STRUCTURES OF (CARBONATO)BIS(2,2'-BIPYRIDINE)COBALT(III) AND (CARBONATO)BIS(1,10-PHENANTHROLINE)COBALT(III) COMPLEXES
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The crystal and molecular structures of cis-(carbonato)bis(2,2-bipyridine)cobalt(III) nitrate pentahydrate, cis-[Co-(C10H8N2)2CO3]NO35H2O and cis-(carbonato)bis(1,10-phenanthroline)cobalt(III) bromide tetrahydrate, cis-[Co-(C12H8N2)2CO3]Br4H2O, have been determined by single-crystal X-ray diffraction methods. The former compound conforms to the monoclinic space group C2/c (Z = 4) with cell parameters a = 10.931 (4) , b = 16.039 (2) , c = 14.435 (2) , = 101.94 (2), and V = 2476 (2) 3. Full-matrix least-squares refinement on 1306 unique reflections with I > 3(I) gave RF = 0.046 and RwF = 0.059. The other compound also conforms to the space group C2/c (Z = 8) with cell parameters a = 28.251 (8) , b = 12.500 (2) , c = 14.299 (3) , = 91.42 (2), and V = 5048 (3) 3. Refinement of 1640 unique reflections with I > 3(I) gave RF = 0.049 and RwF = 0.058. Both compounds contain cations that are slightly distorted from ideal octahedral geometry. The structural parameters are considered with respect to similar cis-(carbonato)polyaminecobalt(III) complexes. Ligand field and vibrational assignments are presented for these complexes. Analysis of the electronic absorption transitions 1T1g(Oh) 1A1g(Oh) and 1T2g(Oh) 1A1g(Oh) yields values of 10Dq and B. 1982, American Chemical Society. All rights reserved.