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organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

2-(4-Chlorophenyl)-5-methyl-6,7,8,9,10,11hexahydrocycloocta[e][1,3]oxazolo[3,2-a]pyridin-12-ium perchlorate
The title compound, C20H21ClNO+āClO4ū, was synthesized and characterized by 1H NMR and X-ray diffraction techniques.

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

Received 9 June 2004 Accepted 14 June 2004 Online 9 July 2004

Comment
In the course of systematic investigations of the size effect of cycloalkane fragments on the reactivity of the corresponding heterocycles based on pyridine, we have previously described the crystal structure of 1-(4-chlorophenacyl)-4-methyl5,6,7,8,9,10-hexahydrocycloocta[b]pyridin-2(1H)-one, (1) (Albov et al., 2004a). Following a study with cyclohexene derivatives (Albov et al., 2004b), we synthesized the title compound, (2).

Key indicators Single-crystal X-ray study T = 293 K é Mean ' (CąC) = 0.004 A R factor = 0.045 wR factor = 0.124 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.

An analysis of bond lengths in the oxazolopyridinium ring system of (2) (Fig. 1 and Table 1) reveals that the pyridinium fragment is certainly aromatic while the N1/C5 chain shows weaker delocalization. The positive charge is located on the N1 atom. The nine-membered bicyclic system is planar to é within 0.0218 (19) A, with atoms C11, C16 and C17 lying in the same plane; atom C10 is displaced from this plane by é 0.125 (4) A. The dihedral angle between the oxazolopyridinium and benzene fragments is 5.33 (15) , indicating that there is considerable conjugation between these aromatic fragments. All these results will be compared with the crystal structures of Žve-membered cycloalcane derivatives currently in progress, as well as with published (Albov et al., 2004b,c) sixand seven-membered cycloalkane derivatives.

Experimental
Compound (1) (2.64 g) was dissolved in 20 ml of sulfuric acid and allowed to stand overnight. The solution then was poured into 100 ml of 3% aqueous solution of perchloric acid. A white precipitate formed and the mixture was kept overnight again for complete
DOI: 10.1107/S1600536804014345 Dmitry V. Albov et al.


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

Acta Cryst. (2004). E60, o1301ąo1302

C20H21ClNO+āClO4-

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organic papers
precipitation. The product was Žltered off and washed with water and acetone (yield 3.20 g, 98%). It was recrystallized from acetonitrile (m.p. 584 K with explosion). 1H NMR (DMSO d6, 400 MHz, p.p.m.): 1.64 (m, 4H, 13 CH2 + 14 CH2), 1.79 (m, 2H, 12 CH2), 1.97 (m, 2H, 15 CH2), 2.64 (s, 3H, 10 CH3), 3.01 (t, 2H, 11 CH2), 3.41 (t, 2H, 16 CH2), 7.69, 7.95 (dd, 4H, Ar), 8.11 (s, 1H, 6 CH), 9.52 (s, 1H, 2 CH). Crystal data
C20H21ClNO+āClO4 Mr = 426.28 Monoclinic, P21 ac é a = 7.8301 (9) A é b = 18.6827 (19) A é c = 13.8840 (14) A = 103.013 (9) é V = 1978.9 (4) A3 Z=4 Dx = 1.431 Mg m 3 Cu K radiation Cell parameters from 25 re¯ections = 30 34 " = 3.23 mm 1 T = 293 (2) K Prism, colourless 0.26 á 0.24 á 0.21 mm max = 74.9 h= 939 k = 0 3 23 l = 0 3 17 1 standard re¯ection frequency: 60 min intensity decay: 2% H-atom parameters constrained w = 1/[' 2(Fo2) + (0.0584P)2], where P = (Fo2 + 2Fc2)/3 (ā/' )max < 0.001 é ā&max = 0.20 e A 3 é ā&min = 0.16 e A 3

Data collection
Enraf Nonius CAD-4 diffractometer Non-proŽled 3/2 scans Absorption correction: none 3977 measured re¯ections 3977 independent re¯ections 2581 re¯ections with I > 2' (I)

ReŽnement
ReŽnement on F 2 R[F 2 > 2' (F 2)] = 0.045 wR(F 2) = 0.124 S = 0.93 3977 re¯ections 254 parameters

Figure 1

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

Table 1

é Selected geometric parameters (A, ).
Cl1īC20 N1īC5 N1īC9 N1īC2 C2īC3 C3īO4 C3īC17 O4īC5 C5īC6 C6īC7 C7īC8 C7īC10 C8īC9 C8īC11 C9īC16 C5īN1īC9 C5īN1īC2 C9īN1īC2 C3īC2īN1 C2īC3īO4 C2īC3īC17 O4īC3īC17 C5īO4īC3 C6īC5īN1 C6īC5īO4 N1īC5īO4 C5īC6īC7 C6īC7īC8 C6īC7īC10 C8īC7īC10 C9īC8īC7 C9īC8īC11 C7īC8īC11 1.740 1.358 1.392 1.413 1.323 1.383 1.453 1.360 1.354 1.397 1.397 1.493 1.363 1.517 1.482 (3) (3) (3) (3) (3) (3) (3) (3) (3) (4) (4) (3) (4) (4) (4) C11īC12 C12īC13 C13īC14 C14īC15 C15īC16 C17īC18 C17īC22 C18īC19 C19īC20 C20īC21 C21īC22 Cl2īO23 Cl2īO21 Cl2īO22 Cl2īO24 C8īC9īN1 C8īC9īC16 N1īC9īC16 C8īC11īC12 C13īC12īC1 C14īC13īC1 C13īC14īC1 C16īC15īC1 C9īC16īC15 C18īC17īC3 C22īC17īC3 O23īCl2īO2 O23īCl2īO2 O21īCl2īO2 O23īCl2īO2 O21īCl2īO2 O22īCl2īO2 1.529 1.503 1.439 1.560 1.493 1.378 1.392 1.377 1.384 1.377 1.378 1.344 1.394 1.409 1.412 116.6 127.4 116.0 112.6 115.5 115.8 118.7 114.9 114.7 121.6 119.7 105.0 110.1 108.3 108.2 109.9 115.0 (4) (4) (5) (5) (4) (3) (3) (4) (4) (4) (4) (3) (3) (3) (3)

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

121.2 (2) 106.75 (19) 132.0 (2) 107.2 (2) 110.2 (2) 132.2 (2) 117.5 (2) 106.34 (18) 122.7 (2) 127.8 (2) 109.50 (19) 117.8 (3) 119.1 (2) 117.5 (3) 123.4 (3) 122.6 (3) 117.7 (3) 119.7 (2)

1 2 5 4

1 2 2 4 4 4

(2) (3) (2) (2) (3) (3) (3) (3) (3) (2) (2) (2) (3) (2) (2) (2) (2)

The authors are indebted to the Russian Foundation for Basic Research for covering the licence fee (project 02-0790322) for use of the Cambridge Structural Database (Allen, 2002).

References
Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004a). Acta Cryst. E60, o1219 o1221. Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004b). Crystallogr. Rep. 49. In the press. Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004c) Acta Cryst. E60, o1096 o1097. 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. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of õ Gottingen, Germany.

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Dmitry V. Albov et al.



C20H21ClNO+āClO4-

Acta Cryst. (2004). E60, o1301ąo1302