Syntheses and crystal structures of new chain-containing iodometallate compounds: [H1,10-phen](H2O)1.41[AgI2], [H1,10-phen](H2O)1.42[CuI2]; [Co(tpy)2][Bi2I8], [Fe(tpy)2][Bi2I8]; [Co(1,10-phen)3][Pb3I8]·H2O, and [Fe(1,10-phen)3][Pb3I8]·0.5(H2O)

• Published in: Solid state sciences Vol. 9; no. 10; pp. 895 - 906
• Main Authors: Tershansy, Meredith A., Goforth, Andrea M., Peterson, LeRoy, Burns, M.C., Smith, Mark D., zur Loye, Hans-Conrad
• Format: Journal Article
• Language: English
• Published: 01-10-2007
• ISSN: 1293-2558
• DOI: 10.1016/j.solidstatesciences.2007.06.018

Three pairs of novel, isostructural polymeric iodometallate compounds, [H1,10-phen](H2O)1.41[Agbeta] (1) ([H1,10-phen]+=[1,10-phenanthrolinium]+), [H1,10-phen](H2O)1.42[Cubeta] (2), [Co(tpy)2][Bi2I8] (3) (tpy=2,2':6'2''-terpyridine), [Fe(tpy)2][Bi2I8] (4), [Co(1,10-phen)3][Pb3I8]*H2O (5) (1,10-phen=1,10-phenanthroline), and [Fe(1,10-phen)3][Pb3I8]*0.5(H2O) (6) have been synthesized solvothermally and characterized by single crystal X-ray diffraction. Compounds 1 and 2 are isostructural and crystallize in the orthorhombic space group Cmma with lattice parameters of a=6.7063(7)A, b=17.6051(18)A, c=12.7088(13)A and a=6.5770(3)A, b=17.5245(8)A, c=12.5515(6)A, respectively. The polymeric anionic chains in 1 and 2 are formed by edge-sharing MI4 (M=Ag, Cu) tetrahedra. Compounds 3 and 4 are isostructural and crystallize in the monoclinic space group P21/n with lattice parameters of a=16.5085(7)A, b=16.0392(7)A, c=16.5115(7)A, beta=97.4710(10) deg and a=16.4478(6)A, b=16.0645(6)A, c=16.4498(6)A, beta=97.4490(10) deg , respectively. Both structures contain the first observed, face-sharing [Bi2I8]2- anion cluster that is linked via corner sharing into infinite zig-zag anionic chains. Compounds 5 and 6 are isostructural and crystallize in the triclinic space group with lattice parameters of a=11.8798(5)A, b=15.2805(7)A, c=16.1889(7)A, alpha=63.9240(10) deg , beta=74.0420(10) deg , gamma=73.2540(10) deg and a=11.7889(5)A, b=15.3224(6)A, c=16.2584(6)A, alpha=64.1920(10) deg , beta=73.5600(10) deg , and gamma=73.7120(10) deg , respectively. Compounds 5 and 6 contain infinite [Pb3I8]2- chains in which the three crystallographically unique Pb2+ ions are found in sets of three trans face-sharing octahedra. These face-sharing trimers are observed in pairs that share three edges, and the pairs are further connected into 1-D chains by edge sharing with neighboring 2X3 units.