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.     

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)     

Electronic Structure of [Cu(C7H4NO3S)2(H2O)4] · 2H2O Crystal

The electronic absorption spectrum and ESR spectrum of the crystal of the title compound [Cu(C₇H₄NO₃S)₂(H₂O)₄] · 2 H₂O, are measured. The experimental results are discussed quantitatively by using the ligand field theory and the radial wave function of non-free Cu(II). The electronic structure of the compound is in agreement with its crystal structure.     

(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.     

Luminescence effects accompanying Ba(BrO3)2 ⋅ H2O crystallization from solution

Kinetics of the Ba(Br₂O₃)₂ ? H₂O precipitation from aqueous solution and the accompanying luminescence effects are studied. Specific features of appearance of luminescence during grinding of Ba(Br₂O₃)₂ ? H₂O crystals are also examined. The origin of luminescence effects is interpreted as the result of electric discharge accompanying cracking of crystals during their growth or grinding.     

Crystal structure of a seven-coordinate cobalt(II) complex with a new polyfunctional hydrazonic ligand, [Co(H4dapis)(OH2)2]Cl2·9/2H2O

A seven-coordinate cobalt(II) complex has been synthesized with a new hydrazonic ligand, H₄dapis, and its crystal structure determined by X-ray diffraction methods and refined toR 0.0564 for 2763 independent reflections. The structure consists of [Co(H₄dapis)(OH₂)2] cations, Cl anions, and lattice H₂O molecules interlinked by hydrogen bonds. The cobalt atom has a distorted pentagonal bipyramidal environment with two axial H₂O molecules and the H₄dapis ligand forming the basal plane.     

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.     

Crystalloluminescence and Mechanoluminescence Spectra of Ba(ClO3)2 · H2O and 2 K2SO4 · Na2SO4 Crystals

Crystalloluminescence and mechanoluminescence of Ba(ClO₃)₂ · H₂O and 2 K₂SO₄ · Na₂SO₄ crystals are investigated. The crystalloluminescence spectra are almost similar to the photoluminescence spectra; however, they differ completely from the mechanoluminescence spectra. The crystalloluminescence excitations may take place due to the various processes: (i) the recombination of ions, (ii) from amorphous to crystalline transition, (iii) from the phase change during the crystallization, and (iv) from the dielectric breakdown by the electric field produced due to the creation of microfracture during the crystal growth. It is concluded that the crystalloluminescence excitation in Ba(ClO₃)₂ · H₂O and 2K₂SO₄ · Na₂SO₄ crystals may be chemical in origin.     

Hydrothermal synthesis and structure of a novel terbium coordination polymer with packing cavities, {[Tb(TCB)1/2(H2TCB)1/2(H2O)](H2O)2}n (H2TCB = 1, 2, 4, 5‐benzenetetracarboxylic acid)

A novel terbium coordination polymer {[Tb(TCB)_1/2(H₂TCB)_1/2(H₂O)](H₂O)₂}_n (H₂TCB = 1, 2, 4, 5‐benzenetetracarboxylic acid) ( 1 ) has been hydrothermally synthesized and determined by single crystal X‐ray diffraction method, which features a very interesting three‐dimensional framework with large packing cavities. It crystallizes in the monoclinic space group P2₁/n with a = 1.0723(4) nm, b = 0.7168(3) nm, c = 1.7155(6) nm, β = 97.079(4)°, V = 1.3086(8) nm³, Z = 4, and final R₁ = 0.0203, wR₂ = 0.0404. In 1, the protonated carboxylate groups are free, the other carboxylate groups are bonded to Tb³⁺ ion in three modes: the chelating bidentate, the bridging bidentate and bridging tridentate. Moreover each Tb³⁺ ion is coordinated by nine oxygen atoms from six carboxylate groups and one water molecule respectively to complete a deformed tricapped trigonal prismatic geometry. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the Mixed Crystals Formation in the Fe(Zn) (HCOO)2–Cd(HCOO)2–H2O System

The solubility in the Fe(HCOO)₂–Cd(HCOO)₂–H₂O and Zn(HCOO)₂–Cd(HCOO)₂–H₂O systems have been studied by the method of physico-chemical analysis at 25 °C and mixed crystals of the type Fe_1-xCd_x(HCOO)₂.2 H₂O and Zn_1-xCd_x (HCOO)₂. 2 H₂O have been obtained. The lattice parameters of the mixed crystals have been calculated. It has been established that the isostructural Fe(HCOO)₂. 2 H₂O and Cd(HCOO)₂. 2 H₂O form isomorphous mixed crystals, whereas the isostructural Zn(HCOO)₂. 2 H₂O and Cd(HCOO)₂. 2 H₂O yield isodimorphous mixed crystals. The difference in the behaviour of the two pairs of formate salts has been attributed to the difference in the Me–O_m, bond lengths in the coordination octahedra, forming the crystal structures.     

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)     

Synthesis and crystal structures of two new complexes [M(OH2)(HDPA)2]·3H2O (M = Mn, Co)

Two new transition metal complexes of [M(OH₂)(HDPA)₂]·3H₂O (M=Mn(1); M=Co(2)) (H₂DPA, 2,6-pyridine-dicarboxylic acid) have been prepared at room temperature from the reaction of MCl₂·6H₂O (M=Mn or Co) and H₂DPA in the mixed solvent of H₂O and EtOH in the presence of piperazine, and were characterized by X-ray analysis, elemental analysis. X-ray analysis reveals that the coordination geometries of Mn²⁺ and Co²⁺ are of octahedron and severely distorted square-based pyramid, respectively. Crystal data: [Mn(OH₂)(HDPA)₂]·3H₂O (1), Mr=459.23, monoclinic, P2(1)/n, a=7.0056(3), b=(23.8125(12), c=10.7444(3) ?, β=99.834(2)°, Z=4, V=1766.28(13) ?³, R ₁=0.0586, wR ₂=0.1448 [I>2σ(I)]; Co(OH₂)(HDPA)₂]·3H₂O (2), Mr=463.22, monoclinic, P2(1)/n, a=7.0014(2), b=23.8346(7), c=10.7212(4) ?, β=99.8540(10)°, Z=4, V=1762.71(10) ?³, R ₁=0.0474, wR ₂=0.1366 [I>2σ(I)].     

X-Ray diffraction and IR-spectroscopic studies of UO2(n-C3H7COO)2(H2O)2 and Mg(H2O)6[UO2(n-C3H7COO)3]2

Single crystals of UO₂(n-C₃H₇COO)₂(H₂O)₂ (I) and Mg(H₂O)₆[UO₂(n-C₃H₇COO)₃]₂ (II) are synthesized. Their IR-spectroscopic and X-ray diffraction studies are performed. Crystals I are monoclinic, a = 9.8124(7) Å, b = 19.2394(14) Å, c = 12.9251(11) Å, β = 122.423(1)°, space group P2₁/c, Z = 6, and R = 0.0268. Crystals II are cubic, a = 15.6935(6) Å, space group $Pa\bar 3$ , Z = 4, and R = 0.0173. The main structural units of I and II are [UO₂(C₃H₇COO)₂(H₂O)₂] molecules and [UO₂(C₃H₇COO)₃]^? anionic complexes, respectively, which belong to AB ₂ ⁰¹ M ₂ ¹ (I) and AB ₃ ⁰¹ (II) crystal chemical groups of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₇COO^?, and M ¹ = H₂O). A crystal chemical analysis of UO₂ L ₂ · nH₂O compounds, where L is a carboxylate ion, is performed.     

Structural features of a new [Fe(nicotinamide)2(H2O)4]·[Fe(H2O)6]·(SO4)2·2H2O complex

A new nicotinamide complex of Fe(II) cation was prepared by reaction between ferrous sulfate and nicotinamide in aqueous solution. The complex was characterized on the basis of elemental analysis, FT IR and UV–VIS spectroscopy, electrochemistry (cyclic voltammetry) and X–ray crystallography. The complex consists of the molecular composition of [Fe(nicotinamide)₂(H₂O)₄]· [Fe(H₂O)₆]·(SO₄)₂·2H₂O. The complex crystallizes in the monoclinic space group P 2₁/c [a = 12.862(3), b = 7.110(3), c = 16.382(3) Å; β = 95.79(2)°]. It has been proven that nicotinamide is coordinated to Fe(II) through the nitrogen atom of its heterocyclic ring. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

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.     

Synthesis, Crystal Structure and Characterization of a New Dabcodiium Hexaaquacobalt(II) Bis(Selenate), (C6H14N2)[Co(H2O)6](SeO4)2

Abstract  

The new hybrid material, cobalt selenate templated by 1,4-diazabicyclo[2.2.2]octane (abbreviated dabco), has been synthesised by the slow evaporation method at room temperature. Its crystal structure was investigated using single crystal X-ray diffraction data. It crystallises in the monoclinic system (space group P2₁/c) with the following unit-cell parameters: a = 12.9169(2) ?, b = 11.9101(2) ?, c = 12.4951(2) ?, β = 108.484(1)°, V = 1823.10(5) ?³ and Z = 4. The supramolecular structure of (C₆H₁₄N₂)[Co(H₂O)₆](SeO₄)₂ consists of isolated [Co(H₂O)]²⁺ and (C₆H₁₄N₂)²⁺ cations and (SeO₄)²⁻ anions linked together by three dimensional hydrogen-bond network. The infrared spectroscopy confirmed the presence of these different entities. The thermal behaviour of the precursor, studied by thermodiffractometry and thermogravimetric analyses, indicates that its decomposition proceeds through three stages giving rise to the cobalt oxide.     

Crystal chemistry of the salts Me+Cl · Me2+Cl2 · 2 H2O

The crystal chemistry of the double salts Me⁺Cl · Me²⁺Cl₂ · 2 H₂O (where (Me⁺ = K, Rb, Cs; Me²⁺ = Mn, Fe, Co, Ni) is considered. It is concluded that these salts crystallize in three types of structures, the Me⁺ ion size being decisive for the structure type. Salts containing the large Cs⁺ ions crystallize in an orthorhombic structure in which [Me²⁺ (H₂O)₂Cl₄] octahedra form chains having common Cl⁻ corners. Salts with the smaller K⁺ ions crystallize in a tricline system, the [Me²⁺ (H₂O)₂Cl₄] octahedra being connected by a common Cl–Cl edge and forming dimers. When the intermediate in size Rb⁺ ions are present in the salts, either of the above structures is possible as well as a monoclinic structure which is intermediate in symmetry. The expected isostructure of the cesium salts was checked by studing the CsCl · NiCl₂ · 2 H₂O–CsCl · MnCl₂ · 2H₂O–H₂O system. A continuous series of mixed crystals is found.     

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.     

Crystal Structure Study of Co(II) Complexes with 2,2′-(1,4-Ethylenedioxyl) Dibenzoic Acid-[Co · L · (H2O)3]n · nH2O· 0.2 nH2O

The structure ofS the title complex [Co. L. (H₂O)₃]_n. nH₂O. 0.2 nH₂O has been established by single crystal X-ray diffraction. Crystals of the complex are monoclinic, space group C2/c with cell constants α = 45.29(4), b=10.631(6), c = 8.015(6) Å, β = 90.65(8)°, Z = 8, D_c = 1.489 g. cm⁻³ The structure was solved and refined to R =0.0478 (wR = 0.0577). In the chain structure, Co(II) ions are hexacoordinated by 0 atoms in an octahedral arrangement. CoO₆ octahedra share corners (bridged) through O atoms of water, with each L^2--ligand binding two adjacent Co atoms.     

A Unique Example of a Co-crystal of [Co(AMTTO)2(H2O)2](NO3)2 and [Co(AMTTO)2(CH3CN)2](NO3)2 (AMTTO = 4-amino-5-methyl-1,2,4-triazol-3(2H)-thione)

A co-crystal of cobalt(II) complexes, Co(AMTTO)₂(CH₃CN)₂]²⁺(NO₃)₂. [Co(AMTTO)₂(H₂O)₂]²⁺(NO₃)₂, compound (1) was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine (AMTTO) in acetonitrile as solvent. Isolated crystals were characterized by elemental analyses, IR spectroscopy as well as X-ray diffraction studies. Crystal data for 1 at 95 K revealed a monoclinic space group P2₁/n, a?=?11.7903(5), b?=?12.1279(5), c?=?14.1443(6) Å, β?=?99.244(4)°, Z?=?2, R₁?=?0.0339. Compound 1 consists of two co-crystallized Co(II) complexes [Co(AMTTO)₂(CH₃CN)₂]²⁺ and [Co(AMTTO)₂(H₂O)₂]²⁺ and four nitrate counter anions In both complexes, cobalt(II) ions are in an octahedral arrangement. Two S, N bidentate AMTTO ligands are coordinated to both Co(II) ions. The coordination sphere of Co1 is completed by two acetonitrile molecules, and these positions are occupied by water molecules for Co2.

Graphic Abstract

A co-crystal of cobalt(II) compound was isolated from the reaction of Co(NO₃)₂?6H₂O and 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine in acetonitrile as solvent.