107 S = 1.03 3007 re¯ections 192 parameters H-atom parameters constrained

Table 1

é Selected geometric parameters (A, ).
Br1īC12 N1īC6 N1īC2 N1īC7 C2īO2 C2īC3 C3īC4 C3īC31 C31īN31 C4īC5 C4īC41 C6īN1īC2 C6īN1īC7 C2īN1īC7 O2īC2īN1 O2īC2īC3 N1īC2īC3 C4īC3īC31 C4īC3īC2 C31īC3īC2 N31īC31īC3 C3īC4īC5 C3īC4īC41 C5īC4īC41 C6īC5īC4 C5īC6īN1 C5īC6īC61 1.896 1.376 1.394 1.460 1.232 1.451 1.372 1.436 1.142 1.397 1.507 123.0 120.4 116.2 121.2 123.7 115.1 121.1 122.1 116.8 177.3 118.7 122.2 119.1 121.2 119.9 120.6 (3) (3) (3) (3) (3) (3) (4) (4) (4) (4) (4) (2) (2) (2) (2) (3) (2) (2) (2) (2) (3) (2) (3) (3) (3) (3) (3) C5īC6 C6īC61 C7īC8 C8īO8 C8īC9 C9īC14 C9īC10 C10īC11 C11īC12 C12īC13 C13īC14 N1īC6īC61 N1īC7īC8 O8īC8īC9 O8īC8īC7 C9īC8īC7 C14īC9īC10 C14īC9īC8 C10īC9īC8 C11īC10īC9 C12īC11īC10 C11īC12īC13 C11īC12īBr1 C13īC12īBr1 C14īC13īC12 C13īC14īC9 1.362 1.493 1.526 1.209 1.485 1.388 1.391 1.390 1.374 1.384 1.376 119.4 109.6 121.0 119.8 119.1 119.3 118.1 122.6 120.1 119.3 121.3 120.0 118.7 119.2 120.8 (4) (4) (4) (3) (4) (4) (4) (4) (4) (4) (4) (2) (2) (2) (2) (2) (3) (2) (2) (3) (3) (3) (2) (2) (3) (3)

Figure 1

ORTEP 3 (Farrugia, 1997) plot of the title molecule and the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

(Sheldrick, 1997); molecular graphics: ORTEP 3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

The authors are indebted to the Russian Foundation for Basic Research for covering the licence fee for use of the Cambridge Structural Database (Allen, 2002) (project No. 0207-90322).

H atoms bonded to C atoms were included in calculated positions and reŽned as riding atoms. Calculated C H bond lengths are in the é range 0.93 0.99 A. For methyl H atoms, Uiso values were set equal to 1.5Ueq of the carrier atoms; for other H atoms, Uiso values were set at 1.2Ueq of the carrier atoms. Data collection: CAD 4 EXPRESS (Enraf Nonius, 1994); cell reŽnement: CAD 4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to reŽne structure: SHELXL97

References
Allen, F. H. (2002). Acta Cryst. B58, 380 388. Enraf Nonius (1994). CAD-4 EXPRESS. Version 5.0. Enraf Nonius, Delft, The Netherlands. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837 838. Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Rybakov, V. B., Bush, A. A., Babaev, E. V. & Aslanov, L. A. (2004). Acta Cryst. E60, 160 o161. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of õ Gottingen, Germany.

Acta Cryst. (2004). E60, o1222ąo1223

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C16H13BrN2O2

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