Metal-Olefin Compounds. VI. The Crystal Structure of Catena-μ-chloro-(cyclooctatetraene)copper(I)

Abstract

A single crystal, three-dimensional X-ray study of catena-p-chloro-(cyclooctatetraene)copper( I ) has been carried out. The structure consists of continuous chains formed by the copper and chlorine atoms extending through the crystal in the a direction with one olefinic bond closely bound to each copper atom. The carbon atoms of the bonded olefinic group are approximately coplanar with the copper and adjacent chlorine atoms of the chain, and the coordination about the copper(1) may be described as a distorted trigonal arrangement. The bond distances and the bond angles associated with the closely bound atoms are: CI-Cu-Cl, 106.4 f 0.1'; CI-Cu-(C1-C2 center), 123.1 f 0 2 O , 130.1 f 0.2'; Cu-C,, 2.073 f 0.010 b.; CU-C~, 2.097 f 0.007 A. A variety of weighting schemes was used in the least-squares data refinement procedures to test the sensitivity of the resulting interatomic distances to the weighting scheme and thus provide a test for systematic errors. Cu-Cl, 2.288 f 0.002 b., 2.284 f 0.002 b.; (9) 0.A crystal structure determination of the compound formed by the reaction of copper(1) chloride and bicyclo[2.2.1] hepta-2,5-diene (norbornadiene) shows that the complex exists as a tetramer, (CTH&!uCl)a, in the solid state with 3 symmetry.The copper and chlorine atoms form an eight-membered tube-shaped ring with one double bond of the olefin coordinated to the copper atom and lying in the plane defined by the copper atom and adjacent chlorine atoms, The copper atom is coordinated to the olefin in an ex0 configuration; one double bond of the olefin is not coordinated. The distorted trigonal planar coordination about copper is similar to that found for potassium dicyanocuprate( I), cyclooctatetraenecopper( I ) chloride, and 2-butynecopper( I) chloride,

Etude structurale de Cu2CI2.NCHC = CH2

“…Grfice au d~veloppe-ment des analyses structurales par rayons X, on a pu mettre en ~vidence et &udier de telles liaisons. Dans le domaine des halog6nures de cuivre(I), nous pouvons citer l'&ude de CuCl.cyclooctadi~ne-l,5 (Van den Hende & Baird, 1963), de CuCl.cyclooctat&ra6ne (Baenziger, Richards & Doyle, 1964), CuCl.norbornadi6ne (Baenziger, Haight & Doyle, 1964), CuCl.trans-cyclooct6ne (Ganis, Lepore & Martuscelli, 1970). Dans tous ces compos6s, la mol&ule organique est exclusivement li& au cuivre par une ou plusieurs liaisons m&al--ol~fine.…”

Dichloro(1-2:5-6-η-cyclooctatetraene)palladium(II)

“…A plan view of the molecule is given in Fig. 1, looking down (Baenziger, Richards & Doyle, 1964), and can be contrasted with the shorter bond lengths of the uncoordinated double bonds [ 1.320 (4), 1.310 (4) A] in the complex and 1.334 (1)/~, in the free molecule (Bastiansen, Hedberg & Hedberg, 1957). The single-bond distances in the complex average 1.478 (12) ~, in comparison with 1.462 (1)/~ for free COT, 1.48 (1) ,~ for COT.CuC1 and 1.46 (3) A in COT.AgNO 3 (Lipscomb & Mathews, 1959).…”

Copper(I) halide complexation to norbornene: (CuCl)5(norbornene)4: A complex of novel structure

“…The (CuClcyclooctatetraene)x solid state structure consists of a continuous (CuC1) x chain with one double bond of the olefin bound to each copper atom. The carbon atoms of the double bond are approximately coplanar with the CuCI 2 unit (Baenziger et al, 1964a). Cu2C12(diallylether) (Oliinik et al, 1986) shows a similar chain cross linked by 7r bound diallylether molecules.…”

“…The existence of (CuBr-l,5-cyclooctadiene)2 and CuBr(cyclooctatetraene) complexes have been reported (van den Hende, 1963;Baenziger, 1964a) but their solid-state structures are unknown.…”