Synthesis and crystal structures of quadruply carboxylate-bridged dimeric lanthanide(III) complexes of betaine

Three dimeric lanthanide(III) complexes, [Eu₂(bet)₈(H₂O)₄](CIO₄)₆ (1), [Tb₂(bet)₈(H₂O)₄](ClO₄)₆ (2), and [Eu₂(bet)₄(H₂O)₈] Cl₆·6H₂O (3) (bet = Me₃N⁺CH₂COO^–, trimethyl-aminoacetate), have been prepared and structurally characterized by X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P2₁/c, with a = 11.7807(8), b = 27.757(5), c = 11.7980(8) Å, = 99.500(4)°, V = 3805.1(8) ų, and Z = 2. Complex 2 is isomorphous to complex 1, crystallizing in the monoclinic space group P2₁/c, with a = 11.7769(14), b = 27.725(3), c = 11.795(5) Å, = 99.668(14)°, V = 3797(2) ų, and Z = 2. Complex 3 crystallizes in the orthorhombic space group Pbca, with a = 12.5664(8), b = 17.8645(9), c = 22.2573(8) Å, V = 4996.6(4) ų and Z = 4. Both complexes 1 and 2 comprise quadruply carboxylate-O,O-bridged [M₂(bet)₄]⁶⁺ dimeric cores (M = Eu, Tb), and each metal ion is further coordinated by two terminal aqua ligands and two monodentate bet carboxylates to form a distorted square-antiprismatic coordination geometry. Complex 3 also has a [Eu₂(bet)₄]⁶⁺ core, in which two bet ligands act in the ¹:¹:₂ bridging fashion, and the other two bet ligands in the less common ²:¹:₂ bridging fashion, namely bridging-chelate mode. Each europium(III) ion in complex 3 is further coordinated by four water molecules to complete a monocapped square antiprism.     

Metal-betaine interactions. IV. Crystal structures of trans-tetraaquabis(betaine)nickel(II) nitrate and trans-diaquatetrakis(pyridine betaine)cobalt(II) bis[trichloro(pyridine betaine)cobaltate(II)]

Two transition metal(II) complexes of betaine (Me₃N⁺CH₂COO^–, designated as BET) and pyridine betaine (C₅H₅N⁺CH₂COO^–, pyBET) have been prepared and investigated by X-ray crystallography and infrared spectroscopy. [Ni(BET)₂(H₂O)₄] (NO₃)₂ (1), (R _F=0.054 for 2518 observed MoK data) comprises slightly distorted octahedral [Ni(BET)₂(H₂O)₄]²⁺ cations in which the Ni(II) atom is centrosymmetrically coordinated by four aqua ligands and twotrans-related unidentate BET ligands, and the uncoordinated carboxy oxygens form intramolecular hydrogen bonds with the aqua ligands. [Co(pyBET)₄(H₂O)₂]·2[Co(pyBET)Cl₃] (2) (R _F=0.029 for 4696 observed data) consists of discrete octahedral [Co(pyBET)₄(H₂O)₂]²⁺ cations and tetrahedral [Co(pyBET)Cl₃]^– anions. In the centrosymmetric cation each of the twotrans-related aqua ligands form a pair of intramolecular hydrogen bonds with the uncoordinated oxygen atoms of two unidentate pyBET ligands. In the anion the cobalt atom is coordinated by one unidentate pyBET ligand and three chloro ligands.     

A novel four-coordinate zinc(II) complex of the di-N-hydroxypropylated tetraaza macrocycle

The compound [Zn(L²)Cl]ClO₄·H₂O (1) (L² = 2,13,-bis(3-hydroxypropyl)-5,16-di-methyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) has been synthesized and structurally characterized. 1 crystallizes in the monoclinic system, space group P2₁/c with a = 8.932(2), b = 16.189(2), c = 22.492(4) Å = 95.34(2)° V = 3238.3(11) ų; and Z = 4. The zinc atom is placed in a highly distorted tetrahedral environment bonding with three nitrogen atoms of the macrocycle and one chlorine atom.     

Hydrogen-bonded coordination network in crystal structures of [Cu(3-PM)4Cl2] and [Cu(4-PM)4Cl]Cl, (PM = pyridylmethanol)

The crystal and molecular structures of [Cu(3-PM)₄Cl₂] (1) and [Cu(4-PM)₄Cl]Cl (2) have been determinated by X-ray crystallography. Complex 1 crystallizes in the triclinic system, space group P–1, with lattice parameters a = 7.972(2) Å, b = 8.293(2) Å, c = 10.707(2) Å, = 105.73(3)°, = 90.04(3)°, = 110.38(3)°, and Z = 1 at 100 K. The coordination geometry of each Cu atom is approximately octahedral formed by four nitrogen atoms of pyridine rings of 3-pyridylmethanol molecules in the equatorial plane and two chlorine atoms occupying the axial positions. The O—HsO, C—HsCl, and O—HsCl intermolecular hydrogen bonds and s stacking link the molecules in 3-D hydrogen-bonded coordination network. Complex 2 crystallizes in the tetragonal system, space group P4/n, with lattice parameters a = 10.464(1) Å, c = 11.339(2) Å, and Z = 2 at 217 K and a = 10.352(1) Å, c = 11.201(2) Å, and Z = 2 at 293 K. The coordination geometry of Cu atom in the [Cu(4-PM)₄Cl]⁺ ion is approximately square pyramidal formed by four nitrogen atoms of pyridine rings of 4-pyridylmethanol molecules in equatorial plane and one chlorine atom in axial position. The O—HsCl and C—HsCl intermolecular hydrogen bonds link the molecules in 2-D hydrogen-bonded coordination network.     

Crystal and molecular structure of di-μ-chloro(dicyandiamide)cadmium(II)

The crystal structure of di--chloro(dicyandiamide)cadmium(II) has been determined and refined by Fourier and least-squares methods toR = 0·037 using three-dimensional X-ray data collected at room-temperature on a single-crystal automated diffractometer. Crystal data are as follows:a = 10·796(7),b = 8·933(5),c = 6·847(3) Å, = 99·9(1) °,Z = 4; space groupP2₁/n. The cadmium atom is surrounded by four chlorine (Cu-Cl = 2·572, 2·607, 2·630, 2·647 Å) and two nitrogen atoms (Cd-N (nitrilic) = 2·358 Å; Cd-N (guanidic) = 2·430 Å) so that the whole polyhedron appears as a slightly distorted octahedron. The chlorine atoms form bridges between adjacent metal atoms so that the coordination octahedra are linked in chains running along [001]. These chains are joined together by dicyandiamide bridges.The authors wish to thank Dr. A. Immirzi (Politecnico di Milano) for the use of his compter programmes.     

Crystal structure of a macrocyclic tetraamine isocyanato zinc(II) complex

The complex, [Zn(L)(NCO)]Cl · 3H₂O (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane), has been synthesized and structurally characterized. 1 crystallizes in the monoclinic system, space group P2₁/n with a = 10.530(3), b = 9.315(2), c = 27.188(3) Å, = 92.58(1)°, V = 2664.1(9)ų, and Z = 4. The zinc atom is in a distorted squarepyramidal environment with the four nitrogen atoms of the macrocycle and one nitrogen atom of the isocyanate ligand.     

Structure of bis(dipropyldithiocarbamate) cadmium(II), [Cd2(n-Pr2dtc)4] (dtc = dithiocarbamate)

The cadmium complex of bis(dipropyldithiocarbamate), [Cd₂(n-Pr₂dtc)₄] (dtc = dithiocarbamate) was crystallized from ethylether. It crystallizes in the monoclinic system, space group P _2I/c, with lattice parameters, a = 8.2532(1), b = 19.4519(1), c = 13.4163(2) Å, = 99.243(1)°, and Z = 4. The X-ray single-crystal structure of [Cd₂(n-Pr₂dtc)₄] reveals that the complex is binuclear in the solid state and the Cd atom has a distorted square-pyramidal coordination environment and four equatorial donors are the two bidentate chelate sulfur atoms from two dtc ligands, of which the sulfur atom from the bridging dtc ligand occupies the apical position of the symmetry-related Cd atom in the dimer structure.     

Preparation and characterization of a bidentate carboxylate-bridged dinuclear cadmium(II) complex with bis(2-pyridylmethyl)amino-3-propionic acid

The carboxylate-bridged dinuclear complex [Cd(-pmpa)(H₂O)](ClO₄)·H₂O (1) (Hpmpa = bis(2-pyridylmethyl)amino-3-propionic acid) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the monoclinic system P2 ₁/n with a = 7.9678(6) Å, b = 17.5103(9) Å, c = 14.3147(9) Å, = 94.1030(10)°, V = 1992.0(2) ų, Z = 4. The carboxylate group of the pmpa ligand adopts a bidentate bridging coordination mode, and the ligand acts as -bridge linking two cadmium(II) ions to form a dinuclear complex. Each cadmium atom is seven-coordinate, with a distorted pentagonal bipyramidal geometry. The cyclic voltammogram of 1 undergoes irreversible one-electron oxidation to the Cd(III) and reversible one-electron reduction to the Cd(I).     

Crystal and molecular structure of bis[pyridine-2-(N-cyanocarboxamidato)]aquocopper(II), Cu(C5H4NCONCN)2(OH2)

Bis[pyridine-2-(N-cyanocarboxamidato)]aquocopper(II), Cu(C₅H₄NCONCN)₂(OH₂), has been prepared and its i.r. spectrum and crystal structure have been determined. The crystals are triclinic (P¯1):a = 11·45(1),b = 10·35(1),c = 7·48(1) Å, = 110·9(1), = 102·2(2), = 108·9(1)°,Z = 2. The X-ray analysis, carried out using three-dimensional Patterson, Fourier and least-squares methods (finalR = 5·7%), showed copper(II) to be pentacoordinated, with two organic ligands chelating through their pyridine [Cu-N = 1·997(4), 1·989(4) Å] and amide nitrogen atoms [Cu-N = 1·980(7), 2·006(6) Å], and with one water molecule at a distance [Cu-OH₂ = 2·335(4) Å] sensibly longer than the usual Cu-O(2·0 Å) coordinate bonds. The coordination polyhedron can be described either as a distorted tetrahedron formed by the nitrogen atoms with an extra position occupied by water or as a trigonal bipyramid having water and two nitrogen atoms in the equatorial plane. The packing determining interactions are the hydrogen bonds formed by water, and a long Cu...N (3·420 Å) contact between the metal and a nitrogen atom from an adjacent molecule.The authors are indebted to Prof. Immirzi who kindly supplied his computer programmes.     

The crystal structure of a N-(2-thiophenyl)-salicylaldiminopiperidino nickel(II) complex

The crystal and molecular structure of the title complex, C₁₈H₁₉N₂OSNi, has been determined by direct methods. The compound crystallizes in monoclinic crystal system witha=11.968(1),b=12.182(1),c=12.399(1) Å, =115.23(1)°, space group P2₁/n. Nickel is in a slightly distorted square-planar environment of two nitrogens [1.881(2) and 1.952(2) Å] and one oxygen [1.856(3) Å] and one sulphur [2.138(2) Å] atom. Ni is 0.005 Å out of the plane of its ligands.     

Redetermination of the structure of bis[chloro-2-(2-hydroxy-4,5-dimethylphenylazo)-5,5-dimethyl-4,5,6,7-tetrahydrobenzothiazol-7-on] copper(II) complex

The crystal structure of C₁₇H₁₈ClCuN₃O₂S (M = 854.78, monoclinic, P2₁/c, a = 8.316(2), b = 18.461(4), c = 11.774(2) Å, = 99.64(3)°, V = 1782.0(7) ų, Z = 4) is formed by dimeric molecules [C₁₇H₁₈ClCuN₃O₂S]₂ with two monomeric units linked together by two chlorine atoms. The Cu atom is coordinated by two chlorine atoms, an oxygen atom, the azo nitrogen atom attached to the benzene ring, and the nitrogen atom of the thiazole ring, in the form of a distorted tetragonal pyramid.     

Synthesis and crystal structure of a macrocyclic azidotetraamine copper(II) complex

The complex [Cu(L)N₃](H₂O)(ClO₄) (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18, 0^7.12]docosane) has been prepared and characterized by X-ray crystallography. 1 crystallizes in the monoclinic space group P2₁/c, with a = 8.907(5), b = 20.036(3), c = 14.773(2) Å, = 103.78(2)°, V = 2560.6(15) ų, and Z = 4. The coordination geometry around the Cu(II) ion is a distorted square-pyramidal with four nitrogen atoms of the macrocycle and one nitrogen atom of the axial azido group.     

Crystal structure oftrans-tetrachlorobis[2-(2-1H-imidazolyl)-1H-imidazolium]cadmium(II), [Cd(H3biim)2Cl4]

The reaction between cadmium(II) chloride and 2,2'-bi-1H-imidazole (H₂biim) in an acidic solution affords [Cd(H₃biim)₂Cl₄] (H₃biim=2-(2-1H-imidazolyl)-1H-imidazolium) in 63% yield. The compound crystallizes in the triclinic space groupP1, wherea=8.072(2),b=8.100(2),c=8.593(2) Å, =75.89(2), =62.94(2), =63.29(1)°,V=446.4(2) ų, andZ=1. The central Cd atom exhibits an octahedral geometry composed of a Cl₄N₂ core. The Cd-N bond distance is 2.392(2) Å. Cd–Cl distances are 2.5919(9) and 2.671(1) Å.     

X-ray structural analysis of a copper(I) adduct of the Rh(III) trihydride [(triphos)RhH3], with triphos = CH3C(CH2PPh2)3

The binuclear compound [(triphos)RhH(-H)₂Cu(diphos^*)]⁺ with triphos = CH₃C(CH₂PPh₂)₃ and diphos^* = o-C₆H₄(CH₂P(C₆H₁₁)₂)₂ has been prepared and characterized. It crystallizes as [CF₃SO₃] salt in the monoclinic P2₁/c space group with Z = 4, a = 13.802(4)Å, b = 19.462(4)Å, c = 26.604(5)Å, = 99.8(3)°, and V = 7041(3)ų. The structure of the complex consists of two metal fragments with hydride ligands bridging the Rh-Cu contact. The hydride ligands were not located by X-rays but, from the arrangement of the heavy atoms and by methods of potential energy, the most probable positions of two hydride ligands bridging the Rh-Cu interaction and one that remains terminal on the rhodium atom, were obtained.     

Mercury(II) halide complexes with N-donor organic ligands: crystal and molecular structure of HgI2R, R = 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, bipyridine

The synthesis, characterization and single crystal X-ray structure of three compounds of general formula HgI₂R (R = phen[1], dmph [2] and bpy[3]) are presented. The crystal data for the three compounds are: [1], triclinic, space group P (#2) a = 7.902(2), b = 9.479(2), c = 10.002(2) Å, = 91.45(2), = 111.34(2), = 100.82(2)° [2]: monoclinic, space group C2/c (#15) a = 15.670(3), b = 11.640(2), c = 9.730(2) Å, = 114.57(3)° [3]: triclinic, space group P1¯ (#2) a = 9.472(1), b = 9.507(1), c = 9.023(1) Å, = 98.46(1), = 102.89(1), = 119.62(1)°. Compounds [1] and [2] are monomers, with highly distorted tetrahedral environments around Hg. In [3], instead, there is a significant intermolecular I···Hg interaction leading to the formation of softly bound dimers linking two pentacoordinated cations. The structure is compared with related ones in the literature.     

X-ray crystal structure of (1-methylthyminato)triethylphosphinegold(I)

The crystal structure of the title compound reveals that the gold atom exists in a linear geometry defined by a P atom [Au-P 2.223(6) Å] and the N(3) atom of the 1-methylthyminate nucleobase [Au-N(3) 2.06(2) Å] with a P-Au-N angle of 178.4(5)°. The crystal lattice is characterized by significant hydrogen bonding contacts involving both the carbonyl oxygen atoms and the solvent water molecule of crystallization. The crystals are monoclinic, space groupP2₁ with unit cell dimensionsa 8.037(1),b=11.329(2),c09.501(1) Å,=104.08(1)°,Z=2. The structure was refined to finalR=0.047 for 2069 reflections which satisfiedI3.0(itI).     

Structural characterization of the edge double-bridged triruthenium cluster complex Ru3(μ-Cl)2(CO)8(PPh3)2

The title compound is Ru₃(-Cl)₂(CO)₈(PPh₃)2. Crystal data: formula C₄₄H₃₀O₈Cl2P2Ru₃;f _w =1122.9; monoclinic,P2₁; cell parameters (at 293 K)a=10.971(2) Å,b=17.066(2) Å,c=11.833(2) Å,=92.91(1)°,V=2213 ų,Z=2, _calcd=1.68, _meas=1.68. Final discrepancy indices areR(F)=0.030,R _W (F)=0.036. The structure consists of an open trinuclear unit involving two metal-metal bonds [Ru(1)-Ru(2)=2.845(1) Å, Ru(2)-Ru(3)=2.860(1) Å]. The open edge of the metal framework [Ru(1)Ru(3)=3.254(1) Å] is supported by two symmetric bridging chloride ligands [Cl(1)-Ru(1)=2.461(2) Å; Cl(1)-Ru(3)=2.464(2) Å; Cl(2)-Ru(1)=2.470(2) Å; Cl(2)-Ru(3)=2.472(2) Å]. Both phosphorus ligands are cis to the Cl atoms and trans to the unique ruthenium atom Ru(2). Geometric features of the edge dibridged complex are discussed.     

Self-assembly in transition metal complexes: structural characterization of a copper histamine nitrate [Cu(II)(him)2(NO3)2]

A new monomeric copper (II) complex with histamine (him), [Cu(II)(him)₂(No₃)₂], has been prepared by the reaction of Cu(NO₃)₂ with histaminium dichloride and its structure was determined by x-ray crystallography. The complex crystallizes in the triclinic system, space group with a = 5.7238(4), b = 8.7094(7), c = 9.2481(11) Å, = 69.693(8), = 73.242(7), = 71.050(7)°, V = 400.84(6) ų, and Z = 1. The structure consists of discrete [Cu(II)(him)₂(NO₃)₂] molecules in which the metal atom is centrosymmetrically coordinated by two histamine ligands forming an equatorial plane with Cu–N(imidazole ring) being 2.032(2) and Cu–N(NH₂ group) being 2.023(2) Å. Two O atoms from nitrate anions coordinate on the elongated axial positions with Cu–O being 2.549(2) Å. In the crystal structure, the molecules are organized by hydrogen bonds forming a two-dimensional network.     

Crystal structure of bis[dihydrobis(3,5-dimethy-1-pyrazolyl)borato]cadmium(II)

The structure of [H₂B(3,5-Me₂pz)₂]₂Cd shows the four nitrogen donor atoms form a pseudotetrahedral arrangement about the cadmium(II). The intraligand N—Cd—N angles are restricted to an average of 91.4° by the chelate rings forcing the interligand N—Cd—N bond angles to average 119.4°. The Cd—N bond distances average 2.21 Å with a range of 0.04 Å. The crystal is in the triclinic space group, P with a = 7.6793(2) Å, b = 8.5992(2) Å, c = 25.0874(4) Å, = 91.0791(2)°, = 97.9769(4)°, = 110.2344(6)°, and Z = 2.     

Crystal and molecular structures oftrans-dichloro-(ethylene) (4-methylpyridine)platinum(II) andtrans-dichloro(ethylene) (2,4,6-trimethylpyridine)platinum(II)

The crystal and molecular structures oftrans-[PtCl₂(C₂H₄)(4-MeC₅H₄N)] (I) andtrans-[PtCl₂(C₂H₄)(2,4,6-Me₃C₅H₂N)] (II) have been determined by single-crystal x-ray methods.I crystallizes in space groupP2₁/c witha= 4.991(1), b=21.658(3), c=10.675(3) Å, =110.17(2) °,Z=4;II is orthorhombic (Pbca) witha=10.295(6),b=12.393(8),c=20.370(10) Å,Z=8.Full-matrix least-squares refinements have given finalR factors of 0.053 (1520 reflections) forI and 0.042. (1412 reflections) forII. The intensities were recorded by counter methods, and only those reflections havingI>3(I) were used in the analyses.In both complexes, platinum is four-coordinate with the two chlorine atoms, the double bond of the ethylene, and the nitrogen atom of the substituted pyridine. The two structures are discussed in terms of the arrangement of the pyridine ligand with respect to the PtCl₂(C₂H₄) moiety.