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organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

2-(4-Chlorophenacyloxy)-4-methyl-6,7,8,9tetrahydro-5H-cyclohepta[b]pyridine

Dmitry V. Albov,* 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

In the known reaction of N-phenacylation of 2-methoxypyridine, the O-phenacyl derivative was occasionally obtained. The title compound, C19H20ClNO2, was studied by 1H NMR and X-ray diffraction techniques.

Received 18 May 2004 Accepted 21 May 2004 Online 29 May 2004

Comment
In the course of our systematic study of the effect of size of cycloalkane fragments on the reactivity of pyridine-based heterocycles (Albov et al., 2004a), we have described earlier the crystal structure of 2-methoxy-4-methyl-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridine, (1) (Albov, Rybakov, Babaev, Fedyanin & Aslanov, 2004). In the reaction of (1) with 4-chlorophenacyl bromide we obtained 1-(4-chlorophenacyl)4-methyl-6,7,8,9-tetrahydro-5H-cyclohepta[b]pyridin-2(1H)one (Albov et al., 2004b). Our attempt to improve the yield in that reaction occasionally led us to the title compound, (2) (Fig. 1).

Key indicators Single-crystal X-ray study T = 293 K é Mean ' (CąC) = 0.003 A R factor = 0.050 wR factor = 0.144 Data-to-parameter ratio = 16.3 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

We can speculatively propose two reasons for this unusual substitution. First, self-condensation of phenacyl bromide releases HBr, which removes methyl as methyl bromide. The consequent treatment of the resultant pyridone with phenacyl bromide yields compound (2). Second, the phenacyl cation may perform electrophilic substitution of the methyl cation. In general, the structures of the bicyclic ring systems in (1) and (2) are very much alike. In both of them cycloheptene rings are in a chair conformation and bond lengths are closely similar. In (2), the torsion angle C20 C15 C14 O14 is 174.32 (19) , indicating conjugation in the benzoyl fragment.

Experimental
Compound (1) (1.70 g) and 4 chlorophenacyl bromide (1.95 g) were boiled in acetonitrile (15 ml) for 6 h. When thin layer chroma tography showed only traces of the starting materials in the solution, the solvent was evaporated and the product was washed with acetone
2

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

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Dmitry V. Albov et al.



C19H20ClNO

DOI: 10.1107/S1600536804012450

Acta Cryst. (2004). E60, o1098ąo1099


organic papers
(yield 1.79 g, 61%). The product was recrystallized from acetone (m.p. 465 467 K). 1H NMR (DMSO d6, 400 MHz, p.p.m.): 1.55 (m, 4H, 7 CH2 + 8 CH2), 1.80 (m, 2H, 9 CH2), 2.65 2.75 (m, 4H, 6 CH2 + 10 CH2), 2.25 (s, 3H, 12 CH3), 5.45 (s, 2H, 13 CH2), 6.45 (s, 1H, 3 CH), 7.49, 7.95 (dd, 4H, Ar). Crystal data
C19H20ClNO2 Mr = 329.81 Triclinic, P1 é a = 6.2691 (16) A é b = 9.2424 (10) A é c = 14.926 (3) A = 94.390 (10) = 98.02 (2) = 94.56 (2) é V = 850.3 (3) A3 Z=2 Dx = 1.288 Mg m 3 Cu K radiation Cell parameters from 25 re¯ections = 32 35 " = 2.06 mm 1 T = 293 (2) K Prism, colourless 0.25 á 0.23 á 0.21 mm max = 74.9 h= 737 k = 11 3 11 l = 0 3 18 1 standard re¯ection every 200 re¯ections intensity decay: 2%

Data collection
Enraf Nonius CAD-4 diffractometer Non-proŽled 3 scans Absorption correction: none 3409 measured re¯ections 3409 independent re¯ections 2390 re¯ections with I > 2' (I) Rint = 0.000

ReŽnement
ReŽnement on F 2 R[F 2 > 2' (F 2)] = 0.050 wR(F 2) = 0.144 S = 0.95 3409 re¯ections 209 parameters H-atom parameters constrained w = 1/[' 2(Fo2) + (0.1026P)2] where P = (Fo2 + 2Fc2)/3 (ā/' )max = 0.001 é ā&max = 0.16 e A 3 é ā&min = 0.15 e A 3

Figure 1

Table 1

ORTEP 3 view (Farrugia, 1997) of (2), with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

é Selected geometric parameters (A, ).
Cl1īC18 N1īC2 N1īC11 C2īO2 C2īC3 O2īC13 C3īC4 C4īC5 C4īC12 C5īC11 C5īC6 C6īC7 C7īC8 C2īN1īC11 N1īC2īO2 N1īC2īC3 O2īC2īC3 C2īO2īC13 C4īC3īC2 C3īC4īC5 C3īC4īC12 C5īC4īC12 C11īC5īC4 C11īC5īC6 C4īC5īC6 1.737 (2) 1.301 (2) 1.3671 (19) 1.362 (2) 1.389 (2) 1.425 (2) 1.350 (2) 1.406 (2) 1.520 (2) 1.3948 (19) 1.539 (2) 1.563 (2) 1.536 (2) 116.25 118.48 124.24 117.28 116.07 119.13 117.02 120.04 121.64 119.09 119.80 121.06 (14) (15) (16) (14) (13) (15) (15) (16) (16) (14) (13) (13) C8īC9 C9īC10 C10īC11 C13īC14 C14īO14 C14īC15 C15īC20 C15īC16 C16īC17 C17īC18 C18īC19 C19īC20 C5īC6īC7 C8īC7īC6 C9īC8īC7 C8īC9īC10 C11īC10īC9 N1īC11īC5 N1īC11īC10 C5īC11īC10 O2īC13īC14 O14īC14īC15 O14īC14īC13 C15īC14īC13 1.509 (2) 1.553 (2) 1.5094 (19) 1.512 (3) 1.222 (2) 1.494 (2) 1.376 (3) 1.395 (3) 1.379 (3) 1.357 (4) 1.397 (4) 1.385 (3) 113.56 115.37 116.06 114.70 115.80 120.78 115.02 123.12 112.46 121.64 121.29 117.06 (12) (14) (14) (14) (13) (13) (12) (13) (15) (17) (16) (15)

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 (Sheldrick, 1997); molecular graphics: ORTEP 3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (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 (project 02-07-90322).

References
Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004a). Crystallogr. Rep. 49. In the press. Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004b) Acta Cryst. E60, o894 o895. Albov, D. V., Rybakov, V. B., Babaev, E. V., Fedyanin, I. V. & Aslanov, L. A. (2004). Acta Cryst. E60, o892 o893. 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. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of õ Gottingen, Germany.

é All H atoms were positioned geometrically (C H 0.93 0.97 A) and reŽned as riding, with Uiso(H) 1.2 or 1.5 Ueq of the parent C atom.

Acta Cryst. (2004). E60, o1098ąo1099

Dmitry V. Albov et al.



C19H20ClNO

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