M. R. Caira

The crystal structures of hexahalouranates. I. Bis(triphenylethylphosphonium) hexachlorouranate(IV) and bis(triphenylethylphosphonium) hexabromouranate(IV)

HANSON, H. P., HERMAN, F., LEA, J. D. & SKILLMAN, S. (1964). Acta Cryst. 17, 1040-1044. HULME, R. & SCRUTON, J. C. (1968). J. Chem. Soc. A, pp. 2448-2452. HULME, R. 8~ SZYMANSKI, J. T. (1969). Acta Cryst. B25, 753-761. JOHNSON, C. K. (1965). ORTEP. Report ORNL-3794. Oak Ridge National Laboratory, Tennessee. KISLIUK, P. (1954). J. Chem. Phys. 22, 86-92. LINDQUIST, I. St. NIGGLI, A. (1956). J. Inorg. Nucl. Chem. 2, 345-347. MENSHUTKIN, I . (1912). Zh. Russ. Fiz. Khim. Ova, 44, 1079-1145. NELSON, J. B. & RILEY, D. P. (1945). Proc. Phys. Soc. London, 57, 160-177. PARK, W. (1969). PhD Dissertation, Univ. of Louisville, Louisville, Kentucky. PAULING, L. (1960). The Nature of the Chemical Bond. Ithaca: Cornell Univ. Press. STEWART, R. F., DAVIDSON, E. R. & SIMPSON, W. T. (1965). J. Chem. Phys. 42, 3175-3187. WILLIAMS, D. E. (1964). A Fortran Lattice Constant Refinement Program, US Atomic Energy Commission Report, IS1052. WILLIAMS, D. E. & RUNDLE, R. E. (1964). J. Am. Chem. Soc. 86, 1660-1666.

The coordination chemistry of divalent cobalt, nickel and copper. Part II. The characterisation of a mixed ligand nickel(II) species and its thermal decomposition products. The crystal structure of (pyridine-2,6-dicarboxylato)(N,N,N′,N′-tetramethyl-1,2-diaminoethane)nickel(II) dihydrate

Abstract The magnetic and spectral properties of the complex Ni(pydca)(tmen)·2H 2 O (1) and those of the thermally-derived species Ni(pydca)(tmen)·H 2 O (2) and Ni(pydca)(tmen) (3) have been studied (pydca = pyridine-2,6-dicarboxylate, tmen = N,N,N,′,N′-tetramethyl-1,2-diaminoethane). Conflicting features in the electronic spectra prevented unambiguous stereo-chemical assignments. The presence of split ν 8 (COO) and ν as (COO) infrared absorption bands in the regions 1350–1400 cm −1 and 1610–1680 cm −1 respectively suggested dissimilar co-ordination of the carboxylate groups. The structure of (1) has been determined by the heavy-atom technique and refined by least-squares. Crystals are triclinic, space group P 1 , with a = 10.806(5), b = 8.626(4), c = 9.825(5) A, α = 114.32(2), β = 91.52(2), γ = 96.67(2)°, d obs = 1.50 (by flotation), d calc = 1.51 g cm −3 and Z = 2. With N obs = 2218, the final R factor was 0.047. Complex (1) is properly formulated as [Ni(pydca)(tmen)(H 2 O)]·H 2 O with Ni in a distorted octahedral environment, being bonded to two O atoms and the N atom of pydca, the two N atoms of tmen and one water molecule. The NiN(amine) distances differ significantly but structural parameters for the two carboxylate groups agree within experimental error. The anomalous spectral splitting appears to be common to analogous species containing fully-substituted diamines. Distorted octahedral and distorted square pyramidal symmetries are assigned to (2) and (3) respectively.

The coordination chemistry of divalent cobalt, nickel and copper—IX: The crystal structure and characterisation of a cationic 5-coordinate Cu(II) complex

Abstract The preparation, properties and X-ray crystal structure of [Cu(ttda)(tmen)](ClO4)2, a complex of divalent copper perchlorate with the ligands N,N,N′,N′-tetramethyl-1,2-diaminoethane (tmen) and bis-(N,N′-dimethyl-acetamido)thioether(ttda) are reported. The crystals are monoclinic with a = 15.35(1), b = 15.04(1), c = 10.91(1) A, β = 98.74(2)°, four formula units per unit cell and space group P21/n. The complex cation is shown to be penta-coordinate with a distorted square pyramidal geometry. Comparison is made with the properties and structure of the previously reported CuCl2·ttda.