Synthesis and Crystal Structure of 4-Aminoquinolinium Dicitratoborate Monohydrate

4-Aminoquinolinium dicitratoborate monohydrate [(4-NH₂)C₉H₆NH][(C₆H₆O₇)₂B] · H₂O (I) has been synthesized for the first time. Single crystals have been studied by X-ray crystallography. The structural units of crystal I are large complex dicitratoborate anions with a spirane structure, 4-aminoquinolinium cations and crystal water molecules. The crystal packing of I is three-dimensional. Seventeen independent contacts O(N)-H?O and N-H?O,O’ form an intricate system of hydrogen bonds.     

Synthesis and photoluminescence of the chiral compounds [ZnLCl2] · EtOH and ZnLCl2, where L is the (+)-3-Carene derivative containing pyrazoline and quinoline fragments: crystal structure of [ZnLCl2] · EtOH

The following chiral compounds were synthesized: [ZnLCl₂] · EtOH (I) and ZnLCl₂ (II), where L is the pyrazolin-5-ol derivative obtained from terpene (+)-3-carene. According to the X-ray diffraction data, the crystal structure of compound I is built of acentric molecules of the mononuclear ZnLCl₂ complex and EtOH molecules. In molecules of the complex, the Zn²⁺ ion is coordinated by two N atoms of the bidentate chelating ligand L and two Cl atoms at the vertices of the distorted tetrahedron. The intermolecular contacts and the hydrogen bonds Cl(1)…H-O(1) between the adjacent ZnLCl₂ molecules result in the formation of chains parallel to the y axis. The reactant L and solvate I possess weak photoluminescence in the visible spectral range. Complex II exhibits more intense photoluminescence at λ_max = 416 and 517 nm.     

Heterometallic complexes of macrocyclic oxamide with polycarboxylates: Syntheses,crystal structures,and magnetic properties

Three complexes with the formula [Co(Ip)(CuL)(H₂O)₂] · H₂O (I), [Co(Ip)(NiL)(H₂O)₂] · H₂O (II), [Co(CuL)₂(Hbtc)(H₂O)] (III), (H₂Ip = m-isophthalic acid; H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; H₃Btc = 1,3,5-benzenetricarboxylic acid) were synthesized and structurally characterized by elemental analysis, IR and UV spectroscopy. Single-crystal X-ray analyses reveal that the complexes I and II contain neutral heterometallic binuclear CoM (for I and II, M = Cu, Ni, respectively) moieties, and complex III contains discrete neutral trinuclear CoCu₂ moieties. The structures of I–III consist of two-dimensional supramolecular architecture formed by strong O-H…O intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I were investigated and discussed in detail.     

Complexes [Cu(H2L)](NO3)2 and [Cu(H2L)Cl]2[CuCl2]Cl · 0.5H2O (H2L is chiral bis(menthane) propylenediaminodioxime): Synthesis and structure

The synthesis of the [Cu(H₂L)](NO₃)₂ complex (I) and of a mixed-valent complex [Cu(H₂L)Cl]₂[CuCl₂]Cl·0.5H₂O (II), where L is chiral bis(menthane) propylenediaminodioxime. According to the data of single-crystal X-ray diffraction analysis, compounds I and II have ionic structures. In complex cations, the Cu²⁺ ion coordinates four N atoms of tetradentate chelate ligand, namely, the H₂L molecule. The coordination surrounding of the Cu atom in I is a distorted square CuN₄, while in II, it is a distorted square pyramid CuN₄Cl. The complex anion [CuCl₂]^? in II has linear structure. The mutual arrangement of oxime groups in H₂L corresponds to amphi-configuration of a ligand and therefore, intramolecular hydrogen bond O...H-O are formed in H₂L. The complex cations in compound II are joined in dimers through hydrogen bonds Cl...H-O. The values μ_eff for I and II are equal to 1.82 and 2.82 μ_B, respectively.     

Crystal structure of {aquaimidazole-[2-(2-carbamoylhydrazone)-propionato]} copper(II) nitrate

The crystal structure of {aquaimidazole[2-(2-carbamoylhydrazone)-propionato]}copper(II) nitrate [Cu(L)Im(H₂O)]NO₃ (I), where HL is the semicarbazone of pyruvic acid, Im is imidazole, is dtermined. The crystal structure of I contains two independent complexes IA and IB in which copper atoms coordinate once deprotonated tridentate HL, imidazole, and water molecules. Outer spheres of the complexes contain nitrate ions. In the compounds studied the coordination polyhedron of the copper atom is a distorted tetragonal pyramid. Its base is composed of carboxyl and carbamide oxygen atoms, azomethine nitrogen of monodeprotonated HL molecules, and the imidazole nitrogen atom. In the crystal, nitrate ions and imidazole molecules link the complexes via hydrogen bonds into 2D networks parallel to the (010) plane. These networks in turn are in pairs arranged into layers along the [010] direction due to hydrogen bonds between water molecules and oxygen atoms of nitrate ions, and also by water molecules and O3 atoms of the neighboring 2D networks. In the crystal, the π-π stacking interaction is observed between the imidazole rings from different layers and there is also a N-O…Cg (π ring) interaction inside the layers.     

pH-dependent syntheses and crystal structures, characterizations, and DFT calculations of complexes with 2,2′-biimidazole and terephthalic acid ligands

The divalent transition metal complexes [Zn(L)₂(H₂O)₂](Tere) (I), [Cd(L)₂(H₂O)₂](Tere]) (II) and [Cd(L)₂(HTere)₂] (III) (L = 2,2’-biimidazole, Tere = terephthalate) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, thermal analysis and single-crystal X-ray diffraction analysis. Complexes II and III have the same starting materials but possess different frame-works and are prepared from H₂Biim and H₂Tere under hydrothermal conditions with different pH values. The crystal structures show I and II have the same coordination circumstances and are coordinated by two H₂O molecules and two neutral bidentate 2,2′-biimidazole ligands. The terephthalate acts as the counter anion. In contrast, complex III contains protonated carboxylate groups coordinated to the metal centre to give neutral species. Furthermore, based on the optimized structures, molecular frontier orbitals, Mulliken charges and IR spetra of complex I and III are investigated by density functional theory. Calculated results show that the energy gap (ΔE _L-H) between HOMO and LUMO of complex III is bigger than that of I. It is revealed that complex III is more stable, and this calculated estimation corresponds with experimental analysis of TGA curves.     

Synthesis and structural characterization of binuclear ytterbium(III) complexes with 2-amino and 3-amino benzoic acid

Two novel homobinuclear ytterbium(III) complexes, [Yb₂(2AMB)₆(H₂O)₄] · 2C₂H₆O (I) and Yb₂(3AMB)₆(H₂O)₄] · 3H₂O (II) (2AMB = 2-aminobenzoic acid, 3AMB = 3-aminobenzoic acid) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis and X-ray crystallography (CIF files CCDC nos. 950103 (I), 921652 (II)). Complex I crystallizes in triclinic space group \(P\bar 1\) and complex II crystallizes in monoclinic space group P2₁/n. X-ray analysis shows that both complexes (I, II) have the dinuclear structure. The central Yb³⁺ ions in both complexes are eight-coordinated adopting distorted YbO₈ dodecahedral geometry. Each Yb³⁺ ion is coordinated to two O atoms from bridging carboxylate, four O atoms from the chelating carboxylate ligands and two O atoms of water molecules. The crystal structure of I and II are stabilized by N-H…O, O-H…O, O-H…N, and C-H…O hydrogen bonds, C-H…π interactions and weak π-π stacking interactions.     

Crystal structures and luminescence of a series of cadmium(II) complexes based on isophorone derivative containing imidazolyl

Three new complexes, [CdL₂(CH₃COO)₂(H₂O)₂] (I), CdL₂Br₂ (II), CdL₂I₂ (III), have been successfully synthesized by self-assembly of corresponding metal salts with (E)-2-(3-(4-(1H-imidazole-1-yl)styryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile (L). The structures of the complexes were determined by single crystal X-ray diffraction analysis (CIF file CCDC nos. 957831 (I), 957792 (II), 957832 (III)). In complex I, central metal is six-coordinated and the crystal packing shows a 3D supramolecular framework. Complexes II and III display the similar 2D supramolecular structures in which the central metals are four-coordination. The luminescent properties were investigated.     

Synthesis and crystal structure of the Ag(I) complex with a cyclic β-diketone, 2-(diphenylacetyl)indan-1,3-dione (L), and the HL molecule

An Ag(I) complex with HL (I), AgL (AgC₂₃H₁₅O₃, II), has been synthesized. Compounds I and II have been studied by X-ray diffraction. The crystals are monoclinic, I: space group P2₁/n, a = 10.459(2) Å, b = 12.354(2) Å, c = 13.390(3) Å, β = 96.67(3)°, Z = 4; II: space group P2₁/c, a = 10.764(2) Å, b = 10.683(2) Å, c = 15.939(3) Å, β = 101.57(3)°, Z = 4. The structural units of the crystal of I are neutral molecules with intramolecular hydrogen bonds. In structure II, the Ag₂O₆ dimeric groups and the ligands form infinite openwork layers perpendicular to the x axis and containing cavities. The layers are penetrated by channels with an oblong cross section. In the crystal of II, all intermolecular distances exceed the sums of the van der Waals radii of the corresponding atoms.     

Synthesis and crystal structure of dibenzo-18-crown-6 oxonium perchlorate trihydrate

A hydrated crystalline ionized adduct of dibenzo-18-crown-6 and perchloric acid DB18C6 · H₃O⁺ · CiO ₄ ^? · 3H₂O (I) is synthesized and characterized by X-ray diffraction. The crystals of I are monoclinic: a = 17.760 Å, b = 12.922 Å, β = 124.27°, Z = 4, space group Cc. The structure of I is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.079 for 3294 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). A DB18C6 molecule has a butterfly conformation with the rough symmetry C _2v . An H₃O⁺ · H₂O dimer is situated on one side of the DB18C6 macrocycle, and the ClO ₄ ^? anion and two other water molecules are on the other side. In the crystal of I, the DB18C6 molecules, H₃O⁺ and ClO ₄ ^? ions, and water molecules are linked through intermolecular (interionic) hydrogen bonds to form broad infinite chains running along the z axis.     

Crystal structure of copper sulfate and thiocyanate complexes with 5-bromo-and 5-nitrosalicylaldehyde thiosemicarbazones

The crystal structures of (5-bromosalicylidenethiosemicarbazido)aquacopper(II) sulfato(5-bromosalicylidenethiosemicarbazido)aquacuprate(II) tetrahydrate (I), (5-nitrosalicylidenethiosemicarbazido)dimethylsulfoxide(methanol)copper(II) sulfate (II), and catena(μ-thiocyanato)(5-nitrosalicylidenethiosemicarbazido)copper(II) (III) were determined. In structure I, the independent part of the unit cell contains four water molecules of crystallization and the cation-anion complex [Cu(H₂O)(L)][Cu(H₂O)(L)(SO₄)] containing two nonequivalent copper complexes (A and B). In these, the metal atom coordinates monodeprotonated 5-bromosalicylaldehyde thiosemicarbazone (HL) and water molecules, and in anion B also a sulfate ion. In complex ions A and B, sulfur, azomethine nitrogen, and phenolic oxygen of the salicylidene thiosemicarbazone fragment, and also water molecule form a distorted planar square around the metal atom. The axial vertex of the pyramid in anion B is occupied by the oxygen atom of the monodentate sulfate anion. In structure II, the independent part of the unit cell contains the (5-nitrosalicylidenethiosemicarbazido)dimethylsulfoxide(methanol)copper(II) complex cation and the sulfate anion. The coordination polyhedron of the central atom is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and dimethyl sulfoxide oxygen. The axial position is occupied by the methanol oxygen atom. In structure III, the copper atom coordinates 5-nitrosalicylaldehyde thiosemicarbazone and the thiocyanate ion, which combines complexes into infinite polymer chains along the [010] direction. The copper coordination polyhedron in III is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and nitrogen of thiocyanate ion, the axial vertex is occupied by sulfur of thiocyanate ion of the neighboring complex.     

Synthesis of optically active Zn(II) complexes with thiosemicarbazones of (+)-camphor (L) and (−)-carvone (L1). The crystal structures of L and [Zn(L)2Cl2]

The optically active complexes [Zn(L)₂Cl₂] (I) and [Zn(L¹)₂Cl₂] (II) (L and L¹ are thiosemicar-bazones of (+)-camphor and (?)-carvone, respectively) were obtained. The crystal structures of L and complex I were determined by X-ray diffraction. The structure of L consists of hydrogen-bonded molecules united into chains. The crystal structure of complex I is built from mononuclear molecules. The coordination polyhedron of the Zn atom is a distorted tetrahedron Cl₂S₂. The molecule L functions as a monodentate ligand. According to data from IR spectroscopy, complex II is structurally similar to complex I.     

Crystal structure and magnetic properties of heterometallic trinuclear Cu2Ni complex containing macrocyclic ligands

One novel heterometallic trinuclear complex of macrocyclic oxamide [Ni(CuL)₂(HBTC)H₂O] (I) (H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,13-dien; H₃BTC = 1,3,5-benzenetricarboxylic acid) has been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, XRD, and single-crystal X-ray diffraction. The crystals crystallize in the monoclinic system, space group P2₁/c, a = 11.435(3), b = 20.646(5), c = 18.430(5) Å, β = 94.131(4)°. The structure of I has oxamido-bridged trinuclear [Cu ₂ ^II Ni^II] units and consists of two-dimensional supramolecular architecture formed by strong intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I was investigated and discussed in detail.     

Hydrothermal synthesis, crystal structure, and photoluminescence of Pb(II) and Mn(II) coordination polymers based on imidazo[4,5-f][1,10]phenanthroline

Two new coordination polymers, [Pb(IDPT)₂(NO₃)₂] (I) and [Mn(IDPT)(SO₄)(H₂O)₂] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P2₁/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) Å, β = 100.47(10)°, V = 2424.0(3) ų, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) Å, β = 99.32(10)°, V = 1490.25(14) ų, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via π-π interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature.     

Synthesis and crystal structure of benzyltrimethylammonium dicitratoborate monohydrate

Benzyltrimethylammonium dicitratoborate [C₆H₅CH₂N(CH₃)₃][(C₆H₆O₇)₂B] · H₂O (I) has been synthesized and separated out in the form of single crystals for the first time. Its crystal structure has been studied by X-ray diffraction. Crystals are triclinic with a = 10.0832(2) Å, b = 11.1232(3) Å, c = 11.9617(3) Å, α = 84.874(1)°, β = 73.520(1)°, γ = 85.550(1)°, Z = 2, space group P-1. The structure has been solved by direct methods and refined by the full-matrix least-squares technique in the anisotropic approximation up to R = 0.0485 (Bruker-Nonius KappaCCD automatic diffractometer, λMoK _α). The crystal structure of compound I is based on centrosymmetric dimers that consist of complex anions and water molecules and linked by the system of hydrogen bonds into a three-dimensional framework. The crystals of compound I contains five asymmetric O-H...O hydrogen bonds. A specific feature of the structure is the formation of -COO...H...H₂O hydrogen bonds, in which the carboxyl proton is considerably shifted towards the water molecule.     

Crystal structures of nitrato-{4-bromo-2-[(2-hydroxyethylimion)methyl]phenolo}-(3,5-Dibromopyridine)copper and nitrato-{2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper

The crystal structures of nitrato-{4-bromo-2-[2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (I) and nitrato-{2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (II) are determined. The crystals of compound I are orthorhombic: a = 14.157(3) Å, b = 15.420(3) Å, c = 17.494(4) Å, space group Pbca, Z = 8, R = 0.067. The crystals of compound II are monoclinic: a = 10.675 Å, b = 13.973 Å, c = 14.007 Å, β = 111.92°, space group P2₁/n, Z = 4, R = 0.0464. In the structures of compounds I and II, the copper atom coordinates, correspondingly, singly deprotonated 4-bromo-2-[(2-hydroxyethylimino)methyl]phenol and 2,4-dibromo-6-[(2-hydroxyethylimino)methyl]phenol molecules, and 3,5-dibromopyridine, and the nitrate ion. The coordination polyhedron of the copper ion in complexes I and II is a slightly distorted tetragonal pyramid. The bases of the pyramids are formed by the imine and pyridine nitrogen atoms and the phenolic and alcoholic oxygen atoms, and the axial vertices are occupied by the oxygen atoms of the monodentate nitrato groups. In the complexes under study, the six-membered metallocycles have asymmetric gauche conformation. In crystal, complexes I are united, due to the slip plane a, through bifurcate hydrogen bonds into infinite chains along the direction [100]. Complexes II in crystal form two-dimensional networks by means of hydrogen bonds.     

Crystal and Molecular Structure of Aqua[1,2-bis(2-(o-hydroxyphenoxy)ethoxy)ethane](isothiocyanato)sodium

The crystals of the hydrated complex of a podand 1,2-bis(2-(o-hydroxyphenoxy)ethoxy)ethane (L) with sodium thiocyanate of the composition [Na(NCS)L(H₂O)] (I) were prepared and studied by X-ray diffraction analysis. The structure of I (space group P2₁/n, a = 12.128 Å, b = 14.221 Å, c = 13.594 Å, β = 113.82°, Z = 4) was solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.055 over all 2970 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). The individual host–guest type molecules are connected in crystal I by hydrogen bonds. The coordination polyhedron of the Na⁺ cation is a distorted pentagonal bipyramid whose base consists of five O atoms of the podand L and whose axial positions are occupied by the O atom of water and the N atom of SCN^–. The sixth O atom of the podand L is not involved in Na⁺ coordination.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

Crystal structure of nitrate tris(4-allylthiosemicarbazide)-chromium(III) hydrate

The crystal structure of nitrate tris(4-allylthiosemicarbazide)chromium(III) hydrate [CrL₃](NO₃)₃(H₂O)_1.05 (I), where L is 4-allylthiosemicarbazide, is determined. The asymmetric unit of the cell of the crystal structure of I contains a complex of a chromium ion with three bidentate coordinated molecules L. The outer coordination sphere of the central atom contains a disordered water molecule and three nitrate ions. The coordination polyhedron of the chromium atom in complex I is an octahedron. In the crystal, the complexes of the compound under study are joined with each other by the outer-sphere nitrato groups into a three-dimensional branched net of hydrogen bonds.     

Cobalt(III) azide dimethylglyoximates with some sulfanilamide derivatives: Synthesis and crystal structures

A number of new Co(III) dimethylglyoximates containing N-pyrimidinylsulfanilamides were obtained. These complexes of the general formula [Co(N₃)(DH)₂L] (I?CV) (where DH is the dimethylglyoxime monoanion and L are N-pyrimidinylsulfanilamides NH₂-C₆H₄-SO₂-NH-R with different substituents R) are expected to have antibacterial properties. Their structures were examined by IR, electronic absorption, and NMR spectroscopy and X-ray diffraction. They were classified among cobalt(III) trans dioximates. In all the complexes obtained, the cobalt atom coordinates to four N atoms of two dimethylglyoxime residues. The octahedral environment of the metal atom is completed with the amino N atom of the neutral molecule L and the N atom of the azide anion. In the crystal structures, complexes I?CV are united through intermolecular hydrogen bonds N-H??O, N-H??N, and O-H??O, in which the groups ?NH₂ and =NH of the ligand L and water molecules (for I, IV, and V) serve as proton donors.