The title compound 5-acetyltricyclo[8.2.2.24,7]hexa-deca-4,6,10,12,13,15-hexaene, C18H18O,is the first example of a mono-π-substituted [2.2]paracyclophane to be structurally characterized. The average bending angles are α = 13.2 and β = 9.9°. The distance between the \u27bottoms\u27 of the practically parallel boat-like benzene nuclei is 3.098(2) Å. The π conjugation between the acetyl group and the substituted benzene cycle is negligible (rotation angle ca 45°) because of steric hindrance

Guryshev, Vyacheslav N.

Lindeman, Sergey V.

Struchkov, Yuri T.

Acta Crystallographica Section C Crystal Structure Communications

English

S. V. Lindeman

Yu. T. Struchkov

V. N. Guryshev

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5-Acetyl[2.2]paracyclophane

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Marquette Universitye-Publications@MarquetteChemistry Faculty Research and Publications Chemistry, Department of1-1-19945-Acetyl[2.2]paracyclophaneSergey V. LindemanMarquette University, sergey.lindeman@marquette.eduYuri T. StruchkovInstitute of Organoelement CompoundsVyacheslav N. GuryshevInstitute of Organoelement CompoundsPublished version. Acta Crystallographica Section C, Vol. 50 (1994): 1747-1749. DOI. © 1994International Union of Crystallography. Used with permission.Acta Cryst. (1994). C50, 1747-1749 5-Acetyl[2.2]paracyclophane SERGEY V. LINDEMAN, YURI T. STRUCHKOV AND VYACHESLAV N. GURYSHEV Institute of Organoelement Compounds, 28 Vavilov Str., Moscow l/7813, Russia (Received 26 August 1993; accepted 25 March 1994) Abstract The title compound 5-acetyltricyclo[8.2.2.24•7]hexa-deca-4,6,10,12,13,15-hexaene, C18H180, is the first ex-ample of a mono-1r-substituted [2.2]paracyclophane to be structurally characterized. The average bending an-gles are a = 13.2 and {:J = 9. 9°. The distance between the 'bottoms' of the practically parallel boat-like ben-zene nuclei is 3.098 (2) A. The 1r conjugation between the acetyl group and the substituted benzene cycle is negligible (rotation angle ca 45°) because of steric hin-drance. Comment In order to study the influence of substituents on the degree of steric strain in [2.2]paracyclophanes (Linde-Acta Crystallographica Section C ISSN0108-2701 ©1994 1748 man, Struchkov & Guryshev, 1986; Lindeman, Maleev, Struchkov & Guryshev, 1990) the structure of 5-acetyl-[2.2]paracyclophane, (1), has been studied. 0 Me (I) The benzene nuclei in molecule (I) (Fig. I) have a boat conformation with bending angles, a, in the range 12.4-14.4 (1)0 (average 13.2°). The Csp2-Csp3 bonds are inclined to the adjacent triangular flaps of the benzene nuclei, exhibiting typical paracyclophane distortion with f3 angles in the range 8.7-10.9 (2)0 (average 9.9°). ll ~C(17) ~3) C(~~-, C(~4<)======~"~~--- "U 0(1) ~ '~,, ~;:::--~~ '1. ~~~6> lYe~) II [C(15) '"~(10) ~..1 ~ ~ / ~~~--~~C(11) , ~ , '--' ~<:( »""" C(12) ~ // C(9) b=====C\ ~q13) C(14~ Fig. 1. Perspective view of structure (I) showing the labelling of the non-H atoms. The Csp3-Csp3 bong lengths are increased by the distortion to 1.585 (2) A (in the bridge nearest to the acetyl substituent) and 1.574 (2) A; the respective twist angles are -12.8 (2) and -12.3 (2)0 • The same sign for both twist angles results in a relative swinging of the benzene rings by ca 3.5° (Fig. 2), while both 'bottom' planes are practically parallel [dihedral angle 0.2 (1)0 ] and located at a distance of 3.098 (2) A from each other. There is little conjugation between the benzene ring and the acetyl group bonded to it and the dihedral angle formed by the acetyl plane and the 'bottom' plane of the ring is 44.9 (1)0 • The carbonyl atom C(l7) is displaced by 0.047 (2) A from this plane in the exo direction and this results in a short intramolecular 0(1)· · ·H(7A) distance of 2.42 (2) A. ' '() }\.-' ) Fig. 2. Orthogonal projection of structure (I) onto the plane parallel to the 'bottoms' of the benzene nuclei showing the relative 'twist' of the benzene cycles. Experimental Crystal data CtsHtsO Mr = 250.32 Monoclinic P2t/C a= 14.724 (3) A b = 7.621 (2) A c = 11.844 (2) A {3 = 95.17 (3) 0 v = 1323.6 (5) ft.? Z=4 Dx = 1.256 Mg m-3 Data collection Siemens P3/PC diffractome-ter ()f2() scans Absorption correction: none 3892 measured reflections 3771 independent reflections 3343 observed reflections [I > 2a(/)] Refinement Refinement on F2 R(F) = 0.0512 wR(F2) = 0.1668 s = 1.057 3768 reflections 244 parameters All H-atom parameters refined w = l/[o-2(F ;) + (0.0969P)2 + 0.2841P] where P = (F; + 2Fl")/3 Mo Ka radiation .x = 0.71069 A Cell parameters from 24 reflections () = 11-12° p, = 0.076 mm- 1 T = 153 (2) K Well formed prisms 0.5 X 0.3 X 0.2 mm Colourless Rint = 0.0154 8max = 33.04 ° h = 0--+ 20 k=0--+11 I = -18 --+ 16 2 standard reflections monitored every 98 reflections intensity variation: 2.5% (fl./o-)max = 0.147 tl.pmax = oAoo e A - 3 tl.pmin = -0.178 e A - 3 Atomic scattering factors from International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) S. V. LINDEMAN, YU. T. STRUCHKOV AND V. N. GURYSHEV 1749 Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (A2) Ueq = (Ij3)~;'L.;Ui)a;a1*a;.a;. X y z Ueq Cl 0.68273 (8) 0.15250 (14) 0.65165 (10) 0.0274 (2) C2 0.65981 (7) 0.05648 (14) 0.74675 (9) 0.0259 (2) C3 0.72487 (8) 0.03463 (15) 0.83931 (9) 0.0267 (2) C4 0.81175 (7) 0.1071 (2) 0.84020 (9) 0.0280 (2) C5 0.82361 (8) 0.2367 (2) 0.75984(11) 0.0310 (2) C6 0.76004 (8) 0.25912 (14) 0.66755 (10) 0.0304 (2) C7 0.63974 (10) 0.1257 (2) 0.53202 (II) 0.0379 (3) C8 0.67785 (13) -0.0432 (2) 0.47417 (13) 0.0496 (4) C9 0.76203 (10) -0.1165 (2) 0.53935 (II) 0.0370 (3) CIO 0.75468 (10) -0.2424 (2) 0.62424 (12) 0.0370 (3) C11 0.82170 (1 0) -0.2579 (2) 0.71410(11) 0.0361 (3) Cl2 0.89799 (9) -0.1487 (2) 0.72201 (11) 0.0349 (3) C13 0.91427 (10) -0.0547 (2) 0.62481 (12) 0.0376 (3) C14 0.84738 (II) -0.0386 (2) 0.53487 ( 11) 0.0390 (3) C15 0.94745 (II) -0.1035 (3) 0.83575 (14) 0.0484 (4) Cl6 0.89244 (9) 0.0251 (2) 0.90810(12) 0.0378 (3) C17 0.57123 (9) -0.0395 (2) 0.74588 (12) 0.0356 (3) C18 0.52467 (II) -0.0402 (2) 0.8536 (2) 0.0460 (4) 01 0.53722 (9) -0.1125 (2) 0.66124 (1 0) 0.0608 (4) Table 2. Selected geometric parameters (A, 0 ) C1---C6 1.397 (2) C7---C8 1.585 (2) CI---C2 1.409 (2) C9---CIO 1.401 (2) C1---C7 1.513 (2) C10----C11 1.390 (2) C2---C3 1.399 (2) C11---C12 1.395 (2) C2---CI7 1.495 (2) CI2---CI3 1.395 (2) C3---C4 1.393 (2) CI2---CI5 1.512 (2) C4---C5 1.393 (2) CI3---CI4 1.389 (2) C4---CI6 1.509 (2) CI5---CI6 1.574 (2) C5---C6 1.384 (2) C17-01 1.214 (2) C6----C 1---C2 116.42 (II) CI4---C9---C8 121.66 (14) C6----C 1---C7 118.14 (II) CIO----C9---C8 120.54 (14) C2---CI---C7 124.64 (II) c 11---C I O----C9 120.82 (13) C3---C2---CI 119.45 (10) C I 0----C 11---C 12 120.85 (12) C3---C2---CI7 118.84 (10) C11---C12---C13 116.65 (13) CI---C2---CI7 121.35 (II) CII---CI2---CI5 121.06 (13) C4---C3-C2 121.48 (10) C13-C12-C15 120.90 (14) C3---C4---C5 116.59 (II) c 14---C 13---C 12 121.01 (13) C3---C4---C16 121.22 (12) c 13---C 14---C9 120.81 (12) C5---C4---C16 121.09 (II) c 12---CI5---C 16 113.37 (11) C6----C5---C4 120.62 (10) C4---C16----C15 112.77 (11) C5---C6----C I 121.29(11) 0 1---C 17 ---C2 121.64 (13) CI---C7---C8 112.33 (II) 01---C17---C18 120.93 (13) C9---C8---C7 112.73 (12) C2 ---C 17 ---C 18 117.43 (12) CI4---C9---CIO 116.54 (13) C3---C4---C 16----C 15 94.8 (2) C8---C7 ---C I---C6 92.50 (15) C4---C 16----C 15--C 12 -12.3 (2) C9---C10----Cli---CI2 -0.1 (2) C16----C15--CI2--C11 -71.7(2) C10---C11---C12---C13 -14.6(2) c 1 O---C9-C8-C7 89.8 (2) C11-C12-C13-C14 14.7 (2) C9-C8-C7-Cl -12.8(2) C12---C13-C14---C9 -0.1 (2) C8---C7 ---C 1---C2 -76.9 (2) c 1---C2---C3---C4 0.6(2) C5-C4---C 16----C 15 -72.9 (2) C2-C3-C4---C5 15.7 (2) c 16----C 15--C 12--C 13 94.4 (2) C3---C4---C5---C6 -15.8(2) c 14---C9---C8---C7 -77.0 (2) C4---C5---C6----C I -0.4 (2) Program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1989). Program(s) used to refine structure: SHELXL93 (Sheldrick, 1993 ). Lists of structure factors, anisotropic displacement parameters, H-atom coordinates, complete geometry and torsion angles have been deposited with the IUCr (Reference: HU1077). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CHI 2HU, England. © 1994 International Union of Crystallography Printed in Great Britain - all rights reserved References Lindeman, S. V., Maleev, A. V., Struchkov, Yu. T. & Guryshev, V. N. (1990). lzv. Akad. Nauk SSSR Ser. Khim. pp. 588-590. Lindeman, S. V., Struchkov, Yu. T. & Guryshev, V. N. (1976). lzv. Akad. Nauk SSSR Ser. Khim. pp. 2007-2010. Sheldrick, G. M. (1989). SHELXTL-Plus. PC version. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1993). SHELXL93. Program for the Refinement of Crystal Structures. Univ. of Gottingen, Germany. Acta Cryst. (1994). C50, 1749-1753 Molecular Structure and Electronic Properties of a 1-Sulfonylindolizine Derivative, 2-Isopropyl-1-methylsulfonyl-indolizine VERONIQUE GmoN, CATHERINE PoTY, GUY EVRARD, DANIEL P. VERCAUTEREN AND FRANc;Ois DURANT Laboratoire de Chimie Moteculaire Structurale, Facultes Universitaires Notre-Dame de Ia Paix, Rue de Bruxelles 61, B-5000 Namur, Belgium Abstract For the title compound, C12H15N02S, both the crystallo-graphic data and theoretical results (ab initio molecular-orbital calculations) indicate a stabilization of the sym-metrical conformation of the sulfone group with respect to the indolizinic bicycle. The crystal packing and the topology of the frontier orbitals clearly suggest a charge-transfer process from the five-membered ring towards the six-membered ring of the indolizine for two adja-cent molecules. Comment Derivatives of 1-sulfonylindolizines are being studied increasingly because of their importance as a new va-riety of L-type calcium-channel blocker and the recog-nition the potential impact of this class of compound on the treatment of ischemic heart disease and hyper-tension. The biochemical studies carried out up to now indeed indicate a new binding site for these molecules associated with the L-type calcium channel (Nokin et al., 1989, 1990; Schmid, Romey, Barhanin & Lazdun-ski, 1989; Polster, Christophe, Van Damme, Houliche & Chatelain, 1990; Chatelain, Baufort, Meysmans & Clinet, 1990; Chatelain, Gubin, Manning & Sissman, 1991; Bois, Romey & Lazdunski, 1991; Gubin et al., 1992; Gibon, Norberg, Vercauteren, Evrard & Durant, 1992; Kenny, Fraser & Spedding, 1993), in addition to Acta Crystal/ographica Section C ISSN 0108-2701 ©1994 

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5-Acetyl[2.2]paracyclophane

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