Synthesis, characterization, and crystal and molecular structures of the coordination compounds, [Me2Ga•O(C5H3N)CH2NMe2] and [Me2Ga•O(C9H6N)]2

1987 ◽  
Vol 65 (4) ◽  
pp. 782-788 ◽  
Author(s):  
Emmanuel C. Onyiriuka ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Heavy Atom ◽  
Amino Nitrogen ◽  
Molecular Structures ◽  
Geometrical Parameters ◽  
Planar System ◽  
Gallium Atom ◽  
Space Group ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal Coordination ◽  
Centrosymmetric Dimers

Crystals of (2-dimethylaminomethyl-3-pyridolato)dimethylgallium are monoclinic, a = 13.443(3), b = 6.7563(3), c = 13.046(2) Å, β = 100.38(1)°, Z = 4, space group I2/m, and those of bis[(8-quinolinolato)dimethylgallium] are monoclinic, a = 9.7340(4), b = 12.7135(5), c = 9.6843(4) Å, β = 117.014(3)°, Z = 2, space group P21/c. Both structures were solved by conventional heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.044 and 0.032 for 1485 and 1567 reflections with I ≥ 3σ(I), respectively. The structure of [Me2Ga•O(C5H3N)CH2NMe2] consists of discrete monomeric molecules which contain tetrahedrally coordinated gallium atoms. The bidentate anionic 2-dimethylaminomethyl-3-pyridolate ligand coordinates Ga via the oxygen and amino nitrogen atoms (Ga—O = 1.892(3), Ga—N = 2.127(4), Ga—C = 1.950(5) and 1.939(6) Å). The structure of [Me2Ga•O(C9H6N)]2 consists of centrosymmetric dimers which contain a nearly planar system of seven fused rings. The Ga atoms are five-coordinate, having distorted trigonal bipyramidal coordination geometry. The dimerization occurs via the formation of a central, planar, four-membered (Ga—O)2 ring in which each asymmetrically bridging oxygen atom occupies an equatorial coordination site on one gallium atom and an axial site on the other. Important geometrical parameters for [Me2Ga•O(C9H6N)]2 are Ga—O(eq) = 1.937(3), Ga—O(ax) = 2.297(3), Ga—N(ax) = 2.211(3), Ga—C(eq) = 1.948(6) and 1.945(5) Å, O(ax)—Ga—N(ax) = 149.7(1)°.

Crystal and molecular structure of the salicylaldehydatogallium dimethyl dimer

1976 ◽  
Vol 54 (8) ◽  
pp. 1278-1284 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Least Squares ◽  
Crystal And Molecular Structure ◽  
Gallium Atom ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Trigonal Bipyramidal ◽  
Centrosymmetric Dimers ◽  
Distorted Trigonal Bipyramidal

Crystals of the salicylaldehydatogallium dimethyl dimer, [C7H5O2•GaMe2]2, are triclinic, a = 9.845(1), b = 8.6892(8), c = 7.4153(6) Å, α = 118.236(5), β = 92.46(1), γ = 115.81(1)°, Z = 1, space group [Formula: see text] The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares procedures to a final R of 0.050 and Rw of 0.064 for 1644 reflections with I ≥ 3σ(I). The structure features a five-coordinate gallium atom having distorted trigonal bipyramidal geometry. Monomer units link via the formation of a four-membered Ga2O2 ring to form the centrosymmetric dimers. Bond lengths in the molecule are: Ga—O(eq), 1.933(3), Ga—O(ax), 2.127(3) and 2.469(3), Ga—C, 1.944(6) and 1.946(5), C—O, 1.333(4) and 1.231(6), C(ar)—C(sp2), 1.432(7), mean C—C(ar), 1.395(8), mean C(sp3)—H, 0.92(4), and mean C(sp2)—H, 0.93(2) Å. Bonds not involving hydrogen have been corrected for thermal motion.

The Crystal and Molecular Structures of Two Modifications of cis-Dichloro-mer-tris-(dimethylphenylphosphine)hydridoiridium(III)

1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker
Keyword(s):  
Heavy Atom ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Ligand ◽  
Ligand Bond

The structures of two crystalline modifications of mer -(Pme2Ph)3H-cis-Cl2IrIII, (1), have been determined from single-crystal X-ray diffraction data. Modification (A) is monoclinic, space group P21/c with a 12.635(1), b 30.605(3), c 14.992(2)Ǻ, β 110.01(2)° and Z = 8. Modification (B) is orthorhombic, space group Pbca with a 27.646(3), b 11.366(1), c 17.252(2)Ǻ and Z = 8. The structures were solved by conventional heavy atom techniques and refined by full-matrix least- squares analyses to conventional R values of 0.037 [(A), 8845 independent reflections] and 0.028 [(B), 5291 independent reflections]. Important bond lengths [Ǻ] are Ir -P(trans to Cl ) 2.249(1) av. (A) and 2.234(1) (B), Ir -P(trans to PMe2Ph) 2.339(2) av. (A) and 2.344(1), 2.352(1) (B), Ir-Cl (trans to H) 2.492(2), 2.518(2) (A) and 2.503(1) (B) and Ir-Cl (trans to PMe2Ph)2.452(2) av. (A) and 2.449(1)(B). Differences in chemically equivalent metal- ligand bond lengths emphasize the importance of non-bonded contacts in determining those lengths.

Copper complexes of Picloram: The crystal and molecular structures of Bis(4-amino-3,5,6-trichloropyridine-2-carboxylato)aquacopper(II) dihydrate and Bis(4-amino-3,5,6-trichloropyridine-2-carboxylato)bis(pyrimidin-2-amine)copper(II)

1983 ◽  
Vol 36 (1) ◽  
pp. 183 ◽  
Author(s):  
EJ O'Reilly ◽  
G Smith ◽  
CHL Kennard ◽  
AH White
Keyword(s):  
Copper Complexes ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Trigonal Bipyramidal ◽  
Distorted Octahedral ◽  
A Cell ◽  
Amine Ligands

The crystal structures of two copper(II) complexes of the herbicide Picloram (4-amino-3,5,6-trichloro- pyridine-2-carboxylic acid) have been determined by single-crystal X-ray diffractometry. Bis(4-amino- 3,5,6-trichloropyridine-2-carboxylato)aquacopper(II) dihydrate (1) is monoclinic, space group C2/c, with Z 4 in a cell of dimensions a 15.593(6), b 7.940(6), c 16.983(6) �, β 107.58(3)�. The structure was refined to a residual R 0.046 for 905 'observed' reflections. Complex (1) is trigonal bipyramidal with the trigonal plane consisting of oxygens from two picolinate ligands [Cu-O 1.995(5) �] and a water molecule [Cu-O 2.080(5) �]. The apical positions are occupied by pyridine ring nitrogens from the Picloram ligands [Cu-N 2.021(5) �]. Bis(4-amino-3,5,6-trichloropyridine- 2-carboxylato)bis(pyrimidin-2-amine)copper(II) (2) is monoclinic, space group P2,/c, with Z 4 in a cell of dimensions a 12.3 11(5), b 15.435(5), c 15.320(6) �, β 115.95(3)�, and gave a final R 0.059 for 2429 'observed' reflections. In complex (2), the copper(II) atom has a tetragonally distorted octahedral stereochemistry with the Picloram ring nitrogens once again occupying the two axial positions [Cu-N 2.586(7) and 2.611(7) �]. The square plane consists of two carboxylato oxygens [Cu-O 1.941(6) and 1.960(7) �] and two hetero-nitrogens from pyrimidin-2-amine ligands [Cu-N 2.048(6) and 2.054(6) �].

Monomere und dimere Oxotrihalogenoselenate(IV): Darstellung, Struktur und Eigenschaften von [As(C6H5)4]SeOCl3 und [N(C2H5)4]SeOCl3 / Monomerie and Dimeric Oxotrihalogenoselenates(IV): Preparation, Structure and Properties of [As(C6H5)4]SeOCl3 and [N(C2H5)4]SeOCl3

1983 ◽  
Vol 38 (1) ◽  
pp. 20-29 ◽  
Author(s):  
Bernt Krebs ◽  
Marita Hucke ◽  
Michael Hein ◽  
Andreas Schäffer
Keyword(s):  
Polymer Chains ◽  
Monoclinic Space Group ◽  
Structure And Properties ◽  
Reaction Products ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Centrosymmetric Dimers

Abstract The monomeric SeOCl3- ion, which can be prepared as the tetraphenylarsonium salt from SeOCl2 and As(C6H5)4Cl, was structurally characterized by a low-temperature single crystal X-ray diffraction analysis. [As(C6H5)4]SeOCl3 is monoclinic, space group P21/c, with a = 9,332(3), b = 13,761(4), c = 18,985(6) Å, β = 110,97(3)° (at -135 °C), Z = 4; it contains a novel type of ψ-trigonal bipyramidal oxotrichloroselenate(IV) anion which is not associated to dimers or polymer chains as in known structures. The equatorial positions are occupied by doubly bonded oxygen (Se-O 1,601(3) Å) and by one Cl(Se-Cl 2,234(1) Å), the axial Se-Cl bonds (2,430(1) and 2,475(1) Å) being significantly longer. [N(C2H5)4]SeOCl3, which was obtained as crystals by oxidation of trichloroselenate(II), is triclinic, space group P1̄, with a = 10,607(3), b = 8,950(2), c = 8,862(2) Å, α = 119,79(2)°, β = 101,07(2)°, γ = 96,28(2)°, Z = 2. The X-ray structure analysis shows the anions to be present as centrosymmetric dimers Se2O2Cl62- like in the [P(C6H5)4]+ salt, with two tetragonal SeOCl4 pyramids linked through a Cl···Cl edge and the lone pairs trans to the axial Se-O bonds (1,589(4) Å). Se-Cl bond lengths are 2.270(1) and 2,351(2) Å (terminal); 2,698(1) and 2,920(1) Å (bridging). The results show that the nature of the reaction products of the Lewis acid SeOCl2 with halogenides as bases changes very sensitively with small variations in cations and environment. The vibrational spectra are discussed.

Synthesis, characterization, and X-ray structures of Rh(I) monocarbonyl complexes containing unsymmetric tridentate pyrazolylgallate ligands

1986 ◽  
Vol 64 (3) ◽  
pp. 566-574 ◽  
Author(s):  
David A. Cooper ◽  
Steven J. Rettig ◽  
Alan Storr
Keyword(s):  
Addition Reaction ◽  
Heavy Atom ◽  
Coordination Geometry ◽  
Space Group ◽  
X Ray ◽  
Square Planar ◽  
Text Interaction ◽  
Cl Atom ◽  
Centrosymmetric Dimers ◽  
Oxidative Addition Reaction

The reaction of the [Rh(CO)2Cl]2 dimer with the Na+[Me2Ga(N2C3H3)(OCH2(C5H4N))]− ligand has yielded the planar four-coordinate species [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO), (LRh(CO)), displaying the tridentate gallate ligand in a meridional coordination mode. In addition, a second product, of similar geometry but with one of the Me groups on the Ga replaced by a Cl atom, viz, [(Cl)MeGa(N2C3H3)(OCH2(C5H4N))]Rh(CO), has also been isolated and characterized. The former complex undergoes a facile oxidative addition reaction with MeI, the transient six-coordinate Rh(III) species produced being rapidly converted, in a methyl migration step, to the five-coordinate Rh(III) acetyl complex, LRh(COMe)I. Crystals of [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO) are monoclinic, a = 13.139(2), b = 13.324(2), c = 17.352(2) Å, β = 103.251(7)°, Z = 8, space group I2/a, and those of [(Cl)MeGa(N2C3H3)(OCH2(C5H4N))]Rh(CO) are triclinic, a = 8.846(2), b = 12.714(3), c = 7.631(2) Å, α = 93.82(1), β = 113.94(1), γ = 107.99(1)°, Z = 2, space group [Formula: see text] Both structures were solved by conventional heavy-atom methods and were refined by full-matrix least-squares procedures to final R values of 0.029 and 0.048 for 1890 and 1939 reflections with I ≥ 3σ(I), respectively. Both molecules display irregular square planar coordination geometry about Rh with Rh—O = 2.038(3) and 2.048(3), Rh—N(pyrazolyl) = 2.022(4) and 2.025(7), Rh—N(pyridyl) = 2.038(3) and 2.020(6), Rh—CO = 1.778(5) and 1.808(9) Å, respectively, for the two compounds. Molecules of [Me2Ga(N2C3H3)(OCH2(C5H4N))]Rh(CO) form weakly associated, centrosymmetric dimers via an intermolecular [Formula: see text] interaction of 3.5445(7) Å.

Synthesis of Bis(6-methylquinolin-8-yl)phenylarsine and tris(6-methylquinolin-8-yl)-arsine and certain of their bivalent palladium and zerovalent molybdenum complexes. Crystal and molecular structures of Dichloro- and Diiodo-[bis(6-methylquinolin-8-yl)phenylarsine]palladium(II)

1982 ◽  
Vol 35 (11) ◽  
pp. 2193 ◽  
Author(s):  
GL Roberts ◽  
BW Skelton ◽  
AH White ◽  
SB Wild
Keyword(s):  
Least Squares ◽  
Heavy Atom ◽  
Chelating Agent ◽  
Molecular Structures ◽  
Arsenic Trichloride ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Square Planar

The potentially tridentate chelating agent bis(6-methylquinolin-8-yl)phenylarsine (AsN2) and quadridentate tris(6-methylquinolin-8-yl)arsine (AsN2) have been prepared from 6-methyl-8-lithio-quinoline and dichlorophenylarsine or arsenic trichloride, respectively. Both ligands behave as bidentates in complexes of the type [PdX2(AsN2)] and [PdX2(AsN2)] (where X = Cl or I) and as tridentates in [Mo(CO)3(AsN2)] and [Mo(CO)3(AsN2)]. The crystal and molecular structures of [PdCl2(AsN2)],CH2Cl2 and [PdI2(AsN2)] have been determined by single-crystal X-ray analysis. The dichloro complex crystallizes in space group P1 (Ci1; No.2) with a 9.963(3), b 8.555(3), c 16.102(7) �; α 86.64(3), β 82.13(3), γ 85.84(3)�; U 1354.3(9) �3 and Z = 2. The structure was solved by heavy-atom methods and refined by least squares to R 0.044 for 2530 'observed' reflections with 1>3σ(I). The coordination geometry of the palladium(II) atom is pseudo-square-planar in which the potentially tridentate AsN2 is behaving as a bidentate only. There is no evidence of interaction of the remaining 6-methylquinolin-8-yl group with the metal centre, although a weak interaction between the solvent of crystallization and the metal may be present. The diiodo complex similarly crystallizes in the centrosymmetric triclinic space group P1 (Cil ; No.2) with a 13.590(5), b 10.035(2), c 9.435(2) �; α 102.68(2), β 90.10(2), γ 92.99(2)�; U 1253.5(6) �3 and Z = 2. Least- squares refinement led to a convergence with R 0.038 for 3461 'observed' reflections. The structure of this complex was similar to that of the dichloro analogue.

scholarly journals Synthesis and Structure Features of Tetraphenylantimony 2,3-Difluoro- and 2,3,4,5,6-Pentafluorobenzoate

2020 ◽  
Vol 12 (4) ◽  
pp. 51-62
Author(s):  
A. Efremov ◽  
Keyword(s):  
Diffraction Analysis ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Trigonal Bipyramidal ◽  
Cambridge Crystallographic Data Center ◽  
Redistribution Reaction ◽  
Distorted Trigonal Bipyramidal Coordination ◽  
Distorted Trigonal Bipyramidal

Tetraphenylantimony 2,3-difluorobenzoate (1) and tetraphenylantimony 2,3,4,5,6-pentafluorobenzoate (2) was obtained by the interaction of pentaphenylantimony with 2,3-difluorobenzoic and 2,3,4,5,6-pentafluorobenzoic acids in benzene with a yield of up to 98 %. The compounds were also synthesized by the ligand redistribution reaction between pentaphenylantimony and triphenylantimony dicarboxylates. The compounds have been identified by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction data, the antimony atoms in compounds 1 and 2 have a distorted trigonal-bipyramidal coordination with the oxygen atom in axial positions. X-ray diffraction analysis was performed on a D8 QUEST diffractometer (Bruker). The crystallographic parameters of the unit cell of the compounds: 1 space group Р1 ̅, а = 9.857(5), b = 10.154(7), c = 14.362(11) Å, α = 83.74(4)°, β = 82.59(3), γ = 68.34(2)°, V = 1321.9(16) Å3, ρcalc = 1.475 g/cm3, Z = 2; 2 space group Р21/с, а = 16.186(9), b = 8.771(6), c = 20.413(13) Å, α = 90.00°, β = 113.073(17), γ = 90.00°, V = 2666(3) Å3, ρcalc = 1.597 g/cm3, Z = 4. The OSbO axial angles are slightly different and amount to 177.90(5)º in 1 and 179.00(5)º in 2. The sums of the CSbC equatorial angles are 356.89(9)º (1), 355.85(7)º (2). The Sb–Ceq distances in compounds 1 and 2 are 2.116(2), 2.119(2), 2.118(2) and 2.1073(17), 2.1158(18), 2.1152(19) Å respectively, which are significantly shorter than the Sb–Сax bond lengths (2.169(2) and 2.1617(19) Å). The organization of molecules in the crystals of compounds is due to hydrogen bonds and CHπ-interactions of the aryl and carboxyl ligands. The main difference between structures 1 and 2 is the different Sb–O bond lengths (2.2864(18) and 2.3168(18) Å), which is due to an increase in the electronegativity of the carboxyl ligand in 2, caused by the presence of five electronegative fluorine atoms in the benzoate substituent. Complete tables of atom coordinates, bond lengths and valence angles are deposited at the Cambridge Crystallographic Data Center (No. 1980908 (1); 1977189 (2); [email protected]; http://www.ccdc.cam.ac.uk/data_request/cif).

Thiophenophane metal complexes. III. Preparation, X-ray structure, and properties of 2,5,7,10-tetrathia[12] (2, 5) thiophenophane, L, and [Ag2L2]2+, its dinuclear silver complex cation

1990 ◽  
Vol 68 (4) ◽  
pp. 644-649 ◽  
Author(s):  
C. Robert Lucas ◽  
Shuang Liu ◽  
Michael J. Newlands ◽  
Jean-Pierre Charland ◽  
Eric J. Gabe
Keyword(s):  
Mass Spectra ◽  
Fast Atom Bombardment ◽  
Complex Cation ◽  
Ligand Molecule ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal Coordination ◽  
Distorted Trigonal Bipyramidal

Preparations of the thiophenophane C12H18S5(L3), and its binuclear silver(I) complex cation [Ag2(L3)2]2+ are described. The 13C and 1H nmr spectra of L3 and the ir and fast atom bombardment mass spectra of the complex are reported. X-ray structures of L3 and [Ag2(L3)2](ClO4)2 have been determined. For L3: space group P21/n, a = 10.8866(2), b = 9.4419(4), c = 14.9608(2) Å, β = 97.132(1)°, Z = 4, Rf = 0.057, Rw = 0.045. For [Ag2(L3)2] [ClO4]2: space group P21/n,a = 9.2717(3), b = 19.8697(2), c = 10.2654(4) Å, β = 100.592(2)°, Z = 2, Rf = 0.036, Rw = 0.030. The effect of structure on the ligand's ability to form complexes is discussed. The centrosymmetric dinuclear cation has slightly distorted trigonal bipyramidal coordination geometry about each silver. The silver atoms are linked by one bridging thioether sulfur from each ligand. The remaining three sites on each silver are occupied by two terminal thioether sulfurs from one ligand molecule and one from the other ligand molecule. The complex is remarkably stable photochemically and chemically but under certain specific conditions reacts with loss of ligand. This stability is discussed with respect to structure. Keywords: binuclear silver(I) thiophenophane complex.

Synthesis and Crystal and Molecular Structures of the N,N-Dimethylethanol-aminogallane and N,N-Dimethylethanolaminogallium Dimethyl Dimers

1975 ◽  
Vol 53 (1) ◽  
pp. 58-66 ◽  
Author(s):  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Molecular Structures ◽  
Methyl Groups ◽  
Steric Interactions ◽  
Full Matrix ◽  
Space Group ◽  
Trigonal Bipyramidal Geometry ◽  
Crystal And Molecular Structures ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal

Crystals of the N,N-dimethylethanolaminogallane dimer 1a are monoclinic, a = 8.540(1), b = 7.0433(7), c = 12.227(6) Å, β = 92.94(3)°, Z = 2, space group P21/c and crystals of the N,N-dimethylethanolaminogallium dimethyl dimer 1b are orthorhombic, a = 15.608(3), b = 11.655(2), c = 10.266(2) Å, Z = 4, space group Pccn. Both structures were determined by Patterson and Fourier syntheses and were refined by full-matrix least-squares procedures to final R values of 0.039 and 0.053 for 1062 and 1155 reflections with 1 ≥ 3σ(I) respectively. Both structures feature well-separated centrosymmetric dimeric units occurring via the formation of four-membered Ga2O2 rings. The five-coordinate gallium atoms have distorted trigonal bipyramidal geometry. Steric interactions between methyl groups in 1b are believed responsible for the lengthening of the axial Ga—N distance from 2.279(3) in 1a to 2.471(4) Å in 1b. Other bond distances are: for 1a; Ga—O (axial), 2.053(3), Ga—O, 1.911(3), Ga—H, 1.50(7) and 1.73(5), O—C, 1.369(5), N—C, 1.466 – 1.485(6), C—C, 1.512(7), and mean C—H, 1.05; for 1b; Ga—O (axial), 2.078(3), Ga—O, 1.913(3), Ga—C, 1.936(6) and 1.948(7), O—C, 1.382(7), N—C, 1.452–1.482(7−8), C—C, 1.516(9), and mean C—H, 1.01 Å.

The Phenomenon of Intramolecular Attractive S---O Interactions: Synthesis and Structure of (1,10-Phenanthroline)copper(II) Complexes with Isonitroso-(4-methylthiazol-2-yl)acetamide and Isonitroso-(4-methylthiazol-2-yl)-(benzothiazol-2-yl)methanide

1997 ◽  
Vol 52 (3) ◽  
pp. 323-330 ◽  
Author(s):  
Konstantin V. Domasevitch ◽  
Vera V. Ponomareva ◽  
Andrey A. Mokhir ◽  
Eduard B. Rusanov ◽  
Joachim Sieler ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Oxygen Atom ◽  
Chlorine Atom ◽  
Carbonyl Oxygen ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
Trigonal Bipyramidal ◽  
Bidentate Chelate

Abstract Isonitroso-(4-methylthiazol-2-yl)acetamide H (L1), isonitroso-(4-methylthiazol-2-yl)(benzo-thiazol-2-yl)methanide H(L2) and their copper(II) complexes of composition [Cu(Phen){L1}(ClO4)] (1) and [Cu(Phen){L2}Cl]*C2H5OH (2) have been prepared. Crystal and molecular structures of the complexes have been determined from X-ray diffractioon data (1: monoclinic, space group P21/c, with a = 11.611(2), b = 10.259(2), c = 17.869(4) Å, β = 104.67(3)°, V = 2059.1(7) Å3, Z = 4; R1 = 0.046 for the 2522 unique reflections with I > 2σ(I). 2: triclinic, space group P1̄, with a = 8.351(1), b = 10.876(1), c = 14.891(2) Å, a = 96.170(8)°, β = 94.201(9)°, γ = 106.721(9)°, V = 1280.1(2) Å3, Z = 2; R1 = 0.034 for the 4038 unique reflections with I > 2σ(I)). In the structure of 1 the coordination polyhedron of Cu2+ is a distorted square pyramid with an oxygen atom of the CIO4 counter anion in the apex (C u -O 2.505(3) Å); in complex 2 the copper atom adopts fivefold coordination of a slightly distorted trigonal-bipyramidal geometry with a chlorine atom in the equatorial plane (Cu-Cl 2.3504(9) A). Ethanol of crystallization gives rise to a hydrogen bond at the chlorine atom. In both structures the oximic anions are coordinated to the metal center in a bidentate chelate manner via the nitrogen atom of the nitroso group and the carbonyl oxygen atom (1) or via the benzothiazole nitrogen atom (2) (Cu-O, Cu-N in the range 1.963(2) -2.031 (2) Å). The thiazole group of the ligands takes no part in the coordination. The nitroso oxygen atoms possess short intramolecular contacts with thiazole sulphur atoms, with d(S--- O) at 2.605(3) (1) and 2.676(3) A (2), which may be attributed to a strong intraligand interaction.

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