Synthesis, crystal, and molecular structure of the solvated complex [MoO2(L)] · DMF (L2− = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol anion)

A new dioxomolybdenum(VI) complex, [MoO₂(L)] · DMF, where L^2? = 2-[N-(2-hydroxynaphthylidene)amino]propane-1,2,3-triol, has been synthesized. Its structure has been determined by X-ray diffraction analysis. The Mo atom is octahedrally coordinated by two oxo ligands that are in cis-positions with respect to each other, two oxygen atoms, the nitrogen atom of the tridentate bis(chelate) ligand L, and the DMF oxygen atom.     

Synthesis,crystal structure and luminescent properties of two complexes containing [Au(CN)2] − building blocks

Two supramolecular complexes, {{Ni(H₂O)(phen)₂[Au(CN)₂]}[Au(CN)₂]?·?1.5H₂O} _n (1) (phen?=?1,10-phenanthroline) and [H₂teta][Au₂(CN)₄]?·?2H₂O (2) (teta?=?5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene) have been synthesized and structurally characterized. Complex 1 was a one-dimensional infinite chain constructed by [Au(CN)₂]^? building blocks. In complex 2, there are one cation, one anion, and two water molecules in the asymmetric unit. The two complexes are interconnected through a combination of aurophilic attractions and hydrogen bonds and formed into 3D supramolecular structures. The aqueous solutions of 1 and 2 display interesting luminescence at room temperature.     

Synthesis and structure of new thiourea-containing Cobalt(III) dioximates with the [TiF6]2− anion

The new Co(III) dioximates [Co(DH₂)(D)(Thio)₂]₂[TiF₆] ·2DMF (I), [Co(NioxH)₂(Thio)₂]₂[TiF₆] · 2.25H₂O (II), and [Co(DpgH)₂(Thio)₂]₂[TiF₆] · 4DMF · 1.5H₂O (III) have been synthesized and studied (DH₂ and D are, respectively, the dimethylglyoxime molecule and doubly charged anion; NioxH and DpgH are singly charged anions of 1,2-cyclohexanedione dioxime and diphenylglyoxime, respectively; Thio is thiourea; DMF is dimethylformamide). The composition and structure of the complexes have been studies by IR, UV, and NMR spectroscopy. The crystal structures have been determined by X-ray crystallography. The hydrogen bonds in the structures are formed by fluorine atoms of the [TiF₆]^2? anion with Co(III) complex cations and solvent molecules of crystallization. The amino groups of coordinated thiourea molecules are also involved in the hydrogen bond system, which is responsible for their different arrangement with respect to the equatorial planes of the Co(III) complex cations.     

Synthesis,crystal structures and magnetic properties of a series of new cyano-bridged complexes derived from templates [Ni(CN)4]2− and [Co(III)(CN)6]3−

Three new cyano-bridged complexes 1 [Ni(tn)₂Ni(CN)₄] (tn?=?1,3-diaminopropane), 2 [Cu^II(dipn)Ni^II(CN)₄], and 3 [Cu(dipn)]₆[Co(CN)₆]₄?·?4H₂O (dipn?=?dipropylenetriamine) have been assembled by the templates [Ni(CN)₄]^2? and [Co(CN)₆]^3?. 1 consists of a one-dimensional linear chain–Ni(tn)₂–NC–Ni(CN)₂–CN–Ni(tn)_2? in which the Ni(II) centers are linked by two CN groups. One 1-D zigzag chain of 2 is formed with–Ni(2)–C–N–Cu(1)–N–C–linkages. A 2D structure of 3 is formed by an alternate array of [Co(CN)₆]^3? and [Co][Cu₆] units. For 1, there is an overall weak antiferromagnetic interaction between Ni(II) ions through the–NC–Ni–CN–bridges of the diamagnetic [Ni(CN)₄]^2? anions. 2 exhibits a weak antiferromagnetic exchange interaction between copper(II) ions mediated by [Ni(CN)₄]^2? diamagnetic bridges. Complex 3 exhibits a weak ferromagnetic interaction between nearest Cu^II and Cu^II atoms through–NC–Co–CN–bridges.     

Hydrothermal synthesis and crystal structure of a heteropolyoxotungstate formed by sandwich-type heteropolyanion [Gd(PW11O39)2]11− and reduced [Cu(en)2] + cations

A heteropolyoxotungstate, [Cu(en)₂]₂H₈[Gd(PW₁₁O₃₉)₂] ·?(H₂en)_0.5 ·?3H₂O (1), has been hydrothermally synthesized and characterized by IR, XPS, TGA and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a =?12.651(2) ų, b =?20.559(3) ų, c =?21.729(3) ų, α =?71.379(2), β =?82.829(2), γ =?75.532(2)°, V =?5179.5(14) ų, Z =?2, R ₁ =?0.0702 and ωR ₂ =?0.1479. The heteropolyanion is composed of two monovacant [α-PW₁₁O₃₉]^7? Keggin moieties linked via a Gd atom leading to a sandwich-type structure. The Gd center is in a distorted square antiprismatic coordination environment with eight oxygen atoms, four from each of the two [α-PW₁₁O₃₉]^7?moieties.     

Synthesis and crystal structure of [V_2(μ-S_2)_2(S_2CNEt_2)_4]·2CH_3Cl

[V_2(μ-S_2)_2(S_2CNEt_2)_4].2CH_3Cl was synthesized by the reaction of NaS_2CNEt_2,Li_2S andVOCl_3 at room temperature.Crystal data:M=1061.3,space group Pbca,with the orthorhombicparameters:a=20.123(3),b=20.485(4),c=10.911(3),V=4497.7,Z=4,D_c=1.57g/cm~3,Mo Kσradiation(λ=0.71069()?),μ=13.2 cm~(-1),F(000)=2168.Final R=0.041 and R_w=0.047 for 2288 ob-served reflections with I>3σ(1).The coordination sphere of each V atom in title compound is a dis-torted tetragonal prism composed of two bidentate dithiocarbamate and two S_(2~((2-)) ligands.The V—Vdistance is 2.890 while the V—S distances fall in the range of 2.422—2.505.     

A doubly deprotonated form of calix[6]arene: Crystal and molecular structure of (calix[6]arene-2H)2−·(HNEt 3 + )2

The doubly deprotonated form of calix[6]arene, with two protonated triethylamines as counter-ions, crystallizes in the monoclinic system: space groupP2₁/n,a=8.465(4),b=17.822(8),c=15.182(6) Å,=90.18(4)°,V=2291(2) ų,Z=2. Refinement led to a final conventionalR value of 0.063 for 1046 reflections. The macrocycle conformation is not apinched cone, usual for freeR-calix[6]arene, but a distorted 1,2,3-alternate cone, since the molecule lies on a symmetry center. Furthermore, one of the torsion angles defined by the methylene bridges is near to zero, which is unusual in calixarene structures. Supplementary Data relating to this article (atomic coordinates for hydrogen atoms, anisotropic displacement parameters for oxygen and nitrogen atoms, and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82182 (7 pages).     

Synthesis,crystal structure and magnetic properties of [1-(4′-bromobenzyl)-4-methylquinolinium] [Ni(mnt)2] complex (mnt2 − =maleonitriledithiolate)

A new ion-pair complex, [BrBzMeQl][Ni(mnt)₂] (1) ([BrBzMeQl]⁺?=?1-(4′-bromobenzyl)-2-methylquinolinium; mnt^2??=?maleonitriledithiolate), has been prepared and characterized. X-ray diffraction analysis shows that the Ni(mnt)₂ anion and [BrBzMeQl]⁺ cations of 1 form completely segregated stacking columns, with the Ni?···?Ni distances alternating between 3.717 and 4.466?Å?in the Ni(mnt)₂ stacking column. The variable-temperature magnetic susceptibilities of 1 have been measured over the range 75–300?K and the results reveal that the complex exhibits antiferromagnetic behavior.     

X-ray crystal structure and properties of the [Mo(CN)2O(acetam)] · 2.5H2O complex

The X-ray crystal structure and properties of the [Mo(CN)₂O(acetam)] · 2.5H₂O {acetam = N-[1-(pyridin-2-yl)-ethylidene]diethanetriamine} complex are described. The complex was prepared by the in situ reaction of [Mo(CN)₄O(H₂O)]^2–, 2-acetylpyridine and diethylenetriamine in aqueous solution. The complex is seven coordinated. The Mo atom having a distorted pentagonal bipyramid arrangement with a tetradentate 'half-unit' Schiff base and oxygen ligand in a plane. The properties of the salt, i.r., u.v.–vis. spectra and cyclic voltammetry measurements are described and compared with those of [Mo(CN)₂O(diaceen)] · H₂O {diaceen = N,N-bis[1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine) having the same coordination number for the metal.     

Crystal structure and magnetic properties of a three-dimensional complex constructed from [CuL]2+ and [Fe(CN)6]3− precursors

Self-assembly of the precursor [Cu(L)]²⁺ (L = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane) with hexacyanometalate [Fe(CN)₆]³⁻ produces a 3-D cyano-bridged Cu(II)–Fe(III) bimetallic assembly, [CuL]₂[Fe(CN)₆]ClO₄ · H₂O (1), characterized by single-crystal X-ray diffraction studies, and magnetic measurements. The crystallographic determination reveals that each hexacyanoferromate(III) ion connects four copper(II) ions using four co-planar CN⁻ groups which axially coordinate to the copper ion in a trans fashion forming trans-CuL(N≡C)₂ moieties in (1). Magnetic studies reveal that (1) displays a ferromagnetic interaction between Cu(II) and Fe(III) through the CN linkage.     

Synthesis and crystal structure of [Nd(C6NO2H5)3(H2O)2] n n[ZnCl4]·nCl·2.5nH2O with novel poly-cationic chain

The title complex, [Nd(C₆NO₂H₅)₃(H₂O)₂] _n n[ZnCl₄]·nCl·2.5nH₂O (1), was obtained by hydrothermal reactions and structurally characterized by X-ray diffraction. The crystal structure analysis reveals that the title complex is characteristic of a novel polycationic [Nd(C₆NO₂H₅)₃(H₂O)₂] _n ³ⁿ⁺ one-dimensional chain-like structure.     

Synthesis and crystal structure of (E)-[(2-cyclohexenyl) vinyl]triaryltin

(E)-[(2-Cyclohexenyl)vinyl]triaryltin (aryl=phenyl, p-tolyl) were synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy. The crystal structure of (E)-[(2-cyclohexenyl)vinyl]triphenyltin was also determined by the X-ray diffraction. Experiments show that this compound has the conjugated system, which makes it have possible bioactivity and anti-tumor activity.     

Infrared spectra and molecular structure of excited electronic metastable states of the nitroprusside anion, [Fe(CN)5NO]2−

Na₂[Fe(CN)₅NO].2H₂O (SNP) and Ba[Fe(CN)₅NO].3H₂O (BNP) irradiated at low temperature with light in the green—blue region exhibit two new sets of infrared (IR) bands. These can be assigned to two, long-lived, electronically excited metastable states of the [Fe(CN)₅NO]²⁻ (NP) ion. Upon heating, these states depopulate following decay processes with different onset temperatures. We considerably extend here previous polarized IR data on irradiated SNP (100) plates to include the other basal planes. All IR-active CN, NO and FeN stretching modes and FENO bending modes of NP in both metastable states exhibit frequency down shifts This points to a softening of the corresponding bonds upon excitation. Relative frequency shift values observed for modes associated with the FeNO group are about one order of magnitude larger than the corresponding values for CN stretching modes. This supports the conclusion that the metastable states are reached through an electronic transition involving mainly the metal(nd)-NO bonding. We employ dichroic measurements in SNP to estimate the orientation in the lattice of the transition dipole moment vector corresponding to the NO mode of NP in both metastable states. Results show that the FeNO group is not appreciably bent upon excitation of NP to either of these states.     

The crystal structure of tetraphenylphosphonium pentacyanonitridorhenate(V), (PPh4)3[ReN(CN)5]·7H2O

Summary The crystal structure of (PPh₄)₃[ReN(CN)₅]·7H₂O has been determined from three dimensional X-ray diffraction data. The orange crystals are triclinic, space group , with cell dimensions a=12.514(3), b=15.8514), c=19.030(3) Å, =77.62(2), =84.61(1) and =74.03(2)^o, z=2, D_obsd=1.40(1) g cm^–3 and D_calc=1.37(1) g cm^–3. The anisotropic refinement of 5861 observed reflections converged to R=0.049.The [ReN(CN)₅]^3– ion has a distorted octahedral geometry. Bond distances: ReN=1.68(1), Re–C_av (planar)=2.12(1), Re–C (axial)=2.39(1) Å. The Re atom is displaced by 0.31 Å out of the plane formed by the four carbon atoms towards the nitrido ligand.     

Synthesis and molecular and crystal structure of the octanuclear palladium cluster Pd8(μ3-CO)2(μ2-CO)6(PMe3)7

Treatment of bis(dibenzylideneacetone)palladium with trimethylphosphine under a carbon monoxide atmosphere gives the title complex in good yield. X-ray crystallography has shown the structure of the complex to consist of an octahedron of palladium atoms which is bicapped by two further palladium atoms in an asymmetric fashion. Seven of the eight palladium centres carry terminal trimethylphosphine ligands. Two face-bridging and six edge-bridging CO molecules complete the ligand shell.     

Synthesis and crystal structure of Co(III) dioximates with the complex anion [SbF6]?

The complexes [Co(DioxH)₂L₂][SbF₆] · nH₂O, where DioxH is dimethylglyoxime monoanion (DioxH^?) or 1,2-cyclohexanedione dioxime (NioxH^?), L is aniline (An) or triphenylphosphine (PPh₃), were isolated from the CoX₂ · nH₂O-NaSbF₆-DioxH₂-L system (X = F or CH₃COO) in aqueous methanol. The complexes were studied by UV, IR, and NMR spectroscopy and by X-ray diffraction. The crystal structure of [Co(DH)₂(An)₂][SbF₆] · H₂O (I) and [Co(NioxH)₂(PPh₃)₂][SbF₆] (II) is stabilized by the electrostatic interactions between the Co(III) complex cations and outer-sphere fluorine-containing anions and by hydrogen bonds between structural units.     

Synthesis and crystal structure of a coordination polymer {[Cu2(L)2(Phen)2] · 8H2O} n

A novel metal coordination polymer, {[Cu₂(L)₂(Phen)₂] · 8H₂O} _n (I), has been synthesized by the reaction of Cu(NO₃)₂ with 2,2′-bipyridyl-4,4′-dicarboxylic acid (L) and 1,10-phenanthroline (Phen) at room temperature. The polymer was characterized by IR, elemental analyses and X-ray diffraction. Single-crystal structural analysis reveals that the center Cu²⁺ ions have two coordinated types. The Cu(1) atom has the five-coordinate mode, and Cu(2) forms an is octahedron of the six-coordinate mode. Two Cu²⁺ ions are connected by the O atom of carboxylate group bridges. Complex I contains eight molecules of water clusters and constructed a 1D tape structure.     

Strategy for the synthesis of Di- and polymer tartratogermanates with single-charge cations. Crystal structures of K2[Ge2(OH)2(μ-Tart)2] · 4.5H2O and (NH4)2n [Ge2(μ-O)(μ-Tart)2] n · nMeCN · nH2O

Tartratogermanates of alkaline metals and ammonium are synthesized for the first time using different solvents (water, acetonitrile) and starting reagents (GeO₂ and GeCl₄): dimeric Kat₂[Ge₂(OH)₂(μ-Tart)₂] · 4.5H₂O (H₄Tart is D-tartaric acid, Kat = Na (I) and K (II)) and polymer (NH₄)_2n [Ge₂(μ-O)(μ-Tart)₂] _n · nCH₃CN · nH₂O (III). The complexes are characterized by elemental analysis, IR spectroscopy, and X-ray diffraction analysis. The structure of complex II contains binuclear isolated [Ge₂(OH)₂(μ-Tart)₂]₂-complexes. In complex III, the oxo ligands join the binuclear fragments into polymer chains.     

Preparation, characterization and crystal structure of Na4[Mn(NCS)6]·13H2O

Na₄[Mn(NCS)₆] · 13H₂O was prepared and characterized by chemical analysis, magnetic susceptibility, thermal dehydration reactions, and single crystal X-ray structure analysis. The crystals are triclinic with a=9.310(1)Å, b=9.367(1)Å, c=9.730(2)Å, = 89.89(1)°,=75.33(1)°, =70.72(1)°, space group P¯I.Z=1. The structure is built up from Na(H₂O)₅ S, Na(H₂O)₆, and Mn(NCS)₆, octahedra. All water molecules are coordinated to Na⁺ -ions in terminal as well as bridging fashion. They form O-H···O as well as O-H···S hydrogen bonds.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday