Milton D. Glick

Structures of a labile copper redox couple: sterically constrained copper(II) and copper(I) complexes formed with a simple cyclic pentathia ether, 1,4,7,10,13-pentathiacyclopentadecane

Determination par diffraction RX des structures cristallines des complexes Cu II ([15]ane S 5 ) (ClO 4 ) 2 et Cu I ([15]ane S 5 ) (ClO 4 ). Coordination pyramidale a base carree autour des atomes Cu(II) et tetraedrique deformee autour des atomes Cu(I)

Structure of and bonding in I,5-cyclooctadiene-duroquinone nickel

Abstract The structure of I,5-cyclooctadiene-duroquinone-nickel, C8H12NiC10H12O2, has been determined from a three-dimensional X-ray analysis. The compound crystallizes in a monoclinic unit cell of symmetry P2/n and dimensions a = 14.26 A, b = 7.95 A, c = 14.17 A, and β = 94°27′. There are four molecules per unit cell with each molecule located on a crystallographic two-fold axis. A three-dimensional least-squares refinement yielded a final unweighted discrepancy factor of R1 = 101%. Each discrete monomeric molecule consists of a nickel atom sandwiched between a boat- form I,5-cyclooctadiene ring and a duroquinone ring. The two sets of parallel double bonds in the cyclooctadiene and duroquinone rings are perpendicular; the nickel therefore can be considered to possess an idealized tetrahedral configuration. The cyclooctadiene ring of C2 symmetry shows significant skeletal skewing similar to that present in free I,5-cyclooctadiene, whereas the idealized D2h symmetry of free duroquinone is reduced to C2c in the nickel-complexed duroquinone due to a deformation of the carbonyl groups out of the plane of the ring. The detailed geometry of the rings, and the nature and implications of the bonding are discussed with respect to related complexes.

Encircling of mercury(II) by a macrocyclic ligand: X-ray crystal structure of 1,5,9,13-tetrathiacyclohexadecanemercury(II) perchlorate

The crystal structure of the most stable complex involving HgII co-ordinated to a macrocyclic tetrathia-ether (1,5,9,13-tetrathiacyclohexadecane) reveals that the HgII ion is situated almost in the centre of the four sulphur donor atoms, which themselves are twisted somewhat out of plane, with the inner co-ordination sphere being completed by two unequally bonded perchlorate ions situated along the z axis.

Benzyltriphenylmethylthiomercury; crystal structure determination

The crystal structure of PhCH2HgSCPh3 reveals a linear C–Hg–S bond, a Ph–C–Hg bond angle of 112° and a dihedral angle of 87° between the plane of the benzyl carbons and the plane formed by the mercury atom, the methylene carbon and C-1 on the phenyl group.