Laser Raman studies on compounds 7.O4O.7 and 7.O5O.7

Laser Raman studies on two compounds of the α,ω-bis(4-alkylanilinebenzylidene -4′-oxy)alkane series were carried out in the spectral regions 1140–1220 and 1550–1650 cm^-1 as a function of temperature. Compounds 7.O4O.7 and 7.O5O.7, exhibit SmA and SmF phases. The structural differences between these liquid crystal dimers, having either an odd or an even number of carbon atoms in the spacer, are remarkably existent in the room temperature Raman spectra. The results are rationalized on the basis of the tendency of these compounds to exhibit bent shapes, and how this manifests in the odd-even effect at the molecular level assuming a semi-rigid core region of the dimeric molecule. It is found that the behaviour of the odd spacer dimer (7.O5O.7) agrees with the molecular model, whereas the even spacer dimer (7.O4O.7) behaves in a similar fashion to monomeric compounds such as the nO.m. compounds. In both cases, dynamic changes around the C=N bond have a profound effect both on the molecular shape in the different phases and on phase behaviour.     

Structural and conductivity studies in LiFeP2O7, LiScP2O7, and NaScP2O7

Structural studies of LiScP₂O₇ by Rietveld refinement confirm that this material is isostructural with LiFeP₂O₇ studied previously. However, NaScP₂O₇ shows a structure different from the structural types of the basic group of Na^IM^IIIP₂O₇ known thus far. Systematic ranges for the six structural types of A^IM^IIIP₂O₇ are presented in terms of ion radii sums and ratios. The framework of LiMP₂O₇ (M=Sc, Fe) has rather wide tunnels running along the crystallographic c-axis. This feature has determined our interest to check the ion conductivity in A^IM^IIIP₂O₇ (A=Li, Na; M=Sc, Fe). The bulk conductivity, however, is low in these compounds, 10⁻⁶–10⁻⁷ S/cm at 300 °C, as determined by impedance spectroscopy. In order to facilitate the conductivity via normal lithium sites, heterovalent substitution is used. Received: 30 April 1999 / Accepted: 15 June 1999     

CsTiP2O7

From single‐crystal X‐ray data, cesium titanium pyrophos­phate, CsTiP₂O₇, is found to crystallize in the KAlP₂O₇ structure type. It possesses a three‐dimensional tunnel structure built by the corner‐sharing of distorted TiO₆ octahedra and P₂O₇ pyrophosphate groups. The Cs⁺ cations are in the tunnels.     

Low-dimensional ferromagnetic properties of SrCuV2O7 and BaCuV2O7

The crystal structure of isostructural SrCuV(2)O(7) and BaCuV(2)O(7) consists of one-dimensional (1D) zigzag chains of Cu atoms with next-nearest-neighbor interaction. The main intrachain interaction was found to be ferromagnetic and estimated at 4.6 K (Hamiltonian H approximately -2J). SrCuV(2)O(7) and BaCuV(2)O(7) are new examples in the scanty family of 1D ferromagnets. Isothermal magnetization measurements at 0.08 K and specific heat data showed that MCuV(2)O(7) exhibits antiferromagnetic long-range ordering at T(N) = 1.36 K for SrCuV(2)O(7) and T(N) = 1.47 K for BaCuV(2)O(7). Spin-flop transitions were observed in the antiferromagnetic state at 0.08 K near 0.5 kOe in SrCuV(2)O(7) and 2 kOe in BaCuV(2)O(7). In air, SrCuV(2)O(7) and BaCuV(2)O(7) melted incongruently above 983 and 1018 K, respectively.     

Zur Kenntnis der Phase BaO · Al2O3 · 7 H2O

On the Compound BaO · Al₂O₃ · 7 H₂O On the basis of investigations using ²⁷Al, ¹H NMR, IR and thermoanalytical methods for the compound BaO · Al₂O₃ · 7 H₂O a constitution as Ba_n[Al₂(OH)₈]_n · 3n H₂O with condensed AlO₆ groups, sharing edges, is proposed. Relations between the Ba/Al ratio and the constitution of anions of barium aluminate hydrates are discussed.     

Short-range and long-range magnetic ordering in SrCuP2O7 and PbCuP2O7

Magnetic properties of SrCuP2O7 and PbCu(1-x)ZnxP2O7 (x=0, 0.1, and 0.5) were studied by magnetic susceptibility, chiT, and specific heat, Cp(T). Both data showed that magnetism of SrCuP2O7 and PbCuP2O7 can be described by the one-dimensional (1D) uniform chain model despite the structural features suggesting the presence of zigzag chains with next-nearest-neighbor interactions. The chiT data were fitted by the Bonner-Fisher curve (plus temperature independent and Curie-Weiss terms) with g=2.20 and J/kB=9.38 K for SrCuP2O7 and g=2.17 and J/kB=8.41 K for PbCuP2O7 (Hamiltonian H=J SigmaSiS(i+1)). Magnetic specific heat, Cm(T), exhibited one broad maximum due to short-range ordering and one sharp peak at TN=1.64 K for SrCuP2O7 and TN=1.15 K for PbCuP2O7 due to long-range antiferromagnetic ordering. The characteristic values of the broad maxima on the Cm(T) curves (Cmax and TC(max)) were in good agreement with the theoretical calculations for the uniform 1D S=1/2 Heisenberg chain. Magnetic properties of PbCu0.9Zn0.1P2O7 still obeyed the 1D uniform chain model but those of PbCu0.5Zn0.5P2O7 did not. In air, SrCuP2O7 was stable at least up to 1373 K while PbCuP2O7 melted incongruently above 1180 K.     

Synthesis and structure of double pyrophosphates KFeP2O7 and KGaP2O7

Institute for Crystallography, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 1, pp. 173–175, January–February, 1989.     

Die Kristallstrukturen von K8Ta6O19 · 16H2O und K7NaTa6O19 · 14H2O

The Crystal Structures of K₈Ta₆O₁₉ · 16H₂O and K₇NaTa₆O₁₉ · 14H₂O By alkaline digestion of Ta₂O₅ with p.a. KOH transparent single crystals of the composition K₈Ta₆O₁₉ · 16H₂O are formed. When technical grade KOH is used, the same kind of synthesis yields crystals of the composition K₇NaTa₆O₁₉ · 14H₂O. The latter compound has been given the formula K₈Ta₆O₁₉ · 14H₂O until now. In both cases the isopolyoxoanion [Ta₆O₁₉]⁸ consists of six TaO₆-octahedra connected by edge sharing. This means that the heavy atom partial structure found by Lindquist et al. is confirmed. Additionally the complete structures including the atomic positions of the oxygen atoms of the polyanions as well as those of the cations and crystal water molecules (without hydrogen positions) are determined.     

(Mg1–xCrx)2P2O7, CaCrP2O7, SrCrP2O7 und BaCrP2O7 – Neue Diphosphate des zweiwertigen Chroms

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXXI. (Mg_1–xCr_x)₂P₂O₇, CaCrP₂O₇, SrCrP₂O₇ and BaCrP₂O₇ – New Diphosphates of Divalent Chromium In the quasi‐binary systems A₂P₂O₇/Cr₂P₂O₇ (A = Mg, Ca, Sr, Ba) the solid solution (Mg_1–xCr_x)₂P₂O₇ as well as the new compounds CaCrP₂O₇, SrCrP₂O₇, and BaCrP₂O₇ have been synthesized and characterized for the first time. In the whole experimental range (0.01 < x < 0.94; T = 950 °C) the solid solution (Mg_1–xCr_x)₂P₂O₇ is isotypic to the pure phases β‐Mg₂P₂O₇ and β‐Cr₂P₂O₇; but no phase transition (β → α) to a low‐temperature modification, as in Mg₂P₂O₇ and Cr₂P₂O₇, was found. CaCrP₂O₇ ( A ), SrCrP₂O₇ ( B ), and BaCrP₂O₇ ( C ), phases without detectable homogenity range in the other quasi‐binary systems are not structurally related to each other, but are isotypic to the corresponding compounds containing cobalt. [( A ): P‐1, Z = 2, a = 6.312(2) Å, b = 6.499(2) Å, c = 6.916(2) Å, α = 83.12(3)°, β = 88.37(3)°, γ = 67.72(3)°, 3235 independent reflections, R1 = 0.041, wR2 = 0.112; ( C ): P‐1, Z = 2, a = 5.382(8) Å, b = 7.271(8) Å, c = 7.589(4) Å, α = 103.33(7)°, β = 89.91(9)°, γ = 93.6(1)°, 1571 independent reflections, R1 = 0.085, wR2 = 0.31]. We have reported earlier details on SrCrP₂O₇. The coordination of Cr²⁺ by oxygen is distorted octahedral in ( A) , while in the structures of ( B) and ( C) square‐pyramidal environment is found. The results of UV/VIS‐spectroscopic and magnetic measurements as well as IR‐spectra of the diphosphates are reported.