The structure of β-homopipitzolone (one of the two isomers of an intermediate product in the homocedrole synthesis) has been unequivocally established as 1 O-hydroxy-2,6,9-trimetbyltricyclo[6.3.1.01,6] dodeca-9-ene-5, II, 12-trione with relative IR,2R,6R,8S configuration

Garcia, G.

Guzman, J. A.

Igonin, V. A.

Lindeman, Sergey V.

Mendoza, V.

Nava, Ezequiel Huipe

Struchkov, Yuri T.

English

epublications@Marquette

Marquette Universitye-Publications@MarquetteChemistry Faculty Research and Publications Chemistry, Department of1-1-1993β-HomopipitzoloneEzequiel Huipe NavaInstituto Tecnologico de MoreliaV. A. IgoninInstitute of Organoelement CompoundsSergey V. LindemanMarquette University, sergey.lindeman@marquette.eduYuri T. StruchkovInstitute of Organoelement CompoundsV. MendozaUniversidad Michoacana de San Nicolas de HidalgoSee next page for additional authorsPublished version. Acta Crystallographica Section C, Vol. 49 (1993): 1207-1209. DOI. © 1993International Union of Crystallography. Used with permission.AuthorsEzequiel Huipe Nava, V. A. Igonin, Sergey V. Lindeman, Yuri T. Struchkov, V. Mendoza, G. Garcia, and J. A.GuzmanThis article is available at e-Publications@Marquette: https://epublications.marquette.edu/chem_fac/596Acta Cryst. (I993). C49~ I207-I209 ~-Homopipitzolone E. HUIPE-NAVA Instituto Tecno/ogico de Morelia, Apdo. Postal 13-G, Morelia, Michoacan, Mexico V. A. IGONIN, S. V. LINDEMAN AND Yu. T. STRUCHKOV Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow B-334, Russia V. MENDOZA, E. GARCIA G. AND J. A. GUZMAN Instituto de Investigaciones Quimico-Biologicas, Universidad Michoacana de San Nicolas de Hidalgo, Morelia, Michoacan, Mexico (Received 16 June 1992; accepted 22 December 1992) Abstract The structure of P-homopipitzolone (one of the two isomers of an intermediate product in the homoce-drole synthesis) has been unequivocally established as 1 O-hydroxy-2,6,9-trimetbyltricyclo[6.3.1.01•6]do-deca-9-ene-5, II, 12-trione with relative I R,2R,6R,8S configuration. Comment The thermal (Walls, Padilla, Joseph-Nathan, Giral & Romo, I965; Joseph-Nathan, Mendoza & Garcia, 1977) and catalytic (Sanchez, Yanez, Enriquez & Joseph-Nathan, I981) transformations of perezone produce a mixture of a- and P-pipitzols. In conti-nuation of our investigations in this field, we have prepared the new a- and P-homopipitzolone mixture from modified perezone (Mendoza, Garcia, Reyes & © 1993 International Union of Crystallography 1208 REGULAR STRUCTURAL PAPERS Guzman, 1988). However, the structures of these compounds have not been assigned unambiguously. Thus, the X-ray diffraction study of ,8-homopipitzo-lone ( 1) was undertaken. OH Me (1) Molecule (1) has a tricyclic framework. The cycle A has a distorted chair conformation with the C13-and Cl4-methyl groups in equatorial and axial orientations, respectively. The five-membered cycle B, cis-fused to the cycle A, has a conformation intermediate between la,l2,B-twist and 12,8-envelope. The six-membered cycle C has a distorted 12/J-sofa conformation. The absolute chirality of molecule (1) could not be established objectively and was arbitrarily assigned as IR,2R,6R,8S. The molecule ( 1) exists, in the crystal, in the enol form with a C9=Cl0 double bond [1.337 (3) A] and an 04-hydroxy group. The latter takes part in inter-molecular hydrogen bonding with the 02-oxo group of the molecule related by 21 axes [04· ··02' 2. 735 (2), 04-H4 0.86 (2), H4· ··02' 2.18 (2) A, 04-H4· · ·02' 122 (2t] which results in the formation of infinite chains along the x axis. The relative weakness of this hydrogen bond may be explained by the participa-tion of the 04-H4 group in the- additional intra-molecular interaction 04-H4···01 [04···01 2.712 (3), H4···01 2.21 (3) A, 04-H4···01 117 (2t]. Fig. 1. General view of the molecule (1). Fig. 2. Crystal structure of (1) with the hydrogen-bonded chains of molecules along the x axis. Experimental Crystal data C1sH1s04 Mr = 262.3 Orthorhombic .P212121 a = 9.045 (3) A b = 9.670 (3) A c = 14.807 (4) A v = 1295.1 (7) A3 Z=4 Dx = 1.345 Mg m-3 Mo Ka radiation .\ = 0.71073 A Data collection Siemens P3/ PC diffractome-ter () J2() scans Absorption correction: none 1802 measured reflections 1802 independent reflections 1802 observed reflections [F2: 6.0cr(F)] Refinement Refinement on F Final R = 0.033 wR = 0.032 s = 0.52 1453 reflections 244 parameters All H-atom parameters re-fined Cell parameters from 24 reflections () = 24-26° Jl = 0.097 mm-1 T = 153 K Needles 0.75 X 0.10 X 0.05 mm Colourless Crystal source: from warn ethanol solution Bmax = 50° h=O--tll k = 0 --t 12 l = 0 --t 19 2 standard reflections monitored every 98 reflections intensity variation: ±2.1% w = 1/cr2(F) (A/cr)max = 0.15 0-3 !:l.Pmax = 0.158 e A !:l.pmin = -0.188 e A - 3 Atomic scattering factors from International Tables for X -ray Crystallography (1974, Vol. N) REGULAR STRUCTURAL PAPERS 1209 Table 1. Fractional atomic coordinates and equivalent isotropic thermal parameters (A2) Ueq = fE;'EJU;Ja;aja;.a1. X y z 01 0.0825 (2) 0.7040(2) 0.2957 (1) 02 -0.5281 (2) 0.5810 (2) 0.3200 (2) 03 -0.2181 (2) 0.7018 (2) 0.5323 (1) 04 0.2055 (2) 0.4820(2) 0.3787 (1) C1 -0.1552 (2) 0.6860 (2) 0.3701 (1) C2 -0.1740 (3) 0.8419 (2) 0.3523 (2) C3 -0.3356 (3) 0.8855 (3) 0.3554 (2) C4 -0.4304 (3) 0.8030 (3) 0.2897 (2) C5 -0.4196 (3) 0.6519 (3) 0.3108 (2) C6 -0.2639 (2) 0.5881 (3) 0.3159 (2) C7 -0.2687 (3) 0.4501 (3) 0.3697 (2) C8 -0.1845 (3) 0.4779 (3) 0.4586 (2) C9 -0.0226 (3) 0.4407 (3) 0.4502 (2) CIO 0.0621 (3) 0.5170 (3) 0.3955 (2) Cl1 0.0051 (2) 0.6411 (2) 0.3487 (1) C12 -0.1888 (3) 0.6350 (3) 0.4666 (2) Cl3 -0.0814 (3) 0.9316 (3) 0.4163 (2) C14 -0.2144 (3) 0.5653 (3) 0.2173 (2) C15 0.0330 (4) 0.3157 (3) 0.4994 (2) Table 2. Geometric parameters (A, 0 ) 01-Cll 02-C5 03-C12 04-ClO C1-C2 C1-C6 C1-C11 Cl-C12 C2-C3 C2-Cl3 C3-C4 C2-C1-C6 C2-C1-C11 C2-C1-C12 C6-C1-C11 C6-C1-C12 Cl1-C1-C12 Cl-C2-C3 C1-C2-C13 C3-C2-C13 C2-C3-C4 C3-C4-C5 02-C5-C4 02-C5-C6 C4-C5-C6 C1-C6-C5 C1-C6-C7 C1-C6-C14 C5-C6-C7 C1-C2-C3-C4 C2-C3-C4-C5 C3-C4-C5-C6 C4-C5-C6-C1 C5-C6-C1-C2 C6-C 1-C2-C3 C1-C6-C7-C8 C6-C7 -C8-C 12 C7-C8-C12-C1 1.215 (3) 1.204(3) 1.197 (3) 1.363 (3) 1.540 (3) 1.583 (3) 1.546(3) 1.542 (3) 1.522 (4) 1.534 (4) 1.523 (4) 115.5 (2) 110.1 (2) 116.7 (2) 108.1 (2) 99.0(2) 106.5 (2) 111.9 (2) 112.8 (2) 110.4 (2) 112.1 (2) 110.0 (2) 121.8 (2) 120.7 (2) 117.5 (2) 110.7 (2) 105.8 (2) 112.6 (2) 110.1 (2) -55.9 (3) 58.5 (3) -53.7 (3) 43.7 (3) -39.3 (3) 46.6 (3) 8.2 (3) 20.6 (3) -42.9 (3) C4-C5 C5-C6 C6-C7 C6-C14 C7-C8 C8-C9 C8-C12 C9-C10 C9-C15 C10-Cll C5-C6-C14 C7-C6-C14 C6-C7-C8 C7-C8-C9 C7-C8-C12 C9-C8-C12 C8-C9-C10 C8-C9-C15 C10-C9-C15 04-C10-C9 04-C10-C11 C9-C10-C11 01-C11-C1 01-Cll-C10 C1-Cll-C10 03-C12-C1 03-C12-C8 C1-C12-C8 C8-C12-C1-C6 C12-C1-C6-C7 C1-C12-C8-C9 C12-C8-C9-C10 C8-C9-C10-Cll C9-C10-C11-C1 C10-C11-Cl-C12 C11-C1-C12-C8 Ueq 0.032 (1) 0.044 (1) 0.035 (1) 0.035 (1) 0.020(1) 0.024 (1) 0.033 (1) 0.037 (1) 0.027 (1) 0.021 (1) 0.029 (1) 0.026 (1) 0.027 (1) 0.027 (1) 0.022 (1) 0.023 (1) 0.033 (1) 0.031 (1) 0.042 (I) 1.497 (4) 1.540 (3) 1.555 (4) 1.544 (3) 1.544 (4) 1.513(4) 1.525 (3) 1.337 (3) 1.499 (4) 1.479 (3) 106.0 (2) 111.8 (2) 105.8 (2) 111.5 (2) 103.2 (2) 105.5 (2) 118.3 (2) 118.5 (2) 123.2 (2) 121.3(2) 116.6 (2) 122.1 (2) 122.1 (2) 120.5 (2) 117.3 (2) 128.6 (2) 127.4 (2) 103.9 (2) 46.7 (2) -33.0 (2) 74.1 (3) -43.5 (3) 4.4 (4) 3.9 (3) 27.4 (2) -65.3 (2) All calculations were performed by the SHELXTL-Plus pro-grams (Sheldrick, 1987) with an IBM-PC/AT computer. Abso-lute configuration was not determined because of the lack of anomalous scatterers. 0108-2701/93/061209-03$06.00 Lists of structure factors, anisotropic thennal parameters and H -atom co-ordinates have been deposited with the British Library Docwnent Sup-ply Centre as Supplementary Publication No. SUP 55940 (8 pp.). Copies may be obtained through The Technical Editor, International Union of Crystallography, 5 Abbey Square, Chester CH 1 2HU, England. [CIF ref-erence: VS1002] References Joseph-Nathan, P., Mendoza, V. & Garcia, E. (1977). Tetrahe-dron, 33, 1573-1576. Mendoza, V., Garcia, E., Reyes, M. & Guzman, J. A. (1988). XXIV Congreso Mexicano de Quimica Pura y Aplicada, Quere-taro, Qro., Mexico, Abstr. 161. Sanchez, I. H., Yanez, R., Enriquez, R. & Joseph-Nathan, P. (1981). J. Org. Chern. 46, 2818-2819. Sheldrick, G. M. (1987). SHELXTL-Plus. PC version. Siemens Analytical X-ray instruments, Inc., Madison, Wisconsin, USA. Walls, F., Padilla, J., Joseph-Nathan, P., Giral, F. & Romo, J. (1965). Tetrahedron Lett. pp. 1577-1582. Acta Cryst. (1993). C49, 1209-1211 Structure of 4-Nitrobenzyl N-( 4-Nitrobenzyloxy )trifluoroacetimidate D. M. BROWN AND P. KoNG THoo LIN MRC Laboratory of Molecular Biology, Hills Road, Cambridge CB2 2QH, England L. VAN MEERVELT Laboratorium voor Macromoleculaire Structuurchemie, KV Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium (Received 14 October 1992; accepted 18 December 1992) Abstract The molecular structure of the title compound is characterized by the cisoid geometry of the oximino-ether residue. Comment In experiments that were directed to the synthesis of polyamine analogues, a series of condensations were carried out between primary alcohols and N-tri-fluoroacetamidooxyalkyl derivatives by the Mitsunobu reaction (Mitsunobu, 1981 ). It was hoped that the condensation would lead to N-alkyltrifluoro-acetamidooxy derivatives. However, the sole © 1993 International Union of Crystallography 

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\u3cem\u3eβ\u3c/em\u3e-Homopipitzolone

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