Phase formation in the Li2MoO4-A2MoO4-NiMoO4 (A = K, Rb, Cs) systems, the crystal structure of Cs2Ni2(MoO4)3, and color characteristics of alkali-metal nickel molybdates

The subsolidus regions of the Li₂MoO₄-A₂⁺MoO₄-NiMoO₄ (A⁺ = K, Rb, Cs) systems at 510°C have been triangulated by the intersecting-joins method. The A₂MoO₄-Li₂Ni₂(MoO₄)₃, Li₂MoO₄-A₂Ni₂(MoO₄)₃, A₂Ni₂(MoO₄)₃-Li₂Ni₂(MoO₄)₃ (A = K, Rb, Cs), and ALiMoO₄-A₂Ni₂(MoO₄)₃ (A = K, Rb) joins have been investigated. The subsolidus phase formation study has also been completed by spontaneous flux crystallization. No triple salts have been identified, but only compounds belonging to the boundary binary systems. The crystal structure of Cs₂Ni₂(MoO₄)₃ (a = 10.7538 ?, Z = 4, space group P2₁3, R = 0.0082) belonging to the langbeinite type has been determined. It is built of a three-dimensional framework of vertexsharing MoO₄ tetrahedra and NiO₆ octahedra and cesium ions occupying large out-of-framework cavities. All alkali-metal nickel molybdates are yellow. These compounds are usable as pigments, as judged from their reflection spectra and calculated color characteristics, namely, colorfulness (C), lightness (L), and hue (H).     

Subsolidus phase equilibrium in Cs2MoO4-Al2(MoO4)3-Zr(MoO4)2 system and crystal structure of new ternary molybdate Cs(AlZr0.5)(MoO4)3

The subsolidus area of Cs₂MoO₄-Al₂(MoO₄)₃-Zr(MoO₄)₂ system was studied by X-ray powder diffraction. Two new molybdates with component molar ratios of 1: 1: 1 (S₁) and 5:1:2 (S₂) were synthesized for the first time. The crystallographic parameters of the 5:1:2 compound were determined. Solution- melt crystallization and spontaneous nucleation yielded crystals of new 1:1:1 cesium aluminum zirconium molybdate Cs(AlZr_0.5)(MoO₄)₃. Its formula unit and crystal structure were refined by X-ray diffraction (1592 reflections, R=0.0249). Trigonal crystals: a=12.9441(2) ?, c=12.0457(4) ?, V=1747.86(7) ?³, Z = 6, space group R $ \bar 3 $ \bar 3 . The three-dimensional combined framework of this structure is formed by MoO₄ tetrahedrons linked through common vertices to (Al,Zr)O₆ octahedrons. Cesium atoms occupy large cavities of the framework. Crystallographic position M(1) is occupied by randomly distributed Al³⁺ and Zr⁴⁺ cations.     

Phase formation in the systems Ag2MoO4-MO-MoO3 (M=Ca, Sr, Ba, Pb, Cd, Ni, Co, Mn) and crystal structures of Ag2M2(MoO4)3 (M=Co, Mn)

Phase equilibria in the systems Ag₂MoO₄-MMoO₄ (M=Ca, Sr, Ba, Pb, Ni, Co, Mn) and subsolidus phase relations in the systems Ag₂MoO₄-MO-MoO₃ (M=Ca, Pb, Cd, Mn, Co, Ni) were investigated using XRD and thermal analysis. The systems Ag₂MoO₄-MMoO₄ (M=Ca, Sr, Ba, Pb, Ni) belong to the simple eutectic type whereas in the systems Ag₂MoO₄-MMoO₄ (M=Co, Mn) incongruently melting Ag₂M₂(MoO₄)₃ (M=Co, Mn) were formed. In the ternary oxide systems studied no other compounds were found. Low-temperature LT-Ag₂Mn₂(MoO₄)₃ reversibly converts into the high-temperature form of a similar structure at 450-500°C. The single crystals of Ag₂Co₂(MoO₄)₃ and LT-Ag₂Mn₂(MoO₄)₃ were grown and their structures determined (space group , Z=2; lattice parameters are a=6.989(1) Å, b=8.738(2) Å, c=10.295(2) Å, α=107.67(2)°, β=105.28(2)°, γ=103.87(2)° and a=7.093(1) Å, b=8.878(2) Å, c=10.415(2) Å, α=106.86(2)°, β=105.84(2)°, γ=103.77(2)°, respectively) and refined to R(F)=0.0313 and 0.0368, respectively. The both compounds are isotypical to Ag₂Zn₂(MoO₄)₃ and contain mixed frameworks of MoO₄ tetrahedra and pairs of M²⁺O₆ octahedra sharing common edges. The Ag⁺ ions are disordered and located in the voids forming infinite channels running along the a direction. The peculiarities of the silver disorder in the structures of Ag₂M₂(MoO₄)₃ (M=Zn, Mg, Co, Mn) are discussed as well as their relations with analogous sodium-containing compounds of the structural family of Na₂Mg₅(MoO₄)₆. The phase transitions in Ag₂M₂(MoO₄)₃ (M=Mg, Mn) of distortive or order-disorder type are suggested to have superionic character.     

Etude structurale des molybdates doubles: Cs2Mg(MoO4)2, 4H2O et (NH4)2Mg(MoO4)2, 2H2O

Le sel double Cs₂Mg(MoO₄)₂, 4H₂O cristallise dans le syste`me monoclinique, groupe d'espace P2<sub>1/c</sub> avecZ = 2. La structure ae´te´re´soluea`l'aide d'une synthe`se de Patterson et de sommations de Fourier tridimensionnelles. La valeur finale du facteur de reliabilite´estR = 0.068. L'environnement octae´drique du magne´sium est assure´par quarte mole´cules d'eau et deux atomes d'oxyge`ne de groupements molybdates. Dans le cas du sel (NH₄)₂Mg(MoO₄)₂, 2H₂O qui cristallisee´galement dans le syste`me monoclinique, groupe d'espace P2<sub>1/c</sub> avec Z = 2, l'environnement du magne´sium est assure´par deux mole´cules d'eau et quatre atomes d'oxyge`ne de groupements molybdates. La structure est de type “kro¨hnkite”. La valeur finale du facteur de reliabilite´est: R = 0.061.     

Phase formation in the systems Li2MoO4-K2MoO4-Ln2(MoO4)3 (Ln=La, Nd, Dy, Er) and properties of triple molybdates LiKLn2(MoO4)4

Subsolidus phase relations in the systems Li₂MoO₄-K₂MoO₄-Ln₂(MoO₄)₃ (Ln=La, Nd, Dy, Er) were determined. Formation of LiKLn₂(MoO₄)₄ was confirmed in the systems with Ln=Nd, Dy, Er at the LiLn(MoO₄)₂-KLn(MoO₄)₂ joins. No intermediate phases of other compositions were found. No triple molybdates exist in the system Li₂MoO₄-K₂MoO₄-La₂(MoO₄)₃. The join LiLa(MoO₄)₂-KLa(MoO₄)₂ is characterized by formation of solid solutions.Triple molybdates LiKLn₂(MoO₄)₄ for Ln=Nd-Lu, Y were synthesized by solid state reactions (single phases with ytterbium and lutetium were not prepared). Crystal and thermal data for these molybdates were determined. Compounds LiKLn₂(MoO₄)₄ form isostructural series and crystallized in the monoclinic system with the unit cell parameters a=5.315-5.145 Å, b=12.857-12.437 Å, c=19.470-19.349 Å, β=92.26-92.98°. When heated, the compounds decompose in solid state to give corresponding double molybdates. The dome-shaped curve of the decomposition temperatures of LiMLn₂(MoO₄)₄ has the maximum in the Gd-Tb-Dy region.While studying the system Li₂MoO₄-K₂MoO₄-Dy₂(MoO₄)₃ we revealed a new low-temperature modification of KDy(MoO₄)₂ with the triclinic structure of α-KEu(MoO₄)₂¹ (a=11.177(2) Å, b=5.249(1) Å, c=6.859(1) Å, α=112.33(2)°, β=111.48(1)°, γ=91.30(2)°, space group , Z=2).     

Phase formation in the K2MoO4-Lu2(MoO4)-Hf(MoO4)2 system and the structural study of triple molybdate K5LuHf(MoO4)6

Interactions in the ternary system K₂MoO₄-Lu₂(MoO₄)₃-Hf(MoO₄)₂ have been studied by X-ray powder diffraction and differential thermal analysis. A new triple (potassium lutetium hafnium) molybdate with the 5: 1: 2 stoichiometry has been found. Single crystals of this molybdate have been grown. Its X-ray diffraction structure has been refined (an X8 APEX automated diffractometer, MoK _α radiation, 1960 F(hkl), R = 0.0166). The trigonal unit cell has the following parameters: a = 10.6536(1) ?, c = 37.8434(8) ?, V = 3719.75(9) ?, Z = 6, space group R c. The mixed 3D framework of the structure is built of Mo tetrahedra sharing corners with two independent (Lu,Hf)O₆ octahedra. Two sorts of potassium atoms occupy large framework voids. Original Russian Text ? E.Yu. Romanova, B.G. Bazarov, R.F. Klevtsova, L.A. Glinskaya, Yu.L. Tushinova, K.N. Fedorov, Zh.G. Bazarova, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 5, pp. 815–818.     

Crystal Structure of Ternary Molybdate Rb5FeHf(MoO4)6 — a New Phase in the Rb2MoO4-Fe2(MoO4)3-Hf(MoO4)2 System

Physicochemical analysis (XRPA, DTA) was used to study phase equilibria in a ternary salt system Rb₂MoO₄-Fe₂(MoO₄)₃-Hf(MoO₄)₂ in the subsolidus region. Ternary molybdates with compositions 5:1:3, 5:1:2, and 1:1:1 have been found and synthesized. Crystal and thermal characteristics have been determined. Single crystals of the ternary molybdate Rb₅FeHf(MoO₄)₆ with a composition of 5:1:2 were grown. The crystal structure of the compound was solved using X-ray diffractometry (CAD-4 automatic diffractometer, MoK _α radiation, 1766 F(hkl), R = 0.0298). Hexagonal crystals with unit cell dimensions: a = b = 10.124(1) Å, c =15.135(3) Å, V = 1343.4(4) ų, Z = 2, ρ_calc = 4.008 g/cm³, space group P6₃. The mixed three-dimensional framework of the structure is formed from two sorts of MoO₄ tetrahedra and Fe and Hf octahedra linked through their common O-vertices. Rubidium atoms of three varieties occupy the large voids of the framework.Original Russian Text Copyright © 2004 by B. G. Bazarov, R. F. Klevtsova, A. D. Tsyrendorzhieva, L. A. Glinaskaya, and Zh. G. Bazarova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1038–1043, November–December, 2004.     

Phase formation in the Ag2MoO4-CuO-MoO3 system and the crystal structure of the new double molybdate Ag2Cu2(MoO4)3

Subsolidus phase relations in the Ag₂MoO₄-CuO-MoO₃ oxide-salt ternary system were determined. T-x diagram was plotted for the Ag₂MoO₄-CuMoO₄ quasi-binary join. Double molybdate Ag₂Cu₂(MoO₄)₃ was found to exist on this join. This compound is a superstructure derived from orthorhombic Li₃Fe(MoO₄)₃. Its structure was solved in terms of a subcell (a = 5.0749(3), b = 11.300(2), c = 18.127(3) ?, space group Pnma, Z = 4, R = 0.0678). In the true unit cell, the parameter a is tripled; suggested space group is P2₁2₁2₁. A characteristic feature of the Ag₂Cu₂(MoO₄)₃ structure is infinite columns (extended along axis a) of face-sharing oxygen octahedra, in which disordered silver atoms are located (Ag(21), Ag(22), and Ag(23)) with various degrees of irregularity of their octahedral coordination and a strong anisotropy of thermal vibrations. Distorted CuO₆ octahedra form zigzag ribbons extended in the same direction. MoO₄ tetrahedra, which are arranged according to the pseudo-hexagonal law, link the aforementioned major structural elements into a three-dimensional framework. Trigonal-prismatic voids of the framework are occupied by silver atoms Ag (1). Presumably, the disorder of the silver ions in octahedral columns can be responsible for the increased ion conductivity of silver copper molybdate. A partial order of the same ions is the most likely reason for the appearance of superstructure with the tripled unit cell volume. Original Russian Text ? G.D. Tsyrenova, S.F. Solodovnikov, E.T. Pavlova, E.G. Khaikina, Z.A. Solodovnikova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 802–809.     

Phase formation features in the systems M2MoO4-Fe2(MoO4)3 (M=Rb, Cs) and crystal structures of new double polymolybdates M3FeMo4O15

The systems M₂MoO₄-Fe₂(MoO₄)₃ (M=Rb, Cs) were shown to be non-quasibinary joins of the systems M₂O-Fe₂O₃-MoO₃. New compounds M₃FeMo₄O₁₅ were revealed along with the known MFe(MoO₄)₂ and M₅Fe(MoO₄)₄. The unit cell parameters of the new compounds are a=11.6192(2), b=13.6801(3), c=9.7773(2) Å, β=92.964(1)°, space group P2₁/c, Z=4 (M=Rb) and a=11.5500(9), b=9.9929(7), c=14.513(1) Å, β=90.676(2)°, space group P2₁/n, Z=4 (M=Cs). In the structures of M₃FeMo₄O₁₅ (M=Rb, Cs), a half of the FeO₆ octahedra share two opposite edges with two MoO₆ octahedra linked to other FeO₆ octahedra through the bridged MoO₄ tetrahedra by means of the common oxygen vertices to form the chains along the a axis. The difference between the structures is caused by diverse mutual arrangements of the adjacent polyhedral chains.     

Crystal structure and magnetic properties of Li,Cr-containing molybdates Li3Cr(MoO4)3, LiCr(MoO4)2 and Li1.8Cr1.2(MoO4)3

Single crystals of LiCr(MoO₄)₂, Li₃Cr(MoO₄)₃ and Li_1.8Cr_1.2(MoO₄)₃ were grown by a flux method during the phase study of the Li₂MoO₄-Cr₂(MoO₄)₃ system at 1023 K. LiCr(MoO₄)₂ and Li₃Cr(MoO₄)₃ single phases were synthesized by solid-state reactions. Li₃Cr(MoO₄)₃ adopts the same structure type as Li₃In(MoO₄)₃ despite the difference in ionic radii of Cr³⁺ and In³⁺ for octahedral coordination. Li₃Cr(MoO₄)₃ is paramagnetic down to 7 K and shows a weak ferromagnetic component below this temperature. LiCr(MoO₄)₂ is isostructural with LiAl(MoO₄)₂ and orders antiferromagnetically below 20 K. The magnetic structure of LiCr(MoO₄)₂ was determined from low-temperature neutron diffraction and is based on the propagation vektor . The ordered magnetic moments were refined to 2.3(1) μ_B per Cr-ion with an easy axis close to the [1 1 1¯] direction. A magnetic moment of 4.37(3) μ_B per Cr-ion was calculated from the Curie constant for the paramagnetic region.The crystal structures of the hitherto unknown Li_1.8Cr_1.2(MoO₄)₃ and LiCr(MoO₄)₂ are compared and reveal a high degree of similarity: In both structures MoO₄-tetrahedra are isolated from each other and connected with CrO₆ and LiO₅ via corners. In both modifications there are Cr₂O₁₀ fragments of edge-sharing CrO₆-octahedra.     

Ba3 (VO4)2-K2 Ba(MoO4)2 and Pb3 (VO4)2-K2 Pb(MoO4)2 systems

Phase equilibria in the Ba₃(VO₄)₂-K₂Ba(MoO₄)₂ and Pb3(VO₄)₂-K₂Pb(MoO₄)₂ systems have been investigated. In the first system, a continuous series of substitutional solid solutions with the palmierite structure is formed, and in the second one, the polymorphic transition in lead orthovanadate at 100°C restricts the extent of the palmierite-type solid solution to 10–100 mol % K₂Pb(MoO₄)₂. Original Russian Text ? V.D. Zhuravlev, Yu.A. Velikodnyi, A.S. Vinogradova-Zhabrova, A.P. Tyutyunnik, V.G. Zubkov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1746–1748.     

Synthesis, crystal structure and electrical characterization of two new potassium uranyl molybdates K2(UO2)2(MoO4)O2 and K8(UO2)8(MoO5)3O6

Two new potassium uranyl molybdates K₂(UO₂)₂(MoO₄)O₂ and K₈(UO₂)₈(MoO₅)₃O₆ have been obtained by solid state chemistry . The crystal structures were determined by single crystal X-ray diffraction data, collected with MoKα radiation and a charge coupled device (CCD) detector. Their structures were solved using direct methods and Fourier difference techniques and refined by a least square method on the basis of F² for all unique reflections, with R₁=0.046 for 136 parameters and 1412 reflections with I?2σ(I) for K₂(UO₂)₂(MoO₄)O₂ and R₁=0.055 for 257 parameters and 2585 reflections with I?2σ(I) for K₈(UO₂)₈(MoO₅)₃O₆. The first compound crystallizes in the monoclinic symmetry, space group P2₁/c with a=8.250(1) Å, b=15.337(2) Å, c=8.351(1) Å, β=104.75(1)°, ρ_mes=5.22(2) g/cm³, ρ_cal=5.27(2) g/cm³ and Z=4. The second material adopts a tetragonal unit cell with a=b=23.488(3) Å, c=6.7857(11) Å, ρ_mes=5.44(3) g/cm³, ρ_cal=5.49(2) g/cm³, Z=4 and space group P4/n.In both structures, the uranium atoms adopt a UO₇ pentagonal bipyramid environment, molybdenum atoms are in a MoO₄ tetrahedral environment for K₂(UO₂)₂(MoO₄)O₂ and MoO₅ square pyramid coordination in K₈(UO₂)₈(MoO₅)₃O₆. These compounds are characterized by layered structures. The association of uranyl ions (UO₇) and molybdate oxoanions MoO₄ or MoO₅, give infinite layers [(UO₂)₂(MoO₄)O₂]²⁻ and [(UO₂)₈(MoO₅)₃O₆]⁸⁻ in K₂(UO₂)₂(MoO₄)O₂ and K₈(UO₂)₈(MoO₅)₃O₆, respectively. Conductivity properties of alkali metal within the interlayer spaces have been measured and show an Arrhenius type evolution.     

Refinement of Phase Formation in the Na2MoO4-Hf(MoO4)2 System. Crystal Structure of the New Binary Molybdate Na8Hf(MoO4)6

Phase equilibria in the subsolidus region of the Na₂MoO₄-Hf(MoO₄)₂ system have been investigated. The existence of Na₂Hf(MoO₄)₃ was confirmed, and a new binary molybdate, Na₈Hf(MoO₄)₆, has been found, whose crystal structure with dimensions a = 20.661(3) Å, b = 9.816(1) Å, c = 13.796(3) Å, β = 113.47(1)°, Z = 4, space group C2/_c, _R = 0.023 is similar to that of K₈Hf(MoO₄)₆. In the structure, each HfO₆ octahedron is linked (through common vertices) to six MoO₄ tetrahedra, forming [Hf(MoO₄)₆]⁸⁻ cluster groups. Between the groups are Na⁺ ions having considerably distorted tetragonal pyramidal or octahedral oxygen surroundings; c.n. of sodium here is 5 or 6 versus c.n. = 7–9 of potassium in K₈Hf(MoO₄)₆. The open irregular environment of sodium and the continuous three-dimensional openwork of oxygen polyhedra around sodium suggest that Na₈Hf(MoO₄)₆ or its analogs may be good ion conductors.Original Russian Text Copyright © 2004 by S. F. Solodovnikov, B. G. Bazarov, L. V. Balsanova, Z. A. Solodovnikova, and Zh. G. Bazarova__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1044–1048, November–December, 2004.     

Crystal structures of phosphomolybdyl salts: Pb(MoO2)2(PO4)2 and Ba(MoO2)2(PO4)2

Crystal structures of Pb(MoO₂)₂(PO₄)₂ and Ba(MoO₂)₂(PO₄)₂ were determined. Both compounds contain the molybdyl group MoO₂. The monoclinic unit-cell parameters are a = 6.353(7), b = 12.289(4), c = 11.800 Å, β = 92°56(6), and Z = 4 for the lead salt and a = 6.383(8), b = 7.142(7), c = 9.953(8) Å, β = 95°46(8), and Z = 2 for the barium salt. $\text{P2}{}_1\text{c}$ is the common space group. The R values are respectively R = 0.027 and R = 0.031 for 1964 and 1714 independent reflections. The frameworks built up by a three-dimensional network of monophosphate PO₄ and molybdyl MoO₂ groups are similar, characterized mainly by corner-sharing PO₄ and MoO₆ polyhedra. Two oxygen atoms of each MoO₆ group are bonded to the molybdenum atom only as in other molybdyl salts.     

Binary molybdates K4M2+(MoO4)3 (M2+=Mg, Mn, Co) and crystal structure of K4Mn(MoO4)3

Binary molybdates K₄M²⁺ (MoO₄)₃ (M²⁺=Mg, Mn, Co) isostructural to triclinic \ga-K₄Zn(WO₄)₃ were synthesized, and optimal conditions for their spontaneous crystallization were found. It was established by XRPA and DTA that at 530°C the structure of the compound with cobalt undergoes a transition to the orthorhombic structure of K₄Zn(MoO₄)₃. The structure of K₄Mn(MoO₄)₃ was determined from single crystal diffraction data (a=7.613, b=9.955, c=10.156 Å,α=92.28,β=106.66,γ=105.58°, Z=2, space group $P\bar 1$ , R=0.030). In this compound, Mn has a higher coordination number (CN=5+1) than that of Zn inα-K₄Zn(WO₄)₃ (CN=4+1). The main structural feature is pairs of MnO₆ octahedra linked by the bridging MoO₄ tetrahedra into ribbons stretching along the a axis. The structure is compared with related structures of binary molybdates and other members of the alluaudite family.     

Subsolidus phase relations in the Na2MoO4-CoMoO4-Cr2(MoO4)3 system

Triple molybdate NaCoCr(MoO₄)₃, a phase of variable composition Na₂MoO₄-CoMoO₄-Cr₂(MoO₄)₃ (0 ≤ x ≤ 0.5) having nasicon structure (space group R $ \bar 3 $ \bar 3 c), and triple molybdate NaCo₃Cr(MoO₄)₅ crystallizing in triclinic space group P $ \bar 1 $ \bar 1 were synthesized in the subsolidus region of the Na₂MoO₄-CoMoO₄-Cr₂(MoO₄)₃ ternary salt system. Crystal parameters were calculated for the newly synthesized molybdates and phases. The vibration spectra of Na_{1 − x} Co_{1 − x} Cr_{1 + x} (MoO₄)₃ and electrophysical properties were studied. Upon Na + Co → Cr(III) substitution, chromium cations are distributed to cobalt sites and additional vacancies are generated in the sodium sublattice.     

Phase relations and crystal structures in the systems (Bi,Ln)2WO6 and (Bi,Ln)2MoO6 (Ln=lanthanide)

Several outstanding aspects of phase behaviour in the systems (Bi,Ln)₂WO₆ and (Bi,Ln)₂MoO₆ (Ln=lanthanide) have been clarified. Detailed crystal structures, from Rietveld refinement of powder neutron diffraction data, are provided for Bi_1.8La_0.2WO₆ (L-Bi₂WO₆ type) and BiLaWO₆, BiNdWO₆, Bi_0.7Yb_1.3WO₆ and Bi_0.7Yb_1.3WO₆ (all H-Bi₂WO₆ type). Phase evolution within the solid solution Bi_2−xLa_xMoO₆ has been re-examined, and a crossover from γ(H)-Bi₂MoO₆ type to γ-R₂MoO₆ type is observed at x∼1.2. A preliminary X-ray Rietveld refinement of the line phase BiNdMoO₆ has confirmed the α-R₂MoO₆ type structure, with a possible partial ordering of Bi/Nd over the three crystallographically distinct R sites.     

Structure and properties of double complex salts [Co(NH3)6][Fe(CN)6] and [Co(NH3)6]2[Cu(C2O4)2]3

Double complex salts (DCSs) [Co(NH₃)₆][Fe(CN)₆] (I) and [Co(NH₃)₆]₂[Cu(C₂O₄)₂]₃ (II) and complex [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O (III) are synthesized and investigated by single crystal XRD, crystal optics, and elemental analysis. The crystalline phases of I, II, and III (R-3, P2₁/c, and Pnnm space groups respectively) have the following crystallographic characteristics: a = 10.9804(2) ?, b = 10.9804(2) ?, c = 10.8224(3) ?, V = 1130.03(4) ?³, Z = 3, d _x = 1.65 g/cm³ (I); a = 9.6370(2) ?, b = 10.2452(2) ?, c = 13.2108(3) ?, V = 1932.90(9) ?³, Z = 2, d _x= 1.97 g/cm³ (II), and a = 11.7658(3) ?, b = 11.7254(3) ?, c = 14.1913(4) ?, V = 1304.34(5) ?³, Z = 2, d _x = 1.68 g/cm³ (III). This paper investigates the products of DCS thermolysis in a hydrogen atmosphere: the intermetallic compound CoFe with the bcc parameter a = 2.852 ? for I and a heterogeneous mixture of Co and Cu in the decomposition of II. The coordinated CN⁻ and C₂O₄²⁻ groups then turn into NH₃, hydrocarbons, and CO₂. The dominant hydrocarbon is methane.     

Interactions in the subsolidus region of the Na2MoO4-NiMoO4-Fe2(MoO4)3 system

Phase relations have been investigated in the subsolidus region of the Na₂MoO₄-NiMoO₄-Fe₂(MoO₄)₃ system by X-ray diffraction, differential thermal analysis, and vibrational spectroscopy. The phase of variable composition Na_1−x Ni_1−x Fe_1+x (MoO₄)₃(0≤x≤0.5) with the NASICON structure (space group R c) and the NaNi₃Fe(MoO₄)₅ ternary molybdate crystallizing in the triclinic crystal system (space group P ) have been obtained. A high conductivity was found in Na_1−x Ni_1−x Fe_1+x (MoO₄)₃, which allows one to consider this phase of variable composition as a promising solid electrolyte with sodium ion conduction. Original Russian Text ? N.M. Kozhevnikova, A.V. Imekhenova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 4, pp. 695–700.     

Anion effect on the thermolysis of double complexes [Co(NH3)6][Fe(CN)6] and [Co(NH3)6]4[Fe(CN)6]3

The thermolysis of complexes [Co(NH₃)₆][Fe(CN)₆] and [Co(NH_{3 6}]₄[Fe(CN)₆]₃ under an air or hydrogen atmosphere at 200, 350, and 500°C is studied. The composition and properties of thermolysis products are determined. The oxidative thermolysis yields mixtures of oxides of the central metals; the reductive thermolysis yields intermetallic compounds CoFe. The density of the complexes and the specific surface area of the intermetallic compounds are measured. Average particle sizes are calculated. The morphology and dispersion of the powders are dictated by the shape and density of the crystals of the precursor double salts and the thermolysis temperature. The thermolysis chemism in the oxidative and reductive atmospheres is discussed in the context of the nature of the complex anion. Original Russian Text ? S.I. Pechenyuk, D.P. Domonov, D.L. Rogachev, A.T. Belyavskii, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 7, pp. 1110–1115.