STRUCTURES OF THE 3-1 ADDUCTS OF CADMIUM(II) BROMIDE AND OF CADMIUM(II) CHLORIDE WITH 15-CROWN-5 ETHER - STRUCTURAL-CHANGES INDUCED BY RADIATION

3CdBr2.C10H20O5, M(r) = 1036.9, monoclinic, P2(1)/c, a = 7.535 (6), b = 14.452 (17), c = 11.771 (12) angstrom, beta = 116.54 (2)-degrees, V = 1147 (2) angstrom-3, Z = 2, D(x) = 3.00 g cm-3, Mo K-alpha, lambda = 0.71073 angstrom, mu = 131.2 cm-1, F(000) = 948, T = 295 K, R(F) = 0.036 for 1234 reflextions [I greater-than-or-equal-to 3-sigma(I)] and 105 variables. 3CdCl2.C10H20O5, ordered structure, M(r) = 770.2, monoclinic, P2(1), a = 7.217 (1), b = 14.235 (2), c = 11.255 (1) angstrom, beta = 115.835 (8)-degrees, V = 1040.7 (2) angstrom-3, Z = 2, D(x) = 2.46 g cm-3, Mo K-alpha, F(000) = 732, T = 295 K. 3CdCl2.C10H20O5, disordered structure, second data set, M(r) = 770.2, monoclinic, P2(1)/c, a = 7.231 (3), b = 14.331 (21), c = 11.284 (7) angstrom, beta = 116.00 (2)-degrees, V = 1051 (2) angstrom-3, Z = 2, D(x) = 2.43 g cm-3, Mo K-alpha, mu = 37.9 cm-1, F(000) = 732, T = 295 K, R(F) = 0.035 for 2285 reflexions [I > 3-sigma(I)] and 105 variables. 3CdCl2.C10H20O5, disordered structure, third data set, M(r) = 770.2, monoclinic, P2(1)/c, a = 7.236 (4), b = 14.417 (46), c = 11.312 (13) angstrom, beta = 116.05 (5)-degrees, V = 1060 (4) angstrom-3, Z = 2, D(x) = 2.41 g cm-3, Mo K-alpha, mu = 37.6 cm-1, F(000) = 732, T = 295 K, R(F) = 0.041 for 2073 reflexions [I > 3-sigma(I)] and 105 variables. 3CdCl2.C10H20O5, disordered structure, fourth data set, M(r) = 770.2, monoclinic, P2(1)/c, a = 7.249 (1), b = 14.521 (19), c = 11.350 (5) angstrom, beta = 116.15 (3)-degrees, V = 1072 (2) angstrom-3, Z = 2, D(x) = 2.38 g cm-3, Mo K-alpha, mu = 37.1 cm-1, F(000) = 732, T = 293 K, R(F) = 0.054 for 1862 reflexions [I > 3-sigma(I)] and 105 variables. 3CdCl2.C10H20O5, disordered structure, fifth data set, M(r) = 770.2, monoclinic, P2(1)/c, a = 7.251 (1), b = 14.560 (19), c = 11.360 (5) angstrom, beta = 116.19 (3)-degrees, V = 1076 (2) angstrom-3, Z = 2, D(x) = 2.38 g cm-3, Mo K-alpha, mu = 37.0 cm-1, F(000) = 732, T = 293 K, R(F) = 0.060 for 1713 reflexions [I > 3-sigma-(I)] and 105 variables. For the disordered structures, i.e. the bromide and data sets 2-5 for the chloride, the cell dimensions are the mean of those measured before and after the intensity measurements. The compounds are isostructural; both contain trigonal and pentagonal bipyramidally coordinated Cd atoms which are linked by halogen bridges to form sheets perpendicular to b. The Cd atom at the centre of the crown ether, which is disordered, is bonded by strong Cd-O bonds [Cd-O 2.22 (2) to 2.38 (2) angstrom in the bromide and 2.239 (5) to 2.404 (6) angstrom in the chloride]. The axial Cd-Br bonds [2.812 (3) to 2.878 (2) angstrom] are longer than the equatorial Cd-Br bonds [2.623 (2) to 2.640 (2) angstrom. The axial Cd-Cl bonds range from 2.651 to 2.691 (1) angstrom and the equatorial Cd-Cl bonds from 2.508 (1) to 2.535 (1) angstrom. Both compounds suffer radiation damage which results in changes in the cell dimensions during data collection and, for the chloride, a phase transition occurs in which the crown becomes disordered and the space group changes from P2(1) to P2(1)/c.