The crystal structure of the title compound, C9H1505P, is described. The molecule consists of two cis-fused six-membered rings, both in the chair conformation.

Bennett, Dennis W.

Cremer, Sheldon E.

Lane, Thomas M.

Rodriguez, Oscar P

Sommese, Anthony Gerard

English

epublications@Marquette

Marquette Universitye-Publications@MarquetteChemistry Faculty Research and Publications Chemistry, Department of1-1-1995cis-6-Methoxycarbonyl-2,10-dioxa-1-phosphabicyclo[4.4.0]decane1-OxideThomas M. LaneMarquette UniversityOscar P RodriguezMarquette UniversityAnthony Gerard SommeseMarquette UniversitySheldon E. CremerMarquette UniversityDennis W. BennettUniversity of Wisconsin - MilwaukeePublished version. Acta Crystallographica Section C, C51 (1995): 251-253. DOI. © 1995International Union o f Crystallography.L. TOUPET AND N. KARL 251                                                                                                                                                                              2  6                                            8                                       6                                                    1     2       4                 s               k                    Acta Cryst. (1995). C51,251-253 c is-6- M e tho x y carbon yi- 2,10-d io xa- 1-phosphabicyclo[4.4.0]decane 1-Oxide THOMAS M.  LANE, OSCAR P.  RODRIGUEZ, ANTHONY G.  SOMMESE AND SHELDON E.  CREMER Marquette University, Department of Chemistry, Todd Wehr Chemistry Building, 535 North 14th Street, Milwaukee, WI 53233, USA DENNIS W.  BENNETT University of Wisconsin-Milwaukee, Department of Chemistry, Milwaukee, WI 53201, USA (Received 20 May 1994: accepted 20 July 1994) Abstract The crystal structure of the title compound, C9H1505P, is described. The molecule consists of two cis-fused six- membered rings, both in the chair conformation. Comment The crystal structure of the title compound, (I), was investigated in order to establish the stereochemistry of the methoxycarbonyl group relative to the phospho- ryl group. Since the two analogous model compounds, decalin and 2,10-dioxabicyclo[4.4.0]decane (Descotes, © 1995 Internat ional  Un ion  of  Crysta l lography Printed in Great  Britain - all rights reserved Acta Crystallographica Section C ISSN 0108-2701 ©1995 252 C9H15OsP Lissac, Delmau & Duplan, 1968; Beaulieu, Dickinson & Deslongchamps, 1980) exist in both cis and trans iso- meric forms, the goal was to synthesize both isomeric forms of this bicyclic phosphonate. For some as yet un- known reason only one isomer of the parent compound, 2,10-dioxa- 1-phosphabicyclo[4.4.0]decane 1-oxide, (II), (Ch6rest & Whitham, 1976; Whitham, 1989; Bellard, Postle & Sheldrick, 1978) is produced regardless of the synthetic route employed (Rodriguez, Sommese & Cremer, 1993). It was hoped that the presence of the methoxycarbonyl substituent would lead to both the cis and trans isomers of (I). Surprisingly, as with (II), only the cis isomer of (I) has been observed so far (Ro- driguez, Sommese & Cremer, 1993). The determination of the crystal structure was required in order to assign the cis-fused configuration unambiguously and therefore gain additional information about the apparent stability of the cis configuration (or instability of the trans con- figuration). L. -oM  II O (I) The two rings in (I), like the two rings in (II), are intrinsically non-equivalent in the solid state. Although the non-equivalence of the rings in (I) is not discernible from the P - -O  bond lengths [1.567 (2) and 1.573 (2) ,~,], C9 04 05 C8 Ol c6 c7 03 Fig. 1. Molecular structure of the title compound with displacement ellipsoids at the 35% probability level. which differ by only 0.006 (3) ,~,, i.e. 2or, the bond angle at 02 [119.1 (2) ° ] is significantly wider than the angle at 03 [116.8(2)°]. The P1---C1 bond [1.814(3)A] is, as expected, the longest bond in (I), and is even longer than the corresponding bond in (II) [1.783 (4)A]. The P----C torsion angle in (I) [O2--P1--C1-- -C8 86.8(2) °] is also larger than that in (II) [O1- -P1- -C4- -H7  46.4°]. These differences may be the result of a greater steric and electronic interaction between the methoxycarbonyl group and the phosphoryl group in (I) than between the c~-H atom and the phosphoryl group in (II). Further studies aimed at determining whether the preferential formation of cis-(1) and cis-(II) during the synthesis of these compounds is directed by thermo- dynamic or kinetic control are underway. Experimental The title compound was synthesized by the procedure de- scribed by Rodriguez, Sommese & Cremer (1993). Crystals (m.p. 397-398 K) were grown from a methylene chloride so- lution layered with diethyl ether. Crystal data CgH15OsP Mo Ka radiation Mr = 234.12 A = 0.71069 A Orthorhombic Cell parameters from 21 Pbca reflections a = 26.377 (4) ,~, 0 = 3.09-7.91 ° b = 8.297 (2) ,~, /.t = 0.24 mm- c = 9.994 (2) ,~, T = 298 K V = 2187.2 (8) •3 Plate Z = 8 0.40 x 0.30 x 0.30 mm D~ = 1.422 Mg m -3 Colorless Data collection Picker diffractometer 0-20 scans Absorption correction: none 1690 measured reflections 1426 independent reflections 1021 observed reflections 11 > 2.0a(D] Refinement Refinement on F -~ R(F) = 0.034 wR(F 2) = 0.055 S = 2.55 1021 reflections 138 parameters H-atom parameters not refined Weighting scheme based on measured e.s.d.'s (A/cr)m~x = 0.304 0max = 23.5 ° h = 0--, 28 k = 0---, 8 1 = 0 --~ 10 3 standard reflections frequency: 120 min intensity decay: none .--/-~Pmax = 0.220 e ,~-3 Apmin = -0.260 e ~-3 Extinction correction: Fc* = kFc[1 + (0.001x x F~A"/sin20)] -1/~ Extinction coefficient: x = 0.0042 (3) Atomic scattering factors from International Tables for X-ray Co'stallography ( 1974, Vol. IV, Tables 2.2B and 2.3.1) LANE, RODRIGUEZ, SOMMESE, CREMER AND BENNETT 253 Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (,~2) Ueq = ( 1 /3)~i~jUi )a~ a* ai a) j • . x y z Ueq Pl 0.16207 (3) 0.43031 ( 0) 0.16173 (9) 0.041 (I) Ol 0.17235 (9) 0.5013 (3) 0.2921 (2) 0.057 (1) 02 0.13699 (7) 0.2596 (2) 0.1722 (2) 0.048 (1) 03 0.20979 (7) 0.3968 (3) 0.0715 (2) 0.054 (1) 04 0.07147 (10) 0.7729 (3) 0.1417 (3) 0.082 (2) 05 0.05538 (9) 0.52581 (9) 0.2121 (2) 0.058 (2) CI 0.12217 (12) 0.5540 (4) 0.0553 (3) 0.038 (2) C2 0.0979(1) 0.4501 (4) -0.0567 (3) 0.054 (2) C3 0.0781 (1) 0.2851 (4) -0.0141 (3) 0.060(2) C4 0.1181 ( 1 ) 0.1829 (4) 0.0515 (4) 0.060 (2) C5 0.1552 ( I ) 0.6890 (4) - 0.0[)64 (3) 0.055 (2) C6 0.2037 ( I ) 0.6279 (4) -0.0740 (3) 0.065 (2) C7 0.2371 ( 1 ) 0.5378 (4) 0.0206 (3) 0.066 (2) C8 0.0809 ( 1 ) 0.6332 (4) 0.1394 (3) 0.045 (2) C9 0.0180 (1) 0.5882 (4) 0.3036 (3) 0.062 (2) Table 2. Selected geometric parameters (A,, o) PI - -02 1.567 (2) 02---C4 1.454 (4) C8--C1 1.523 (5) C2--C3 1.527 (5) P l~g l  1.455 (2) 05---C8 1.334 (4) C8--O4 1.186 (5) C3--C4 1.504 (5) P1---O3 1.573 (2) O5---C9 1.441 (4) C1---C2 1.551 (5) C5---C6 1.535 (5) PI---CI 1.814 (3) O3-----~7 1.465 (4) C1~C5 1.548 (5) C7--C6 1.492 (5) O2- -P1~1 112.65 (14) P1 - -O2~4 119.1 (2) P I~ I~8 109.6(2) C1- -C2~3 116.0(3) O2--PI---O3 102.50 (13) C8---O5--C9 116.9 (3) P I l l - - -C2  110.4(2) C2~3- -C4  112.7(3) O2--PI - -CI  107.79(14) P 1----O3---C7 116.8(2) P I - -C I~5 108.4(2) C1- - -C5~6 114.0(3) OI--PI---O3 115.81 (14) O5~8----C 1 111.9(3) C8~1- -C2  110.2 (3) O2~4------C3 110.9 (3) O I - -P I~ I  113.81 (15) O5- -C8~4 122.4(3) C8~-C1---C5 108.0 (3) O3~7----C6 109.3 (3) O3--PI---CI 103.19 (14) C I---C8---O4 125.7 (3) C2--C 1-----425 110.2(3) C5~6- - -C7  112.2(3) O1--PI--O2---C4 171.6 (3) O3- -P I - -O2~4 -63.2 (2) C I - -P1 - - -O2~4 45.2 (2) OI--PI---CI---C8 -38.9 (2) OI--P1--O3---C7 -68.0 (2) O I - -P I - -C I - -C5  78.8 (3) O2--P1--C1---C8 86.8 (2) OI--PI--CI----C2 - 160.4 (3) O3--P1--C1--C5 -47.5 (2) All H-atoms were allowed to ride on the heavy atom with isotropic displacement factors 1.5 times the equivalent isotropic displacement factor of the heavy atom. The methyl group was refined as a rigid rotor. The data were globally sorted and collected using PCXTL data collection software (Weinrach & Bennett, 1991). Cell refinement and data reduc- tion: NRCVAX (Gabe, Le Page, Charland, Lee & White, 1989). Program(s) used to solve structure: NRCVAX SOLVER. Pro- gram(s) used to refine structure: SHELXL93 (Sheldrick, 1993). Molecular graphics: ORTEPII (Johnson, 1976) and PLUTO84 (Motherwell, 1984). Lists of structure factors, anisotropic displacement parameters, H- atom coordinates, bond distances and angles involving non-H atoms and torsion angles have been deposited with the IUCr (Reference: BKI069). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH 1 2HU, England. References Beaulieu, N., Dickinson, R. A. & Deslongchamps, P. (1980). Can. J. Chem. 58, 2531-2536. Bellard, S., Postle, S. R. & Sheldrick, G. M. (1978). Acta Cryst. B34, 1032-1033. Chrrest, M. & Whitham, G. H. (1976). Unpublished results. Descotes, G., Lissac, M., Delmau, J. & Duplan, J. (1968). C. R. Acad. Sci. Ser. C, 267, 1240-1241. Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384-387. Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Motherwell, W. D. S. (1984). PLUTO84. Univ. Chemical Laboratory, Cambridge, England. Rodriguez, O. P., Sommese, A. G. & Cremer, S. E. (1993). Phosphorus Sulfur Silicon, 75, 107- I 10. Sheldrick, G. M. (1993). SHELXL93. Program for the Refinement of Crystal Structures. Univ. of G6ttingen, Germany. Weinrach, J. B. & Bennett, D. W. (1991). J. Appl. Cryst. 24, 91-95. Whitham, G. H. (1989). Personal communication.  6 m    O                                               © 1995 International Union of Crystallography Printed in Great Britain - all rights reserved Acta Crystallographica Section C ISSN 0108-2701 ©1995 

cis-6-Methoxycarbonyl-2,10-dioxa-1-phosphabicyclo[4.4.0]decane 1-Oxide

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cis-6-Methoxycarbonyl-2,10-dioxa-1-phosphabicyclo[4.4.0]decane 1-Oxide

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