[KCl<Subscript>3</Subscript>{H<Subscript>2</Subscript>dabco}]: A Unique 3-D Charge-Assisted Hydrogen-Bonded Hybrid Network of Anionic KCl<Subscript>3</Subscript> Chains and Organic Cations

Abstract  The 3-D hybrid network [KCl₃{H₂dabco}] resulted from the assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O. The compound crystallizes in the trigonal space group R-3c with a = b = 16.0437(2) Å, and c = 22.3094(2) Å. The structure consists in polymeric chains of anionic {KCl₃}²⁻ linked to {H₂dabco}²⁺ units by hydrogen bonds. Each organic cation establishes such charge-assisted H···Cl interactions with two inorganic arrays leading to a 3-D network. Index Abstract  Assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O resulted in a 3-D hybrid network of inorganic {KCl₃}²⁻ chains H-bonded to bridging organic cations.      

Molar Volume and Composition of Oxides of the Same Metal

Abstract The relation between the molar volume of metal oxides and their composition has been discussed. In order to compare molar volume of oxides with different compositions, the volume per one mole of oxygen atoms (M_a/bO) was used. It has been found that molar volumes of oxide phases of the same metal in the composition range 2 > a/b > 0.5 are linear functions of composition. This type of relationship has been proposed as an additional criterion to classify an oxide as a compact structure. Furthermore, in the case of oxides with metal ions in higher oxidation states (M^z+ > M⁴⁺) the increase of the molar volume (relative to the MO₂ oxides) and the formation of framework structures have been found. Graphical Abstract Molar Volume and Composition of Oxides of the Same Metal Andrzej Stokłosa*, Barbara Laskowska Molar volumes of oxide phases of the same metal in the composition range 1>a/b>0.3 are linear functions of composition. The dependence of the effective molar volume (Veff) of the oxides Ma/bO on the composition (a/b) for the transition metal oxides and Ce oxides     

Synthesis and Crystal Structure of a New Binuclear Samarium Complex with Salicylate

Index Abstract  In the dinuclear compound (HPhen)₂[Sm₂(Hsal)₈(H₂O)₂] · 2H₂O (Hsal = o-HOC₆H₄CO₂ ⁻, Phen = 1,10-phenanthroline), intermolecular hydrogen bonds and π–π stacking interactions between parallel aromatic rings result in the formation of a two-dimensional supramolecular network.      

Two Mononuclear Compounds with bis(Pyrimidin-2-yl)amine as a Ligand and as a Hydrogen-bonded Lattice Molecule. Synthesis, Structure and Spectroscopy of {[M(dipm)(H2O)(A)](dipm)(A)(H2O)} (M?=?Cd with A?=?ClO4; and Zn with A?=?BF4)

Abstract  Two isostructural mononuclear compounds with formula {[Cd(dipm)(H₂O)(ClO₄)](dipm)(ClO₄)(H₂O)} (1) {[Zn(dipm)(H₂O)(BF₄)](dipm)(BF₄)(H₂O)} (2) and (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesised and characterised by X-ray crystallography and infrared spectroscopy. The structure of compound 1 has been solved in the space group P2₁/n with a = 18.860(4), b = 8.579(2), c = 20.917(4) ?, β = 101.33(3)°, V = 3318.4(12) ?³, Z = 4 with final R = 0.0454. The structure of compound 2 has also been solved in the space group P2₁/n with a = 19.026(4), b = 8.389(1), c = 20.720(4) ?, β = 101.37(3)°, V = 3242.2(10) ?³, Z = 4 with final R = 0.0689. The geometry around the metal ions is octahedral, and is constituted by four nitrogen atoms from two dipm molecules, an oxygen atom from a water molecule and a semi-coordinating anion atom ( for compound 1 and for compound 2). In the lattice are also present: a non-coordinating water molecule, an anion molecule and a dipm molecule. For compound 1, the Cd–N distances are between 2.296 and 2.328 ?. The distance is 2.310 ? and the is 2.477 ?. The Zn–N distances in compound 2 are between 2.121 and 2.164 ?. The distance is 2.147 ? and the distance is 2.373 ?. A hydrogen bond interaction of the Watson–Crick type is observed between the amine N atom of a dipm ligand to a pyrimidyl N atom and a non-coordinating dipm ligand with N···N distances, which vary from 3.066(5) to 3.109(5) ?. Furthermore medium to strong hydrogen bond interactions are present between oxygen atoms of the water molecules and the anions of the compounds. Index Abstract  Two isostructural mononuclear compounds with formula {[Cd(dipm)(H₂O)(ClO₄)](dipm)(ClO₄)(H₂O)} (1) {[Zn(dipm)(H₂O)(BF₄)](dipm)(BF₄)(H₂O)} (2) and (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesised and characterised by X-ray crystallography and infrared spectroscopy. . Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The First Coordination Compound with 5-methylisoxazole-3-carboxylate: Synthesis and Structural Characterization of [Cu(L<Subscript>2</Subscript>)(H<Subscript>2</Subscript>O)] · H<Subscript>2</Subscript>O

Abstract  The title compound, aquabis(5-methylisoazole-3-carboxylato-O,N)copper(II) monohydrate, [Cu(L₂)(H₂O)] · H₂O is synthesized and characterized by X-ray diffraction, elementary analysis, and IR. The ligand coordinates to the copper center in a bidentate O,N fashion through the carboxylic acid moiety and the heteroaromatic nitrogen atom. The complex crystallizes in the triclinic space group with unit cell parameters a = 8.4080(12)?, b = 8.810(3), c = 10.318(2)?, α = 110.08(3)°, β = 104.81(2)°, γ = 103.149(16)°, V = 650.9(3)?³, Z = 2. In addition, the synthesis of the free acid 5-methylisoazole-3-carboxylic acid and pyridine containing complex bis(5-methylisoazole-3-carboxylato)bispyridinecopper(II) monohydrate is described. Index Abstract  Synthesis and crystal structure of aquabis(5-methylisoazole-3-carboxylato-O,N)copper(II)monohydrate. The first coordination compound of 5-methylisoxazole-3-carboxylic acid.      

Crystal and Molecular Structure of the 1:2 Salt Formed Between 1,2-(4-Pyridyl)Ethane and 2-(4-Hydroxyphenylazo)Benzoic Acid

Abstract  Proton transfer occurred during co-crystallization of 1,2-(4-pyridyl)ethane with 2-(4-hydroxyphenylazo)benzoic acid to yield a salt comprising a 1:2 ratio of 1,2-bis(4-pyridinium)ethane dications and 2-(4-hydroxyphenylazo)benzoate anions. Centrosymmetrically related anions associate by charge-assisted O–H···O hydrogen bonds to form 24-membered {···OC₃N₂C₄OH}₂ synthons. These are connected into a supramolecular polymer via charge-assisted N–H···O hydrogen bonds involving the 1,2-bis(4-pyridinium)ethane dications. The compound crystallizes in the triclinic space group P−1 with a = 8.517(4) ?, b = 9.110(5) ?, c = 10.477(5) ?, α = 96.850(13)°, β = 94.446(12)°, γ = 104.946(10)° and Z = 1 {two anions and a dication}. Index Abstract  Supramolecular chains mediated by charge-assisted O–H···O and N–H···O hydrogen bonding are found in the salt containing a 1:2 ratio of 1,2-bis(4-pyridinium)ethane dications and 2-(4-hydroxyphenylazo)benzoate anions.      

Synthesis, Crystal Structure and DNA-Binding Study of a New Copper(II) Complex Containing Mixed-Ligand of Iminodiacetate Dianion and 6-Nitro-1H-benzimidazole

Abstract  A mixed-ligand complex Cu(IDA)(NBZIM)(H₂O) (IDA = iminodiacetate dianion, NBZIM = 6-nitro-1H-benzimidazole) has been synthesized and characterized by elementary analysis, IR, UV-Vis, molar conductivity and single crystal X-ray diffraction. It crystallizes in the triclinic system, space group P with a = 6.9423(14), b = 9.3100(19), c = 11.754(2) ?, α = 69.61(3), β = 85.87(3), γ = 83.87(3)°, Z = 2, R ₁ = 0.0463 and ωR ₂ = 0.0987. The single crystal X-ray analysis reveals that the Cu(II) atom is coordinated by one tridentate iminodiacetate dianion, one monodentate nitrobenzimidazole molecule and one water molecule, in a distorted square base pyramidal coordination geometry. The iminodiacetate dianion chelates the Cu(II) atom in the meridional mode. A three-dimensional network is formed by hydrogen bonds and stabilized by NBZIM π-π stacking interactions. The interaction of the complex with Fish sperm DNA has also been studied using absorption spectra. Index Abstract  In the crystal of Cu(IDA)(NBZIM)(H₂O), each molecule is linked to other six neighbouring ones by ‘eight’ hydrogen bonds in four cases by means of the ‘symmetry related’ linkage.      

Complementary Supramolecular Aggregation via O–H···O Hydrogen-bonding and Hg···S Interactions in Bis[N,N′-di(2-hydroxyethyl)-dithiocarbamato-S,S′]mercury(II): Hg[S2CN(CH2CH2OH)2]2

Abstract  The central mercury atom in Hg[S₂CN(CH₂CH₂OH)₂]₂ is asymmetrically chelated by two dithiocarbamate ligands leading to a distorted square planar geometry. Molecules aggregate into supramolecular chains via Hg···S interactions that are connected into a three dimensional array by extensive hydrogen bonding interactions. The compound crystallizes in the orthorhombic space group Pna2₁ with a = 13.8173(7) ?, b = 4.5307(1) ?, c = 26.0261(12) ?, and Z = 4. Index Abstract  Molecules associate into supramolecular chains via Hg···S interactions and these are connected into a three dimensional architecture by O–H···O hydrogen-bonding interactions.      

Synthesis and Crystal Structure of Heptyl 3-(3,4-dihydroxyphenyl)-2-propenoate

Abstract  The title compound, C₁₆H₂₂O₄, synthesized by modified Knoevenagel condensation of protocatechualdehyde with monoheptyl-malonate and recrystallized from benzene, was confirmed by single-crystal X-ray diffraction (CCDC 272827). The compound crystallizes in triclinic space group Pī with cell parameters a = 5.296(3) ?, b = 10.711(13) ?, c = 13.870(4) ?, α = 98.84(7)°, β = 90.97(4)°, γ = 96.77(7)° and Z = 2. The structure is the E isomer and its packing is stabilized by intermolecular O–H···O and C–H···O hydrogen bonds. Index Abstract  The title compound, C₁₆H₂₂O₄, synthesized by modified Knoevenagel condensation, was confirmed by single-crystal X-ray diffraction showing its structure is in E isomer and its packing is stabilized by hydrogen bonds.      

Hydrogen-bonded Multicomponent Behavior in Tetra-<Emphasis Type="Italic">iso</Emphasis>-butyl-resorcin[4]arene–1,4-Bis(pyridyl)ethane–Methanol–Water (1/2/0.5/1)

Abstract  Co-crystallization of the tetra-iso-butyl-resorcin[4]arene (1) with 1,4-bis-(pyridyl)ethane (bpe) obtained from methanol yields a molecular solid of the multicomponent host–guest complex 1 · 2(bpe) · 0.5MeOH · H₂O (2) in which 1 assemblies with water molecules to form a hydrogen-bonded dimer. The bpe ligands in both cis- and trans-stereo configurations exist in the complex 2, of which trans-bpe moieties as guests are encapsulated in the capsules constructed by two pairs of opposition bowls of resorcinarenes. Graphical Abstract  The 1,4-bis(pyridyl)ethane (bpe) ligands in both cis- and trans-stereo configurations exist in a multicomponent molecular solid, of which trans-bpe moieties as guests are encapsulated in the capsules constructed by two pairs of opposition bowls of resorcinarenes.      

High Temperature Ionic Liquids: Thermal Properties and Dimorphism in [1-(Methoxycarbonyl) Ethyl] Triphenylphosphonium <Emphasis Type="Italic">p</Emphasis>-Toluenesulfonate

Abstract  Investigation of the thermal properties of triphenylphosphonium p-toluenesulfonates, which are high temperature ionic liquids, reveals that they solidify to a noncrystalline material on fast cooling from the melt. During the study, a second crystalline form of [1-(methoxycarbonyl) ethyl] triphenylphosphonium p-toluenesulfonate (form II) has been obtained. Form II is monoclinic P2₁/c, with a = 11.002(5)?, b = 12.793(5)?, c = 18.805(5)?, and β = 102.498(5)°. Comparison with form I reveals the existence of a common robust structural feature involving interactions between cations and anions. Graphical Abstract  Investigation of thermal properties of ionic liquids has revealed a second crystalline form of [1-(methoxycarbonyl) ethyl] triphenylphosphonium p-toluenesulfonate.      

Synthesis and Crystal Structure of Mixed-valence Hexanuclear Manganase Oxide Complex,Hexakis(μ<Subscript>2</Subscript>-pivalato)-tetrakis(μ<Subscript>3</Subscript>-pivalato)-mono(pyridine)-tris(pivalic acid)-bis(μ<Subscript>4</Subscript>-oxo)dimanganese(III) tetramanganase(II)

Abstract  The complex, [Mn₆O₂(OOCCMe₃)₁₀(HOOCCMe₃)₃(py)], has a hexanuclear structure with a Mn₆O₂ core. This complex crystallizes in the monoclinic space group P2₁/n with a = 17.757(5) ?, b = 27.413(5) ?, c = 22.348(5) ?, β = 90.233(5)°, V = 9,040(4) ?³ and Z = 4. It contains a [Mn₆O₂]¹⁰⁺ core that can be described as two edge-sharing Mn₄ tetrahedra at the centre of each of which tetrahedron lies a μ₄-O²⁻ ion. All Mn atoms are six-coordinate and possess distorted octahedral geometry. Mn₄ exhibits butterfly arrangement with both μ₄-O atoms on the same side of the molecule. The complex is mixed-valence , and the Mn^III centers are assigned as the two central metal ions bridged by two O²⁻ ions. Index abstract  The complex, [Mn₆O₂(OOCCMe₃)₁₀(HOOCCMe₃)₃(py)], has a hexanuclear structure with a Mn₆O₂ core. This complex crystallizes in the monoclinic space group P2₁/n with a = 17.757(5) ?, b = 27.413(5) ?, c = 22.348(5) ?, β = 90.233(5)°, V = 9040(4) ?³ and Z = 4. It contains a [Mn₆O₂]¹⁰⁺ core that can be described as two edge-sharing Mn₄ tetrahedra at the centre of each of which tetrahedron lies a μ₄-O²⁻ ion. All Mn atoms are six-coordinate and possess distorted octahedral geometry. Mn₄ exhibits butterfly arrangement with both μ₄-O atoms on the same side of the molecule. The complex is mixed-valence , and the Mn^III centers are assigned as the two central metal ions bridged by two O²⁻ ions.      

A Unusual Bridging Mode of Diphenylhydantoin in Pentaaquabis[(5,5-Diphenylhydantoinato)Potassium]

Abstract  A new complex of diphenylhydantoin, pentaaquabis[(5,5-diphenylhydantoinato)potassium], has been synthesized and the structure has been solved by X-ray diffraction. The crystals are monoclinic, space group C2/c, with a = 34.959(5) ?, b = 8.273(4) ?, c = 11.692(2) ?, β = 109.069(13)°, M _r = 670.80, V = 3196.0(17) ?³, Z = 4 and R = 0.050. The potassium cations are assembled in dimers bridged through the carbonyl O atoms of the anions. The metal atom is in a distorted octahedral coordination environment. Index Abstract  In pentaaquabis[(5,5-diphenylhydantoinato)potassium] the potassium cations are coupled in dimers through the carbonyl O atoms of the anions.      

1,3-Bis(4-Pyridinylcarbonyl)-2-Imidazolidinethione and Its First Cluster Complex: Synthesis,Crystal Structure and Luminescence Properties

Abstract  The first cluster complex of 1,3-bis(4-pyridinylcarbonyl)-2-imidazolidinethione (4-bpit) with CuI was prepared and characterized. Single crystal X-ray diffraction analysis established that the compound crystallizes in the monoclinic system, space group C2/m, with a = 15.601(3), b = 12.438(3), c = 12.570(3)?, β = 110.02(3), Z = 4, V = 2291.8(8)?³. This compound is also a coordination polymer with one-dimensional double-ribbon structure containing the adaptable rhomboid Cu₂I₂ cluster unit. The solution-state luminescence spectra showed that the high-energy emission may be associated with a ligand-to-ligand charge-transfer excited state. Graphical Abstract  The first cluster complex of 1,3-bis(4-pyridinylcarbonyl)-2-imidazolidinethione (4-bpit) with CuI was prepared and characterized. This compound is also a coordination polymer with one-dimensional double-ribbon structure containing the adaptable rhomboid Cu₂I₂ cluster unit. The solution-state luminescence spectra showed that the high-energy emission may be associated with a ligand-to-ligand charge-transfer excited state.     

Intermolecular Hydrogen Bonds and the Supramolecular Structure of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-Bis(<Emphasis Type="Italic">p</Emphasis>-tolylsulfonyl)diethylenetriamine

Abstract  The title compound N,N′-bis(p-tolylsulfonyl)diethylenetriamine (1) was synthesized and its crystal structure determined by X-ray diffraction. Adjacent molecules of 1, symmetrically related through a c-glide, are linked by alternating hydrogen bonds that form molecular chains along [0 0 1]. Two molecular chains occur in each unit cell and pack to form alternating layers in a three-dimensional supramolecular structure. The compound crystallizes in the Pca2₁ space group stabilized by the inclusion of solvent dichloromethane molecules in structural voids between molecules of 1. The dichloromethane molecules are related through a twofold screw rotation axis and are not disordered. Index Abstract  Intermolecular hydrogen bonds involving sulfonamide moieties of title compound afford a supramoleular structure that accommodates the inclusion of dichloromethane in alternating layers.      

Crystal Structure of bis(18-Crown-6)-bis(formato-O) dicaesium dihydrate

Abstract  The crystal structure of the title compound, [2Cs⁺(C₁₂H₂₄O₆)₂(CHO₂ ⁻)₂(H₂O)₂], was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁ /n with cell parameters a = 10.4278(7) ?, b = 10.0183(5) ?, c = 18.2383(12) ?, β = 93.723(5)°, V = 1910.3(2) ?³ and Z = 2. The Cs cations are bonded to each of the six O atoms of a crown ether ring, two water molecules, and one O atom of a formato anion. As a result of that, a centrosymmetric dimeric dinuclear complex is formed. The two halves of the dimer are connected by a ring of formato anions and water molecules which are linked by O–H···O hydrogen bonds. Index Abstract  The title compound, bis(18-crown-6)-bis(formato-O), caesium dihydrate, features a centrosymmetric dimeric dinuclear complex where two Cs cations are coordinated by six O atoms of a crown ether ring. The two halves of this complex are held together by a ring of formato anions and water molecules which are linked by hydrogen bonds.      

Crystal and Molecular Structure of Dichloro(ethylenediamine)gold(III) Nitrate: [Au(NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>CH<Subscript>2</Subscript>NH<Subscript>2</Subscript>)Cl<Subscript>2</Subscript>]NO<Subscript>3</Subscript>

Abstract  The gold(III) atom in [Au(NH₂CH₂CH₂NH₂)Cl₂]NO₃ is chelated by the ethylenediamine (en) ligand and the approximately square planar geometry is completed by two chloride atoms. Weak Au···O and Au···Cl contacts are noted above and below the square plane leading to a tetragonally distorted octahedron for the gold(III) center. Extensive charge-assisted hydrogen bonding of the type N–H···O leads to the formation of a 2-D array and layers are consolidated into a 3-D network via C–H···O and C–H···Cl contacts. The compound crystallizes in the orthorhombic space group Pbca with a = 10.3380(11) ?, b = 8.2105(7) ?, c = 19.625(2) ?, and Z = 8. Index Abstract  Square planar complex cations form additional Au···O and Au···Cl interactions to form a tetragonally distorted octahedron for gold. The ionic components are connected into a 2-D array via charge-assisted N–H···O hydrogen bonding interactions.      

Synthesis and Structure of [Fe<Subscript>3</Subscript>O(O<Subscript>2</Subscript>CCH<Subscript>2</Subscript>OMe)<Subscript>6</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>][FeCl<Subscript>4</Subscript>]

Abstract  The structure of [Fe₃O(O₂CCH₂OMe)₆(H₂O)₃][FeCl₄] · 2.5H₂O has been determined. The three iron atoms and the μ₃-oxo are coplanar. Each carboxylic ligand is bidentate and links two iron atoms in the cluster. The clusters are linked by intra-trimer hydrogen bonding to form a zigzag motif that forms sheets via hydrogen bonding involving disordered waters of hydration. The [FeCl₄]⁻ anion is intercalated between the hydrogen-bonded sheets. Crystal data: space group P2₁/n, a = 10.276(2), b = 22.793(5), c = 17.091(3) ?, β = 96.66(3)°, V = 3976(1) ?³, Z = 4, R = 0.0837, wR ₂ = 0.1836. Graphical Abstract  The structure of [Fe₃O(O₂CCH₂OMe)₆(H₂O)₃][FeCl₄] · 2.5H₂O has been determined in which the clusters are linked by intra-trimer hydrogen bonding to form a zigzag motif that forms sheets via hydrogen bonding involving disordered waters of hydration.      

Synthesis and Crystal Structure of a New Mo(V) Complex of Cyano Ligands

Abstract  A new complex, [H₃teta][Mo(CN)₈] · H₂O, (teta = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene), has been synthesized and characterized by IR spectrum, element analysis and single crystal X-ray diffraction: monoclinic, space group P2(1)/c with a = 10.8553(8) ?, b = 12.4854(8) ?, c = 22.6348(15) ?, α = 90.00°, β = 97.3080(10)°, γ = 90.00°, Mr = 609.63, v = 3042.8(4), Z = 4. There are one [H₃teta]³⁺, one [Mo(CN)₈]³⁻ and one water molecule in the asymmetric unit. The complex is interconnected through hydrogen bond and formed into a 3D porous network. Graphical Abstract  A new complex, [H₃teta][Mo(CN)₈] · H₂O, has been synthesized and characterized by IR spectrum, element analysis and single crystal X-ray diffraction. And it shows a 3D porous network through hydrogen bonds.      

Crystal Structure of Meso-tetrakis[4-(pentyloxy)phenyl]porphyrin

Abstract  The crystal structure of the title compound, C₆₄H₇₀N₄O₄, has been determined by single crystal X-ray diffraction methods. The title compound crystallizes in the monoclinic space group P2(1)/c with cell dimensions a = 13.8946(3) ?, b = 16.1069(3) ?, c = 12.1974(2) ?, β = 93.4050(10)°, Z = 2. The porphyrin core to be composed of four pyrrole rings linked through methane carbon bridges. Each molecule lies across a crystallographic inversion center. The porphyrin core is planar, which facilitates π-electron delocalization. The inner nitrogen H atoms are found localized on opposite pyrrole rings and these rings differ structurally from the other two pyrrole rings. The imino H atoms form bifurcated intramolecular hydrogen bonds with the adjacent unprotonated N atoms due to the contract porphyrin core. Graphical Abstract  The crystal structure of meso-tetrakis[4-(pentyloxy)phenyl]porphyrin is reported in this paper.