Infinite Three-dimensional Network Research Articles

3,5-Lutidine penta-aqua sulfate complexes of first-row transition metals: [M(3,5-lutidine)(H2O)5]SO4, with M = Mn, Co, Ni, and Zn.

The reactions of MnSO4·H2O, CoSO4·7H2O, NiSO4·6H2O and ZnSO4·7H2O with 3,5-lutidine (3,5-di-methyl-pyridine) yield crystals of penta-aqua-(3,5-di-methyl-pyridine-κN)manganese(II) sulfate, [Mn(C7H9N)(H2O)5]SO4, (1), penta-aqua-(3,5-di-methyl-pyridine-κN)cobalt(II) sulfate, [Co(C7H9N)(H2O)5]SO4, (2), penta-aqua-(3,5-di-methyl-pyridine-κN)nickel(II) sulfate, [Ni(C7H9N)(H2O)5]SO4, (3), and penta-aqua-(3,5-di-methyl-pyridine-κN)zinc(II) sulfate, [Zn(C7H9N)(H2O)5]SO4, (4), which were characterized by single-crystal X-ray diffraction. The four crystals are isostructural, demonstrating near identical unit-cell parameters and atomic positions. The metal atoms are all octa-hedrally coordinated, with one lutidine ligand and five water ligands. The sulfate dianion hydrogen bonds with the coordinated water mol-ecules of the dicationic metal complex salts, generating infinite three-dimensional networks.

Synthesis, crystal structure and Hirshfeld surface analysis of the 1-(3,6-dihydropyrimidin-2-yl)urea salt structurally related to dihydropyrimidinon-2-ylurea-type RNA-binding ligands

The postmulticomponent synthesis and crystal structure of 1-(3,6-dihydropyrimidin-2-yl)urea salt, 5-(ethoxycarbonyl)-4-methyl-6-phenyl-2-ureido-3,6-dihydropyrimidin-1-ium chloride monohydrate, C15H21O4N4+·ClH2O; structurally related to dihydropyrimidinon-2-ylurea-type RNA-binding ligands is reported. The structure of this new type of hydrated organic salt was investigated by FT-IR, NMR and HRMS methods, and its structure was unambiguous confirmed using X-ray single crystal diffraction techniques. X-ray diffraction analysis show that this material crystallizes in the monoclinic space group P21/c (N°14), Z = 4 with the 3,6-dihydropyrimidin-1-ium ring in a pucked-boat conformation attached to the ester group in an s−trans relationship. The molecular structure and crystal packing are stabilized by intermolecular N − H···O, O − H···O, and N − H···Cl hydrogen bonds formed an infinite three-dimensional (3D) network. Furthermore, the Hirshfeld surface analysis confirms that the most important contributions for the crystal packing are the C − H···H (52.5%), C − H···C (17.8%), C − H···O (15.4%) and N − H···Cl (5.80%) surface contacts.

Preparation, structure, characterization and theoretical DFT study of two new hybrid compounds

Two new hybrid compounds, (C4H16N3)(ClO4)2Cl and (C5H8N3O)NO3, have been prepared and characterized by single crystal X-ray diffraction, elemental analysis, CP-MAS-NMR and IR spectroscopies. In the atomic arrangement of (1) the diethylenetriaminium organic cations and the perchlorate anions are linked to each other by N–H⋯O and C–H⋯O hydrogen bonds forming pores extending along the c-axis direction. The Cl− anions which are housed inside these pores and connect them through N–H⋯Cl and C–H⋯Cl hydrogen bonds form an infinite three-dimensional network. In (2), the 2-amino-4-methyl-6-oxo-3,6-dihydropyrimidin-1-ium organic cations are linked together by C–H⋯O hydrogen bonds to form corrugated chains extending along b-axis direction. The nitrate anions are located between these chains and connect them through N–H⋯O hydrogen bonds to form an infinite three-dimensional network. The 13C and 15N CP-MAS NMR spectra are discussed and the vibrational absorption bands were identified by infrared spectroscopy. The HOMO and LUMO energies and Molecular Electrostatic Potential surface were derived from DFT theoretical calculations.

Crystal structures of chlorido-[dihy-droxybis-(1-imino-eth-oxy)]arsanido-κ3 N,As,N']platinum(II) and of a polymorph of chlorido-[dihy-droxybis-(1-imino-prop-oxy)arsanido-κ3 N,As,N']platinum(II).

Each central platinum(II) atom in the crystal structures of chlorido-[dihy-droxybis-(1-imino-eth-oxy)arsanido-κ3 N,As,N']platinum(II), [Pt(C4H10AsN2O4)Cl] (1), and of chlorido-[dihy-droxybis-(1-imino-prop-oxy)arsanido-κ3 N,As,N']platinum(II), [Pt(C6H14AsN2O4)Cl] (2), is coordinated by two nitro-gen donor atoms, a chlorido ligand and to arsenic, which, in turn, is coordinated by two oxygen donor ligands, two hydroxyl ligands and the platinum(II) atom. The square-planar and trigonal-bipyramidal coordination environments around platinum and arsenic, respectively, are significantly distorted with the largest outliers being 173.90 (13) and 106.98 (14)° for platinum and arsenic in (1), and 173.20 (14)° and 94.20 (9)° for (2), respectively. One intra-molecular and four classical inter-molecular hydrogen-bonding inter-actions are observed in the crystal structure of (1), which give rise to an infinite three-dimensional network. A similar situation (one intra-molecular and four classical inter-molecular hydrogen-bonding inter-actions) is observed in the crystal structure of (2). Various π-inter-actions are present in (1) between the platinum(II) atom and the centroid of one of the five-membered rings formed by Pt, As, C, N, O with a distance of 3.7225 (7) Å, and between the centroids of five-membered (Pt, As, C, N, O) rings of neighbouring mol-ecules with distances of 3.7456 (4) and 3.7960 (6) Å. Likewise, weak π-inter-actions are observed in (2) between the platinum(II) atom and the centroid of one of the five-membered rings formed by Pt, As, C, N, O with a distance of 3.8213 (2) Å, as well as between the Cl atom and the centroid of a symmetry-related five-membered ring with a distance of 3.8252 (12) Å. Differences between (2) and the reported polymorph [Miodragović et al. (2013 ▸). Angew. Chem. Int. Ed. 52, 10749-10752] are discussed.

Crystal structure, thermal behavior and luminescence of a new Manganese(Ⅱ) coordination polymer constructed with 1, 10-phenanthroline-5, 6-dione and 2, 5-dihydroxyl-1, 4-terephthalic acid

A new Mn(II) coordination polymer, [Mn0.5(PHDI)0.5(DHTA)0.5]n was synthesized under hydrothermal conditions (PHDI = 1,10-phenanthroline-5,6-dione, DHTA = 2,5-dihydroxyl-1,4-terephthalic acid). Crystallographic data for 1: Monoclinic, space group C2/c, with a = 16.6224(12) Å, b = 11.2536(8) Å, c = 9.3621(7) Å, α = 90°, β = 97.7800(10)°, γ = 90°, V = 1735.2(2)Å3, Z = 8, C10H5Mn0.50NO4, Mr = 230.62, Dc = 1.766 g/cm3, F(000) = 932, μ = 0.820 mm−1, R1 = 0.0356, wR2 = 0.0753. The metal center Mn(II) is six-coordinated, in which two nitrogen atoms come from a chelating didentate ligand of the PHDI, and four oxygen atoms come from four different carboxylic acid ligands of the DHTA, forming a deformed octahedral geometry. The two metal Mn are connected by four single dentate coordination oxygen atoms of two carboxylic acid of the DHTA, and continue to extend in different directions to form an infinite three-dimensional network structure. Additionally, the O(3)–H(3)···O(1), O(3)–H(3)···O(2)i hydrogen bonds further stabilize the structure of 1. The IR, TGA behaviors, Luminescence and PXRD of 1 have been studied in detail.

Synthesis, structure, and photoluminescence properties of lanthanide based metal organic frameworks and a cadmium coordination polymer derived from 2,2′-diamino-trans 4,4′-stilbenedicarboxylate

Abstract Two isostructural lanthanide-based metal - organic frameworks, {[Ln(C16H12N2O4)(CHO2)(OH2)·2(C5H11NO)]}n, Ln = Yb (1) and Tm (2), and a cadmium(II) coordination polymer,{[Cd2(C16H12N2O4)(NO3)·4(C3H7NO)]}n, were synthesized by the combination of the respective metal nitrate and 2,2′-diamino-trans 4,4′-stilbenedicarboxylate (C16H12N2O4) under solvothermal conditions [C5H11NO = diethylformamide and C3H7NO = dimethylformamide]. Their structures were determined by X-ray single crystal analysis, X-ray powder diffraction, Fourier transformed infrared spectroscopy, elemental analysis, thermogravimetric analysis and solid state photoluminescence spectroscopy. Both lanthanide structures are infinite three-dimensional non-penetrating networks with extremely large diamond shape accessible channels of cross-sectional dimensions [30 A x 12 A] and with the amino-functional groups projecting into the channels. The cadmium-based structure is a one-dimensional coordination polymer with both the carboxylate and the amino groups coordinating the cadmium atoms, which resulted in a large increase in the rigidity of the ligand. Ligand-based fluorescence was exhibited by all three networks, with the cadmium based structure showing the highest intensity and longest fluorescence radiative lifetime.

Synthesis, X-ray single crystal structure, likelihood of occurrence of intermolecular contacts, spectroscopic investigation and DFT quantum chemical calculations of zwitterionic complex: 1-Ethylpiperaziniumtrichlorozincate (II)

The synthesis and the X-ray structure of the Zn(II) zwitterionic complex:1-ethylpiperaziniumtrichlorozincate (II) are described. In the atomic arrangement, the ZnCl3N entities, grouped in pairs, are deployed along the b-axis to form layers. The organic entities are inserted between these layers through NH⋯Cl and CH⋯Cl hydrogen bonds to form infinite three-dimensional network. The 3D Hirshfeld surfaces were investigated for intermolecular interactions. The optimized geometry, Mulliken charge distribution, molecular electrostatic potential (MEP) maps and thermodynamic properties have been calculated using the Lee-Yang-Parr correlation functional B3LYP with the LanL2DZ basis set. The HOMO and LUMO energy gap and chemical reactivity parameters were made. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray crystal structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks and of the IR bands.

Crystal Structure, Thermal Behavior and Vibrational Spectra of 4,4’Diamoniumdiphenylmethan Sulfate Hydrate

Single crystals of the 4,4’-diamoniumdiphenylmethan sulfate hydrate, denoted DDPS, were grown by slow evaporation solution technique at room temperature. The compound was characterized by single crystal X-ray diffraction, IR and thermal analysis (TG-DTA). It crystallizes in the monoclinic system (space group C2/c) with the following unit cell dimensions: a = 17.7635(10) A, b = 9.3796(10) A, c = 27.5676(10) A, β = 97.367(2), V = 4555.2(6) A. The structure was solved by the direct method and refined to final R value of 0.0472 for 2108 independent reflections. The anions are hydrogen bonded to each other, forming clusters [HS2O8]3﹣ parallel to the plan (a, b). The water molecules connect these clusters via O-H···O hydrogen bonds. The organic cations are attached to the clusters through N-H···O hydrogen bonds, forming an infinite three-dimensional network.

Synthesis and structure elucidation of new μ-oxamido-bridged dicopper(II) complex with in vitro anticancer activity: A combined study from experiment verification and docking calculation on DNA/protein-binding property

A new oxamido-bridged dicopper(II) complex with formula of [Cu2(deap)(pic)2], where H2deap and pic represent N,N′-bis[3-(diethylamino)propyl]oxamide and picrate, respectively, was synthesized and characterized by elemental analyses, molar conductance measurements, IR and electronic spectral study, and single-crystal X-ray diffraction. The crystal structure analyses revealed that the two copper(II) atoms in the dicopper(II) complex are bridged by the trans-deap2− ligand with the distances of 5.2116(17)Å, and the coordination environment around the copper(II) atoms can be described as a square-planar geometry. Hydrogen bonding and π–π stacking interactions link the dicopper(II) complex into a three-dimensional infinite network. The DNA/protein-binding properties of the complex are investigated by molecular docking and experimental assays. The results indicate that the dicopper(II) complex can interact with HS-DNA in the mode of intercalation and effectively quench the intrinsic fluorescence of protein BSA by 1:1 binding with the most possible binding site in the proximity of Trp134. The in vitro anticancer activities suggest that the complex is active against the selected tumor cell lines, and IC50 values for SMMC-7721 and HepG2 are lower than cisplatin. The effects of the electron density distribution of the terminal ligand and the chelate ring arrangement around copper(II) ions bridged by symmetric N,N′-bis(substituted)oxamides on DNA/BSA-binding ability and in vitro anticancer activity are preliminarily discussed.

Crystal chemistry of aluminium carboxylates: From molecular species towards porous infinite three-dimensional networks

This account describes the crystal chemistry of aluminium in association with O-donor organic ligands, such as polycarboxylates. In this overview, molecular assemblies of aluminium-based species are discussed from the background knowledge of the polycationic species occurring in aqueous solution. The use of hydro/solvothermal synthetic route has led to the generation of novel crystalline extended three-dimensional networks, of metal-organic frameworks (MOFs) type, with consequent porosity properties. The first illustration of such materials was the aluminium-containing MIL-53 (Materials Institute Lavoisier – number 53), obtained from the hydrothermal reaction of aluminium salt source with terephthalic acid. This finding gave rise to the development of new series of porous aluminium MOF-like materials, some of which are now produced at the industrial scale. This review presents a description of various crystalline structures, from a classification based on the nuclearity of the aluminium-centered building units, involved in the construction of the framework.

A novel 3D energetic coordination polymer containing Co(II) atoms in a pentanuclear cluster

A novel coordination polymer [Co5(OH)2(dnbpdc)4(H2O)6]·16H2O (1) (dnbpdc = 6,6′-dinitro-4,4′-biphenyldicarboxylic acid) is obtained from a hydrothermal reaction. The structure of complex 1 is characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction analysis. The title compound (C56H70Co5N8O56, Mr = 2045.85) crystallizes in the triclinic space group P-1 with a = 11.9349(2) A, b = 12.1895(2) A, c = 15.420(2) A, α = 109.390(7)°, β = 94.786(1)°, γ = 108.027(9)°, V = 1968.4(4) A3, Z = 1, Dc = 1.726 g/cm3, F(000) = 1045, μ(MoKα) = 1.154 mm–1, T = 133(2) K, the final R = 0.0316 and wR = 0.0692 for 7032 observed reflections with I > 2σ(I). The coordination polymer is built of a pentanuclear Co(II) cluster, four dnbpdc ligands, two hydroxyl groups, six coordination water and sixteen crystal water molecules. Ligand oxygen atoms exhibit three types of coordination modes (monodentate, syn-syn bridging bidentate and bridging tridentate). Moreover, the infinite three-dimensional supramolecular network is generated by coordination and hydrogen bonds. The thermal stability of complex 1 is evaluated by differential scanning calorimetry and thermogravimetric analysis.

Crystal structure of 4-formyl-pyridine semicarbazone hemihydrate.

The mol­ecule of the title compound C7H8N4O·0.5H2O, alternatively called (E)-1-(pyridin-4-yl­methyl­ene)semi­carb­azide hemihydrate, is in the E conformation and is almost planar; the r.m.s. deviation of the positions of the atoms of the pyridine ring from the best-fit plane is 0.0039 Å. The C, N and O atoms of the rest of the mol­ecule sits close on this plane with a largest deviation of 0.115 (4) Å for the O atom of the semicarbazone moiety. There is an intra­molecular N—H⋯N hydrogen bond. In the crystal, mol­ecules are linked into an infinite three-dimensional network by classical N—H⋯Os (s = semicarbazone) and Ow—H⋯N (w = water) hydrogen bonds.

Synthesis and physico-chemical studies of a novel organo-metallic compound CdCl2(C6H4FNH2)2

A new Cd(II) complex with the monodentate ligand 3-fluoroaniline, CdCl2(C6H4FNH2)2, has been prepared and characterized by single crystal X-ray diffraction, solid state NMR, IR, Raman and UV–visible spectroscopies. In the complex, the Cd(II) ion is surrounded by four chlorine atoms and two nitrogen atoms, forming a chain of edge-charing octahedra spreading along the a-axis direction. These chains are interconnected via NH…Cl hydrogen bonds to form inorganic layers parallel to the (a, b) plane. The organic 3-fluorophenyl groups are inserted between these layers and are interconnected via CH…F hydrogen bonds to perform an infinite three-dimensional network. Intermolecular π–π stacking interactions between neighboring aromatic rings are also observed with a face-to-face distance of 3.6816 (4)Å. The 13C and 19F CP-MAS NMR spectra are in agreement with the X-ray structure. DFT calculations allow the attribution of the carbon peaks to the different atoms. The absorption bands of the Cd2Cl4N2 units were identified by Raman spectroscopy. The solid-state UV–vis spectrum of the complex has been assigned to ligand and charge transfer transitions.

Crystal Structure and Physicochemical Characterization of Ambazone Monohydrate, Anhydrous, and Acetate Salt Solvate

The crystal structures of the monohydrate and anhydrous forms of ambazone were determined by single-crystal X-ray diffraction (SC-XRD). Ambazone monohydrate is characterized by an infinite three-dimensional network involving the water molecules, whereas anhydrous ambazone forms a two-dimensional network via hydrogen bonds. The reversible transformation between the monohydrate and anhydrous forms of ambazone was evidenced by thermal analysis, temperature-dependent X-ray powder diffraction and accelerated stability at elevated temperature, and relative humidity (RH). Additionally, a novel ambazone acetate salt solvate form was obtained and its nature was elucidated by SC-XRD. Powder dissolution measurements revealed a substantial solubility and dissolution rate improvement of acetate salt solvated form in water and physiological media compared with ambazone forms. Also, the acetate salt solvate displayed good thermal and solution stability but it transformed to the monohydrate on storage at elevated temperature and RH. Our study shows that despite the requirement for controlled storage conditions, the acetate salt solvated form could be an alternative to ambazone when solubility and bioavailability improvement is critical for the clinical efficacy of the drug product.

Crystal structure of (E)-1-methyl-2-[2-(2-methoxphen-yl)ethen-yl]-4-nitro-1H-imidazole.

In the asymmetric unit of the title compound, C13H13N3O3, the 2-(2-methoxphen­yl)ethenyl unit is connected to the methyl-nitro­imidazole 1-methyl-4-nitro-1H-imidazole moiety. The mol­ecule is quasi-planar and the planes of the two rings form a dihedral angle of 0.92 (11)°. The crystal packing can be described as layers parallel to the (011) plane, stabilized by inter­molecular C—H⋯O hydrogen bonding, resulting in the formation of an infinite three-dimensional network linking these layers. Strong π–π stacking inter­actions are observed, viz. benzene–benzene, imidazole–imidazole and benzene–imidazole rings, with centroid–centroid distances of 3.528 (2), 3.457 (2) and 3.544 (2) Å, respectively. Intensity statistics indicated twinning by non-merohedry, with refined weighs of the twin components of 0.3687:0.6313.

Synthesis and physico-chemical studies of a novel coordination compound ZnCl2(C6H4FNH2)2

A new Zn(II) complex with the monodentate ligand 3-fluoroaniline, ZnCl2(C6H4FNH2)2, has been prepared and characterized by single crystal X-ray diffraction, Solid state NMR, IR and UV-visible spectroscopies. The Zn(II) ion, located on a special position, is tetracoordinated by two nitrogen atoms of two 3-fluoroaniline monodentate ligands and two chlorine ligands. In the atomic arrangement, the ZnCl2(NH2)2 entities are interconnected via N-H…Cl hydrogen bonds to form inorganic layers parallel to the (b, c) plane. The organic 3-fluorophenyl groups are located between these layers and connect each other via C-H…F hydrogen bonds to perform an infinite three-dimensional network. The F atom of the 3-fluoroaniline ligand is disordered over two positions. An F-F interaction between neighboring fluorine atoms contributes also to the structure cohesion. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure. DFT calculations allow the attribution of the carbon peaks to the different independent atoms. Solid-state UV-Vis spectrum of the complex has been assigned to ligand and charge transfer transitions.

Crystal structure of bis-Isonicotinoyl hydrazone of 2,5-diformylpyrrole

bis-Isonicotinoyl hydrazone of 2,5-diformylpyrrole existing in the crystal in the form of a tetrahydrate of the hydrazone tautomeric form is synthesized and its structure is described. In the crystal, an infinite three-dimensional network of hydrogen bonds is formed by hydrazone molecules. The neighboring hydrazone molecules are bonded by intermolecular π stacking interactions. A quantum chemical calculation of the geometry and total energy of possible tautomers in vacuum and an aqueous solution is performed.

3,4-Diaminobenzonitrile

The non-H atoms in the structure of the title mol­ecule, C7H7N3, are almost coplanar (r.m.s. deviation = 0.018 Å). The two amine groups each donate two and accept one weak N—H⋯N hydrogen bonds. N—H⋯N hydrogen bonding between the amine and nitrile groups results in chains parallel to [101] in the crystal structure. The chains are cross-linked by N—H⋯N hydrogen bonds between amine groups, giving rise to an infinite three-dimensional network.

Two polymorphs of 1,8-dichloroanthracene

A second, monoclinic, polymorph of the title compound, C(14)H(8)Cl(2), has been found. In addition to the structure of this monoclinic form, the structure of the previously described orthorhombic form [Desvergne, Chekpo & Bouas-Laurent (1978). J. Chem. Soc. Perkin Trans. 2, pp. 84-87; Benites, Maverick & Fronczek (1996). Acta Cryst. C52, 647-648] has been redetermined at low temperature and using modern methods. The low-temperature structure of the orthorhombic form is of significantly higher quality than the previously published structure and additional details can be derived. A comparison of the crystal packing of the two forms with a focus on weak intermolecular C-H···Cl interactions shows the monoclinic structure to have one such interaction linking the molecules into infinite ribbons, while two crystallographically independent C-H···Cl interactions give rise to an interesting infinite three-dimensional network in the orthorhombic crystal form.

N-(5-Amino-1H-1,2,4-triazol-3-yl)pyridine-2-carboxamide

The title compound, C8H8N6O, was obtained by the reaction of 3,5-diamino-1,2,4-triazole with ethyl 2-picolinate in a glass oven. The dihedral angles formed between the plane of the amide group and the pyridine and triazole rings are 11.8 (3) and 5.8 (3)°, respectively. In the crystal, an extensive system of classical N—H⋯N and N—H⋯O hydrogen bonds generate an infinite three-dimensional network.