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organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

1-(4-Chlorophenacyl)-4-methyl-5,6,7,8,9,10hexahydrocycloocta[b]pyridin-2(1H)-one

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 pyridone ring of the title compound, C20H22ClNO2, single and double bonds alternate, though allowing some degree of delocalization. Two C atoms in the cyclooctene ring are disordered, indicating some ¯exibility of the large ring.

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

Comment
In the course of our systematic study of the size effect of cycloalkane fragments on the reactivity of pyridine-based heterocycles, we have previously described the crystal structure of 4-methyl-5,6,7,8,9,10-hexahydrocycloocta[b]pyridin2(1H)-one, (1), (Albov, Mazina et al., 2004). Following our investigations of cycloheptene derivatives (Albov, Rybakov, Babaev, Fedyanin & Aslanov, 2004; Albov, Rybakov, Babaev & Aslanov, 2004), we have now synthesized the title compound, (3) (Fig. 1).

Key indicators Single-crystal X-ray study T = 293 K é Mean ' (CąC) = 0.003 A Disorder in main residue R factor = 0.050 wR factor = 0.137 Data-to-parameter ratio = 17.4 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

In the pyridone ring of (3), the single and double bonds alternate (Table 1), though allowing some degree of delocalization. Atoms C8 and C9 of the cyclooctene ring are disordered over two sites each, forming two conformations with occupancies of 0.719 (7) and 0.281 (7), respectively. The torsion angle C21 C16 C15 O15 is 25.6 (3) , the same as in a related cycloheptene derivative (Albov, Rybakov, Babaev & Aslanov, 2004). The dihedral angle between the benzene and pyridone rings is 57.96 (8) .

Experimental
For the preparation of 2 methoxy 4 methyl 5,6,7,8,9,10 hexahydro cycloocta[b]pyridine, (2), compound (1) (8.30 g), methyl iodide (7.78 g) and silver carbonate (6.00 g) were boiled in 70 ml of benzene for 50 h. The reaction ¯ask was protected against light. The mixture was then Žltered and the solvent was evaporated (yield 5.04 g, 57%). The product was recrystallized from chloroform (m.p. 313 314 K).1H NMR (DMSO d6, 400 MHz, p.p.m.): 1.33 (m, 2H, 8 CH2), 1.41 (m, 2H, 9 CH2), 1.60 (m, 2H, 7 CH2), 1.70 (m, 2H, 6 CH2), 2.25 (s, 3H, 13 CH3), 2.71 (t, 2H, 6 CH2), 2.80 (t, 2H, 11 CH2), 3.60 (s, 3H, O CH3), 6.31 (s, 1H, 3 CH). Atoms are numbered as in the title compound (Fig. 1).
DOI: 10.1107/S1600536804014163 Dmitry V. Albov et al.


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

Acta Cryst. (2004). E60, o1219ąo1221

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organic papers
ReŽnement
ReŽnement on F 2 R[F 2 > 2' (F 2)] = 0.050 wR(F 2) = 0.137 S = 1.05 4125 re¯ections 237 parameters H-atom parameters constrained w = 1/[' 2(Fo2) + (0.0608P)2 + 0.1283P] where P = (Fo2 + 2Fc2)/3 (ā/' )max = 0.001 é ā&max = 0.29 e A 3 é ā&min = 0.42 e A 3

Table 1

é Selected geometric parameters (A, ).
Cl1īC19 N1īC12 N1īC2 N1īC14 C2īO2 C2īC3 C3īC4 C4īC5 C4īC13 C5īC12 C5īC6 C6īC7 C7īC8B C7īC8A C8AīC9A C12īN1īC2 C12īN1īC14 C2īN1īC14 O2īC2īN1 O2īC2īC3 N1īC2īC3 C4īC3īC2 C3īC4īC5 C3īC4īC13 C5īC4īC13 C12īC5īC4 C4īC5īC6 C5īC6īC7 C8BīC7īC6 C6īC7īC8A 1.737 1.392 1.396 1.462 1.242 1.418 1.352 1.425 1.509 1.368 1.514 1.532 1.403 1.560 1.536 (2) (2) (3) (2) (2) (3) (3) (3) (3) (3) (3) (4) (15) (6) (8) C9AīC10 C8BīC9B C9BīC10 C10īC11 C11īC12 C14īC15 C15īO15 C15īC16 C16īC21 C16īC17 C17īC18 C18īC19 C19īC20 C20īC21 C9AīC8AīC7 C10īC9AīC8A C7īC8BīC9B C8BīC9BīC10 C9AīC10īC11 C11īC10īC9B C12īC11īC10 C5īC12īN1 C5īC12īC11 N1īC12īC11 N1īC14īC15 O15īC15īC16 O15īC15īC14 C16īC15īC14 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 510 (4) 48 (2) 641 (10) 527 (3) 507 (3) 508 (3) 217 (2) 490 (3) 386 (2) 386 (2) 383 (2) 379 (3) 376 (2) 380 (2)

Figure 1

ORTEP 3 view (Farrugia, 1997) of (3), with the atom numbering scheme. Atomic displacement ellipsoids are drawn at the 50% probability level. Only the major components of disordered atoms C8 and C9, namely C8A and C9A, are shown.

For the preparation of 1 (4 chlorophenacyl) 4 methyl 5,6,7,8,9,10 hexahydrocycloocta[b]pyridin 2(1H) one, (3), compound (2) (5.00 g) and 4 chlorophenacyl bromide (5.70 g) were boiled in acetonitrile for 6 h. When thin layer chromatography showed only traces of source compounds in the solution, the solvent was evaporated and the product was washed with acetone (yield 3.54 g, 42%). The product was recrystallized from acetone (m.p. 453 455 K).1H NMR (DMSO d6, 400 MHz, p.p.m.): 1.45 (m, 4H, 8 CH2 + 9 CH2), 1.62 (m, 4H, 7 CH2 + 10 CH2), 1.70 (m, 2H, 6 CH2), 2.20 (s, 3H, 13 CH3), 2.63 (t, 2H, 6 CH2), 2.70 (t, 2H, 11 CH2), 5.45 (s, 2H, 14 CH2), 6.13 (s, 1H, 3 CH), 7.53, 8.08 (dd, 4H, Ar). Atom numbering as in Fig. 1. Crystal data
C20H22ClNO2 Mr = 343.84 Triclinic, P1 é a = 8.239 (3) A é b = 9.115 (3) A é c = 12.42 (1) A = 111.20 (4) = 93.80 (4) = 96.76 (3) é V = 857.6 (9) A Z=2 Dx = 1.332 Mg m 3 Mo K radiation Cell parameters from 25 re¯ections = 13 15 " = 0.24 mm 1 T = 293 (2) K Prism, colourless 0.22 á 0.20 á 0.18 mm max = 28.0 h = 10 3 10 k = 12 3 11 l = 0 3 16 1 standard re¯ection every 200 re¯ections intensity decay: 3%

122.83 (16) 122.10 (16) 114.93 (16) 119.92 (19) 124.9 (2) 115.15 (18) 123.5 (2) 119.16 (18) 119.9 (2) 120.9 (2) 119.43 (18) 119.96 (18) 113.53 (18) 111.3 (5) 115.6 (2)

113.6 (4) 114.3 (3) 118.7 (10) 111.3 (8) 117.0 (2) 111.8 (3) 117.23 (18) 119.85 (17) 122.01 (18) 118.14 (16) 112.31 (15) 121.25 (16) 120.99 (16) 117.76 (15)

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

3

Data collection
Enraf Nonius CAD-4 diffractometer Non-proŽled 3 scans Absorption correction: none 4125 measured re¯ections 4125 independent re¯ections 2645 re¯ections with I > 2' (I)

References
Albov, D. V., Mazina, O. S., Rybakov, V. B., Babaev, E. V., Chernyshev, V. V. & Aslanov, L. A. (2004). Crystallogr. Rep. 49, 158 168. Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004). 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. Allen, F. H. (2002). Acta Cryst. B58, 380 388. Acta Cryst. (2004). E60, o1219ąo1221

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organic papers
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.

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