Structure Characterization of EDTA Transition Metal Complexes (II) Study on Ba[Co(HEDTA)H2O]2 · 4H2O

The d-d transition spectrum of Ba[Co(HEDTA)H₂O]₂ · 4H₂O crystal was measured at room temperature and experimental results are explained quantitativley by using the ligand field theory and the radial wave function of non-free Co(II) ion. The crystal structures and the electronic structures of M/Co-EDTA (M=Ba, Sr, Ca, Mg) complexes are also discussed.     

Structure Charcterization of EDTA Transition Metal Complexes (I) Study on Sr[Co(HEDTA)H2O]2 · 4 H2O

The d-d transition spectrum of Sr[Co(HEDTA)H₂O]₂ · 4 H₂O crystal was recorded at room temperature and experimental results are discussed quantitatively. Using the ligand field theory and the radial wave function of non-free Co(II), the d-d transition energy levels of the title compound were calculated. And the results are seen to be in good agreement with the experimental values.     

Crystal and molecular structure of di-μ-bromobromopentakis(benzimidazole)dicopper(II) monobromide tetrahydrate [Cu2Br3(C7H6N2)5]Br·4H2O

A new complex compound. [Cu₂Br₃(C₇H₆N₂)₅]Br·4H₂O, has been synthesized and its crystal structure investigated by single-crystal X-ray methods. The crystals are isostructural with those of the [Cu₂Cl₃(C₇H₆N₂)₅]Cl·4H₂O salt. They are orthorombic, space group Pnma with 4 formula units in a cell of dimensions:a+19.923(1),b+17.555(2),c+12.0523(4)Å. The structure was refined by full-matrix least-squares to giveR+0.047 andR _w+0.053 for 3569 intensities above 3σ(I). As in the chloride compound, the complex cation consists of pairs of distorted trigonal bipyramidal Cu(II) centers which share an edge by two equatorial bromide ions. The Cu...Cu nonbonding distance in the complex in 3.4894(7)Å. The two Cu?Br?Cu bridges are not equivalent and their geometry is slightly different from that in the chloride complex. Comparison of the investigated structure to other binulear bis(μ-halide) bridged copper(II) complexes of similar structure has been made.     

A Novel Coordination Structure of Dichromates Bonding to Copper (II): [Cu(bipy)2(Cr2O7)] · 2 H2O

Dark-green multimetal compound crystal [Cu(bipy)₂(Cr₂O₇)]· 2 H₂O was obtained from aqueous solution of Cu(NO₃)₂, K₂Cr₂O₇ and bipyridine. The crystal structure was determined by X-ray crystallography: triclinic P1 , a = 7.716(3) Å, b = 9.656(3) Å, c = 15.517(5)Å, α = 77.41(3)°, β = 81.04(3)°, γ = 82.33(3)°, Z = 2. In this compound, two chromium atoms and a copper atom are linked by two oxo bridges (Cu(II) O Cr(VI) O Cr(VI)). The copper coordination polyhedron corresponds to a five-coordinated distorted trigonal bipyramid.     

(C2N2H10)2Mg(HP2O7)2·2H2O synthesis and crystal structure

(C₂N₂H₁₀)₂Mg(HP₂O₇)₂·2H₂O, is a new inorganic organic hybrid structure. It has been synthetized using wet chemistry. Its crystal structure consists of cis- and trans-edge sharing [MgO₄(H₂O)₂] octahedra resulting in chains, which are linked via [HP₂O₇] units to form [Mg(HP₂O₇)₂(H₂O)₂]⁴⁻ layers. The Mg²⁺ cations and the ethylendiammonium cations are located on centers of inversion. The ethylendiammonium cations are alternately located in the interlayer space. The cohesion of the crystal is well ensured by coulombic interactions between anions and cations and by several hydrogen bonds. The diphosphate anion shows an eclipsed conformation.     

Synthesis and crystal structure of [CuCl(phen)2]3H3V10O28 · 7 H2O

The new compound, [CuCl(phen)₂]₃H₃V₁₀O₂₈ · 7 H₂O, was prepared by reaction of an aqueous KVO₃ solution (pH 3) with an aqueous solution of CuSO₄ · 5 H₂O in which 1,10‐phenanthroline (phen) and KCl were added. The crystal structure of the compound was determined, and the proton position in H₃V₁₀O₂₈^3– were calculated by the bond length/bond number method and also determined from difference electron density map. The protons are bound to colinearly arranged μ–OV₂ and μ–OV₃ groups which is the common protonation type in trihydrogen decavanadates. The structure crystallizes in P1 space group symmetry. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of zdenekite NaPbCu5(AsO4)4Cl · 5H2O

The crystal structure of the mineral zdenekite NaPbCu₅(AsO₄)₄Cl · 5H₂O was established (Bruker SMART CCD diffractometer, synchrotron radiation, λ = 0.6843Å, R = 0.096 for 1356 reflections). Single-crystal X-ray diffraction study demonstrated that zdenekite belongs to the monoclinic system with the unit-cell parameters a = 10.023(7) Å, b = 19.55(1) Å, c = 10.023(6) Å, β = 90.02(1)°, sp. gr. P2₁/n, Z = 4. The structure consists of polyhedral layers parallel to the (010) plane. These layers are formed by Cu? polyhedra φ = O, Cl, H₂O) and AsO₄ tetrahedra. Distorted Na octahedra and Pb 7-vertex polyhedra and H₂O molecules coordinated to these metal atoms are located between the layers.     

Synthesis and physicochemical characterization of a porous coordination polymer of Sn-Cu xylarate: The structure of [Sn4Cu8.5(HL)2(L)4O2(OH)(H2O)12.5] · 17.2H2O

A porous coordination polymer of Sn-Cu xylarate [Sn₄Cu_8.5(HL)₂(L)₄O₂(OH)(H₂O)_12.5] · 17.2H₂O (H₅ L is xylaric acid) is synthesized for the first time and characterized by chemical analysis, IR spectroscopy, and X-ray diffraction. Centrosymmetric heterometallic fragments [Sn₄Cu₆(HL)₂(L)₄O₂(H₂O)₆] (A) including copper Cu1–3 and tin Sn1,2 atoms are distinguished in the structure. The Cu4(OH)_0.5(H₂O)_2.5 bridges connect A units into chains running along the c axis, and the Cu5(OH)(H₂O) bridges connect A fragments into layers perpendicular to the c axis. The Cu4,5 atoms form a framework whose voids accommodate the crystallization water molecules.     

The Characteristics of EDTA's Transition Metal Complexes (III) The d-d Transition Spectrum and Structure Characteristic of [Pb.Ni(HEDTA)H2O] Cl Crystal

The electronic absorption spectrum of crystals of the title compound [Pb.Ni(HEDTA) H₂O] Cl was recorded and discussed quantitatively. Using ligand field theory and the radial wave function of bound Ni(II) ion, the d-d transition energy levels of crystals of [Pb.Ni(HEDTA) H₂O] Cl, Ca [Ni(EDTA)] · 4H₂O, [Li.Ni(HEDTA) H₂O], [NiH₂EDTA)H₂O] were calculated. The different structure characteristics of EDTA's metal complexes are evidently shown in their d-d transition spectra.     

Cs2Ni(SO4)2 · 6H2O (CNSH) crystal: Growth and some properties

Large single crystals of cesium-nickel sulfate hexahydrate Cs₂Ni(SO₄)₂ · 6H₂O of optical quality were grown for the first time. The crystal structure and the optical and thermogravimetric properties of this compound were investigated.     

On the (MgxNi1–x)SeO4 · 6 H2O and (MgxCu1–x)SeO4 · 5 H2O mixed crystal formation

Mixed crystals (Mg_xNi_1–x)SeO₄ · 6 H₂O and (Mg_xCu_1–x)SeO₄ · 5 H₂O have been prepared studying the solubility in the MgSeO₄–NiSeO₄–H₂O and MgSeO₄–CuSeO₄–H_2O systems at 25 °C. It has been shown that the monoclinic structure of MgSeO₄ · 6 H₂O is unstable and undergoes a change into tetragonal structure due to the included nickel ions (about 4 at %). The lattice parameters of (Mg_{xNi 1–x})SeO₄ 6 H₂O have been calculated. It has been established that the magnesium ions incorporate isodimorphously in the crystal structure of CuSeO₄ · 5 H₂O which could be an indication of the existence of MgSeO₄ · 5 H₂O isostructural with the triclinic CuSeO₄ 5 H₂O. The distribution coefficients of the salt components between the liquid and solid phases have been calculated.     

Polymeric copper(II)-orotato complexes, [(C5H2N2O4)Cu(H2O)2]n

The compound [(C₅H₂N₂O₄)Cu(H₂O)₂]_n has been synthesized and its structure determined at room temperature. The primary coordination sphere at the Cu ion is square planar with the orotate dianion coordinating at the metal through heterocyclic nitrogen atom and adjacent oxygen of the carboxylate group, the remaining coordination sites are occupied by two water molecules. The orotate dianion is tricoordinated to one copper via N₁ and one oxygen of the carboxylato group and to another copper atom via the other oxygen of the carboxylato group. The coordination at copper is extended to five by the other oxygen of the carboxylate group of another orotate molecule. Thus, the molecules are associated to form chains, the carboxylato group acting as a bridge between the metal ions, the orotato-group being tridentate. The title compound crystallizes in the monoclinic space group. P2₁/n₁ with a = 9.515(5), b = 6.925(2), c = 11.861(6) Å, = 95.285(9)°, D _calc = 2.17 g cm^–3, and z = 4.     

Three‐Dimensional Structure Constructed via Hydrogen Bonds and π‐π Stacking Interaction. Crystal Structure of [Cu(AFO)2(H2O)2](ClO4)2.2(AFO).2H2O (AFO = 4,5‐Diazafluoren‐9‐one)

The structure of the title complexes [Cu(AFO)₂(H₂O)₂](ClO₄)₂.2(AFO).2H₂O (AFO = 4,5‐Diazafluoren‐9‐one)has been established by single‐crystal X‐ray diffraction. The complex crystallizes in the triclinic space group P‐1 with cell constants a = 7.659(3) Å, b = 11.066(3) Å, c = 14.203(5) Å, alpha = 75.16(3)°, β = 79.87(3)°, gamma = 85.71(3)°, Z = 1. The structure was solved by direct methods and refined to R₁ = 0.0595 (wR₂ = 0.1164). The X‐ray analysis reveals that a pair of AFO ligands chelate to a Cu(II) atom in an asymmetric fashion with one Cu‐N bond being much longer than the other, the Cu(II) atom is further coordinated by a pair of aqua ligands to form an elongated octahedral geometry. In the crystal of the complex, the mononuclear complex cations [Cu(AFO)₂(H₂O)₂]²⁺, uncoordinated AFO molecules, lattice water molecules and perchlorate anions are assembled into 3‐D structure via hydrogen bonds and π‐π stacking interaction.     

New zeotype borophosphates with chiral tetrahedral topology: (H)0.5M1.25(H2O)1.5[BP2O8]·H2O (M = Co(II) and Mn(II))

Two new isostructural open‐framework zeotype transition metal borophosphate compounds, (H)_0.5M_1.25(H₂O)_1.5[BP₂O₈]·H₂O (M = Co(II) and Mn(II)) were synthesized by mild hydrothermal method. The structure of compounds were characterized by single‐crystal X‐ray diffraction which have ordered, alternating, vertex‐sharing BO₄, PO₄, and (MO₄)OM(H₂O)₂ groups with hexagonal, P 6₁ 2 2 (No 178) space group and unit cell parameters for Co a = 9.4960(6) Å, c = 15.6230(13) Å, for Mn a = 9.6547(12) Å, c = 15.791(3) Å, Z = 1 for both of them. TGA/DTA analysis, IR spectroscopy were used for characterization. Magnetic susceptibility measurements for both of the compound indicate strong antiferromagnetic interaction between metal centers. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and Spectral Studies of ZnKPO4 · 6H2O Crystals

Zinc Potassium Phosphate Hexahydrate (ZPPH) is analogous to naturally occurring struvite. ZPPH crystals are grown by slow evaporation technique. These crystals are characterised by x‐ray and infrared studies. Powder x‐ray pattern indicates the orthorhombic crystal structure analogous to struvite with unit cell parameters a = 5.964, b = 5.808 and c = 12.495 Å. Infrared spectrum is characteristic of H₂O and PO₄^3‐ radicals.     

Structure of a Manganese (II) Complex Containing Saccharin and 1,10-Phenanthroline: [Mn(Sacch)2(o-Phen)2(H2O)2] · H2O

The X-ray crystal structure of the mononuclear manganese(II) complex containing saccharin and 1,10-phenanthroline, [Mn(Sacch)₂(o-Phen)₂(H₂O)₂] · H₂O, is reported. The manganese atom has a geometrical structure of hexa-coordinated distorted octahedron, saccharins interact with the central atom through water molecules.     

A Novel Structure of Bipyridine Coordinated with Copper (II): [Cu(bipy) (H2O)3] · (NO3)2

The crystal structure of the mononuclear copper (II) complex containing a 2,2′-bipyridine and three water molecules, [Cu(bipy) (H₂O)₃]. (NO₃)₂, is reported. The copper coordination polyhedron is a five-coordinated distorted pyramid.     

The Crystal Structure of the Cluster Complex [{Co(phen)2}2V4O12] · H2O

The crystal structure of [{Co(phen)₂}₂V₄O₁₂] · H₂O consists of hexanuclear bimetallic clusters [{Co(phen)₂}₂V₄O₁₂]. The cyclic [V₄O₁₂]^4‐ anion acts as a bidentate bridging ligand between the two [Co(phen)₂]²⁺ cations. The π‐π stacking interactions between the parallel 1,10‐phenantroline (phen) groups play a significant role in stabilizing this structure. The title compound crystallizes in the P2₁/c space group.     

Electron Paramagnetic Resonance of VO2+ in M2Zn(SeO4)2 · 6H2O(M=K,Rb) Single Crystals

The EPR spectrum of VO²⁺ has been studied in single crystals of K₂Zn(SeO₄)₂ · 6H₂O and Rb₂Zn(SeO₄)₂ ∼ 6H₂O at ∼9.45 GHz. VO²⁺ substitutes for Zn²⁺ have preferential orientations in the lattice. The V = O of the intense vanadyl center is nearly along the longest Zn H₂O direction. Spin-Hamiltonian parameters have been evaluated from single crystal as well as from powder spectra.     

Synthesis, structure and characterization of a new inorganic-organic hybrid complex (C3H5N2)2[Cd(C3H4N2)2Nb2O3F8]·2H2O

(C₃H₅N₂)₂[Cd(C₃H₄N₂)₂Nb₂O₃F₈]·2H₂O (C₃H₄N₂=imidazole) (1) was prepared from the hydrothermal reaction of Nb₂O₅, 3CdSO₄·8H₂O, C₃H₄N₂, HF and H₂O at 403 K, and characterized by single crystal X-ray diffraction and IR spectra. 1 crystallizes in the orthorhombic system, space group Pba2, with a=11.0192(9), b=16.8012(14), c=6.8717(6) ?, and Z=2. The crystal is made up of [Cd(C₃H₄N₂)₂Nb₂O₃F₈]²⁻ anions, [C₃H₅N₂]⁺ complex cations and H₂O molecules of crystallization. And the backbone of the compound is a one dimension coordination polymeric chain containing the anions. The complex cations and anions are linked through hydrogen bonding interactions. Co-crystallized water molecules fill in the pores and hydrogen bond to the host. Bond valence sums show that O1, O3 and F3 have much more negative charge, which are in agreement with the crystal structure that they act as bridging atoms.Supplementary material CCDC-606794 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at http://www.ccdc.cam.ac.uk/ const/retrieving.html or from the Cambridge Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk.