Cyanoplatinate Halides - Synthesis, Crystal Structure Analyses and Vibrational Spectroscopy of Compounds A2[Pt(CN)4X2] (A = Rb, Cs; X = Cl, Br, I)

Crystal structures of the cyanoplatinates A(2)[Pt(CN)(4)X-2] (A = Rb Cs, X = Cl, Br, I) have been determined by single-crystal analysis and X-ray powder diffraction The compounds were synthesized by metathesis from Ba[Pt(CN)(4)] 4 H2O and alkali metal sulfates and by subsequent oxidation with the respective halogens The crystals were grown by slowly concentrating respective aqueous solutions The Pt-IV cations are octahedrally coordinated by four cyanide ligands and two halogen atoms, the latter being located in trans positions Rb-2[Pt(CN)(4)Cl-2] triclinic P (1) over bar (Z = 2) a = 6 7779(2), b = 9 3149(3) c = 9 6707(3) A alpha = 89 37(0), beta = 76 05(0), gamma = 72 98(0)degrees, V = 565 42(2) angstrom(3) N'(hkl)= 5616, R(F)(N') = 0 0273 Rb-2[Pt(CN)(4)I-2] monoclinic, P2(1)/c (Z = 2), a = 7 4239(2), b = 9 2486(2), c = 9 1189(2) A, beta = 107 22(3)degrees, V = 598 04(6) A(3), N'(hkl) = 2917 R(F)(N') = 0 0295 Cs-2[Pt(CN)(4)I-2] monoclinic P2(1/c) (Z = 2), a = 7 6740(4) b = 9 5397(5) c = 9 3474(5) A beta = 106 46(0)degrees V = 656 3(2) A(3) Z = 2 N'(hkl) = 2738 R(F)(N') = 0 0283 Cs-2[Pt(CN)(4)Cl-2] monoclinic C2/c (Z = 4) a = 17 947(4), b = 7395(2), c = 12 031(3) A, beta = 131 904(1)degrees V = 1188 4(5) A(3), R-wp = 2 77, Cs-2[Pt(CN)(4)Br-2] monoclinic, C2/c (Z = 4), a = 18 404(1), b = 7 2819(5), c = 12 4156(8) A, beta = 132 156(1)degrees V = 1233 5(1) A(3) N'(hkl) = 2566, R(F)(N') = 0 0268 All compounds were characterized by differential thermal analysis thermogravimetry and infrared and Raman spectroscopy