New Mg-based 4,4'-biphenyldicarboxylate coordination polymer with layered crystal structure.

New magnesium 4,4'-biphenyldicarboxylate (BPDC) was solvothermally synthesized in the presence of N,N'-dimethylformamide (DMF). The crystal structure with formula Mg(3)(BPDC)(3)(DMF)(4) and denoted as NICS-7 was solved in monoclinic symmetry with space group Pn (no. 7) and unit cell parameters a = 12.6433(7) Å, b = 13.3950(5) Å, c = 19.9230(8) A, beta = 107.131(5) °. The structure consists of MgO(6) linear arranged trimers with common vertices connected through BPDC ligands forming extended 2-dimensional layered hybrid structure. Each terminal Mg atom within trimeric clusters is coordinated by two dimethylformamide molecules, respectively. Layers of Mg(3)(BPDC)(3)(DMF)(4) are stabilized by non-coordinated dimethylformamide molecules located within the voids in crystallographically disordered manner. Thermal properties of NICS-7 were determined by thermogravimetric and temperature-programmed X-ray diffraction. The structure remains stable only up to 50 °C. At higher temperatures, the removal of non-coordinated dimethylformamide molecules causes formation of amorphous Mg-BPDC phase.

The novel crystal structure with Zr6O4(OH)4 core and hydrazine carboxylate ligands, and its thermal properties.

The title compound, [Zr(6)(OH)(4)O(4)(N(2)H(3)COO)(12)] · 14H(2)O, was prepared with a novel multi-step synthetic pathway. The structure contains a Zr(6)(µ(3)-OH)(4)(µ(3)-O(4))(12+) core on which twelve hydrazine carboxylate anions are bound to form neutral coordination molecules. The coordination mode of carboxylate ligand is exclusively N,O-bidentate chelating, which is observed for the first time in this class of compounds. The title compound is also the first example of isolated Zr(IV) oxo clusters with cubic symmetry. The structure is stabilized with an extensive hydrogen bond network between coordination and water molecules, and amongst the solvent water molecules themselves. Thermogravimetric studies have shown that the prepared [Zr(6)(OH)(4)O(4)(N(2)H(3)COO)(12)] · (14)H(2)O decomposed in several consecutive steps characterized by evolution of H(2)O, CO, CO(2), N(2) and H(2), finally yielding ZrO(2). The decomposition mechanism is rather complex and includes the formation of a series of amorphous intermediates.

Bis{(R)-1-(3-amino-sulfonyl-4-meth-oxy-phen-yl)-N-[2-(2-eth-oxy-phen-oxy)eth-yl]propan-2-aminium} adipate tetra-hydrate.

The title compound, 2C20H29N2O5S(+)·C6H8O4 (2-)·4H2O, which was found to be optically active, is a relatively rare example of a chiral compound crystallizing in the triclinic crystal system. The dihedral angles between the phenyl rings of the cations are 60.03 (15) and 62.03 (16)°, while the C atoms of the anion are almost coplanar (r.m.s. deviation 0.085 Å) and all trans to each other. In the crystal, the components are connected by an extensive network of N-H⋯O and O-H⋯O hydrogen bonds. The sulfonamide groups link the cations into pairs via two N-H⋯O hydrogen bonds about the pseudo-inversion centre, leading to the formation of R 2 (2)(8) rings. The anions are stacked in between four cationic pairs. Pairs of water mol-ecules bridge the larger building units, forming hydrogen bonds with the remaining two O atoms of the anion.

Polymorphism of LaTaTiO6.

Two polymorphs of LaTaTiO6, i.e. monoclinic and orthorhombic, were synthesized by solid-state reaction technique. Both were found to be isostructural with analogous niobium compounds which were used as structural models. Structural characterization was performed on X-ray powder data by Rietveld refinement procedure which resulted in final Rwp values of 7.01 and 7.52% for orthorhombic and monoclinic form, respectively. Comparisons between both title compounds are given and their plausibility is proved by bond valence sums and global instability index calculations. For the monoclinic polymorph, dielectric properties measured at 1 MHz are also given.

Synthesis, Crystal Structure and Magnetic Properties of a new Hydroxylammonium Fluoroferrate.

This paper reports on the synthesis of a new hydroxylammonium fluoroferrate, with the formula (NH3OH)3FeF6, obtained after dissolving iron powder in hydrofluoric acid and adding solid NH3OHF. This new compound has been characterized by chemical and thermal analysis, single-crystal X-ray diffraction, and magnetic measurements. The title compound crystallizes trigonal, R3c, with cell parameters a = 11.4154(2) Å, c = 11.5720(2) Å, Z = 6. The structure consists of NH3OH+ cations and isolated FeF63- octahedra in which the central ion lies on a threefold axis. The oxygen and nitrogen atoms of the hydroxylammonium cations are donors of hydrogen bonds to fluoride anions, resulting in a network of hydrogen bonds between counterions. The effective magnetic moment µeff = 5.8 BM was calculated and perfectly matches the expected value of high-spin Fe(III) ions. The thermal decomposition of the compound was studied by TG, DSC, and X-ray powder diffraction.

Structure of LaTi2Al9O19 and reanalysis of the crystal structure of La3Ti5Al15O37.

The non-perovskite compound LaTi(2)Al(9)O(19) was synthesized and structurally characterized by conventional X-ray powder diffraction and shown to be isostructural with SrTi(3)Al(8)O(19), as confirmed by bond-valence sum calculations. The dielectric properties of LaTi(2)Al(9)O(19) at 1 MHz were measured. The crystal structure of La(3)Ti(5)Al(15)O(37), which is referred to as the most complex structure solved ab initio from X-ray powder diffraction (XRPD) to date, is shown to be incorrect.

Efficient, stable, tunable, and easy to synthesize, handle and recycle luminescent materials: [H2NMe2]3[Ln(III)(2,6-dipicolinolate)3] (Ln = Eu, Tb, or its solid solutions).

Three compounds with the general formulae [H(2)N(Me)(2)](3)[Ln(2,6-dpa)(3)] were prepared from cheap and readily available reactants. Microcrystalline compounds could be isolated in high yields (>80%) by a simple filtration, after only one hour reaction time in refluxing DMF. The Eu and Tb compounds have been structurally characterized by single crystal X-ray diffraction. The compounds have unusual high-absorption coefficients (>95%) and quantum efficiencies (approximately 70%). Furthermore, they are thermally stable up to 250 degrees C and appear to be UV and water tolerant. The emission colour of the final compound can be easily fine-tuned, by varying the Eu:Tb ratio during the preparation.

3-Benzamido-1-benzoyl-1H-pyrrol-2(5H)-one.

In the title compound, C(18)H(14)N(2)O(3), one of the phenyl rings is almost coplanar with the pyrrole ring [dihedral angle = 2.56 (14)°], whereas the other one is tilted by 63.01 (6)° with respect to the pyrrole ring. Since the NH group is shielded from possible acceptors, this group is not involved in hydrogen bonding.

Preparation, Characterization and Crystal Structure of [Cu2(O2CH)4(nicotinamide)2].

The novel copper(II) coordination compound, [Cu2(O2CH)4(nia)2] (nia = nicotinamide), was isolated from the reaction mixture containing Cu2(OH)2CO3, nicotinamide, methanoic acid and ethanol. The new complex was characterized by X-ray single crystal diffraction and other standard physico-chemical methods. The structure contains binuclear centrosymmetric molecules in which two central atoms are bridged by four methanoate bridges forming a paddle-wheel structure type. The fifth coordination site completing the distorted square pyramid around copper is occupied by aromatic nitrogen of nicotinamide. The molecules pack together via hydrogen bonds resulting in a formation of extended supramolecular sheets. The results of other physical measurements are also in a complete agreement with the obtained structure.

Order-disorder of oxygen anions and vacancies in solid solutions of La2TiO5 and La4Ga2O9.

Successful Rietveld refinements of seven compounds with the formulae La2Ti((1-x))Ga(x)O((5-x/2)), where x = 0.00, 0.20, 0.50, 0.70, 0.90, 0.95 and 1.00, were performed in order to describe the solid solubility between orthorhombic (Pnam) La2TiO5 and monoclinic (P2(1)/c) La4Ga2O9. The relationship between the end-member structures, which are already known, is discussed; the space-group change is a consequence of ordering the oxygen vacancies that become more numerous as Ga is substituted for Ti. The structures of the solid solutions are also described. The lengths of cell edges obey Vegard's rule.

Complexation of molybdenum(V) with glycolic acid: an unusual orientation of glycolato ligand in {Mo2O4}2+ complexes.

(PyH)5[Mo(V)OCl4(H2O)]3Cl2 and (PyH)n[Mo(V)OBr4]n reacted with glycolic acid (H2glyc) or its half-neutralized ion (Hglyc(-)) to afford a series of novel glycolato complexes based on the {Mo(V)2O4}2+ structural core: (PyH)3[Mo2O4Cl4(Hglyc)]. (1)/ 2CH 3CN (1), (PyH) 3[Mo 2O 4Br 4(Hglyc)].Pr(i)OH(2), (PyH)2[Mo2O4(glyc) 2Py 2] (3), (PyH) 4[Mo 4O 8Cl 4(glyc) 2].2EtOH (4), and [Mo 4O 8(glyc) 2Py 4] (5) (Py = pyridine, C 5H 5N; PyH(+) = pyridinium cation, C 5H 5NH (+) and glyc (2-) = a doubly ionized glycolate, (-)OCH 2COO (-)). The compounds were fully characterized by X-ray crystallography and infrared spectroscopy. The Hglyc (-) ion binds to the {Mo 2O 4} (2+) core through a carboxylate end in a bidentate bridging manner, whereas the glyc (2-) ion adopts a chelating bidentate coordination through a deprotonated hydroxyl group and a monodentate carboxylate. The orientations of glyc (2-) ions in 3- 5 are such that the alkoxyl oxygen atoms occupy the sites opposite the multiply bonded oxides. {(C6H5) 4P}[Mo(VI)O 2(glyc)(Hglyc)] ( 6), an oxidized complex, features a reversed orientation of the glyc(2-) ion. The theoretical DFT calculations on the [Mo(V)2O4(glyc) 2Py 2](2-) and [Mo(VI)O2(glyc)2](2-) ions confirm that binding of glycolate with the alkoxyl oxygen to the site opposite the MoO bond is energetically more favorable in {Mo(V)2O4}(2+) species, whereas a reversed orientation of the ligand is preferred in Mo(VI) complexes. An explanation based on the orbital analysis is put forward.