Yoshie Inomata

CHARACTERIZATION AND CRYSTAL STRUCTURES OF ZINC(II) AND CADMIUM(II) COMPLEXES WITH D-(-)-QUINIC ACID

Zinc(II) and cadmium(II) complexes with D -(−)-quinic acid (H 5 quina), [Zn(H 4 quina) 2 ] and [Cd(H 4 quina) 2 ](H 2 O), have been prepared and characterized by means of infrared spectra and thermal analysis. Crystal structures of both complexes have been determined by X-ray diffraction. The crystal of [Zn(H 4 quina) 2 ] is monoclinic with the space group C 2. The zinc(II) atom is in a trigonal antiprism geometry, ligated by two carboxylato oxygen atoms and two hydroxyl oxygen atoms from two molecules of quinic acid, and two carboxylato oxygen atoms of two neighboring molecules. This complex consists of polymers bridged by a carboxylato oxygen atom. The crystal of [Cd(H 4 quina) 2 ](H 2 O) is monoclinic with space group P 2 1 . The cadmium atom is in a monocapped trigonal prism geometry. There are two types of quinic acid in this complex. One quinic acid molecule chelates with a cadmium atom by a carboxylato oxygen atom and a hydroxyl oxygen atom, and coordinates with a neighboring cadmium atom by a carboxylato oxygen atom. The other quinic acid molecule chelates with a cadmium atom by two oxygen atoms of a carboxyl group, and chelates with a neighboring cadmium atom by two hydroxyl oxygen atoms. This complex consists of polymers bridged by carboxylato oxygen atoms and hydroxyl oxygen atoms.

Synthesis, properties and crystal and molecular structure of isothiocyanato [N,N-bis(2-hydroxyethyl)glycinato]copper(II) monohydrate

Abstract The crystal and molecular structure of the title copper(II) complex was determined by the X-ray diffraction method. The crystal is monoclinic with the space group Cc , Z =4, a = 14.567(2), b= 6.970(1), c = 11.051(2) ) A, β = 93.67(1)°. Full matrix least-squares refinements have led to a final R value of 0.057 for 1080 reflections. The copper atom is ligated by one carboxylato oxygen atom, two hydroxyl oxygen atoms and one nitrogen atom of the ligand, and one nitrogen atom and one sulfur atom of the isothiocyanate ion. The copper atom is at the center of the typical tetragonal-bipyramidal geometry. One hydroxyl oxygen atom and sulfur atom are at the apical positions and their bond lengths to the copper atom are longer than usual. The other four atoms form a square around the copper atom. The complex forms a one-dimensional polymer chain through the isothiocyanate ion.

The syntheses of lanthanide metal complexes with diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid and the comparison of their crystal structures

Abstract Four lanthanide metal (Dy, Ho, Er, Yb) complexes with diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid (H5dtpa) have been prepared and characterized by using their infrared absorption spectra and thermal analyses. The crystal and molecular structures of (NH4)2[M(dtpa)]·4H2O (M: Dy, Ho, Er, Yb) were determined by a single-crystal X-ray diffraction method. The crystals of these complexes were iso-morphous to each other: monoclinic, space group P 1 , Z=2. The central metal atom is nine-coordinated, in a tricapped trigonal prism geometry, to three N and five O atoms of dtpa5−, and a carboxylato oxygen atom from an adjacent complex ion, resulting in the formation of a binuclear structure. These six M–O and three M–N bond lengths increase with the lengthening of the radius of the metal ion.

The metal complexes of amino acids and their N-substituted derivatives—VII. The i.r. spectra and normal coordinate analyses of bivalent metal complexes with N-methylglycine and N-phenylglycine

Twelve complexes of bivalent metals with N-methylglycine (sarcosine) and N-phenylglycine have been prepared over wide pH ranges and characterized by means of i.r. powder diffuse reflection, electronic spectra and magnetic susceptibility. These complexes are classified into two types, either with or without chloride ions, from elemental analyses: the former type (A) consists of ML2·nH2O (M = Co, Ni, Cu, Zn for L = sarcosinate anion; M = Co, Ni, Cu, Zn, Cd for L = N-phenylglycinate anion), which appear to be octahedral complexes. The metal is coordinated through a nitrogen atom, a carboxyl oxygen atom and water molecules or the carboxyl oxygen atoms of neighboring molecules. The latter type (B) consists of CoCl2 (HL)2·2H2O, ZnCl2 (HL)2 and CdCl2 (HL) (HL = sarcosine), in which the ligand has a zwitterion structure and has metal ions coordinated through only a carboxyl oxygen atom, but does not chelate through a nitrogen atom. In the cadmium (II) complex, a chloride ion seems to bridge to two cadmium (II) ions. In order to assign the observed frequencies of i.r. spectra in detail, normal coordinate analyses have been carried out for the complexes of the A type. The frequency separation of COO− antisymmetric and symmetric vibrations of A type complexes with sarcosine increases in the order: Co (II) < Ni (II) < Zn (II) < Cu (II). These separations of A type complexes with sarcosine and N-phenylglycine are larger than those of the corresponding complexes with glycine, alanine and other α-amino acids. The frequencies of metal-nitrogen and metal-oxygen stretching vibrations increase in the order: Co (II) < Zn (II) < Ni (II) < Cu (II) for sarcosine A type complexes.

Synthesis, properties, and crystal and molecular structure of N,N-bis(2-hydroxyethyl)glycinato copper (II) perchlorate monohydrate

The synthesis and X-ray diffraction study of the title copper(II) complex have been carried out. The crystal is monoclinic with the space group P21/n, Z = 4, a = 12.646(2), b = 9.369(1), c = 10.619(2) A, β = 108.69(1)°. Full matrix least-squares refinements have led to a final R value of 0.052 for 2996 reflections. The ligand coordinates to the copper atom so as to form three five-membered chelate rings. The copper atom is in a trigonal-bipyramidal geometry, ligated by a nitrogen atom, a carboxylato oxygen atom, two hydroxyl oxygen atoms and a carboxylato oxygen atom of the neighboring unit. The complex forms a one-dimensional polymer chain through the carboxylato group and is charged positively. The perchlorate ion does not coordinate to the copper atom and is located within a bundle of the polymer chains of the complex. Some properties of the complex are discussed.

Characterization and crystal structures of copper(II), cobalt(II), and nickel(II) complexes with two kinds of piperidine carboxylic acids

Abstract Copper(II) complex with dl -piperidine-3-carboxylic acid ( dl -Hpipe-3):[Cu( dl -pipe-3) 2 (H 2 O)] and cobalt(II) and nickel(II) complexes with piperidine-4-carboxylic acid (Hpipe-4):[M(Hpipe-4) 2 (H 2 O) 4 ]Cl 2 (M: Co, Ni) have been prepared and characterized by means of IR and powder diffuse reflection spectra, thermal analysis, and magnetic susceptibility. The crystal structures of these complexes have been determined by X-ray diffraction. The crystal of [Cu( dl -pipe-3) 2 (H 2 O)] is orthorhombic with the space group Pbcn. The copper atom is in a square pyramidal geometry, ligated by two carboxylato oxygen atoms, two nitrogen atoms, and a water molecule. One molecule of this complex consists of either d -piperidine-3-carboxylic acid or l -piperidine-3-carboxylic acid. The crystals of [M(Hpipe-4) 2 (H 2 O) 4 ]Cl 2 are monoclinic with space group P 2 1 / n . In these complexes the metal atom is in an octahedral geometry ligated by two carboxylato oxygen atoms and four water molecules.

Syntheses and crystal structures of zinc(II) complexes with three kinds of piperidine carboxylic acids

Abstract Zinc(II) complexes with dl -piperidine-2-carboxylic acid (Hpipe-2), dl -piperidine 3-carboxylic acid (Hpipe-3), and piperidine-4-carboxylic acid (Hpipe-4):ZnCl2(Hpipe 2)2, ZnCl2(Hpipe-3)2(H2O)3, and ZnCl2(Hpipe-4) have been prepared and characterized by means of IR spectra and thermal analysis. The crystal structures of [ZnCl2(Hpipe-3)2]·3H2O and [ZnCl2(Hpipe-4)] have been determined by X-ray diffraction. The crystal of [ZnCl2(Hpipe-3)2]·3H2O is monoclinic with the space group P21/c. The zinc atom is in a tetrahedral geometry, ligated by two carboxylato oxygen atoms and two chlorine atoms. The crystal of [ZnCl2(Hpipe-4)] is triclinic with space group P1. This complex consists of a binuclear molecule bridged by two carboxylato oxygen atoms. The zinc atom is in a tetrahedral geometry ligated by two carboxylato oxygen atoms and two chlorine atoms.

Syntheses, properties, and crystal and molecular structures of bromo[N,N-bis(2-hydroxyethyl)glycinato]copper(II) and aquabromo[N,N-bis(2-hydroxyethyl)glycinato]copper(II)

Abstract The syntheses and characterization of bromo[ N , N -bis(2-hydroxyethyl)glycinato]copper(II) ( 1 ) and aquabromo [ N , N -bis(2-hydroxyethyl)glycinato]copper(II) ( 2 ) are presented. X-ray crystal structure determinations of both complexes have been carried out. Complex 1 crystallizes in the monoclinic system, space group P 2 1 / n , with Z =4 and unit cell parameters a =12.910(2), b =8.478(1) and c =8.894(2) A, and β=105.11(1)°. Complex 2 crystallizes in the orthorhombic system, space group P 2 1 2 1 2 1 , with Z =4 and unit cell parameters a =8.7672(9), b =15.594(3) and c =7.4996(5) A. In complex 1 the copper atom is in a trigonal bipyramidal geometry, while complex 2 has a distorted octahedral configuration.

Synthetic, Spectroscopic and X-ray Crystallographic Studies of Bivalent metal Complexes with Amino Acids Having a Thiazolidine Ring. II. Properties of Bivalent Metal Complexes with Racemic 4-Thiazolidinecarboxylic Acid

Complexes of the type ML2·nH2O (M = Co, Ni, Zn, Cd,) and ZnCl2(HL)2 have been prepared, where HL is racemic 4-thiazolidinecarboxylic acid (CH2SCH2NHCHCOOH). Each complex was characterized by elemental analysis, powder diffuse reflection, infrared absorption, NMR spectroscopy magnetic susceptibility, thermal analysis and powder X-ray diffraction. These measurements suggest that in the first type of complex the ligand coordinates to a metal with a nitrogen atom and an oxygen atom, while in the second type of complex, the zinc atom is ligated with a carboxyl oxygen atom of this ligand which has a zwitterion structure, and two chlorine atoms. The IR spectrum of recemic 4-thiazolidinecarboxylic acid is the same as that of (S)-4-thiazolidinecarboxylic acid, but the IR spectra of the metal complexes are different from those of the corresponding metal complexes wit (S)-4-thiazolidinecarboxylic acid.

Complexes of nickel(II), copper(II), zinc(II) and cadmium(II) with 4-hydroxy-L-proline

Complexes of four bivalent metals with 4-hydroxy-L-proline have been prepared and characterized by means of infrared absorption, powder diffuse reflection, electronic spectra, magnetic susceptibility, and thermal analysis. The complexes appear to be of three distinct types. The first type includes ML2·nH2O (M = Ni, Zn, Cu, L = 4-hydroxy-L-prolinato anion), and CuClL·H2O is a second type. In both the ligand chelates metal ions through the nitrogen atom of the pyrrolidine ring and the oxygen atom of the carboxylato group. CuL2 appears to adopt a cis geometry, and in the second type a chloride ion seems to bridge to two copper(II) ions. CdCl2HL is a third type, in which the cadmium ion is coordinated through the oxygen atom of the carboxylato group and chloride ions, but is not coordinated through the nitrogen atom.