Äîęķėåíō âį˙ō čį ęũøā īîčņęîâîé ėāøčíû. Āäđåņ îđčãčíāëüíîãî äîęķėåíōā : http://www.chem.msu.ru/eng/misc/babaev/papers/093e.pdf Äāōā čįėåíåíč˙: Thu Jan 20 21:49:06 2011 Äāōā číäåęņčđîâāíč˙: Sat Feb 12 03:11:38 2011 Ęîäčđîâęā:

organic papers
Acta Crystallographica Section E

Structure Reports Online
ISSN 1600-5368

2-(4-Chlorophenyl)-5-methyl-7,8,9,10tetrahydro-6H-cyclohepta[e][1,3]oxazolo[3,2-a]pyridin-11-ium perchlorate
The title compound, C19H19ClNO+āClO4ū, was synthesized and characterized by 1H NMR and X-ray diffraction techniques.
Received 15 April 2004 Accepted 21 May 2004 Online 29 May 2004

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: lbov@biocryst.phys.msu.su

Comment
In the course of systematic investigations of the effect of the size of cycloalkane fragments on the reactivity of the corresponding heterocycles based on pyridine, we have previously described the crystal structure of 1-(4-chlorophenacyl)-4methyl-1,5,6,7,8,9-hexahydro-2H-cyclohepta[b]pyridin-2-one, (1) (Albov et al., 2004a). Following a corresponding 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) = 0.002 A R factor = 0.042 wR factor = 0.107 Data-to-parameter ratio = 15.9 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) shows its aromaticity. The nineé membered bicyclic system is planar to within 0.0216 (9) A: atoms C10, C11, C15 and C16 lie in the same plane, while atoms C12, C13 and C14 are displaced from that plane by é 1.421 (3), 1.507 (3) and 1.322 (2) A, respectively. The cycloheptene ring has a chair conformation. The benzene ring is é planar to within 0.0033 (9) A, with atoms Cl1 and C3 in the same plane. The dihedral angle between the oxazolopyridinium and benzene fragments is 3.77 (7) , indicating that there is considerable conjugation between these aromatic fragments. All these results will be compared with the crystal structures of Žve- and eight-membered cycloalkane derivatives which are in progress, as well as with published (Albov et al., 2004b) sixmembered cycloalkane derivatives.

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

For the preparation of (2), 1.80 g of (1) was dissolved in 15 ml of sulfuric acid and kept overnight. The solution was then poured into 100 ml of a 3% aqueous solution of perchloric acid. A white preci
DOI: 10.1107/S1600536804012462 Acta Cryst. (2004). E60, o1096ąo1097

o1096

Dmitry V. Albov et al.



C19H19ClNO+āClO4


organic papers
pitate formed and the mixture was kept overnight again for complete precipitation. The product was Žltered off and washed with water and acetone (yield 2.15 g, 96%). It was recrystallized from acetonitrile (m.p. 573 K with explosion). 1H NMR (DMSO d6, 400 MHz, p.p.m.): 1.70 (m, 2H, 13 CH2), 1.83 (m, 2H, 12 CH2), 1.99 (m, 2H, 14 CH2), 2.67 (s, 3H, 10 CH3), 3.05 (t, 2H, 11 CH2), 3.44 (t, 2H, 15 CH2), 7.65, 8.00 (dd, 4H, Ar), 8.08 (s, 1H, 6 CH), 9.58 (s, 1H, 2 CH). Crystal data
C19H19ClNO+āClO4 Mr = 412.25 Monoclinic, P21 ac é a = 7.894 (3) A é b = 18.492 (3) A é c = 13.271 (2) A = 101.46 (2) é V = 1898.6 (8) A3 Z=4 Dx = 1.442 Mg m 3 Cu K radiation Cell parameters from 25 re¯ections = 33 35 " = 3.35 mm 1 T = 293 (2) K Prism, colourless 0.20 á 0.20 á 0.20 mm max = 75.0 h= 939 k = 0 3 23 l = 0 3 16 1 standard re¯ection every 200 re¯ections intensity decay: 4%

Data collection
Enraf Nonius CAD-4 diffractometer Non proŽled 3 scans Absorption correction: none 4010 measured re¯ections 3901 independent re¯ections 3310 re¯ections with I > 2' (I) Rint = 0.004

Figure 1

ORTEP 3 (Farrugia, 1997) plot of the molecule and atom numbering scheme of compound (2). Displacement ellipsoids are drawn at the 50% probability level.

ReŽnement
ReŽnement on F 2 R[F 2 > 2' (F 2)] = 0.042 wR(F 2) = 0.107 S = 0.98 3901 re¯ections 246 parameters H-atom parameters constrained w = 1/[' 2(Fo2) + (0.0892P)2] where P = (Fo2 + 2Fc2)/3 (ā/' )max = 0.001 é ā&max = 0.19 e A 3 é ā&min = 0.21 e A 3

H atoms were included in calculated positions (C H 0.93 é 1.5 (methyl H) or 0.97 A) and reŽned as riding, with Uiso 1.2Ueq(carrier 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 (Farrugia, 1999).
(2) (2) (2) (3) (3) (3) (2) (2) (2) (2) (2) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1)

Table 1

é Selected geometric parameters (A, ).
Cl1īC19 O4īC5 O4īC3 N1īC5 N1īC9 N1īC2 C2īC3 C3īC16 C5īC6 C6īC7 C7īC8 C7īC10 C5īO4īC3 C5īN1īC9 C5īN1īC2 C9īN1īC2 C3īC2īN1 C2īC3īO4 C2īC3īC16 O4īC3īC16 O4īC5īN1 O4īC5īC6 N1īC5īC6 1.729 1.337 1.394 1.342 1.384 1.402 1.345 1.455 1.382 1.369 1.427 1.517 106.7 122.0 107.4 130.6 106.8 108.8 133.7 117.5 110.3 127.3 122.4 (1) (1) (1) (1) (1) (1) (2) (2) (2) (2) (2) (2) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) (1) C8īC9 C8īC11 C9īC15 C11īC12 C12īC13 C13īC14 C14īC15 Cl2īO21 Cl2īO22 Cl2īO23 Cl2īO24 C7īC6īC5 C6īC7īC8 C6īC7īC10 C8īC7īC10 C9īC8īC7 C9īC8īC11 C7īC8īC11 C8īC9īN1 C8īC9īC15 N1īC9īC15 C8īC11īC12 1.367 1.516 1.476 1.528 1.510 1.501 1.529 1.364 1.372 1.400 1.417 117.4 120.0 119.2 120.9 121.1 117.6 121.3 117.1 124.5 118.4 112.6

The authors are indebted to the Russian Foundation for Basic Research for covering the licence fee for use of the Cambridge Structural Database (project No. 02-07-90322).

References
Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004a). Acta Cryst. E60, o894 o895. Albov, D. V., Rybakov, V. B., Babaev, E. V. & Aslanov, L. A. (2004b). Crystallogr. Rep. 49. In the press. 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.

Acta Cryst. (2004). E60, o1096ąo1097

Dmitry V. Albov et al.



C19H19ClNO+āClO4

o1097