The effect of steric bulk on coordination sphere geometry for BiCl3 complexes with bulky heterocyclic imidazolethione ligands

The synthesis and characterization of three new complexes, BiCl3(mipit)2, BiCl3(emit)2 and BiCl3 (mnpit) 2 are reported where emit = 1-ethyl-3-methyl-2(3H)-imidazolethione; mnpit = 1-methyl-3-(1-propyl)-2(3H)-imidazolethione; mipit = 1-methyl-3-(2-propyl)-2(3H)-imidazolethione. X-ray crystallographic results are reported for the mnpit and mipit complexes whereas the structure of the emit complex is under reinvestigation because of disorder. BiCl3(mnpit)2 crystallizes in a triclinic space group (P ) with lattice parameters: a = 9.4223(6) A, b = 10.6275(6) A, c = 12.8860(8) A, α = 108.329(1)°, β = 90.388(1)°, γ = 115.200(1)°, V = 1093(1) A3, Z = 2. BiCl3 (mipit) 2 crystallizes in a triclinic space group (P ) with lattice parameters: a = 10.4347(8) A, b = 11.0018(9) A, c = 11.2075(9) A, α = 95.827(1)°, β = 104.890(1)°, γ = 117.064(1)°, V = 1071(1) A3, Z = 2. Both complexes show the same pattern with two BiL2Cl4 (L = ligand) octahedra sharing a common edge through bridging chlorine atoms and the ligands occup...

[1]  Daniel J. Williams,et al.  Main group metal halide complexes with sterically hindered thioureas part XVIII: The synthesis, characterization, and X-ray crystallographic study of a BiCl3 complex with 1-methyl-2(3H)-imidazolethione , 2006 .

[2]  Daniel J. Williams,et al.  The preparation, characterization and X-ray structural analysis of tetrakis[1-methyl-3-(2-propyl)-2(3H)-imidazolethione]zinc(II) tetrafluoroborate and tetrakis[1-methyl-3-(1-butyl)-2(3H)- imidazolethione]zinc(II) tetrafluoroborate , 2006 .

[3]  R. Hancock,et al.  Structural effects of the lone pair on lead(II), and parallels with the coordination geometry of mercury(II). Does the lone pair on lead(II) form H-bonds? Structures of the lead(II) and mercury(II) complexes of the pendant-donor macrocycle DOTAM (1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazac , 2004, Inorganic chemistry.

[4]  Daniel J. Williams,et al.  The preparation and structural characterization of 1-methylimidazolium and 1,3-dimethylimidazolium tetrachlorobismuthate(III) , 2003 .

[5]  Daniel J. Williams,et al.  1-Methyl-3-alkyl-2(3H)imidazolethione Complexes of Metal Halides: A Thematic-Ligand Approach to Involve Undergraduates in Research Projects , 2002 .

[6]  D. Reger,et al.  Control of the stereochemical impact of the lone pair in lead(II) tris(pyrazolyl)methane complexes. Improved preparation of Na[B[3,5-(CF3)2C6H3]4]. , 2001, Inorganic chemistry.

[7]  Daniel J. Williams,et al.  Main Group Metal Halide Complexes with Sterically Hindered Thioureas: Part XVII. The Crystal and Molecular Structures of Two New Tellurium Chloride Complexes with 1,3-dimethyl-2(3H)-imidazolethione , 2000 .

[8]  J. Glusker,et al.  Lone Pair Functionality in Divalent Lead Compounds , 1998 .

[9]  Daniel J. Williams,et al.  Stereochemical Consequences of the Bismuth Atom Electron Lone Pair, a Comparison between MX(6)E and MX(6) Systems. Crystal and Molecular Structures of Tris[N-(P,P-diphenylphosphinoyl)-P,P-diphenylphosphinimidato]bismuth(III), [Bi{(OPPh(2))(2)N}(3)], -indium(III), [In{(OPPh(2))(2)N}(3)].C(6)H(6), and , 1996, Inorganic Chemistry.

[10]  K. Wynne.  Factors involved in the stereochemistry of AX6E systems of the heavy main group elements , 1973 .

[11]  Aaron M. Lee,et al.  Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. I Large-Cation (2,2′-Bipyridinium and 1,10-Phenan- throlinium) Salts of Polyhalobismuthate(III) Ions , 1998 .

[12]  Daniel J. Williams,et al.  Di-μ-chlorobis[1,3-dimethyl-2(3H)-imidazolethione]dichlorobismuth(III), C20H32Bi2Cl6N8S4 , 1982 .

[13]  A. Corradi,et al.  X-Ray crystal structures of µ4-chloro-{tris[trichloro(thiosemicarbazide)-bismuth(III)]}[tris(thiosemicarbazide)bismuth(III)] hexachlorobismuthate(III) chloride and catena-µ-chloro-dichlorobis(ethylenethiourea)-bismuth(III) , 1978 .

[14]  A. Corradi,et al.  Cationic and anionic bismuth(III) in chloro-thiourea complexes: crystal structure of [Bi(tu)6][Bi{(tu)1.5Cl1.5}Cl3]2(tu = thiourea) , 1977 .