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]NO3·5H2O and cis-(carbonato)bis(1,10-phenanthroline)cobalt(III) bromide tetrahydrate, cis-[Co-(C12H8N2)2CO3]Br·4H2O, 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) Å, b = 16.039 (2) Å, c = 14.435 (2) Å, β = 101.94 (2)°, and V = 2476 (2) Å3. Full-matrix least-squares refinement on 1306 unique reflections with I > 3σ(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) Å, b = 12.500 (2) Å, c = 14.299 (3) Å, β = 91.42 (2)°, and V = 5048 (3) Å3. Refinement of 1640 unique reflections with I > 3σ(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.
author list (cited authors)
Niederhoffer, E. C., Martell, A. E., Rudolf, P., & Clearfield, A.