The structures and phase transitions in 4-aminopyridinium tetraaquabis(sulfato)iron(III), (C5H7N2)[FeIII(H2O)4(SO4)2].

The organic-inorganic hybrid compound 4-aminopyridinium tetraaquabis(sulfato)iron(III), (C5H7N2)[FeIII(H2O)4(SO4)2] (4apFeS), was obtained by slow evaporation of the solvent at room temperature and characterized by single-crystal X-ray diffraction in the temperature range from 290 to 80 K. Differential scanning calorimetry revealed that the title compound undergoes a sequence of three reversible phase transitions, which has been verified by variable-temperature X-ray diffraction analysis during cooling-heating cycles over the temperature ranges 290-100-290 K. In the room-temperature phase (I), space group C2/c, oxygen atoms from the closest Fe-atom environment (octahedral) were disordered over two equivalent positions around a twofold axis. Two intermediate phases (II), (III) were solved and refined as incommensurately modulated structures, employing the superspace formalism applied to single-crystal X-ray diffraction data. Both structures can be described in the (3+1)-dimensional monoclinic X2/c(α,0,γ)0s superspace group (where X is ½, ½, 0, ½) with modulation wavevectors q = (0.2943, 0, 0.5640) and q = (0.3366, 0, 0.5544) for phases (II) and (III), respectively. The completely ordered low-temperature phase (IV) was refined with the twinning model in the triclinic P{\overline 1} space group, revealing the existence of two domains. The dynamics of the disordered anionic substructure in the 4apFeS crystal seems to play an essential role in the phase transition mechanisms. The discrete organic moieties were found to be fully ordered even at room temperature.

Synthesis and characterization of four organic-inorganic salts: sulfates of 2-aminopyridinium derivatives.

Hybrid materials, fabricated by the combination of inorganic and organic components, have potential applications in chemistry and are endowed with the advantages of both building elements. There are several types of intermolecular interactions present in these hybrid compounds, including electrostatic forces, π-π stacking and hydrogen-bonding interactions, the latter playing an important role in the construction of three-dimensional architectures and stabilizing supramolecular crystal structures. Analysis of the intermolecular interactions and their influence on packing modes therefore requires focused scientific attention. Four new organic-inorganic salts, namely 2-amino-4-methyl-3-nitropyridinium hydrogen sulfate, C6H8N3O2+·HSO4-, bis(2-amino-4-methyl-3-nitropyridinium) sulfate, 2C6H8N3O2+·SO42-, 2-amino-3-methylpyridinium hydrogen sulfate, C6H9N2+·HSO4-, and bis(2-amino-3-methylpyridinium) sulfate monohydrate, 2C6H9N2+·SO42-·H2O, have been synthesized and characterized by X-ray diffraction. The crystal structures are stabilized by intra- and intermolecular hydrogen bonds, as well as by weak π-π stacking and lp-π (lp is lone pair) interactions. Hirshfeld surface analysis was employed in order to study intermolecular interactions.

Synthesis, structure and characterization of five new organically templated metal sulfates with 2-aminopyridinium.

The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic-inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur-oxygen-metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid-state materials. A series of novel organically templated metal sulfates of 2-aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single-crystal X-ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2-aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C5H7N2)[Al(H2O)6](SO4)2·4H2O, (I); type 2 for bis(2-aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Co(H2O)6]3(SO4)4·2H2O, (II), and bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Mg(H2O)6]3(SO4)4·2H2O, (III); and type 3 for bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate), (C5H7N2)2[Ni(H2O)6](SO4)2, (IV), and bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate), (C5H7N2)2[Zn(H2O)6](SO4)2, (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge-assisted hydrogen-bonded pairs with sulfate anions and the presence of π-π interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen-bond formation. As a consequence, extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures.

Physical and Structural Characterization of Imidazolium-Based Organic-Inorganic Hybrid: (C3N2H5)2[CoCl4].

(C3N2H5)2[CoCl4] (ICC) was characterized in a wide temperature range by the single-crystal X-ray diffraction method. Differential scanning calorimetry revealed two structural phase transitions: continuous at 245.5 K (from phase I to II) and a discontinuous one at 234/237 K (cooling/heating) (II → III). ICC adopts monoclinic space groups C2/c and P21/c in phase (I) and (III), respectively. The intermediate phase (II) appears to be incommensurately modulated. Dynamic properties of polycrystalline ICC were studied by means of dielectric spectroscopy and proton magnetic resonance ((1)H NMR). The presence of a low frequency dielectric relaxation process in phase III reflects libration motion of the imidazolium cations. The temperature dependence of the (1)H spin-lattice relaxation time indicated two motional processes with similar activation energies that are by about an order of magnitude smaller than the activation energy obtained from dielectric studies. There are no abrupt changes in the (1)H relaxation time at the phase transitions indicating that the dynamics of the imidazolium rings gradually varies with temperature; that is, it does not change suddenly at the phase transition. Negative values of the Weiss constant and the intermolecular exchange parameter were obtained, confirming the presence of a weak antiferromagnetic interaction between the nearest cobalt centers. Moreover, the magnitude of zero field splitting was determined. The AC susceptibility measurements show that a slow magnetic relaxation is induced by small external magnetic field.

Crystal structure of an organic-inorganic hybrid compound based on morpholinium cations and a ß-type Anderson polyanion.

A new organic-inorganic hybrid compound, penta-morpholinium hexa-hydrogen hexa-molybdoferrate(III) sulfate 3.5-hydrate, (C4H10NO)5[Fe(III)(OH)6Mo6O18](SO4)·3.5H2O, was obtained from an aqueous solution. The polyoxidomolybdate (POM) anion is of the Anderson ß-type with a central Fe(III) ion. Three of five crystallographically independent morpholinium cations are disordered over two sets of sites. An intricate network of inter-molecular N-H⋯O and O-H⋯O inter-actions between cations, POMs, sulfate anions and non-coordinating water mol-ecules creates a three-dimensional network structure.

Crystal structure of new organically templated copper sulfate with 2-amino-pyridinium.

The title compound, (C5H7N2)2[Cu(H2O)6](SO4)2·4H2O [systematic name: bis(2-aminopyridinium) hexaaquacopper(II) bis(sulfate) tetrahydrate], comprises axially elongated hexa-aqua-coordinated octa-hedral Cu(II) ions located on an inversion centre, non-coordinating sulfate anions, 2-amino-pyridinium cations and lattice water mol-ecules. The crystal structure is built of successive inorganic and organic layers extending parallel to (001) that are connected by an extensive three-dimensional hydrogen-bonded network of the type O-H⋯O and N-H⋯O, as well as π-π inter-actions [centroid-centroid distance 3.4140 (14) Å, offset 0.277 Å].

Synthesis and characterization of [(CH3)2NH2][Na0.5Cr0.5(HCOO)3]: a rare example of luminescent metal-organic frameworks based on Cr(III) ions.

A novel formate [(CH3)2NH2][Na0.5Cr0.5(HCOO)3] (DMNaCr) was prepared by a solvothermal method. This compound crystallizes in the perovskite-type metal formate framework (space group R3[combining macron]) with disordered dimethylammonium (DMA(+)) cations. X-ray diffraction, DSC, Raman and IR studies show that in contrast to the isostructural iron analogue [(CH3)2NH2][Na0.5Fe0.5(HCOO)3] (DMNaFe), DMNaCr does not exhibit any structural phase transition at low temperatures. This behavior has been attributed to the smaller flexibility of the perovskite-like framework in DMNaCr when compared with that of DMNaFe. Dielectric permittivity data reveal pronounced dielectric relaxation that is attributed to the dynamical rotation of DMA(+) ions. Electron absorption and photoluminescence studies show that this material exhibits efficient emission at low temperatures. A detailed analysis of the optical properties shows that chromium ions are located at the site of intermediate crystal field strength with Dq/B = 2.29.

Crystal structure of tris-(piperidinium) hydrogen sulfate sulfate.

In the title molecular salt, 3C5H12N(+)·HSO4 (-)·SO4 (2-), each cation adopts a chair conformation. In the crystal, the hydrogen sulfate ion is connected to the sulfate ion by a strong O-H⋯O hydrogen bond. The packing also features a number of N-H⋯O hydrogen bonds, which lead to a three-dimensional network structure. The hydrogen sulfate anion accepts four hydrogen bonds from two cations, whereas the sulfate ion, as an acceptor, binds to five separate piperidinium cations, forming seven hydrogen bonds.

Synthesis and order-disorder transition in a novel metal formate framework of [(CH3)2NH2]Na(0.5)Fe(0.5)(HCOO)3].

We report the synthesis, crystal structure, thermal, dielectric, Raman, infrared, and magnetic properties of [(CH3)2NH2][Na(0.5)Fe(0.5)(HCOO)3] (DMNaFe), the first metal formate framework templated by organic cations, presenting an ABO3 perovskite architecture with NaO6 octahedra as building blocks of the framework. On the basis of Raman and IR data, assignment of the observed modes to respective vibrations of atoms is proposed. We have found that DMNaFe undergoes a structural phase transition at 167 K on cooling. According to the X-ray diffraction, the compound shows R3[combining macron] symmetry at 293 K and triclinic P1[combining macron] symmetry at 110 K. The DMA(+) cations are dynamically disordered in the high-temperature phase and the phase transition is associated with ordering of the DMA(+) cations and distortion of the metal formate framework. The dielectric studies reveal pronounced dielectric dispersion that can be attributed to slow dynamics of the DMA(+) cations. Based on the low-temperature magnetic studies, this compound is a weak ferromagnet with a critical temperature 8.5 K.

Structure, phonon properties, and order-disorder transition in the metal formate framework of [NH4][Mg(HCOO)3].

We report the synthesis, crystal structure, thermal, dielectric, IR, and Raman studies of [NH4][Mg(HCOO)3] formate. Single-crystal X-ray diffraction shows that it crystallizes in the hexagonal space group P6322, with orientationally disordered NH4(+) ions located in the cages of the network. Upon cooling, [NH4][Mg(HCOO)3] undergoes a phase transition at around 255 K to the ferroelectric P63 structure. Raman and IR spectra show a strong increase in intensity of the N-H stretching bands as well as narrowing of the bands related to the NH4(+) ions upon cooling. These changes indicate that the phase transition is due to orientational ordering of the NH4(+) ions. Analysis of the Raman data show, however, that the rotational and translational motions of NH4(+) do not freeze completely at the phase transition but exhibit further slowing down below 255 K, and the motional freezing becomes nearly complete below 140 K.

Investigation of structure-properties relationship in a novel family of halogenoantimonates(III) and halogenobismuthates(III) with morpholinium cation: [NH2(C2H4)2O]MX4. Crystal structure, phase transitions and dynamics of molecules.

Three new organic-inorganic hybrids based on halogenoantimonates(III) and halogenobismuthates(III) with the morpholinium cation, [NH2(C2H4)2O]SbCl4, [NH2(C2H4)2O]SbBr4 and [NH2(C2H4)2O]BiBr4, have been prepared and characterized with DSC, TGA, DTA and single-crystal X-ray diffraction. The common feature of the crystal structures of the studied compounds is the presence of polyanionic ([MX4]∞(-)) and morpholinium (head-to-tail configuration) chains, which expand themselves parallel to each other. The antimonate derivatives are isomorphous, crystallizing in a centrosymmetric orthorhombic Pbca space group and show no phase transitions (PTs) between 110 and 370 K. On the other hand, [NH2(C2H4)2O]BiBr4 undergoes two first-order structural PTs: I ↔ II at 321/343 K (cooling/heating) and II ↔ III at 285/289 K (cooling/heating). The mechanism of the PTs is discussed on the basis of crystallographic data and (1)H NMR and infrared spectroscopy. The PT at 343 K is accompanied by a spectacular switching of the spin-lattice T1 relaxation pathway. Structural parameters analysis has been performed to discuss a structure-properties relationship.

Dielectric response and specific heat studies of Cd2Nb2O7 ceramics obtained from mechano-synthesized nanopowders.

Cd(2)Nb(2)O(7) is still an interesting ferroelectric material because of its high permittivity value at helium temperatures and a variety of dielectric relaxation processes, the origin of which is still puzzling. We prepared hot-pressed ceramics, with grain sizes from 100 to 150 nm, obtained from Cd(2)Nb(2)O(7) nanopowders synthesized by high-energy milling of CdO and Nb(2)O(5) and studied their dielectric response and thermal properties. The nanoceramics were characterized by X-ray diffraction and their dielectric properties were measured at temperatures from 4K to 575K. Dielectric response of the nanoceramics was found to consist of a huge anomaly at ~150K with complex dielectric absorption and three relaxation processes apparent in frequency and temperature dependences of the imaginary part of permittivity in the temperature range from 18K to 145K. The anomaly at ~150K is related to overlapping contributions from the Curie point (shifted downward because of the size effect) and a dielectric relaxation process. The behavior of three relaxation modes observed at temperatures below 145K is discussed, based on the model proposed by Malcherek of polar nanoregions in the orthorhombic phase of Cd(2)Nb(2)O(7) and the theory of dielectric response of ferroelectric relaxors by Bokov and Ye.

Anomalous thermal expansion of an organic crystal--implications for elucidating the mechanism of an enantiotropic phase transformation.

Two enantiotropic polymorphs of a dumbbell shaped molecule possess similar packing arrangements, in principle, but one of the polymorphs shows anomalously anisotropic thermal expansion while the other does not.

From six- to five-coordinated Sb(III) in [(CH3)3PH]3[Sb2Cl9]: transition pathways from single-crystal X-ray diffraction.

[(CH(3))(3)PH](3)[Sb(2)Cl(9)] experiences four phase transitions which were found by means of calorimetry, thermogravimetry and X-ray diffraction. The crystal structure was solved in the space group P6(3)/mmc at 382 K (phase I), Pnam at 295 K (phase II) and Pna2(1) at 175 K (phase V). We observed an unusual increase in symmetry from the monoclinic to the orthorhombic form at the IV --> V transition. The parent hexagonal high-temperature phase I consists of highly disordered [(CH(3))(3)PH](+) cations and [Sb(2)Cl(9)](3-) anions with an octahedral environment of Sb(III). The transition from phases I to II is associated with the ordering of [(CH(3))(3)PH](+) cations. Moreover, the successive transformations from phases I to V are related to the change in the arrangement of Cl atoms in [Sb(2)Cl(9)](3-) anions from the discrete 'face-sharing bioctahedra' (phase I) to two corner-sharing square pyramids. A mechanism for the phase transitions is proposed. It is observed that weak C-H...Cl interactions are responsible for the structure arrangement in low-temperature phases.

Dynamic behavior of the Jahn-Teller distorted Cu(H(2)O)(6)(2+) ion in Cu(2+) doped Cs(2)[Zn(H(2)O)(6)](ZrF(6))(2) and the crystal structure of the host lattice.

The temperature dependence of the X- and Q-band EPR spectra of Cs(2)[Zn(H(2)O)(6)](ZrF(6))(2) containing approximately 1% Cu(2+) is reported. All three molecular g-values vary with temperature, and their behavior is interpreted using a model in which the potential surface of the Jahn-Teller distorted Cu(H(2)O)(6)(2+) ion is perturbed by an orthorhombic "strain" induced by interactions with the surrounding lattice. The strain parameters are significantly smaller than those reported previously for the Cu(H(2)O)(6)(2+) ion in similar lattices. The temperature dependence of the two higher g-values suggests that in the present compound the lattice interactions change slightly with temperature. The crystal structure of the Cs(2)[Zn(H(2)O)(6)](ZrF(6))(2) host is reported, and the geometry of the Zn(H(2)O)(6)(2+) ion is correlated with lattice strain parameters derived from the EPR spectrum of the guest Cu(2+) complex.