A. M. Manotti Lanfredi

Spectral Properties and Crystal Structure of Bis(μ-thiocyanato-N,S)bis(thiocyanato-N)-tetrakis(5,7-dimethyl[1,2,4]triazolo[1,5-α]pyrimidine-N3)dicopper(II) and of Tetrakis(5,7-dimethyl[1,2,4]triazolo[1,5-α]pyrimidine-N3)platinum(II)hexa(thiocyanato-S)platinate(IV).

Abstract The preparation, spectroscopic studies and the crystal structure of Cu(dmtp) 2 (NCS) 2 ( I ) and Pt(dmtp) 4 Pt(SCN) 6 ( II ) (dmtp stands for the 5,7-dimethyl[1,2,4]triazolo[1,5- a ] pyrimidine ligand) are described. Crystals of I are monoclinic, space group C 2/ c , with a = 19.088(7), b = 11.516(8), c = 20.118(7) A, β = 104.51(4)°, Z = 28; crystals of II are monoclinic, space group P 2 1 / n , with a = 16.914(8), b = 11.474(9), c = 11.893(7) A, β = 91.52(4)°, Z = 2. The structures of I and II have been solved from diffractometer data by Patterson and Fourier methods and refined by full-matrix least-squares to R = 0.044 for I and 0.051 for II . The structure of I consists of centrosymmetric dimers [Cu(dmtp) 2 (NCS) 2 ] 2 , in which the copper atoms, bridged by two thiocyanate groups, are in a square pyramidal arrangement involving two isothiocyanate nitrogen atoms and two triazole nitrogen atoms from two dmtp ligands in the basal plane and a thiocyanate sulphur atom from the centrosymmetric complex in the apical position. The structure of II consists of square planar [Pt(dmtp) 2 ] 2+ cations, in which the platinum atom is bound to four triazole nitrogen atoms from dmtp ligands and of octahedral [Pt(SCN) 6 ] 2− anions with the metal bound to sulphur atoms of thiocyanate anions.

The reactivity of HRu3(CO)9C2But. Synthesis and crystal structure of Ru3(CO)7{(C2But)[PhC2(H)Ph](C2Ph2)}

Abstract The title complex was obtained by treating HRu3(CO)9C2But with C2Ph2 or (η-C5H5)2Ni2(C2Ph2), and its structure was determined by X-ray methods. Crystals of the complex are monoclinic, space group P21/n with Z = 4 in a unit cell of dimensions: a = 17.230(11), b = 22.753(13), c = 9.229(8) A, β = 93.57(7)°. The structure was solved from diffractometer data by Patterson and Fourier methods and refined by full-matrix least squares to R = 0.055 for 3041 observed reflections. The complex consists of an isosceles triangle of ruthenium atoms, bound to seven terminal carbonyls. One diphenylacetylene ligand, on one side of this triangle, forms two σ and one π bonds with the metal atoms. On the opposite side an organic ligand, formed by oligomerization of C2Ph2 and the C2But group from the starting compound with shift of the hydridic hydrogen on C2Ph2, interacts through σ and η bonds with all the metal atoms. Important features in the formation of the title complex are the attack of C2Ph2 to α-carbon atom of the acetylide in the starting complex and the hydridic hydrogen shift on the new organic chain. The role of the title complex in the reaction sequence of HRu3(CO)9C2But with alkynes is dicussed.

Insertion reaction of carbon disulfide into copper-carbon bonds of aromatic organocopper(I) compounds, in the presence of 2,2′-bipyridine and 1,10-phenanthroline. X-ray diffraction structures of the [(CuS3C-o-tolyl)phen], [(CuS3C-o-tolyl)2phen] and [Cu2(S3C-o-tolyl)(S2C-o-tolyl)bipy] complexes

Abstract In the presence of nitrogen chelating ligands (LL=2,2′-bipyridine, 1,10-phenanthroline) the insertion reaction of CS2 into the copper-carbon bond of arylcopper(I) compounds (ArPh, o- and p-tolyl) gave adducts of Cu(I) dithiocarboxylates with LL, whose stoicheiometry depended upon the ligand and the aryl moiety. Co-formation of perthio and perthiodithio derivatives was suggested by hydrolysis of the rough products. The adducts were identified by comparison with authentic samples, prepared by other routes and characterized by IR spectra. Crystal structures were established by X-ray diffraction analyses for the [(CuS3C-o-T)phen] (I), [(CuS3C-o-T)2phen] (II) and [Cu2(S3C-o-T)(S2C-o-T)bipy] (III) complexes. Crystal data: C20H15CuN2S3 (I), space group P 1 with a = 14.135(3), b = 7.659(3), c = 9.115(3) A, α=73.33(2), β=96.89(3), γ=96.73(3)° and Z=2; C28H22Cu2N2S6 (II), space group P 1 with a = 12.385(2), b = 11.865(3), c = 11.331(2) A, α = 114.35(3), β = 89.48(2), γ = 105.75(2)° and Z = 2; C26H22Cu2N2S5 (III), space group P21/n, a = 25.057(4), b = 10.188(3), c = 10.960(3) A, β = 100.58(3)° and Z = 4. In I and II the original tetrameric structure of the copper perthiocarboxylate, under the action of the new LL ligand, turns to mononuclear and binuclear, respectively, according to the Cu:LL ratios. In I the metal atom is pseudo-tetrahedrally coordinated by two N atoms from phen and two S atoms from the bidentate chelating o-tolyldithiocarboxylate ligand; complex II can be considered arising from I by electrophilic attack of the trigonally arranged metal atom of an ‘additional’ CuS3C-o-T chelate unit on the terminal perthio S atom of the tetrahedral moiety. In the structure of III, which is the first example of a perthiodithiocarboxylate with an ortho substituent in the aryl group, tetrahedral and trigonal arranged copper(I) atoms, doubly bridged by perthio- and dithioarylate groups, are present.

Polymeric chains of tetranuclear hydroxo-o-phthalatocuprate(II) units and silver(I)–aromatic interactions in the crystal structure of Ag[Cu2(C8H4O4)2(OH)].5H2O

The crystal structure of Ag[Cu2(C~H404)~(OH)I.5H20, CI6H9AgCu209.5H20, has been determined from diffractometer data by Patterson and Fourier methods and refined to R = 0.079 for 2359 counter reflections: a = 11.388 (11), b = 11.772 (12), c = 7.875 (9) A, ,~ = 100.3 (1), fl = 80.2 (1), y = 102.2 (1) °, space group P i , Z = 2. The structure consists of centrosymmetric tetranuclear [ C u 2 ( C s H 4 0 4 ) 2 ( O H ) ] 2 2 anions (linked in polymeric chains by bridging ophthalate anions), Ag ~ cations and water molecules. The tetranuclear hydroxo-o-phthalatocuprate(II) anions contain two independent Cu atoms linked by triplybridging hydroxo O atoms and by carboxylate bridges from o-phthalate anions. The coordination polyhedron of Cu(1) is a trigonal bipyramid whose equatorial plane is tbrmed by three O atoms from three bridging carboxylates [ C u O = 2.049 (10), 2.101 (10), 2.233 (12) A], the axial positions being occupied by an O atom from an OHion [ C u O = 1.911 (11) A] and by an O atom from a monodentate carboxylate group [ C u O = 1.923 (11) AI. The coordination of Cu(2) is square pyramidal, the basal plane comprising two O atoms from OHions [ C u O = 1.955 (9), 1-949 (9) /k] and two O atoms from two bridging carboxylates [ C u O = 1-924(10), 1.928(10) AI. Another O atom from a bridging carboxylate is at the apex of the pyramid [ C u O = 2.352 (13) /k]. The Ag I ion is linked to this last O atom [ A g O = 2.264 (12) ,~,1 and to two water molecules [ A g O w = 2.328 (25), 2.536 (26) AI, and interacts with a benzene C C bond [ A g (midpoint of C C ) = 2.431 (16) ,~1, so that Ag-aromatic complexes, in a distorted tetrahedral configuration, are present.

The structure of (o‐phthalato)bis(pyridine)copper(II) with bridging and chelating o‐phthalate anions

[Cu(C5HsN)2(CaH404)] , M r = 385.9, is monoclinic, space group P21/c, with a = 18.199(6), b = 11.991 ( 1 4 ) , c = 1 7 . 9 2 3 ( 8 ) , ~ , f l = 119.98(2) ° , V = 3388 (4)/~ 3, Z = 8, D x = 1.51, D m = 1 . 5 1 M g m -3, F(000) = 1576, 2(Cu Ks) = 1.54178 ,A, #(Cu Ks) = 1.999 mm -~. R = 0.055 for 5425 observed reflections. 0567-7408/81/122159-05501.00 The structure consists of two crystallographically independent square-pyramidal [Cu(C 5HsN) 2 (C8H404)] complexes linked in polymeric chains by bridging phthalate anions which also act as chelating ligands through two O atoms from one carboxylate group. Pentacoordination of Cu involves two N atoms (one at the apex of the pyramid) from two pyridine molecules, one O atom from the monodentate carboxylate of an

The crystal and molecular structure of barium diaquadi(o-phthalato)cuprate(II) dihydrate. An example of the chelating behaviour of the o-phthalate anion

The crystal structure of barium diaquadi(o-phthalato)cuprate(II) dihydrate has been determined from diffractometer data by Patterson and Fourier methods and refined by block-diagonal least squares to R = 0.032 for 1749 observed reflections. Unit-cell constants are: a = 9. 155 (9), b = 7.831 (8), c = 13.498 (14) ,~, fl = 95. I (1) °. The space group is P2~ with Z = 2. In the structure, discrete [Cu(H20)2(CsH404)212complex anions are present, containing two non-equivalent o-phthalate anions: one acting as a monodentate ligand, the other as a bidentate chelating ligand. The Cu complexes are held together by interactions with Ba 2+ ions and by hydrogen bonds with water molecules. The coordination polyhedron of Cu is a square pyramid whose base is formed by one water molecule [Cu-Ow = 1.971 (10) ~], one O atom [Cu-O = 1-946 (8) AI from the monodentate o-phthalate ligand and two O atoms [Cu-O = 1-907 (7), 1.972 (9) fi,] from the chelating ophthalate ligand. Another water molecule is at the apex of the pyramid [Cu-O w = 2.289 (9) A I. Ba 2~ cations are surrounded by nine O atoms (three from the water molecules): the coordination polyhedron is a distorted trigonal prism with lateral centred faces. The Ba-O bond distances are in the range 2-670-3-055/k.

The crystal and molecular structure of bis(thiocarbohydrazide-N,S)cadmium dichloride

The crystals of bis(thiocarbohydrazideN,S)cadmium dichloride, Cd(SC(NHNH 2 ) 2 ) 2 Cl 2 , belong to monoclinic space group P2 1 /c. The structure of the compound, determined from three-dimensional data, consists of trans -octahedral complexes where the ligand molecule forms pentatomic chelate rings with N,S as donor atoms. The chlorine atoms lie along the normal to the plane containing metal and organic molecules. The distances CdN=2.34(3) and CdS=2.59(1) A are slightly shorter than those found in non-chelate cadmium complexes; CdCl=2.73(1) A is very close to the sum of ionic radii. The configuration of the ligand, with on -NH 2 group turned towards SC, repeats that of crystallized thiocarbohydrazide. Some differences, however, in distances, planarity, and angles between complexed or free ligand can be detected. The complexes are held together in layers parallel to (102) by weak hydrogen bonds NH⋯Cl.

Manganese(I) carbonyls with σ-bonded alkynyl ligands. The crystal structure of [Co2 (CO)6][PhCCMn(CO)4{P(C6H11)3}]

The preparation of some σ-alkynylmanganese(I) carbonyl complexes is described. The crystal structure of the compound [Co2(CO)6] [PhCCMn(CO)4(PCy3)] (Cy = cyclohexyl) has been established by X-ray diffraction.

New rhodium(I) complexes with the bridging 1,8-naphthyridine-2-one ligand

Preparation de complexes di- ou trinucleaires de Rh avec la forme anionique de la naphtyridine-1,8 one-1 et une diolefine: Rh 2 (μ-Onapy) 2 (CO) 4 et [Rh 3 (μ-Onapy) 2 (CO) 4 (COD)] +

The crystal srtucture of calcium diiodate(V) hexahydrate

Abstract The crystals of calcium diiodate(V) hexahydrate, Ca(IO3)2. 6H2O are orthorhombic, space group Fdd2 with 8 molecules in the unit cell. The structure consists of pyramidal anions joined to one another in chains by intermolecular I ... O interactions. The chains are held together by calcium ions and by hydrogen bonds between water molecules and anions. The coordination polyhedron around calcium can be described as a square antiprism, with distances Ca- O=2.43-2.57 A. In the pyramidal anion the distances between oxygen and iodine atoms are I-O=1.78, 1.90, 1.85 A. The environment of the iodine atom is approximately octahedral: the coordination is completed by two water molecules and by one oxygen atom of another anion.