Twinned tetragonal structure and equation of state of NaTh2F9

The crystal structure and stability of NaTh₂F₉ have been studied using thermal analysis, powder X-ray diffraction at atmospheric conditions, and single-crystal X-ray diffraction at high pressure. Sodium dithorium fluoride is stable at least up to 5.0 GPa at room temperature and to 954 K at ambient pressure. In contrast to earlier investigations, which have reported the structure to be cubic (, Z=4), we observe a tetragonal distortion of the lattice. The actual crystal structure (, Z=4) is twinned and composed of corner-sharing distorted ThF₉ tricapped trigonal prisms and distorted NaF₆ octahedra. The twinning element is a three-fold axis from cubic symmetry. The ThF₉ polyhedra are rigid and it is the volume changes of the octahedra around the Na atoms that have the major contribution to the bulk compressibility. The zero-pressure bulk modulus B₀ and the unit-cell volume at ambient pressure V₀ are equal to 99(6) GPa and 663.1(1.0) Å³, respectively, with the fixed first pressure derivative of the bulk modulus B′=4.00. An inspection of the known crystalline phases in the system NaF-ThF₄ reveals that their bulk moduli increase with the increasing ThF₄ content.     

The structural investigation of Ba4Bi3F17

The anion-excess ordered fluorite-related phase Ba₄Bi₃F₁₇ has been synthesized by a solid state reaction of BaF₂ and BiF₃ at 873 K. The crystal structure of Ba₄Bi₃F₁₇ has been studied using electron diffraction and X-ray powder diffraction (a=11.2300(2) Å, c=20.7766(5) Å, S.G. , R_I=0.020, R_P=0.036). Interstitial fluorine atoms in the Ba₄Bi₃F₁₇ structure are considered to form isolated cuboctahedral 8 : 12 : 1 clusters. The structural relationship between Ba₄Bi₃F₁₇ and similar rare-earth-based phases is discussed.     

Synthesis and crystal structure of new uranyl tungstates M2(UO2)(W2O8) (M=Na, K), M2(UO2)2(WO5)O (M=K, Rb), and Na10(UO2)8(W5O20)O8

The solid-state reactions of UO₃ and WO₃ with M₂CO₃ (M=Na, K, Rb) at 650°C for 5 days result, accordingly the starting stoichiometry, in the formation of M₂(UO₂)(W₂O₈) (M=Na (1), K (2)), M₂(UO₂)₂(WO₅)O (M=K (3), Rb (4)), and Na₁₀(UO₂)₈(W₅O₂₀)O₈ (5). The crystal structures of compounds 2, 3, 4, and 5 have been determined by single-crystal X-ray diffraction using Mo(Kα) radiation and a charge-coupled device detector. The crystal structures were solved by direct methods and Fourier difference techniques, and refined by a least-squares method on the basis of F² for all unique reflections. For (1), unit-cell parameters were determined from powder X-ray diffraction data. Crystallographic data: 1, monoclinic, a=12.736(4) Å, b=7.531(3) Å, c=8.493(3) Å, β=93.96(2)°, ρ_cal=6.62(2) g/cm³, ρ_mes=6.64(1) g/cm³, Z=4; 2, orthorhombic, space group Pmcn, a=7.5884(16) Å, b=8.6157(18) Å, c=13.946(3) Å, ρ_cal=6.15(2) g/cm³, ρ_mes=6.22(1) g/cm³, Z=8, R1=0.029 for 80 parameters with 1069 independent reflections; 3, monoclinic, space group P2₁/n, a=8.083(4) Å, b=28.724(5) Å, c=9.012(4) Å, β=102.14(1)°, ρ_cal=5.83(2) g/cm³, ρ_mes=5.90(2) g/cm³, Z=8, R1=0.037 for 171 parameters with 1471 reflections; 4, monoclinic, space group P2₁/n, a=8.234(1) Å, b=28.740(3) Å, c=9.378(1) Å, β=104.59(1)°, ρ_cal=6.13(2) g/cm³,  g/cm³, Z=8, R1=0.037 for 171 parameters with 1452 reflections; 5, monoclinic, space group C2/c, a=24.359(5) Å, b=23.506(5) Å, c=6.8068(14) Å, β=94.85(3)°, ρ_cal=6.42(2) g/cm³,  g/cm³, Z=8, R1=0.036 for 306 parameters with 5190 independent reflections. The crystal structure of 2 contains linear one-dimensional chains formed from edge-sharing UO₇ pentagonal bipyramids connected by two octahedra wide (W₂O₈) ribbons formed from two edge-sharing WO₆ octahedra connected together by corners. This arrangement leads to [UW₂O₁₀]²⁻ corrugated layers parallel to (001). Owing to the unit-cell parameters, compound 1 probably contains similar sheets parallel to (100). Compounds 3 and 4 are isostructural and the structure consists of bi-dimensional networks built from the edge- and corner-sharing UO₇ pentagonal bipyramids. This arrangement creates square sites occupied by W atoms, a fifth oxygen atom completes the coordination of W atoms to form WO₅ distorted square pyramids. The interspaces between the resulting [U₂WO₁₀]²⁻ layers parallel to plane are occupied by K or Rb atoms. The crystal structure of compound 5 is particularly original. It is based upon layers formed from UO₇ pentagonal bipyramids and two edge-shared octahedra units, W₂O₁₀, by the sharing of edges and corners. Two successive layers stacked along the [100] direction are pillared by WO₄ tetrahedra resulting in sheets of double layers. The sheets are separated by Na⁺ ions. The other Na⁺ ions occupy the rectangular tunnels created within the sheets. In fact complex anions W₅O₂₀¹⁰⁻ are built by the sharing of the four corners of a WO₄ tetrahedron with two W₂O₁₀ dimmers, so, the formula of compound 5 can be written Na₁₀(UO₂)₈(W₅O₂₀)O₈.     

Two new octahedral/pyramidal frameworks containing both cation channels and lone-pair channels: syntheses and structures of Ba2MnMn2(SeO3)6 and PbFe2(SeO3)4

The hydrothermal syntheses, single crystal structures, and some properties of Ba₂Mn^IIMn₂^III(SeO₃)₆ and PbFe₂(SeO₃)₄ are reported. These related phases contain three-dimensional frameworks of vertex (FeO₆) and vertex/edge linked (MnO₆) octahedra and SeO₃ pyramids. In each case, the MO₆/SeO₃ framework encloses two types of 8 ring channels, one of which encapsulates the extra-framework cations and one of which provides space for the Se^IV lone pairs. Crystal data: Ba₂Mn₃(SeO₃)₆, M_r=1201.22, monoclinic, P2₁/c (No. 14), a=5.4717 (3) Å, b=9.0636 (4) Å, c=17.6586 (9) Å, β=94.519 (1)°, V=873.03 (8) Å³, Z=2, R(F)=0.031, wR(F²)=0.070; PbFe₂(SeO₃)₄, M_r=826.73, triclinic, (No. 2), a=5.2318 (5) Å, b=6.7925 (6) Å, c=7.6445 (7) Å, α=94.300 (2)°, β=90.613 (2)°, γ=95.224 (2)°, V=269.73 (4) Å³, Z=1, R(F)=0.051, wR(F²)=0.131.     

The iron potassium diarsenate KFeAs2O7 structural, electric and magnetic behaviors

Crystals of a new potassium iron (III) diarsenate (KFeAs₂O₇) have been grown and characterized by single crystal X-ray diffraction. It crystallizes in the triclinic space group , with a=7.662(1) Å, b=8.402(2) Å, c=10.100(3) Å, α=90.42(3)°, β=89.74(2)°, γ=106.39(2)°, V=623.8(3) Å³ and Z=4. The final agreement factors are R=0.0342, wR=0.0889, S(F²)=1.01; the structural model is validated by bond valence sum (BVS) and charge distribution (CD) methods. The structure consists of corner-sharing FeO₆ octahedra and As₂O₇ diarsenate groups, the three-dimensional framework delimits tunnels running along [0 1 0] direction where the potassium ions reside. The crystal structure of the title compound is different from that of the monoclinic KAlP₂O₇ type but structural relationships exist between the frameworks. Impedance measurements (frequency/temperature ranges: 5-13,000 Hz/526-668 K) show KFeAs₂O₇ an ionic conductor being the conductivity 2.76×10⁻⁷ S cm⁻¹ at 568 K and E_a is 0.47 eV. The BVS model suggests that the most probable potassium conduction pathway is along b-direction. Magnetic measurements reveal the Curie—Weiss type paramagnetic behavior over the range 30-300 K and ferromagnetic below 29.3 K.     

Synthesis, X-ray crystal structure and vibrational spectroscopy of the acidic pyrophosphate KMg0.5H2P2O7·H2O

The hydrated potassium hemimagnesium dihydrogen pyrophosphate KMg_0.5H₂P₂O₇·H₂O was synthesized. It crystallizes in the triclinic system, space group (n. 2), Z=2, with the following unit-cell parameters: a=6.8565(2) Å, b=7.3621(3) Å, c=7.6202(3) Å, α=81.044(2)°, β=72.248(2)°, γ=83.314(3)°, V=360.90(2) Å³. The structure was obtained by single-crystal X-ray diffractometry, and a full-matrix least-squares refinement based on F² gave a final R index of =0.0368 (wR=0.0975), utilizing 1446 observed reflections with I>2σ(I). The crystal packing consists in a three-dimensional network made by layers parallel to ab plane of PO₄ double tetrahedra and MgO₆ octahedra, linked by hydrogen bonds, while K atoms form complex coordination within cavities between tetrahedra and octahedra. The dihydro-pyrophosphate anion (H₂P₂O₇)²⁻ shows bent eclipsed conformation and the Mg²⁺ ion lies on inversion center. No coincidences observed between most of infrared and Raman spectral bands confirmed the centrosymmetric structure of the title compound; the vibrational spectra point to a bent POP bridge angle.     

Synthesis and properties of pyrazine-pillared Ag3Mo2O4F7 and AgReO4 layered phases

The new pyrazine-pillared solids, AgReO₄(C₄H₄N₂) (I) and Ag₃Mo₂O₄F₇(C₄H₄N₂)₃ (C₄H₄N₂=pyrazine, pyz) (II), were synthesized by hydrothermal methods at 150 °C and characterized using single crystal X-ray diffraction (I—P2₁/c, No. 14, Z=4, a=7.2238(6) Å, b=7.4940(7) Å, c=15.451(1) Å, β=92.296(4)°; II—P2/n, No. 13, Z=2, a=7.6465(9) Å, b=7.1888(5) Å, c=19.142(2) Å, β=100.284(8)°), thermogravimetric analysis, UV-Vis diffuse reflectance, and photoluminescence measurements. Individual Ag(pyz) chains in I are bonded to three perrhenate ReO₄^- tetrahedra per layer, while each layer in II contains sets of three edge-shared Ag(pyz) chains (π-π stacked) that are edge-shared to four Mo₂O₄F₇^3- dimers. A relatively small interlayer spacing results from the short length of the pyrazine pillars, and which can be removed at just slightly above their preparation temperature, at >150-175 °C, to produce crystalline AgReO₄ for I, and Ag₂MoO₄ and an unidentified product for II. Both pillared solids exhibit strong orange-yellow photoemission, at 575 nm for I and 560 nm for II, arising from electronic excitations across (charge transfer) band gaps of 2.91 and 2.76 eV in each, respectively. Their structures and properties are analyzed with respect to parent ‘organic free’ silver perrhenate and molybdate solids which manifest similar photoemissions, as well as to the calculated electronic band structures.     

Syntheses, crystal structures and Raman spectra of Ba(BF4)(PF6), Ba(BF4)(AsF6) and Ba2(BF4)2(AsF6)(H3F4); the first examples of metal salts containing simultaneously tetrahedral BF4 and octahedral AF6 anions

In the system BaF₂/BF₃/PF₅/anhydrous hydrogen fluoride (aHF) a compound Ba(BF₄)(PF₆) was isolated and characterized by Raman spectroscopy and X-ray diffraction on the single crystal. Ba(BF₄)(PF₆) crystallizes in a hexagonal space group with a=10.2251(4) Å, c=6.1535(4) Å, V=557.17(5) Å³ at 200 K, and Z=3. Both crystallographically independent Ba atoms possess coordination polyhedra in the shape of tri-capped trigonal prisms, which include F atoms from BF₄⁻ and PF₆⁻ anions. In the analogous system with AsF₅ instead of PF₅ the compound Ba(BF₄)(AsF₆) was isolated and characterized. It crystallizes in an orthorhombic Pnma space group with a=10.415(2) Å, b=6.325(3) Å, c=11.8297(17) Å, V=779.3(4) Å³ at 200 K, and Z=4. The coordination around Ba atom is in the shape of slightly distorted tri-capped trigonal prism which includes five F atoms from AsF₆⁻ and four F atoms from BF₄⁻ anions. When the system BaF₂/BF₃/AsF₅/aHF is made basic with an extra addition of BaF₂, the compound Ba₂(BF₄)₂(AsF₆)(H₃F₄) was obtained. It crystallizes in a hexagonal P6₃/mmc space group with a=6.8709(9) Å, c=17.327(8) Å, V=708.4(4) Å³ at 200 K, and Z=2. The barium environment in the shape of tetra-capped distorted trigonal prism involves 10 F atoms from four BF₄⁻, three AsF₆⁻ and three H₃F₄⁻ anions. All F atoms, except the central atom in H₃F₄ moiety, act as μ₂-bridges yielding a complex 3-D structural network.     

Alignment of acentric MoO3F3 anions in a polar material: (Ag3MoO3F3)(Ag3MoO4)Cl

(Ag₃MoO₃F₃)(Ag₃MoO₄)Cl was synthesized by hydro(solvato)thermal methods and characterized by single-crystal X-ray diffraction (P3m1, No. 156, Z=1, a=7.4488(6)Å, c=5.9190(7) Å). The transparent colorless crystals are comprised of chains of distorted fac-MoO₃F₃³⁻ octahedra and MoO₄²⁻ tetrahedra anions, as suggested by the formulas Ag₃MoO₃F₃ and Ag₃MoO₄⁺, and are connected through Ag⁺ cations in a polar alignment along the c-axis. One Cl⁻ anion per formula unit serves as a charge balance and connects the two types of chains in a staggered fashion, offset by . In MoO₄²⁻, the Mo atom displaces towards a single oxide vertex, and in MoO₃F₃³⁻, the Mo displaces towards the three oxide ligands. The ordered oxide-fluoride ligands on the MoO₃F₃³⁻ anion is important to prevent local inversion centers, while the polar organization is directed by the Cl⁻ anion and interchain dipole-dipole interactions. The dipole moments of MoO₃F₃³⁻ and MoO₄²⁻ align in the negative c-axis direction, to give a polar structure with no cancellation of the individual moments. The direction and magnitude of the dipole moments for MoO₃F₃³⁻ and MoO₄²⁻ were calculated from bond valence analyses and are 6.1 and 1.9 debye (10⁻¹⁸ esu cm) respectively, compared to 4.4 debye for polar NbO₆ octahedra in LiNbO₃, and 4.5 debye for polar TiO₆ octahedra in KTiOPO₄ (KTP).     

New one-dimensional uranyl and neptunyl iodates: crystal structures of K3[(UO2)2(IO3)6](IO3)·H2O and K[NpO2(IO3)3]·1.5H2O

The uranyl and neptunyl(VI) iodates, K₃[(UO₂)₂(IO₃)₆](IO₃)·H₂O (1) and K[NpO₂(IO₃)₃]·1.5H₂O (2), have been prepared and crystallized under mild hydrothermal conditions. The structures of 1 and 2 both contain one-dimensional _∞¹[AnO₂(IO₃)₃]¹⁻(An=U,Np) ribbons that consist of approximately linear actinyl(VI) cations bound by iodate anions to yield AnO₇ pentagonal bipyramids. The AnO₇ units are linked by bridging iodate anions to yield chains that are in turn coupled by additional iodate anions to yield ribbons. The edges of the ribbons are terminated by monodentate iodate anions. For 1 and 2, K⁺ cations and water molecules separate the ribbons from one another. In addition, isolated iodate anions are also found between _∞¹[UO₂(IO₃)₃]¹⁻ ribbons in 1. In order to aid in the assignment of oxidation states in neptunyl containing compounds, a bond-valence sum parameter of 2.018 Å for Np(VI) bound exclusively to oxygen has been developed with b=0.37 Å. Crystallographic data (193 K, MoKα, λ=0.71073): 1, triclinic, , a=7.0609(4) Å, b=14.5686(8)  Å, c=14.7047(8)  Å, α=119.547(1)°, β=95.256(1)°, γ=93.206(1)°, Z=2, R(F)=2.49% for 353 parameters with 6414 reflections with I>2σ(I); (203 K, MoKα, λ=0.71073): 2, monoclinic, P2₁/c, a=7.796(4)  Å, b=7.151(3)  Å, c=21.79(1)  Å, β=97.399(7)°, Z=4, R(F)=6.33% for 183 parameters with 2451 reflections with I>2σ(I).     

Jahn-Teller-distorted dimeric anions in (cat)[Mn2F8(H2O)2]·2H2O (cat = pipzH2, dabcoH2) and (dabcoH2)2[Mn2F8(H2PO4)2]

Using biprotonated dabco (1,4-diazabicyclo[2.2.2]octane) or pipz (piperazine) as counter cations, mixed-ligand fluoromanganates(III) with dimeric anions could be prepared from hydrofluoric acid solutions. The crystal structures were determined by X-ray diffraction on single crystals: dabcoH₂[Mn₂F₈(H₂O)₂]·2H₂O (1), space group P2₁, Z = 2, a = 6.944(1), b = 14.689(3), c = 7.307(1) Å, β = 93.75(3)°, R₁ = 0.0240; pipzH₂[Mn₂F₈(H₂O)₂]·2H₂O (2), space group , Z = 2, a = 6.977(1), b = 8.760(2), c = 12.584(3) Å, α = 83.79(3), β = 74.25(3), γ = 71.20(3)°, R₁ = 0.0451; (dabcoH₂)₂[Mn₂F₈(H₂PO₄)₂] (3), space group P2₁/n, Z = 4, a = 9.3447(4), b = 12.5208(4), c = 9.7591(6) Å, β = 94.392(8)°, R₁ = 0.0280. All three compounds show dimeric anions formed by [MnF₅O] octahedra (O from oxo ligands) sharing a common edge, with strongly asymmetric double fluorine bridges. In contrast to analogous dimeric anions of Al or Fe(III), the oxo ligands (H₂O (1,2) or phosphate (3)) are in equatorial trans-positions within the bridging plane. The strong pseudo-Jahn-Teller effect of octahedral Mn(III) complexes is documented in a huge elongation of an octahedral axis, namely that including the long bridging Mn-F bond and the Mn-O bond. In spite of different charge of the anion in the fluoride phosphate, the octahedral geometry is almost the same as in the aqua-fluoro compounds. The strong distortion is reflected also in the ligand field spectra.     

Subsolidus phase equilibria and properties in the system Bi2O3:Mn2O3±x:Nb2O5

Subsolidus phase relations have been determined for the Bi-Mn-Nb-O system in air (750-900 °C). Phases containing Mn²⁺, Mn³⁺, and Mn⁴⁺ were all observed. Ternary compound formation was limited to pyrochlore (A₂B₂O₆O′), which formed a substantial solid solution region at Bi-deficient stoichiometries (relative to Bi₂(Mn,Nb)₂O₇) suggesting that ≈14-30% of the A-sites are occupied by Mn (likely Mn²⁺). X-ray powder diffraction data confirmed that all Bi-Mn-Nb-O pyrochlores form with structural displacements, as found for the analogous pyrochlores with Mn replaced by Zn, Fe, or Co. A structural refinement of the pyrochlore 0.4000:0.3000:0.3000 Bi₂O₃:Mn₂O_3±x:Nb₂O₅ using neutron powder diffraction data is reported with the A and O′ atoms displaced (0.36 and 0.33 Å, respectively) from ideal positions to 96g sites, and with Mn²⁺ on A-sites and Mn³⁺ on B-sites (Bi_1.6Mn²⁺_0.4(Mn³⁺_0.8Nb_1.2)O₇, (?227), a=10.478(1) Å); evidence of A or O′ vacancies was not found. The displacive disorder is crystallographically analogous to that reported for Bi_1.5Zn_0.92Nb_1.5O_6.92, which has a similar concentration of small B-type ions on the A-sites. EELS spectra for this pyrochlore were consistent with an Mn oxidation between 2+ and 3+. Bi-Mn-Nb-O pyrochlores exhibited overall paramagnetic behavior with negative Curie-Weiss temperature intercepts, slight superparamagnetic effects, and depressed observed moments compared to high-spin, spin-only values. At 300 K and 1 MHz the relative dielectric permittivity of Bi_1.600Mn_1.200Nb_1.200O₇ was ≈128 with tan δ=0.05; however, at lower frequencies the sample was conductive which is consistent with the presence of mixed-valent Mn. Low-temperature dielectric relaxation such as that observed for Bi_1.5Zn_0.92Nb_1.5O_6.92 and other bismuth-based pyrochlores was not observed. Bi-Mn-Nb-O pyrochlores were readily obtained as single crystals and also as textured thin films using pulsed laser deposition.     

Crystal chemistry and ion-exchange properties of the layered uranyl iodate K[UO2(IO3)3]

Single crystals of the potassium uranyl iodate, K[UO₂(IO₃)₃] (1), have been grown under mild hydrothermal conditions. The structure of 1 contains two-dimensional sheets extending in the [ab] plane that consist of approximately linear UO₂²⁺ cations bound by iodate anions to yield UO₇ pentagonal bipyramids. There are three crystallographically unique iodate anions, two of which bridge between uranyl cations to create sheets, and one that is monodentate and protrudes in between the layers in cavities. K⁺ cations form long ionic contacts with oxygen atoms from the layers forming an eight-coordinate distorted dodecahedral geometry. These cations join the sheets together. Ion-exchange reactions have been carried out that indicate the selective uptake of Cs⁺ over Na⁺ or K⁺ by 1. Crystallographic data (193 K, MoKα, ): 1, orthorhombic, Pbca, a=11.495(1) Å, b=7.2293(7) Å, c=25.394(2) Å, Z=8, R(F)=1.95% for 146 parameters with 2619 reflections with I>2σ(I).     

Synthesis, crystal structure, and magnetic properties of the manganate La2Ca2MnO6(O2) related to the hexagonal perovskite-type structure

The compound La₂Ca₂MnO₆(O₂) has been synthesized from La₂Ca₂MnO₇ heated at 1123 K under high pressure (4 GPa) with KClO₃ as oxygen source. The crystal structure has been refined from X-ray powder data in the space group. The unit-cell parameters are a=5.6335(2) Å and c=17.4879(8) Å. Perpendicular to the c-axis, the structure is built up by the periodic stacking of two close packed [LaO₃] layers separated by a layer of composition [Ca₂O₂] containing (O₂)²⁻ peroxide ions. This oxide belongs to the family of compounds formulated as [A′₂O_2−δ][A_nB_n−1O_3n] for n=2 and δ=0. It is the first member of the series where the thickness of the perovskite slab corresponds to one [BO₆] (B=Mn) octahedron. The structural relationships with La₂Ca₂MnO₇ are discussed and the magnetic properties show that in both phases manganese is tetravalent.     

Synthesis and structural investigation of the compounds containing HF2 anions: Ca(HF2)2, Ba4F4(HF2)(PF6)3 and Pb2F2(HF2)(PF6)

Three new compounds Ca(HF₂)₂, Ba₄F₄(HF₂)(PF₆)₃ and Pb₂F₂(HF₂)(PF₆) were obtained in the system metal(II) fluoride and anhydrous HF (aHF) acidified with excessive PF₅. The obtained polymeric solids are slightly soluble in aHF and they crystallize out of their aHF solutions. Ca(HF₂)₂ was prepared by simply dissolving CaF₂ in a neutral aHF. It represents the second known compound with homoleptic HF environment of the central atom besides Ba(H₃F₄)₂. The compounds Ba₄F₄(HF₂)(PF₆)₃ and Pb₂F₂(HF₂)(PF₆) represent two additional examples of the formation of a polymeric zigzag ladder or ribbon composed of metal cation and fluoride anion (MF⁺)_n besides PbF(AsF₆), the first isolated compound with such zigzag ladder. The obtained new compounds were characterized by X-ray single crystal diffraction method and partly by Raman spectroscopy. Ba₄F₄(HF₂)(PF₆)₃ crystallizes in a triclinic space group P1¯ with a=4.5870(2) Å, b=8.8327(3) Å, c=11.2489(3) Å, α=67.758(9)°, β=84.722(12), γ=78.283(12)°, V=413.00(3) Å³ at 200 K, Z=1 and R=0.0588. Pb₂F₂(HF₂)(PF₆) at 200 K: space group P1¯, a=4.5722(19) Å, b=4.763(2) Å, c=8.818(4) Å, α=86.967(10)°, β=76.774(10)°, γ=83.230(12)°, V=185.55(14) ų, Z=1 and R=0.0937. Pb₂F₂(HF₂)(PF₆) at 293 K: space group P1¯, a=4.586(2) Å, b=4.781(3) Å, c=8.831(5) Å, α=87.106(13)°, β=76.830(13)°, γ=83.531(11)°, V=187.27(18) Å³, Z=1 and R=0.072. Ca(HF₂)₂ crystallizes in an orthorhombic Fddd space group with a=5.5709(6) Å, b=10.1111(9) Å, c=10.5945(10) Å, V=596.77(10) Å³ at 200 K, Z=8 and R=0.028.     

Combinatorial topology of uranyl molybdate sheets: syntheses and crystal structures of (C6H14N2)3[(UO2)5(MoO4)8](H2O)4 and (C2H10N2)[(UO2)(MoO4)2]

Two new mixed organic-inorganic uranyl molybdates, (C₆H₁₄N₂)₃[(UO₂)₅(MoO₄)₈](H₂O)₄ (1) and (C₂H₁₀N₂)[(UO₂)(MoO₄)₂] (2), have been obtained by hydrothermal methods. The structure of 1 [triclinic, , Z=1, a=11.8557(9), b=11.8702(9), c=12.6746(9) Å, α=96.734(2)°, β=91.107(2)°, γ=110.193(2)°, V=1659.1(2) Å] has been solved by direct methods and refined on the basis of F² for all unique reflections to R1=0.058, which was calculated for the 5642 unique observed reflections (|F_o|?4σ_F). The structure contains topologically novel sheets of uranyl square bipyramids, uranyl pentagonal bipyramids, and MoO₄ tetrahedra, with composition [(UO₂)₅(MoO₄)₈]⁶⁻, that are parallel to (−101). H₂O groups and 1,4-diazabicyclo [2.2.2]-octane (DABCO) molecules are located in the interlayer, where they provide linkage of the sheets. The structure of 2 [triclinic, , Z=2, a=8.4004(4), b=11.2600(5), c=13.1239(6) Å, α=86.112(1)°, β=86.434(1)°, γ=76.544(1)°, V=1203.14(10) Å] has been solved by direct methods and refined on the basis of F² for all unique reflections to R1=0.043, which was calculated for 5491 unique observed reflections (|F_o|?4σ_F). The structure contains topologically novel sheets of uranyl pentagonal bipyramids and MoO₄ tetrahedra, with composition [(UO₂)(MoO₄)₂]²⁻, that are parallel to (110). Ethylenediamine molecules are located in the interlayer, where they provide linkage of the sheets. All known topologies of uranyl molybdate sheets of corner-sharing U and Mo polyhedra can be described by their nodal representations (representations as graphs in which U and Mo polyhedra are given as black and white vertices, respectively). Each topology can be derived from a simple black-and-white graph of six-connected black vertices and three-connected white vertices by deleting some of its segments and white vertices.     

Crystal structure and vibrational spectrum of the NaCaMg2F7 pyrochlore

The crystalline structure of NaCaMg₂F₇ was determined using single crystal X-ray diffraction. This compound crystallizes in the cubic pyrochlore structure, i.e., space group , lattice parameter: and Z=8. All atoms occupy special crystalline sites, but Na and Ca are randomly distributed in the anti-cristobalite sub-lattice of the pyrochlore structure. The vibrational spectrum was determined by polarized Raman scattering and infrared reflectance. The number of observed Raman and infrared active phonons is larger than that predicted by the factor group analysis of the pyrochlore structure. The anomalous vibrational spectrum is discussed in terms of a disorder-induced symmetry lowering mechanism.     

Crystal structure and electronic properties of the new compounds, U6Fe16Si7 and its interstitial carbide U6Fe16Si7C

The new compounds U6Fe16Si7 and U6Fe16Si7C were prepared by arc-melting and subsequent annealing at 1500 °C. Single-crystal X-ray diffraction showed that they crystallize in the cubic space group (No. 225), with unit-cell parameters at room temperature a=11.7206(5) Å for U6Fe16Si7 and a=11.7814(2) Å for U6Fe16Si7C. Their crystal structures correspond to ordered variants of the Th6Mn23 type. U6Fe16Si7 adopts the Mg6Cu16Si7 structure type, whereas U6Fe16Si7C crystallizes with a novel “filled” quaternary variant. The inserted carbon is located in octahedral cages formed by six U atoms, with U-U interatomic distances of 3.509(1) Å. Insertion of carbon in the structure of U6Fe16Si7 has a direct influence on the U-Fe and Fe-Fe interatomic distances. The electronic properties of both compounds were investigated by means of DC susceptibility, electrical resistivity and thermopower. U6Fe16Si7 is a Pauli paramagnet. Its electrical resistivity and thermopower point out that it cannot be classified as a simple metal. The magnetic susceptibility of U₆Fe₁₆Si₇C is best described over the temperature range 100-300 K by using a modified Curie-Weiss law with an effective magnetic moment of 2.3(2) μ_B/U, a paramagnetic Weiss temperature, θ_p=57(2) K and a temperature-independent term χ₀=0.057(1) emu/mol. Both the electrical resistivity and thermopower reveal metallic behavior.     

The mercury chromates Hg6Cr2O9 and Hg6Cr2O10—Preparation and crystal structures, and thermal behaviour of Hg6Cr2O9

The basic mercury(I) chromate(VI), Hg₆Cr₂O₉ (=2Hg₂CrO₄·Hg₂O), has been obtained under hydrothermal conditions (200 °C, 5 days) in the form of orange needles as a by-product from reacting elemental mercury and K₂Cr₂O₇. Hydrothermal treatment of microcrystalline Hg₆Cr₂O₉ in demineralised water at 200 °C for 3 days led to crystal growth of red crystals of the basic mercury(I, II) chromate(VI), Hg₆Cr₂O₁₀ (=2Hg₂CrO₄·2HgO). The crystal structures were solved and refined from single crystal X-ray data sets. Hg₆Cr₂O₉: space group P2₁2₁2₁, Z=4, a=7.3573(12), b=8.0336(13), , 3492 structure factors, 109 parameters, R[F²>2σ(F²)]=0.0371, wR(F² all)=0.0517; Hg₆Cr₂O₁₀: space group Pca2₁, Z=4, a=11.4745(15), b=9.4359(12), , 3249 structure factors, 114 parameters, R[F²>2σ(F²)]=0.0398, wR(F² all)=0.0625. Both crystal structures are made up of an intricate mercury-oxygen network, subdivided into single building blocks [O-Hg-Hg-O] for the mercurous compound, and [O-Hg-Hg-O] and [O-Hg-O] for the mixed-valent compound. Hg₆Cr₂O₉ contains three different Hg₂²⁺ dumbbells, whereas Hg₆Cr₂O₁₀ contains two different Hg₂²⁺ dumbbells and two Hg²⁺ cations. The Hg^I-Hg^I distances are characteristic and range between 2.5031(15) and 2.5286(9) Å. All Hg₂²⁺ groups exhibit an unsymmetrical oxygen environment. The oxygen coordination of the Hg²⁺ cations is nearly linear with two tightly bonded O atoms at distances around 2.07 Å. For both structures, the chromate(VI) anions reside in the vacancies of the Hg-O network and deviate only slightly from the ideal tetrahedral geometry with average Cr-O distances of ca. 1.66 Å. Upon heating at temperatures above 385 °C, Hg₆Cr₂O₉ decomposes in a four-step mechanism with Cr₂O₃ as the end-product at temperatures above 620 °C.     

Disordered pyrochlore CsMgInF6 at high pressures

High pressure behaviour of disordered pyrochlore CsMgInF₆ (Pnma, Z=4) has been studied with powder and single-crystal X-ray diffraction to 8.0 and 6.94 GPa, respectively, in diamond anvil cells at room temperature. The material is structurally stable to at least 8.0 GPa with no ordering of the In³⁺ and Mg²⁺ cations. The P-V data are fitted by a Birch-Murnaghan equation of state with the zero-pressure bulk modulus B₀=33.4(3) GPa and the unit-cell volume at ambient pressure V₀=603.2(4) Å³ for the first pressure derivative of the bulk modulus B′=4.00. The major contribution to the bulk compressibility arises from the changes in the coordination sphere around the Cs atoms. The effect of hydrostatic pressure on the crystal structure of CsMgInF₆ is comparable to the effect of chemical pressure induced by the incorporation of ions of different sizes into the A and B sites in defect AB²⁺B′³⁺F₆ pyrochlores.