Single crystal X-ray diffraction analysis of the structure of methyl 4-methyl-3,5-dioxo-1-phenyl-2-oxaspiro[5.5]undecane-4-carboxylate

Article abstract of DOI:10.1007/s10947-010-0155-3

A single crystal X-ray diffraction study of the crystals of methyl 4-methyl-3,5-dioxo-1-phenyl-2-oxaspiro[5.5]undecane-4-carboxylate shows that phenyl and methoxycarbonyl substituents are in the equatorial position on the one side of the dioxopyran ring with twist boat conformation.

Full text of DOI:10.1007/s10947-010-0155-3

Journal of Structural Chemistry. Vol. 51, No. 5, pp. 996-997, 2010
Original Russian Text Copyright © 2010 by N. F. Kirillov, V. S. Melekhin, and Z. G. Aliev
SINGLE CRYSTAL X-RAY DIFFRACTION ANALYSIS
OF THE STRUCTURE OF METHYL 4-METHYL-3,5-DIOXO-
1-PHENYL-2-OXASPIRO[5.5]UNDECANE-4-CARBOXYLATE
N. F. Kirillov,1 V. S. Melekhin,1 and Z. G. Aliev2
UDC 547.281:546.47:547.384
A single crystal X-ray diffraction study of the crystals of methyl 4-methyl-3,5-dioxo-1-phenyl-2-
oxaspiro[5.5]undecane-4-carboxylate shows that phenyl and methoxycarbonyl substituents are in the
equatorial position on the one side of the dioxopyran ring with twist boat conformation.
Keywords: dioxopyran, spiroheterocycles, zinc enolates, single crystal X-ray diffraction analysis .
The interaction of dimethyl 2-(1-bromocyclohexylcarbonyl)-2-methylmalonate with zinc and benzaldehyde has lead
to the formation of methyl 4-methyl-3,5-dioxo-1-phenyl-2-oxaspiro- [5.5]undecane-4-carboxylate isolated as one isomer.
In order to study the spatial structure of the synthesized compound, we have performed the single crystal X-ray
diffraction analysis. Colorless faceted ꢀ19H22O5 crystals of the tetrahedral prismatic shape belong to the triclinic crystal
system: a = 6.530(1) Å, b = 11.106(1) Å, c = 12.526(1) Å, ꢀ = 71.94(1)ꢁ, ꢂ = 88.03(1)ꢁ, ꢃ = 86.50(1)ꢁ, V = 861.9(2) Å3,
M = 330.37, dx = 1.273 g/cm3, Z = 2, P-1 space group. A set of experimental reflections was obtained using and automated
four-circle KM-4 (KUMA DIFFRACTION) diffractometer with ꢄ-geometry by ꢅ/ꢆ -scanning on monochromated ꢁꢂKꢀ
radiation (2 ꢇ 50ꢁ). In total, 3578 reflections were measured, out of which 2720 were independent (R(int) = 0.0310).
Absorption was not taken into account (ꢈ = 0.092 mm–1). The structure was solved by the direct method using the SIR92
program [4] with subsequent calculations of the electron density maps. Hydrogen atom were set geometrically. Full-matrix
anisotropic refinement (non-hydrogen atoms) by the least squares method was performed using the SHELXL-97 program
package [5] and was completed when R1 = 0.0443 and wR2 = 0.1261 for 2383 reflections with I ꢉ 2ꢊ(I) and R1 = 0.0497 for
all 3578 reflections. 217 parameters were refined; ꢋꢌmax = 0.208 Å–3, ꢋꢌmin = –0.267 Å–3; GOOF 1.044.
The general view of the molecule is shown in Fig. 1. The pyran ring has the twist boat conformation. Phenyl and
methoxycarbonyl substituents are in the equatorial position. The methoxycarbonyl group plane is bisectorial against the
heterocycle. The phenyl ring plane forms an angle of 72.3ꢁ with the ꢃ1, ꢀ4, and ꢀ5 atom plane; the ꢃ1ꢀ5ꢀ6ꢀ7 torsion angle
is 138.9ꢁ. All bond lengths and bond angles are within the range of standard values for the corresponding atoms [1]. They
also comply with the results of the studied dioxopyrans of a different structure [2, 3]. Table 1 lists the bond lengths in the
pyran heterocycle. No short intermolecular contacts were found in the crystal.
The work was supported by RFBR (grant No. 07-03-96035).
1Perm State University; kirillov@psu.ru. 2Institute of Problems of Chemical Physics, Russian Academy of Sciences,
Chernogolovka; Translated from Zhurnal Strukturnoi Khimii, Vol. 51, No. 5, pp. 1026/1027, September-October, 2010.
Original article submitted September 23, 2009.
996
0022-4766/10/5105-0996 © 2010 Springer Science+Business Media, Inc.

Fig. 1. General view of the molecule.
TABLE 1. Bond Lengths in the Pyran Ring and Its Substituents, d (Å)
Bond
d
Bond
d
Bond
d
Bond
d
O(1)–C(1)
O(2)–C(1)
O(4)–C(18)
C(1)–C(2)
1.343(2)
1.197(2)
1.193(2)
1.525(2)
C(2)–C(18)
C(2)–C(17)
C(4)–C(16)
C(5)–C(6)
1.525(2)
1.543(2)
1.535(2)
1.509(2)
O(1)–C(5)
O(3)–C(3)
C(4)–C(12)
1.461(2)
1.206(2)
1.546(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
1.537(2)
1.519(2)
1.559(2)
REFERENCES
1. F. H. Allen, O. Kennard, D. G. Watson, et al., J. Chem. Soc. Perkin Trans., 12, S1-S19 (1987).
2. V. Sofiyev, G. Navarro, and D. Trauner, Org. Lett., 10, No. 1, 149 (2008).
3. L. C. Souza, D. O. Imbroisi, C. A. De Simone, et al., Acta Crystallogr., E65, o250 (2009).
4. A. Altomare, G. Cascarano, C. Giacovazzo, and A. Gualardi, J. Appl. Cryst., 26, 343 (1993).
5. G. M. Sheldrick, Shelxl-97, Programs for Crystal Structure Analysis, Univ. Göttingen, Germany (1997).
997