STRUCTURE OF WOLFRAM SALT ANALOGS [M(-CHXN)2BR]BR2[M = PD, PT-CHXN = (-)-1,2-CYCLOHEXANEDIAMINE]

trans-Dibromobis[(-)-1(R),2(R)-cyclohexanediamine]palladium(IV)-bis[(-)-1(R),2(R)-cyclohexanediamine]palladium(II) tetrabromide, [Pd(C6H14N2)2Br2][Pd(C6H14N2)2]Br4, M(r) = 936.2, MDO1: monoclinic, a = 24.464 (3), b = 7.073 (1), c = 10.586 (2) angstrom, beta = 102.504 (6)degrees, V = 1788.4 (4) angstrom 3, Z = 2; superposition structure: orthorhombic, I222, a = 23.884 (3), b = 7.073 (1), c = 5.293 (1) angstrom, V = 894.2 (2) angstrom 3, Z = 1, D(x) = 1.783 g cm-3, F(000) = 558, Ag K-alpha (lambda = 0.56087 angstrom), mu = 36.3 cm-1, T = 295 K, R(F) = 0.032 for 1390 observed unique reflexions [I > 3-sigma(I)]. trans-Dibromobis[(-)-1(R),2(R)-cyclohexanediamine]platinum(IV)-bis[(-)-1(R),2(R)-cyclohexanediamine]platinum(II) tetrabromide, [Pt(C6H14N2)2Br2][Pt(C6H14N2)2]Br4, M(r) = 1326.4, MDO1: monoclinic, a = 24.478 (3), b = 7.022 (1), c = 10.747 (1) angstrom, beta = 102.668 (7)degrees, V = 1802.4 (3) angstrom 3, Z = 2; superposition structure: orthorhombic, I222, a = 23.884 (3), b = 7.022 (1), c = 5.374 (1) angstrom, V = 901.3 (2) angstrom 3, Z = 1, D(x) = 2.443 g cm-3, F(000) = 622, Mo K-alpha (lambda = 0.71073 angstrom), mu = 144.5 cm-1, T = 295 K, R(F) = 0.036 for 2697 reflexions [I > 3-sigma(I)]. [Pt(C6H14N2)2-Cl2][Pt(C6H14N2)2]Cl4, M(r) = 1059.6, MDO1: monoclinic, a = 24.810 (4), b = 6.820 (1), c = 10.316 (2) angstrom, beta = 101.999 (3)degrees, V = 853.7 (3) angstrom 3, Z = 2. The superposition structures are isomorphous with the platinum chloride compound [Larsen & Toftlund (1977). Acta Chem. Scand. Ser. A, 31, 182-186]. They are built up of M(IV)-X...M(II) chains parallel to the c axis, but with two half-weight halide ions indicating disorder. Pd(IV)-Br = 2.521 (4), Pd(II)-Br = 2.782 (4) and Pd-N = 2.058 (3) angstrom. PdN4 is tetrahedrally distorted with N-Pd-N = 177.6 (8)degrees. Pt(IV)-Br = 2.498 (1), Pt(II)-Br = 2.884 (1), Pt-N = 2.064 (3) angstrom and N-Pt-N = 177.7 (4)degrees. Diffuse reflexions could be indexed in terms of a twinned monoclinic cell with a(m) = (a(o)2 + c(o)2)1/2, b(m) = b(o), c(m) = 2c(o), beta = 90 + arctan(c(o)/a(o))degrees. The complexes crystallize with a disordered structure of OD (order-disorder) type, the orthorhombic cell corresponds to the superposition structure and the monoclinic to the MDO (maximum degree of order) structure. Diffuse scattering was also observed for the Pt-Cl complex.