The neutral cluster amminehexa‐μ2‐chlorido‐μ4‐oxido‐tris(1,4,6‐triazabicyclo[3.3.0]oct‐4‐ene)tetracopper(II)

The title compound, [Cu₄Cl₆O(C₅H₉N₃)₃(NH₃)], is a neutral conformationally chiral cluster which crystallizes under the conditions described in this paper as a racemic conglomerate. It contains four Cu^II atoms in a tetrahedral coordination with a central O atom lying on a crystallographic threefold axis. Six chloride anions bridge the four Cu^II atoms. Three Cu^II atoms are bound by an N atom of a monodentate 1,4,6‐triazabicyclo[3.3.0]oct‐4‐ene (Htbo) ligand and the remaining Cu^II atom is bound by a terminal ammine ligand. The geometry at each copper center is trigonal bipyramidal, produced by the bound N atom of Htbo or ammonia, the O atom in the axial position, and three chloride ions in the equatorial plane. The chloride anions form an octahedron about the oxygen center. The copper–ammonia bond lies along the crystallographic threefold axis, along which the molecules are packed in a polar head‐to‐tail fashion.     

Synthesis and crystal structure of heteronuclear La( III )‐Cu(II ) complex { [LaCu2(NTA)2(4,4′‐bpy)(H2O)3]NO3·5H2O}n

A novel La( III )‐Cu( II ) heterometallic coordination polymer {[LaCu₂(NTA)₂(4,4′‐bpy)(H₂O)₃]NO₃·5H₂O]_n, where H₃NTA denotes nitrilotriacetic acid and 4,4′‐bpy denotes 4, 4‐bipyridine, was synthesized and characterized by IR spectrum, elemental analysis and X‐ray diffraction. The complex crystallizes in the triclinic space group Pi with cell parameters a = 1.33710(10) nm, b = 1,44530(10) nm, c =1.0949(2) nm, α = 71.905(7)°, β = 74.327(7)°, γ = 64.427(9)°, V = 1.7912(4) nm³and Z = 2. It consists of heterometallic units, in which each La( II ) ion is coordinated in a distorted monocapped square antiprism by three oxygen atoms from water molecules and six carboxyl oxygen atoms from five NTA^3? ions, and each Cu( I ) ion is coordinated by one nitrogen atom from 4,4′‐bpy and one nitrogen atom, three oxygen atoms from NTA^3?. In the title complex, La( I ) ions and Cu( II ) ions are connected by the heterometallic bridging of NTA^3?, constructing a two‐dimensional network structure along the [110]. And it is extended into an infinite three‐dimensional network structure by the formation of homometallic bridging of Cu‐4, 4′‐bpy‐Cu, exhibiting a certain inclusion ability.     

Bis(2,2′‐bipyridine)iodo­(oxo)tri‐μ3‐sulfido‐tricopper(I)tungsten(VI)

The title nest‐shaped cluster, [Cu₃WIOS₃(C₁₀H₈N₂)₂], has been synthesized by the reaction of (NH₄)₂[WOS₃], CuI and 2,2′‐bipyridine (bipy) in dimethyl­formamide under a purified nitro­gen atmosphere. The cluster has a neutral skeleton containing the bipy ligands, and the central W atom is tetra­hedrally coordinated by three S atoms and one O atom. The three Cu atoms are divided into two different kinds. Two Cu atoms adopt distorted tetra­hedral geometry, with each Cu atom coordinated by two S atoms and the two N atoms of a bipy ligand. The other Cu atom adopts a trigonal mode surrounded by two S atoms and one I atom.     

Crystallographic report: Polymeric [3‐(triphenylgermyl)‐3‐o‐methoxyphenylpropionato]trimethyltin(IV)

The polymeric chains of [Sn(CH₃)₃(C₂₈H₂₅O₃Ge)]_n contain trimethyltin moieties bridging two neighboring 3‐(triphenylgermyl)‐3‐o‐methoxypropionate ligands via carboxyl groups. The germanium atom has a distorted tetrahedral geometry and the tin atom has a distorted trigonal‐bipyramidal geometry, the latter with three methyl groups in the equatorial plane and oxygen atoms defining the axial positions. Copyright © 2005 John Wiley & Sons, Ltd.     

Bis(μ‐3‐nitrobenzene‐1,2‐dicarboxyl­ato)‐κ8O1,O2:O2,O3;O3,O2:O2,O1‐bis­[triaqua­(2‐carboxy‐3‐nitro­benzoato‐κ2O,O′)lanthanum(III)] dihydrate

The title compound, [La₂(C₈H₃NO₆)₂(C₈H₄NO₆)₂(H₂O)₆]·2H₂O, consists of dimeric units related by an inversion center. The two La^III atoms are linked by two bridging bidentate carboxyl­ate groups and two monodentate carboxyl­ate groups. Each La^III atom is nine‐coordinated by six O atoms from five different carboxyl­ate groups and three from water mol­ecules. Hydrogen bonds between the water mol­ecules and between the solvent water and a carboxyl­ate O atom are observed in the structure. In the crystal packing, there are slipped π–π stacking inter­actions between the parallel benzene rings. Both hydrogen‐bonding and π–π inter­actions combine to stabilize the three‐dimensional supra­molecular network.     

A novel dinuclear bismuth(III) coordination compound: bis(μ‐pyridine‐2,6‐dicarboxylato)‐κ4O2,N,O6:O6′;κ4O2:O2′,N,O6‐bis[(azido‐κN)(1,10‐phenanthroline‐κ2N,N′)bismuth(III)] tetrahydrate

A novel dinuclear bismuth(III) coordination compound, [Bi₂(C₇H₃NO₄)₂(N₃)₂(C₁₂H₈N₂)₂]·4H₂O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy‐dispersive X‐ray spectroscopy, IR, X‐ray photoelectron spectroscopy and single‐crystal X‐ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi^III centre is seven‐coordinated by three O atoms and four N atoms. The coordination geometry of each Bi^III atom is distorted pentagonal–bipyramidal (BiO₃N₄), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O—H...O hydrogen bonds, resulting in the formation of a three‐dimensional supramolecular structure. Two types of π–π stacking interactions are found, with centroid‐to‐centroid distances of 3.461 (4) and 3.641 (4) Å.     

Tris(2,6‐di‐tert‐butyl‐4‐methyl­phenol­ato‐O)(tri­phenyl­phosphine oxide‐O)samarium(III)

In the title complex, [Sm(C₁₅H₂₃O)₃(C₁₈H₁₅OP)], the central metal atom is coordinated by three O atoms of the aryl­oxo ligands and by one O atom of the tri­phenyl­phosphine oxide mol­ecule resulting in a distorted tetrahedral geometry. The Sm—O_Ar distances (Ar is aryl) range from 2.122 (2) to 2.190 (2) Å and the Sm—O_PPh3 bond length is 2.306 (2) Å.     

Crystallographic report: A coordination polymer containing [Zn(NO3)(H2O)2(btp)2]+ units bridged by btp ligands (btp = 2,6‐bis(N′‐1,2,4‐triazolyl)pyridine)

A zinc(II) coordination polymer has been formed from Zn(NO₃)₂ and 2,6‐bis(N′‐1,2,4‐triazolyl)pyridine (btp) ligands in which each zinc(II) atom is coordinated by three nitrogen donor atoms from btp and three oxygen donor atoms from a nitrate and two water molecules. Copyright © 2003 John Wiley & Sons, Ltd.     

trans‐Bis(dimethyl sulfoxide‐κO)bis(3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylato‐κ2N1,O2)copper(II)

The title compound, [Cu(C₉H₅N₂O₃)₂(C₂H₆OS)₂], consists of octahedrally coordinated Cu^II ions, with the 3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylate ligands acting in a bidentate manner [Cu—O = 1.9116 (14) Å and Cu—N = 2.1191 (16) Å] and a dimethyl sulfoxide (DMSO) molecule coordinated axially via the O atom [Cu—O = 2.336 (5) and 2.418 (7) Å for the major and minor disorder components, respectively]. The whole DMSO molecule exhibits positional disorder [0.62 (1):0.38 (1)]. The octahedron around the Cu^II atom, which lies on an inversion centre, is elongated in the axial direction, exhibiting a Jahn–Teller effect. The ligand exhibits tautomerization by H‐atom transfer from the hydroxyl group at position 3 to the N atom at position 4 of the quinoxaline ring of the ligand. The complex molecules are linked through an intermolecular N—H...O hydrogen bond [N...O = 2.838 (2) Å] formed between the quinoxaline NH group and a carboxylate O atom, and by a weak intermolecular C—H...O hydrogen bond [3.392 (11) Å] formed between a carboxylate O atom and a methyl C atom of the DMSO ligand. There is a weak intramolecular C—H...O hydrogen bond [3.065 (3) Å] formed between a benzene CH group and a carboxylate O atom.     

Bis(μ‐4‐chloro­benzoato‐κ2O:O)bis[(2‐aminopyridine‐κN)silver(I)]

The title compound, [Ag₂(C₇H₄ClO₂)₂(C₅H₆N₂)₂], lies about an inversion centre and the Ag atom is three‐coordinated by two O atoms and one N atom from three different ligands. The 4‐chloro­benzoate anion acts as a monodonor ligand, bridging two inversion‐related Ag atoms of the compound into a dimer. There are weak intermolecular N—H⋯O hydrogen bonds in the structure.     

Bis(η5‐isopropyltetramethylcyclo­pentadienyl)(tetrahydroborato‐κ3H,H′,H′′)(tetrahydrofuran‐O)‐samarium(III): a lanthanidocene complex with a tridentate tetrahydroborato ligand

The lanthanidocene complex [Sm(BH₄)(C₁₂H₁₉)₂(C₄H₈O)], (I), shows a distorted tetrahedral arrangement around the central Sm^III atom. It consists of two η⁵‐isopropyltetramethylcyclopentadienyl ligands, one tetrahydroborato (BH₄^?) ligand bridging via H atoms to the lanthanide atom and one coordinating tetrahydrofuran (thf) molecule. The BH₄^? unit of (I) coordinates as a tridentate ligand with three bridging H atoms and one terminal H atom [Sm—B—H4 176 (2)°]. The η⁵‐isopropyl­tetra­methylcyclopentadienyl ligands of this bent‐sandwich complex [Cp1—Sm—Cp2 133.53 (1)° where Cp denotes the centroid of the cyclopentadienyl ring] adopt staggered conformations.     

Complexes of Cu2(μ‐OAc)4(H2O)2 with 1,10‐Phenanthroline and Comparison with those of 2,2′‐Bipyridine. Crystal Structure of the Dimer [Cu(OAc)2(phen)](μ‐H2O)

The two complexes of composition Cu₂(OAc)₄(phen)(H₂O)₂ ( 1 ) andCu₂(OAc)₄(phen)₂(H₂O) ( 2 ) have been synthesized and characterized by chemical analysis and IR and electronic spectroscopies. Compound 2 has the structure of a dimer with a phenanthroline molecule and two monodentate acetate groups coordinated to each copper atom and a water molecule as the only bridging ligand between them. Each copper atom has a distorted square‐planar pyramidal coordination, determined by two oxygen atoms at 1.94(3) and 1.959(3) Å, two nitrogen atoms at 2.023(4) Å and the oxygen atom of the bridging water molecule at 2.289(2) Å. The distance between the two copper atoms is of 4.29 Å and the angle Cu(1)‐O(3)‐Cu(1A) 139.2(2)°. The water molecule is involved in two intramolecular hydrogen bonds with non coordinated oxygen atoms. The distance between the molecules of phenanthroline is 3.75 Å. Magnetic and EPR results for Cu₂(OAc)₄(phen)(H₂O)₂ ( 1 ), Cu₂(OAc)₄(phen)₂(H₂O) ( 2 ), Cu₂(OAc)₄(bipy) ( 3 ) and Cu₂(OAc)₄(bipy)₂(H₂O)₂ ( 4 ) have been analysed and compared. For 1 and 3 an antiferromagnetic dimer unit [Cu₂(μ‐OAc)₄] with 2J = ?325 and ?292 cm^?1, respectively, and other two copper atoms without significant magnetic interaction are present. Triplet signals are detected in the EPR spectra. In 2 and 4 there is no practically magnetic exchange and the orthorhombic signals are observed in the EPR spectra.     

Tetrakis(μ‐guanidino­acetic acid‐κ2O:O′)­bis­[(nitrato‐κO)copper(II)]

The title compound, [Cu₂(NO₃)₂(C₃H₇N₃O₂)₄], forms a centrosymmetric dimer, with the two Cu²⁺ ions separated by 2.6525 (6) Å. The asymmetric unit contains a Cu atom coordinated to two guanidino­acetic acid ligands (via one carboxyl­ate O atom from each ligand) and to a nitrate group. The inversion centre in P generates the entire mol­ecule, in which each Cu atom is coordinated to four carboxyl­ate and to one nitrate O atom; ignoring the Cu—Cu separation, the geometry about each Cu atom is square pyramidal. The amino acid ligand is in the zwitterionic form. Strong N—H?O hydrogen bonds lead to a three‐dimensional supramolecular structure, in which the N?O distances are in the range 2.931 (4)–3.278 (3) Å, with N—H?O angles ranging from 128 to 170°.     

Triaquatris(2,6‐dinitrophenolato‐κ2O1,O2)yttrium(III)

In the title compound, [Y(C₆H₃N₂O₅)₃(H₂O)₃], the Y atom is nine‐coordinate with a slightly distorted tricapped trigonal prismatic coordination geometry. The Y^III ion is coordinated to three bidentate 2,6‐di­nitro­phenolate ligands and three water mol­ecules. The Y—O bond distances are in the range 2.217 (3)–2.754 (4) Å, with the Y—O distances from the nitro groups being longer than those from the water mol­ecules and the phenol groups. The coordinated NO₂ groups are almost coplanar with the benzene rings.     

(4‐Aminopyridine‐κN1)(phthalocyaninato‐κ4N)zinc(II) tetrahydrofuran disolvate

The title compound, [Zn(C₃₂H₁₆N₈)(C₅H₆N₂)]·2C₄H₈O, consists of one (phthalocyaninato)zinc (ZnPc) unit, a coordinated 4‐aminopyridine (4‐ap) molecule and two tetrahydrofuran (THF) solvent molecules. The central Zn atom is (4+1)‐coordinated by four isoindole N atoms of the Pc core and by the pyridine N atom of 4‐aminopyridine. The Zn atom is displaced by 0.4464 (8) Å from the isoindole N₄ plane towards the pyridine N atom. The crystal structure is stabilized by intermolecular amine–phthalocyaninate N—H...N hydrogen bonds and π–π interactions between the aggregated Pc rings, which form molecular layers, and by weak van der Waals interactions between the layers. As well as hindering the aggregation of ZnPc molecules by occupying an axial position, the amino group will add new interactions which will favor applications of ZnPc, for example, as a sensitizer of photodynamic therapy.     

Trans influence in a mer‐octahedral triiodidolanthanide: triiodidotris(tetrahydrofuran‐κO)ytterbium(III)

The structure of the six‐coordinate title complex, [YbI₃(C₄H₈O)₃], is the first mer‐octahedral form of an LnI₃L₃ lanthanide (Ln) compound with neutral L ligands, and is closely related to that of several of the seven‐coordinate LnX₃L₄ series of compounds, where X = Cl, Br or I and L = tetrahydrofuran (THF), isopropanol, pyridine or water. A structural trans effect can be assigned to YbI₃(THF)₃, in contrast to the LnX₃L₄ compounds, where steric and crystal packing effects are significant. The Yb—I bond lengths are 2.9543 (4) and 2.9151 (6) Å for I trans and cis to I, respectively, and the Yb—O bond lengths are 2.299 (5) and 2.251 (3) Å for O trans and cis to I, respectively. The crystal packing allows for six contact distances as weak C—H...I interactions in the range 3.10–3.24 Å. The title molecule has a crystallographic twofold axis passing through a THF O atom, the trans I atom and the Yb atom.     

Tetraaqua‐1κO,2κ3O‐(μ‐2,4‐dinitrophenolato‐1κ2O1,O2:2κO1)(2,4‐dinitrophenolato‐1κ2O1,O2)dilithium(I): a dinuclear lithium(I) complex

The title complex, [Li₂(C₆H₃N₂O₅)₂(H₂O)₄], contains two kinds of Li atoms, viz. five‐coordinated and four‐coordinated. The five‐coordinated Li ion has a tetragonal–pyramidal geometry, with a water molecule in the apical position and four O atoms from two 2,4‐dinitrophenolate (2,4‐DNP) ligands in the basal plane. The four‐coordinated Li ion has a tetrahedral geometry, with three water molecules and one phenolate O atom of a 2,4‐DNP ligand. The Li ions are bridged by a phenolate O atom, giving the complex a dinuclear structure. The crystal packing is stabilized by O—H...O hydrogen‐bonding interactions involving the water molecules and nitro O atoms.     

fac‐Tris(2‐ethyl‐4‐oxo‐4H‐pyran‐3‐olato‐κ2O3,O4)­iron(III) and its aluminium(III) analog

The crystal structures of the title iron(III) and aluminium(III) ethyl maltolate complexes, [Fe(C₇H₇O₃)₃] and [Al(C₇H₇O₃)₃], respectively, are isomorphous. In each case, the three bidentate ligand mol­ecules are bound to the metal atom, forming a distorted octahedral coordination geometry in a fac configuration.     

A tetranuclear copper(II) cluster: bis(μ‐4‐chlorobenzoato‐κ2O:O′)(4‐chlorobenzoato‐κ2O,O′)(4‐chlorobenzoato‐κO)tetrakis(μ3‐2‐pyridylmethanolato‐κ4N,O:O:O)tetracopper(II)

The title compound, [Cu₄(C₇H₄ClO₂)₄(C₆H₆NO)₄], consists of isolated tetranuclear clusters, where the Cu²⁺ cations are five‐ and sixfold coordinated by O atoms from the 4‐chlorobenzoate anions and by pyridine N and methanolate O atoms from bidentate 2‐pyridylmethanolate ligands. While three Cu atoms are six‐coordinated by an NO₅ donor set forming distorted octahedra, the fourth Cu atom is five‐coordinated by an NO₄ donor set forming a distorted tetragonal–pyramidal coordination around the Cu atom. The nucleus is a deformed cubane‐like Cu₄O₄ structure, with Cu...Cu distances in the range 3.0266 (11)–3.5144 (13) Å.     

Two lanthanum(III) complexes containing η2‐pyrazolate and η2‐1,2,4‐triazolate ligands: intramolecular C—H...N/O interactions and coordination geometries

The lanthanum(III) complexes tris(3,5‐diphenylpyrazolato‐κ²N,N′)tris(tetrahydrofuran‐κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C₁₅H₁₁N₂)₃(C₄H₈O)₃]·C₄H₈O, (I), and tris(3,5‐diphenyl‐1,2,4‐triazolato‐κ²N¹,N²)tris(tetrahydrofuran‐κO)lanthanum(III), [La(C₁₄H₁₀N₃)₃(C₄H₈O)₃], (II), both contain La^III atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer‐distorted octahedral geometry, while complex (II) has a fac‐distorted configuration. The difference in the coordination geometries and the existence of asymmetric La—N bonding in the two complexes is associated with intramolecular C—H...N/O interactions between the ligands.