Crystal structure of complexes of bivalent Co,Ni, and Cd with anions of benzoic and 2-(acetylamino)-5-nitrobenzoic acids

The structure of three complexes of bivalent metals (cobalt, nickel, and cadmium) with anions of benzoic (HL ¹) and 2-(acetylamino)-5-nitrobenzoic (HL ²) acids, namely, [Co₂¹ (H₂O)₂(μ-C₄H₄N₂)] _n (I), [NiL²(H₂O)₅]L² · 2H₂O (II), and [Cd(μ-L ²)₂(H₂O)₂] _n · 2nH₂O (III), is determined. In chainlike structure I, cobalt atoms are connected by bridging pyrazine molecules; structure II contains isolated complexes. In structure III, centrosymmetric (CdOCO)₂ cycles and polymeric ribbons are formed due to the coordination of the carboxylate group of the L ² ligand to two cadmium atoms.     

Syntheses and Structural Characterization of Three New Alkaline Earth Metal Supramolecular Coordination Compounds Based on Atza Ligand (Atza = 5<Emphasis Type="Bold">-</Emphasis>Aminotetrazole<Emphasis Type="Bold">-</Emphasis>1<Emphasis Type="Bold">-</Emphasis>Acetato Anion)

Abstract  

Reactions of alkaline earth metal salts M(NO₃)₂ (M = Mg, Ca, Sr) and ligands 5-aminotetrazole-1-acetic acid (Hatza) in water/methanol solution, respectively, produced three new complexes [Mg(atza)₂(H₂O)₄] (1), [Ca(atza)₂(H₂O)₄] (2) and [Sr(atza)₂(H₂O)₃]^.2H₂O (3). These compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compounds 1 and 2 have a mononuclear structure and the same coordination mode. Compound 3 has a 1D polymeric chain structure. In 1–3, amido group (–NH₂) of atza ligand forms hydrogen bond N(5)–H(5)···N(O) with the neighboring carboxylate-O, tetrazolate-N or water molecule which stabilized the supramolecular assemblies.     

Iron-Chloranilate Intercalation Compounds: Synthesis,Crystal Structures,and Thermal Properties

Abstract

Hydrogen bond supported new iron-chloranilate assemblies, {(Hpy)[Fe(CA)₂(H₂O)₂](H₂O)}_n (py = pyridine, H₂CA = chloranilic acid, C₆H₂O₄Cl₂) (1), and [(phz)₂[Fe(CA)₂(H₂O)₂](H₂O)₂]_n (phz = phenazine, C₁₂H₈N₂) (2) have been synthesized and characterized. Compound 2 crystallizes in the monoclinic, space group C2/m (#12), with a= 29.135(6) Å, b= 16.886(6) Å, c = 15.017(5) Å, ß = 165.907(1)°, V= 1798(2) ų, Z = 2. In both the compounds two chloranilate dianions and two water molecules are coordinated to the iron ion making anionic monomers [Fe(CA)₂(H₂O)₂]^?, which are the building blocks of the compounds. The coordination environment around the iron ion in the building block is a distorted octahedron, where two water molecules sit on the trans position to each other. [Fe(CA)₂(H₂O)₂]^? anions form common layer structures, supported by hydrogen bonds. Hpy⁺ are intercalated in between the layers of 1 by electrostatic and hydrogen bonding interactions and phz are intercalated in that of 2 by electrostatic interactions. DSC traces of 1 show anomaly at 174 K, indicating phase transition in the compound.     

Synthesis,structures, and luminescent properties of a series of coordination compounds based on O,N-donor ligands

Four novel coordination compounds, namely, [Cd₂(pydc)₂(bpp)₂(H₂O)₂]? bpp?2H₂O (1), [Zn(Hpydc)₂]?3H₂O (2), [Cd(dhb)₂(phen)₂] (3), and [Zn(L)(phen) (H₂O)] (4) (H₂pydc?=?2,6-pyridinedicarboxylic acid, Hdhb?=?2,6-dihydroxybenzoic acid, H₂L?=?5-((2'-cyano-1,1'-biphenyl-4-yl) methoxy)isophthalic acid, bpp?=?1,3-bis(4-pyridyl)propane, and phen?=?1,10-phenanthroline) have been hydrothermally synthesized and characterized by IR spectroscopy, thermogravimetric analysis and X-ray single crystal diffraction analyses. Compounds 1, 2 and 3 feature zero-dimensional (0D) structures and 1 is further extended to one-dimensional (1D) chain structure through C-H???O hydrogen bonding interactions. Compound 4 exhibits 1D chain structure. The luminescent properties of compounds 3 and 4 have also been studied.     

Two Novel Purely Inorganic Coordination Polymers Constructed From Bivalent Transition Metal Ions and Paratungstate Clusters

Abstract  

The new polymeric compounds (NH₄)₈[Cu(H₂O)₂H₂W₁₂O₄₂]·10H₂O (1) and (NH₄)₄[Co(H₂O)₂][Co(H₂O)₄]₂[H₂W₁₂O₄₂]·8H₂O (2) have been synthesized in aqueous solution and characterized by elemental analysis, TG analysis. Single crystal X-ray diffraction revealed that the [H₂W₁₂O₄₂]¹⁰⁻ (named paratungstate-B) units act as tetradentate and octadentate ligands, respectively. In compound 1, two neighboring paratungstate-B clusters are linked by [Cu(H₂O)₂]²⁺ units leading to the formation of 1D chain. In crystal of 2, each cobalt ion links two paratungstate-B clusters, while each [H₂W₁₂O₄₂]¹⁰⁻ block is surrounded by two [Co(H₂O)₂]²⁺ and four [Co(H₂O)₄]²⁺ bridging cations resulting a 2D sheet formed parallel to the [10[`1]] [10\bar{1}] plane.     

Crystal structure of triethylentetraammonium bis monohydrogen-monophosphate dihydrate β-NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3(HPO4)2·2H2O

The salt triethylentetraammonium bis monohydrogen-monophosphate dihydrate is orthorhombic Pbca with unit cell dimensions a = 8.963(2), b = 10.326(2), c = 17.381(4)Å; Z = 4; D_m = 1.540 g cm^–3; D _x = 1.562 g cm^–3. The examination of the structure shows a layer arrangement parallel to the axis: planes of [HPO₄]^2– tetrahedra alternate with planes of [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺. The [HPO₄]^2– tetrahedra are connected through O(W)s--H···O hydrogen bonds, so that infinite chains of the composition [HPO₄(H₂O)]_n ^2n– are formed in the structure parallel to the axis. The structure of this compound is built from [HPO₄]^2– anions, [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺ cations and zeolitic water molecules connected by hydrogen bonds.     

Crystal structures of mixed ligand complexes containing saccharinate and nicotinamide: [Cu(saccharinato)2 (nicotinamide) (H2O)]⋅(H2O) and [M(nicotinamide)2 (H2O)4]⋅(saccharinate)2 (M = Ni2+, Co2+)

[M(saccharinato)₂(H₂O)₄] (M = Cu²⁺, Ni²⁺, Co²⁺) react with nicotinamide to form mixed ligand complexes, [Cu(saccharinato)₂(nicotinamide)(H₂O)](H₂O) (1) and [M(nicotinamide)₂(H₂O)₄](saccharinate)₂ (2: M = Ni²⁺; 3: M = Co²⁺), and their crystal structures have been determined by X-ray diffraction. In 1, the Cu²⁺ atom in an octahedral configuration is coordinated by two monodentate saccharinato ligands in the trans arrangement through the deprotonated ring nitrogens, by two bidentate nicotinamide ligands, one through the pyridyl ring nitrogen and the other through the amide oxygen, and by a water molecule, thus forming a nicotinamide-bridged one-dimensional extended structure. In the isomorphous complexes 2 and 3, the octahedral metal atom, which rides on a crystallographic center of symmetry, is coordinated by two monodentate nicotinamide ligands through the ring nitrogens and four water molecules to form a discrete [M(nicotinamide)₂(H₂O)₄]^{2 +} structural unit, which captures up and down two saccharinate ions, each through three hydrogen bonds: two hydrogen bonds between two water ligands and the ring N and the carbonyl O atoms and one between the amide N of the nicotinamide ligand and the carbonyl O.     

Palladium (II) compounds with diaminocarboxylic acids: Crystal structures of [Pd(H2Cdta)] · H2O, [Pd(H3Edtp)Cl] · 2H2O, and (H6Edtp)[PdCl4] · 4H2O

The crystal structures of three Pd(II) compounds with diamine tetracarboxylates in different protonation states are determined, namely, [Pd(H₂ Cdta)] · H₂O (I), [Pd(H₃ EdtpCl] · 2H₂O (II), and (H₆ Edtp)[PdCl₄] · 4H₂O (III) (R ₁ = 0.0230, 0.0313, and 0.0277 for 3040, 3377, and 3809 reflections with I > 2σ(I) for I–III, respectively). Crystals I and II are built of neutral complexes [Pd(H₂ Cdta)] and [Pd(H₃ Edtp)Cl], respectively, and crystallization water molecules. Crystal III consists of [PdCl₄]²⁻ anionic complexes, H₆ Edtp ²⁺ cations, and water molecules. In I, one of the protonated acetate groups of the H₂ Cdta ²⁻ ligand forms a very weak additional Pd-O bond [2.968(2) Å] over the 2N + 2O coordination square. In II and III, the protonated propionate groups of the H₃ Edtp ⁻ ligand and the H₆ Edtp ²⁺ cation are not involved in Pd coordination and the coordination squares consist of the 2N + O + Cl and 4Cl atoms, respectively. __________ Translated from Kristallografiya, Vol. 48, No. 2, 2003, pp. 278–282. Original Russian Text Copyright ? 2003 by Polyakova, Poznyak, Sergienko.     

Nickel(II) and Cobalt(II) Complexes with Symmetrical Four-Dentate Ligands: Crystal Structures,Characterization, and Initial DNA Binding Mechanism Research

Abstract  

Four new nickel(II) and cobalt(II) complexes of Schiff base ligands: [Ni(L)Cl₂]·2H₂O (I), [Ni(L)(H₂O)₂] (NO₃)₂ (II), [Ni(L)(H₂O)₂] (ClO₄)₂ (III), and [Co(L) (H₂O)₂] (NO₃)₂ (IV) (L = 1,3-[bis(pyridine-2-imino)]propane) have been synthesized. The four complexes have been fully characterized by elemental analysis, IR, absorption spectra, emission spectra, and single-crystal X-ray diffraction analysis. The binding of the four complexes to calf thymus DNA (CT DNA) has been investigated by absorption spectra and emission spectra. The results of the two methods indicate that the action mode of complex I with DNA is intercalative mainly, and the action mode of complexes II, III, IV with DNA cannot be concluded, it should be sustained by other experimental measurements.     

Crystal structure,thermal analysis and IR spectroscopy investigations of N,N‐dimethyl‐1,3‐propanediammonium monohydrogenmonophosphate trihydrate

A new organic monohydrogenmonophosphate (C₅H₁₆N₂)HPO₄.3H₂O (abbreviate as MPAP) is prepared by reacting H3PO4 with N, N‐dimethyl‐1,3‐propanediamine. This compound crystallizes in the orthorhombic crystal system, space group Pca2₁. Unit cell parameters are a % 8.1445(1) Å, b % 11.7734(2) Å, c % 12.9021(2) Å, with, Z % 4 and ρ_m % 1.31 g cm⁻³. The structure was solved, using the direct methods and refined against F² to a reliability R factor of 0.0257. Three types of hydrogen bonds participate to the structural cohesion: O(P)—H…O, O(W)—H…O and N—H…O. The first one connects HPO₄ groups in infinite chains. This organization of the phosphoric groups creates voids in which are located the water molecules which are themselves connected by the second type of hydrogen bonds to the adjacent phosphoric groups that lead to a typical layer organization of a polyanion [HPO₄.(H₂O)₃ ]²ⁿ⁻_n. The third hydrogen bond type is responsible for the cohesion between the two‐dimensional polyanions. Thus, a framework in a threedimensional way is then created. The thermal decomposition of MPAP shows a large endothermic effect corresponding to the elimination of the water molecules and a set of endotherms which are probably due to the evolution of ammonia from the structure and the decomposition. The title compound was also characterized by IR spectroscopy, the interpretation of the spectra is based on theoretical analyses and literature data. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Syntheses,Crystal Structures and Physical Properties of Cd(II) and Mn(II) Complexes with <Emphasis Type="Italic">Trans</Emphasis>-1,2-di(4-pyrindyl)ethylene and <Emphasis Type="Italic">P</Emphasis>-(carboxyl-methyloxy)-benzenecarboxylic Acid

Abstract  

Two complexes [Cd₂(dpe)₃(H₂O)₈]·(dpe)·(hssal)₂·(H₂O)₂ 1, [Mn(dpe)₂(Hpcmb)₂·(H₂O)₂] 2, (dpe = trans-1,2-di(4-pyrindyl)ethylene; H₂hssal = sulphosalicylic acid; H₂pcmb = p-(carboxyl-methyloxy)-benzenecarboxylic acid) has been prepared, and was characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structure indicates in complex 1 that Cd(II) is a distorted octahedral coordination geometry. The hssal²⁻ anions are localized between 2-D sheets {[Cd(dpe)₂(H₂O)₄]²⁺(dpe)}n and {{[Cd(dpe)₂(H₂O)₄]²⁺}n as count anions and bridge to further connect these 2-D sheets through hydrogen bond O–H···O to form 3-D structure. The complex 2 is a single molecule structure. In 2, Each Mn(II) atom is six-coordinated with a distorted octahedral coordination geometry. The single molecule units are extended into three-dimensional structure via π–π, hydrogen bonding interactions. The thermogravimetric behavior and luminescent property of complex 1 were investigated.     

Synthesis and Crystal Structure of 2,13-Bis(acetamido)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0<Superscript>1.18</Superscript>,0<Superscript>7.12</Superscript>]docosane Tetrachlorocobalt(II)dihydrate

Abstract The novel ionic compound [H₂bdtd][CoCl₄] · 2H₂O (1) was prepared by the reaction between CoCl₂ and 2,13-bis(acetamido)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane (bdtd) in adjusted to pH 3.0 by 1.0 M HCl and structurally characterized. The crystals are monoclinic C2/c with a = 18.7777(9), b = 9.7356(4), c = 20.0884(9) ?, β = 109.6340(10)°, V = 3458.9(3) ?³, Z = 4. The dication H₂bdtd occupies a special position about an inversion center. The cobalt(II) atom in the anion is in a distorted tetrahedral environment with four chloride ligands. The crystal structure is stabilized by a variety of hydrogen-bonding contacts involving the dication, chloride anions and solvent water molecules. Cyclic voltammetry of [CoCl₄]²⁻ anion in 1 undergoes irreversible one-electron reduction to the Co^II/Co^I. Graphical abstract The crystal structure of the ionic compound [H₂bdtd][CoCl₄] · 2H₂O (1) consists of [H₂bdtd]²⁺ cation, [CoCl₄]²⁻ anion and water molecules joined together by ionic interaction and hydrogen bonds. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hydrothermal crystallization and X-ray structure determination of a new decavanadate with mixed cations [Mn(H2O)6]2[N(CH3)4]2[V10O28]·2H2O

A new decavanadate with mixed cations, [Mn(H₂O)₆]₂[N(CH₃)₄]₂[V₁₀O₂₈]·2H₂O (1), was crystallized from a hydrothermal reaction between MnCO₃ and V₂O₅ in the presence of N(CH₃)₄Br at 100°C. The structure of 1, as determined by x-ray single crystal analysis, consists of cations and anions of hexa-aqua manganese [Mn(H₂O)₆]²⁺, tetramethyl ammonium [N(CH₃)₄]⁺ and decavanadate [V₁₀O₂₈]^6–. The extended H-bonding between the [Mn(H₂O)₆]²⁺ and [V₁₀O₂₈]^6– ions gives rise to a pseudo- two-dimensional network in the crystal lattice x-ray crystallographic data for 1: monoclinic P2₁/n, a = 9.1499(5), b = 12.8725(7), c = 18.625(1) Å, = 92.252(1)°, V = 2192.0(2) ų, MZ = 2, and D _calcd = 2.22 g cm^–3.     

Crystal and molecular structure of complex compound [Fe3O(CH3COO)6(H2O)3]2[ZnCl4] ⋅ 2H2O

The X-ray crystal structure of trinuclear iron acetate [Fe₃O(CH₃COO)₆(H₂O)₃]₂ [ZnCl₄] ? 2H₂O was determined. The crystal has a ionic structure. It is monoclinic, a = 25.363(7), b = 14.533(4), c = 15.692(4) Å, β = 103.11(2)°, space group _C2/c, and R = 0.0685. The structure of the cationic complex [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ is typical of trinuclear iron(III) compounds containing a μ₃-O bridge: the iron atoms are situated at the vertices of an almost equilateral triangle with the O atom at the center. Each Fe atom is coordinated by four O atoms of bridging carboxy groups, the μ₃-bridging O atom, and the water molecule in the trans position to the latter O atom. Mössbauer spectroscopy evidence indicates the high-spin state (_S = 5/2) of the iron(III) ions.     

Sovolthermal Synthesis and Crystal Structure of Two CdII Coordination Polymers of Benzenedicarboxylic

Abstract  Two cadmium coordination polymers of benzenedicarboxylic: [C₈H₆CdO₅]_n (1) and [C₈H₁₀CdO₇]_n·4H₂O (2), have been synthesized by sovolthermal method and characterized by single-crystal X-ray diffraction. Our experimental results suggest that complex 1 crystallizes in orthorhombic space group Pbcm with a = 6.4978(8) ?, b = 6.9475(9) ?, c = 18.319(2) ?, and Z = 4. Structural analysis reveals that complex 1 features a three-dimensional framework structure formed by strong coordination bond and weak hydrogen bond force. Complex 2 crystallizes in orthorhombic space group Pcca with a = 7.293(2), b = 9.980(3), c = 19.889(6), and Z = 4. Complex 2 exhibits a layered framework structure formed by extensive inter-chain hydrogen bond interaction. Index Abstract  Two cadmium coordination polymers of benzenedicarboxylic: [C₈H₆CdO₅]_n (1) and [C₈H₁₀CdO₇]_n·4H₂O (2), have been synthesized by sovolthermal method and characterized by single-crystal X-ray diffraction      

Structures of mixed-ligand Manganese(II) compounds [Mn(Heida)(Phen)]2 · 7H2O and [Mn2(Edta)(Phen)] · 4H2O

The crystal structures of [Mn(Heida)(Phen)]₂ · 7H₂O (I) and [Mn₂(Edta)(Phen)] · 4H2O (II) are studied by X-ray diffraction [R ₁ = 0.0375 (0.0283) and wR ₂ = 0.0954 (0.0662) for 5449 (3176) observed reflections in I (II), respectively]. Structure I contains mononuclear mixed-ligand complexes [Mn(Heida)(Phen)] and [Mn(Heida)(Phen)(H₂O)]. In structure II, the [Mn(Edta)]²⁻ anionic complexes and the [Mn(Phen)(H₂O)₂]²⁺ cationic complexes are linked by the bridging carboxyl groups into the tetramers with C ₂ symmetry. In both compounds, two independent Mn atoms have different coordination numbers (6 and 7). __________ Translated from Kristallografiya, Vol. 47, No. 2, 2002, pp. 280–285. Original Russian Text Copyright ? 2002 by Polyakova, Sergienko, Poznyak.     

Synthesis and Crystal Structure of the Heteronuclear Decavanadates Complex: [Fe(phen)<Subscript>3</Subscript>]<Subscript>2</Subscript>·[V<Subscript>10</Subscript>O<Subscript>28</Subscript>]·15H<Subscript>2</Subscript>O

Abstract  

A new decavanadate metal complex [Fe(phen)₃]₂·[V₁₀O₂₈]·15H₂O (phen = 1,10-phenanthroline) has been synthesized from a hydrothermal reaction and the crystal structure has been determined by means of single-crystal X-ray diffraction. The crystal structure analysis reveals that the polyoxoanions are decorated with the [Fe(phen)₃]³⁺ cations, and that the water molecules play the bridge role on the packing modes. They are further contacted to form supramolecular networks through extensive hydrogen bonding.     

Two New Salts Based on Bis(1,2,5-thiadiazole-3,4-dithiolate)nickelate Anion with Substituted Benzyl 4-ethylpyridinium: Syntheses,Crystal Structures and Properties

Abstract  

Two new salts based on [Ni(tdas)₂]²⁻ (tdas²⁻ = 1,2,5-thiadiazole-3,4-dithiolate) anion, [Bz4EtPy]₂[Ni(tdas)₂] (1) and [4ClBz4EtPy]₂[Ni(tdas)₂] (2), have been prepared by reaction of Na₂tdas, NiCl₂·6H₂O, and [Bz4EtPy]Br ([Bz4EtPy]⁺ = 1-benzyl-4-ethylpyridinium) or [4ClBz4EtPy]Br ([4ClBz4EtPy]⁺ = 1-(4′-chlorobenzyl)-4-ethylpyridinium), and characterized by elemental analyses, UV, IR, MS spectrum, molar conductivity and single crystal X-ray diffraction. Single-crystal X-ray diffraction analyses indicate that the two salts crystallize in a triclinic system with space group P−1. The unit cell contains two [Bz4EtPy]⁺/[4ClBz4EtPy]⁺ and one [Ni(tdas)₂]²⁻ anion in which the anion exhibits a quasi-planar structure. The crystals of 1 and 2 are stabilized through C–H···S and C–H···Ni hydrogen bonds, π···π stacking interactions and S···Cl short interactions.     

Structural features of 3d metal compounds with 1-hydroxyethylidenediphosphonic acid

Structural features of 3d metal complexes with anions of 1-hydroxyethylidenediphosphonic acid (HEDP, H₄ L), in which the M: HEDP ratios are equal to 1: 2, 1: 1, 3: 2, and 5: 2, are discussed. The Cu(II): HEDP = 1: 2 complexes are characterized by five types of structures: monomeric structures trans-[Cu(H_{4 ? n} L)₂(H₂O)₂]^{2 ? 2n} , cis-[Cu(H_{4 ? n} L)₂(H₂O)₂]^{2 ? 2n} , and [Cu(L)₂]^6?; the dimeric structure { [Cu(H₂ L)(H₂O)]₂(μ ₂-H₂ L)₂}^4? ; and the polymeric chain structure {[Cu(μ ₂-H₂ L)₂]^2?}_∞. Six coordination modes exhibited by HEDP in the Cu(II) compounds are described.