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Crystallography Reports, Vol. 48, No. 2, 2003, pp. 280­282. Translated from Kristallografiya, Vol. 48, No. 2, 2003, pp. 315­317. Original Russian Text Copyright © 2003 by Al'bov, Rybakov, Babaev, Aslanov.

STRUCTURE OF ORGANIC COMPOUNDS

X-ray Mapping in Heterocyclic Design: X. X-ray Diffraction Study of 4-Methyl-6,7,8,9-Tetrahydro-2-Quinolone
D. V. Albov, V. B. Rybakov, E. V. Babaev, and L. A. Aslanov
Faculty of Chemistry, Moscow State University, Vorob'evy gory, Moscow, 119899 Russia e-mail: albov@biocryst.phys.msu.su
Received November 18, 2002

Abstract--The structure of 4-methyl-6,7,8,9-tetrahydro-2-quinolone is studied by the single-crystal X-ray diffraction technique (a = 6.6890(17) å, b = 7.926(2) å, c = 8.993(3) å, = 85.50(2)°, = 68.22(2)°, = 82.89(2)°, Z = 2, and space group P 1 ). The structure is solved by direct methods and refined to R1 = 0.0592 and wR2 = 0.1206. In the crystal, intermolecular hydrogen bonds link molecules into centrosymmetric dimers. © 2003 MAIK "Nauka / Interperiodica".

INTRODUCTION This work continues our structural investigations of the heterocyclic compounds that are able to undergo various rearrangements, in particular, cyclization reactions [1­10]. As in our previous papers, we step-by-step perform the X-ray diffraction studies of all the intermediates and final products of multistage cyclization reactions and rearrangements. Substituted pyridones are interesting objects for these investigations, because they are characterized by a high reactivity. In this study, we determined the structure of 4-methyl-6,7,8,9-tetrahydro-2-quinolone. At present, data on its molecular and crystal structures are not available in the Cambridge Structural Database (Version 04.02) [11]. EXPERIMENTAL 4-Methyl-6,7,8,9-tetrahydro-2-quinolone (I) was synthesized according to the procedure described in [12]:
CH3 O + O
1H

graphite monochromator, scan mode) at room temperature. The unit cell parameters were determined and refined using 25 reflections in the range 13°­15°. Selected experimental parameters and crystal data are included in Table 1. Since the crystals of the compound studied are small in size and have small linear absorption coefficients, the data were not corrected for absorption. The primary
Table 1. Crystal data and details of the X-ray diffraction experiment and refinement of structure I Compound Molecular weight Crystal system Space group a, å b, å c, å , deg , deg , deg V, å3 Z calcd, g/cm3 µ(MoK), cm­1 Crystal size, mm max, deg Number of reflections with I 2(I)/number of parameters R1/wR2 max/min, e/å3 C10H13NO 163.21 Triclinic P1 6.6890(17) 7.926(2) 8.993(3) 85.50(2) 68.22(2) 82.89(2) 439.1(2) 2 1.235 0.080 0.30 â 0.30 â 0.30 26 1618/162 0.0592/0.1206 0.203/­ 0.141

CH3

H2N

O I

N H

O

NMR spectrum was recorded on a Bruker The AM-360 spectrometer (field strength, 8.46 T; operating frequency, 360.14 MHz for protons; DMSO-d6; internal standard, TMS). Based on the available data, the NMR signals were assigned as follows (, ppm): 11.50 (s) H(1); 5.90 (s) H(3); 2.48 (t) H(9A), H(9B); 2.34 (t) H(6A), H(6B); 2.03 (s) H(1A), H(1B), H(1C); 1.72 (m) H(7A), H (7B), H(8A), H(8B). The intensities of diffraction reflections were measured on a CAD4 diffractometer [13] (MoK radiation,

1063-7745/03/4802-0280$24.00 © 2003 MAIK "Nauka / Interperiodica"


X-RAY MAPPING IN HETEROCYCLIC DESIGN Table 2. Bond lengths d (å) for non-hydrogen atoms in structure I Bond N(1)­C(2) N(1)­C(10) C(2)­O(2) C(2)­C(3) C(3)­C(4) C(4)­C(5) C(4)­C(11) C(5)­C(10) C(5)­C(6) C(6)­C(7) C(7)­C(8) C(8)­C(9) C(9)­C(10) d 1.3541(16) 1.3830(18) 1.2578(17) 1.4107(18) 1.374(2) 1.4172(18) 1.5122(18) 1.3541(17) 1.514(2) 1.503(2) 1.451(2) 1.509(2) 1.4754(18)

281

Table 3. Bond angles (deg) for non-hydrogen atoms in structure I Angle C(2)­N(1)­C(10) O(2)­C(2)­N(1) O(2)­C(2)­C(3) N(1)­C(2)­C(3) C(4)­C(3)­C(2) C(3)­C(4)­C(5) C(3)­C(4)­C(11) C(5)­C(4)­C(11) C(10)­C(5)­C(4) C(10)­C(5)­C(6) C(4)­C(5)­C(6) C(7)­C(6)­C(5) C(8)­C(7)­C(6) C(7)­C(8)­C(9) C(10)­C(9)­C(8) C(5)­C(10)­N(1) C(5)­C(10)­C(9) N(1)­C(10)­C(9) 125.10(10) 120.04(11) 124.34(12) 115.61(13) 121.00(12) 120.58(11) 118.99(12) 120.43(13) 118.52(13) 119.81(11) 121.65(11) 113.50(12) 114.38(16) 112.60(13) 111.96(12) 119.14(11) 125.08(13) 115.78(11)

Table 4. Parameters of interatomic contacts in structure I D­H N(1)­H(1) C(7)­H(7A) C(8)­H(8B) C(11)­H(11C) d(D­H) 0.82(1) 1.07(2) 0.99(2) 0.89(2) d(D···A) 2.772(1) 3.515(2) 3.536(2) 3.547(2) d(H···A) 1.96(1) 2.66(2) 2.58(2) 2.81(2) DHA 174(1) 137(1) 163(1) 141(2) A O(2) O(2) O(2) O(2) Symmetry operation (2­x; 1­y; 1­z) (1­x; 1­y; 1­z) (x; y; z­1) (x­1; y; z)

Note: D is a donor, A is an acceptor, and H is a hydrogen atom; the d distances and angles are given in angstroms and degrees, respectively.

processing of the experimental data was performed with the WinGX98 program package [14], and all further calculations were performed with the SHELX97 program package [15]. The crystal structure was solved by direct methods. The positional and thermal parameters were refined in the anisotropic approximation for all the non-hydrogen atoms. The hydrogen atoms were located from the difference Fourier synthesis and refined in the isotropic approximation. The interatomic distances and bond angles are listed in Tables 2 and 3, respectively. The parameters of the interatomic contacts involving the hydrogen atoms are given in Table 4. The crystal data for compound I are deposited in the Cambridge Structural Database (deposit no. 198666). The molecular structure of I and the atomic numbering are shown in the figure, which was drawn with the use of the PLUTON96 program [16].
CRYSTALLOGRAPHY REPORTS Vol. 48 No. 2 2003

RESULTS AND DISCUSSION In molecule I, the N(1)C(2)C(3)C(4)C(5)C(10) sixmembered ring is planar within 0.014 å. The O(2), C(6), C(9), and C(11) atoms lie in the plane of this ring. The C(7) and C(8) atoms deviate from this plane by -0.236 and 0.425 å, respectively. In crystal I, intermolecular hydrogen bonds link molecules into centrosymmetric dimers (figure, Table 4). In the Cambridge Structural Database (Version 04.02) [11], we found a compound with a similar structure, namely, 7,8-dihydro-7methyl-2,5(1H,6H)-quinoline-2,5-dione (II) [17]
O

H3C II

N H

O


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AL'BOV et al.

C(11) C(6) C(7) C(8) C(4) C(5)

In the coming months, we are going to study the reactivity of compound I and to perform X-ray structure analysis of the products obtained. ACKNOWLEDGMENTS We acknowledge the support of the Russian Foundation for Basic Research in the payment of the license for using the Cambridge Structural Database, project no. 99-07-90133. REFERENCES
1. V. B. Rybakov, S. G. Zhukov, E. V. Babaev, et al., Kristallografiya 44 (6), 1067 (1999) [Crystallogr. Rep. 44, 997 (1999)]. 2. V. B. Rybakov, S. G. Zhukov, E. V. Babaev, et al., Kristallografiya 45 (1), 108 (2000) [Crystallogr. Rep. 45, 103 (2000)]. 3. V. B. Rybakov, S. G. Zhukov, E. V. Babaev, et al., Kristallografiya 45 (2), 292 (2000) [Crystallogr. Rep. 45, 261 (2000)]. 4. V. B. Rybakov, S. G. Zhukov, K. Yu. Pasichnichenko, and E. V. Babaev, Koord. Khim. 26 (9), 714 (2000). 5. V. B. Rybakov, S. G. Zhukov, E. V. Babaev, and E. J. Sonneveld, Kristallografiya 46 (3), 435 (2001) [Crystallogr. Rep. 46, 385 (2001)]. 6. V. B. Rybakov, S. I. Troyanov, E. V. Babaev, et al., Kristallografiya 46 (5), 1069 (2001) [Crystallogr. Rep. 46, 986 (2001)]. 7. V. B. Rybakov, E. V. Babaev, K. Yu. Pasichnichenko, and E. J. Sonneveld, Kristallografiya 47 (1), 76 (2002) [Crystallogr. Rep. 47, 69 (2002)]. 8. V. B. Rybakov, E. V. Babaev, and V. V. Chernyshev, Kristallografiya 47 (3), 473 (2002) [Crystallogr. Rep. 47, 428 (2002)]. 9. V. B. Rybakov, E. V. Babaev, and K. Yu. Pasichnichenko, Kristallografiya 47 (4), 678 (2002) [Crystallogr. Rep. 47, 622 (2002)]. 10. V. B. Rybakov, E. V. Babaev, A. A. Tsisevich, et al., Kristallografiya 47 (6), 1042 (2002) [Crystallogr. Rep. 47, 973 (2002)]. 11. F. H. Allen and O. Kennard, Chem. Design Autom. News 8 (1), 589 (1993). 12. T. Kato, M. Sato, M. Noda, and T. Itoh, Chem. Pharm. Bull. (Tokyo) 28, 2244 (1980). 13. Enraf­Nonius CAD4 Software: Version 5.0 (Enraf­Nonius, Delft, Netherlands, 1989). 14. L. J. Farrugia, WinGX98: X-Ray Crystallographic Programs for Windows (Univ. of Glasgow, UK, 1998). 15. G. M. Sheldrick, SHELX97: Program for the Solution and Refinement of Crystal Structures (Univ. of GÆttingen, Germany, 1997). 16. A. L. Spek, PLUTON96: Molecular Graphics Program (Univ. of Utrecht, Netherlands, 1996). 17. P. Dorigo, R. M. Gaion, D. Fraccarollo, et al., J. Med. Chem. 36, 2475 (1993). 18. W. R. Busing and H. A. Levy, Acta Crystallogr. 17, 142 (1964).

C(3) O(2)

C(10) C(9)

C(2) N(1) H(1)

Molecular structure with the atomic numbering and formation of the centrosymmetric dimer in structure I.

In both structures, the ellipsoids of thermal vibrations of the C(7) and C(8) atoms (the numberings are identical; see figure) are elongated almost perpendicular to the plane of the heterocyclic system. As a consequence, the distance between the C(7) and C(8) atoms is significantly shorter [1.451(2) å] than the C(5)­C(6), C(6)­C(7), C(8)­C(9), and C(9)­C(10) distances (Table 2). However, with allowance made for strong anisotropy of the thermal parameters [18], the C(7)­ C(8) distance is 1.58 å, which is consistent with the sp3 hybridization. The structure of the heterocyclic fragment of the bicycle in molecules I and II corresponds to the pyridone, rather than pyridol, tautomer. The fusion of the cyclohexene and pyridone fragments in molecule I along the C(5)­C(10) double bond results in a slight shortening of this bond (1.354 å) in comparison with the other double bond, namely, C(3)­ C(4) (1.374 å); that is, the carbocyclic fragment slightly contracts the bond in the adjacent heterocycle. Note that the environment of the C(5)­C(10) double bond in the bicycle includes the C(4), C(6), C(9), and N(1) atoms and has an asymmetric configuration: the C(6)­C(5)­C(4) exocyclic angle is 121.7°, whereas the C(9)­C(10)­N(1) angle is only 115.8°. This leads to a close spacing between the C(9)H2 methylene fragment and the nitrogen atom, which should be considered in the analysis of the reactivity of molecule I. For example, in the alkylation reactions, the N(1) nitrogen atom can be considerably shielded by the C(9) methylene link.

Translated by I. Polyakova
CRYSTALLOGRAPHY REPORTS Vol. 48 No. 2 2003