Determination of A0 for CH335Cl and CH337Cl from the ν4 infrared and Raman bands

The ν₄ infrared and Raman bands of CH₃Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH₃³⁵Cl, including A₀ = 5.20530 ± 0.00010 cm^?1 and D_K = (8.85 ± 0.13) × 10^?5cm^?1. For CH₃³⁷Cl an incomplete set of constants was obtained from the infrared band, and A₀ = 5.2182 ± 0.0010 cm^?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is $\text{r(}\text{CH) = 1.0854 ± 0.0005}\text{A}\text{?}$, $\text{r(}\text{CCl) = 1.7760 ± 0.0003}\text{A}\text{?}$, and <(HCH) = 110°.35 ± 0°.05.     

Etude Cristallographique Et Magnetique De Fe2GeS4 Structures Magnetiques A 85 Et 4,2°K

Fe₂GeS₄ crystallizes in the orthorhombic space group Pnma; the cell parameters are: $\text{a = 12,467}\text{A}\text{?}$, $\text{b = 7,213}\text{A}\text{?}$, $\text{c = 5,902}\text{A}\text{?}$; the crystal structure is isotype with olivine.A magnetic study by the extraction method shows that Fe₂GeS₄ is paramagnetic until 108°K, then antiferromagnetic until 69°K and finally antiferro- and ferrimagnetic at lower temperatures.Neutron diffraction reveals the magnetic structures at 85 and 4,2°K and explains the anisotropy transition at 69°K.     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

Crystal structure of and evidence of a lattice distortion in (Me2ø2P)(TCNQ)2

(Dimethyldiphenylphosphonium)⁺(7,7,8,8-tetracyanoquinodimethanide)^?₂ is monoclinic, space group C_c, with a = 32.01(2), b = 6.56(1), $\text{c = 15.72(2)}\text{A}\text{?}$, β = 107.4(8)°. The TCNQ's stack plane-to-plane in columns parallel to b with (i) a mean interplanar spacing of 3.28 Å along the conducting chains and (ii) an exocyclic bond to quinonoid ring overlap of adjacent molecules. The conductivity along b, the needle axis, varies as $\text{σ = σ}{}_0\text{exp}\text{(}\text{?E}{}_{\mathrm{a}}\text{kT}\text{)}$ where σ_{300 K} = 0.05 S cm^?1 and E_a = 0.20 eV (Diethyldiphenylphosphonium)⁺(7,7,8,8-tetracyanoquinodimethanide)^?₂ is similarly monoclinic, space group C_c, with a = 31.48(2), b = 6.51(1), $\text{c = 15.48(2)}\text{A}\text{?}$, β = 104.2(8)°. The conductivity at 300 K and activation energy, both determined along b, are 1–10 S cm^?1 and 0.05 eV respectively. There is evidence of a lattice distortion in the dimethyl analogue only.     

A new ferroelectric compound: Methylammonium trichloromercurate (CH3NH3HgCl3)

Measurements of the dielectric constants revealed a ferro- to paraelectric transition in methylammonium trichloromercurate (CH₃NH₃HgCl₃). Thermal analysis by differential scanning calorimetry indicates a transition temperature of Tc ≈ 60°C. The structures of both phases were determined from single crystal X-ray measurements. The ferroelectric phase crystallizes at room temperature in the polar trigonal space group $\text{P}\text{3}{}_2\text{(a = b =}\text{7.8117(3)}\text{, c =}\text{9.826(3)}\text{A}\text{?}\text{, Z =}\text{3}\text{)}$. The refinement of the ferroelectric structure included the fractional contribution of the two domains present. The paraelectric phase has monoclinic symmetry (space group C2 with $\text{a =}\text{13.816(2)}\text{, b =}\text{7.880(1)}\text{, c =}\text{9.734(3)}\text{A}\text{?}\text{, β =}\text{90.49(5)°}\text{, Z =}\text{6}\text{)}$ and contains an almost completely disordered methylammonium group while order with pronounced thermal motion is observed in the ferroelectric phase.     

Preparation and structural studies of lithium substituted nickel phosphorus trisulphide,Li2NiP2S6

Crystals of Li₂NiP₂S₆ may be prepared by direct combination of stoichiometric amounts of Li₂S, phosphorus, nickel and sulphur in a temperature gradient towards 750°C. The structure determined by X-ray powder diffraction is monoclinic C2/m with $\text{a = 5.926}\text{A}\text{?}\text{, b = 10.917}\text{A}\text{?}\text{, c = 6.718}\text{A}\text{?}\text{, β = 104.4°}$, and is based on the NiPS₃ layer structure with two Ni atoms substituted by lithium, and with two lithium atoms in the van der Waals gap.     

Charge-density wave instability and nonlinear transport in Tl0.3MoO3 a new blue molybdenum oxide bronze

Single crystals of Tl_0.3MoO₃ blue bronze were grown by the temperature gradient flux technique for the first time. Tl_0.3MoO₃ crystalizes with monoclinic symmetry, space group C2, C2/m or Cm, $\text{a = 18.486(1)}\text{A}\text{?}$, $\text{b = 7.5474(6)}\text{A}\text{?}$, $\text{c = 10.0347(7)}\text{A}\text{?}$, β = 118.377(6)° and appears to be isostructural with the K_0.3MoO₃ blue bronze. The physical properties of Tl_0.3MoO₃ are similar to those of the K₃MoO₃ and Rb₃MoO₃ phases. The resistivity of Tl_0.3MoO₃ is highly anisotropic and its temperature susceptibility (4.2–300K) decreases sharply with decreasing temperature near the transition seen in the resistivity. The onset of another transition <60K is also indicated by the susceptibility data. Non-linear current-voltage (I–V) characteristics observed at ～70K above applied threshold voltages of the order of ～300mV/cm suggest the sliding of charge density condensate.     

The accommodation of trivalent gold in Silver Chloride

Gold-doped silver chloride annealed in a chlorine atmosphere at 300°C is shown to contain precipitates of AgAuCl₄, a compound not previously reported. The substance melts at 265 ± 2°C and has a monoclinic unit cell with $\text{a = 11.124 ± 0.008}\text{A}\text{?}$, $\text{b = 4.105 ± 0.002}\text{A}\text{?}$, $\text{c = 6.539 ± 0.006}\text{A}\text{?}$ and β = 93.11 ± 0.05°. Its optical absorption spectrum is discussed and the method of precipitate formation in silver chloride is described in terms of an internal oxidation type of process.     

Proprietes magnetiques et etude par effet Mössbauer du thiosilicate Fe2SiS4

Fe₂SiS₄$\text{(a = 12,407}\text{A}\text{?}\text{, b = 7,198}\text{A}\text{?}\text{, c = 5,812}\text{A}\text{?}$, space group Pnma) has the olivine structure; the ferrous ions are located in two kinds of sites: one half in planes of mirror symmetry m, the other half in centers of symmetry. 1?.The magnetic study of this compound by means of magnetization measurements and Mössbauer effect, indicates from 127 K an antiferromagnetic arrangement along oy for the m sites, and an induced partial order of the same kind for the 1? sites. At 33 K, the Fe²⁺ spins in 1? sites are completely ordered and at the same time takes place a rearrangement of the magnetic structure. The observed complex model is analogous to that of Fe₂GeS₄, i.e. antiferromagnetic along 0x and ferrimagnetic along Oz.     

Ionic transport in the lithium nitride bromides,Li6NBr3 and Li1 3N4Br

The ionic and electronic conductivities of the lithium nitride bromides Li₆NBr₃ and Li_{1 3}N₄Br have been studied in the temperature range from 50 to 220°C and 120 to 450°C, respectively. Both compounds are practically pure lithium ion conductors with negligible electronic contribution. Li₆NBr₃ has an ionic conductivity Ω of 2 × 10^-6Ω^-1cm^-1 at 100°C and an activation enthalpy for σT of 0.46 eV. Li_{1 3}N₄Br shows a phase transition at about 230°C. The activation enthalpy for σT is 0.73 eV below and 0.47 eV above this temperature. The conductivities at 150 and 300°C were found to be 3.5 × 10^-6 Ω^-1cm^-1 and 1.4 × 10^-3Ω^-1cm^-1, respectively. The crystal structure is hexagonal at room temperature with $\text{a = 7.415 (1)}\text{A}\text{?}$ and $\text{c = 3.865 (1)}\text{A}\text{?}$.     

Optical mode softening in the incommensurate phase of Sr2Nb2O7

In the incommensurate phase below about 220°C of Sr₂Nb₂O₇, the soft mode, of which frequency decreases toward 215°C has been found by the Raman scattering measurements in the $\text{b(cc)}\text{b}$ scattering geometry. The level repulsion and the intensity transfer between the soft mode and another low frequency mode are clearly observed. The uncoupled soft mode frequency ω_s has been found to be expressed as ω_s =A(T_tr?T)^β, where β= 0.38 ± 0.02. Pressure dependence of the soft mode has also been measured up to 24kbar. No remarkable pressure dependence has been observed.     

Lithium aluminum nitride,Li3AlN2 as a lithium solid electrolyte

Single phase of Li₃AlN₂ was prepared from the mixture of Li₃N/AlN = 1.2 to 1.5 in molar ratio at 700°C and at 900°C. It crystalizes in the cubic system derived from antifluorite-type structure having the lattice parameter $\text{a = 9.470}\text{A}\text{?}$. It is a pure ionic conductor having conductivity of 5 × 10^?8ω^?1cm^?1 at room temperature and an activation energy of 52 kJ/ mol. Its decomposition voltage was 0.85 V at 104°C. The TiS₂/Li₃AlN₂/Li cell could be discharged at a constant current of 45 μA/cm² at 104°C.     

Microwave spectrum of 2-propene-1-imine,CH2CHCHNH

The reactive species, 2-propene-1-imine, has been identified by its microwave spectrum as a pyrolysis product of diallylamine vapor (100 mTorr, 400°C). Two entirely planar forms are observed, both with an “s-trans” CCCN configuration. The lower energy rotamer has an “anti” CCNH configuration, with $\text{r}\text{CC = 1.453(3)}\text{A}\text{?}$, $\text{r}\text{CC = 1.336(4)}\text{A}\text{?}$, and ∠ CCC = 122.9(3)° and a dipole moment of 2.01(2) D with 1.13(1) D and 1.66(2) D “a” and “b” components. The higher energy rotamer has a “syn” CCNH configuration and a dipole moment of 2.51(2) D with 2.39(2) and 0.77(3) D the “a” and “b” components. From relative intensity measurements, the ground state energy difference is determined to be 0.9 ± 0.1 kcal mole^?1.     

Magnetic and structural studies of Cr2O5 and Cr3O8

The infrared spectra, indexed X-ray powder diffraction patterns, magnetic susceptibilities between 80 and 300 K, and electron paramagnetic resonance spectra at 80 and 300 K are reported for Cr₂O₅ and Cr₃O₈. The results indicate that both oxides are Cr³⁺/Cr⁶⁺ mixed-valence compounds which contain CrO₆ octahedra and CrO₄ tetrahedra in different ratios. The valence formula for Cr₂O₅ is Cr³⁺₂Cr⁶⁺₄O₁₅ and that of Cr₃O₈ is Cr³⁺₂Cr⁶⁺₇O₂₄. The X-ray powder data for Cr₂O₅ and Cr₃O₈ could be indexed on the basis of a monoclinic unit cell $\text{(a = 12.01(2), b = 8.52(1), c = 9.39(1)}\text{A}\text{?}\text{β = 92.0(1)°)}$ and an orthorhombic unit cell $\text{(a = 12.01(7), b = 36.60(7) and c = 3.82(1)}\text{A}\text{?}\text{)}$, respectively.     

Sinusoidally modulated structure of a partially oxidized platinum complex,K1.6Pt(C2O4)2·1.2H2O

X-ray examination of the partially oxidized platinum complex K_1.6Pt(C₂O₄)₂·1.2H₂O has revealed that the crystal lattice is sinusoidally modulated. The cell constants of the fundamental lattice are a = 9.749(9), b = 11.403(18), $\text{c = 10.694(8)}\text{A}\text{?}$, α = 99.54(9), β = 115.81(9), γ = 102.32(17)° and the space group is P1?. The structure analysis of the fundamental structure shows that the bisoxalatoplatinum groups are stacked face-to-face along the b axis to form a tetradic distorted linear chain. The main and satellite reflections appear regularly at intervals of $\text{∣0.32a}{}^1\text{-0.38b}{}^1\text{+0.05c}{}^1\text{∣}$ in the reciprocal space. The components of the amplitude of the sinusoidal modulation wave were determined to be 0.195, 0.076 and 0.107 Å along the a,b and c axes, respectively.     

Microwave spectrum of fluorodihydroxy borane,BF(OH)2

Fluorohydroxy borane, BF(OH)₂, has been identified in the hydrolysis of trifluoroborane by microwave spectroscopy. The rotational and centrifugal distortion constants have been determined for the normal and d₂ species. From these constants the molecular structure has been determined. This molecule does not have C₂ symmetry and the structural parameters are $\text{r}\text{(BO}{}_1\text{) = 1.360}\text{A}\text{?}$, $\text{r}\text{(BO}{}_2\text{) = 1.365}\text{A}\text{?}$, ∠FBO₁ = 118.2°, and ∠FBO₂ = 121.0°. The inertia defects establish the planarity of the molecule. The dipole moment of 1.818 ± 0.007 D has been obtained from the measurements of the Stark effects.     

The average structure of 5.10-Dihydro-5.10-Diethylphenazinium-Iodide (E2P·I1.6): A new linear chain Polyiodide compound

Upon oxidation of 5.10-dihydro-5.10-diethylphenazine (E₂P) with iodine golden-green lustrous crystals of a compound with stoichiometry E₂P.I_1.6 were isolated. The compound crystallizes in the tetragonal space group D₄² with $\text{a = 12.321(2)}\text{A}\text{?}$ and $\text{c = 5.330(2)}\text{A}\text{?}$. The E₂P and I form interpenetrating incommensurate sublattices along c, with an iodine repeat distance of 9.7 Å. Static susceptibility measurements at room temperature give χ_g = + 0.994 × 10^?6g^?1 × cm³. This corresponds to one unpaired electron spin per two formular units. Single-crystal EPR indicates that the paramagnetism is associated with weakly interacting E₂P⁺ cation radicals. The 300K-d.c. conductivity of 3×10^?2Ω^?1cm^?1 and activation energy of 0.17±0.02eV for single crystals is consequently associated with the polyiodide chains, and not with the E₂P⁺ cation radicals.     

Crystal growth,structure, electron paramagnetic resonance and magnetic properties of (NH4)2V3O8

A method to grow single crystals of ammonium vanadate (IV, V) (NH₄)₂V₃O₈ has been devised. The crystal structure is tetragonal P4bm; residual factor is R = 0.030. Cell parameters are $\text{a = 8.891 ± 0.004}\text{A}\text{?}$ and $\text{c = 5.582 + 0.002}\text{A}\text{?}$. The V⁵⁺ atom lies at the center of a triangular pyramide (VO₄ tetrahedron) while the V⁴⁺ atom is on A 4-fold rotation axis at the center of a square-based pyramide VO₅ whose symmetry point group is almost C_4v with the short V = O bond lying along the 4-fold axis parallel to the c edge of the tetragonal cell. Crystals are thin platlets with (001) cleavage planes. The platlets have very often a square or rectangular shape limited by {100} or {110} planes. Each single crystal was not large enough to record a good e.p.r. spectrum, but by sticking on the same quartz plate a score of them it was possible to gather enough crystals so to record correct spectra and by orienting the plate to obtain resonance lines separately for g_∥ = 1.9263 et g_τ = 1.9755. Measurements at 283 K on powder samples gave times for spin-spin relaxation T₂ = 0.4 × 10^?7s and for spin-lattice relaxation T₁ = 1.6 × 10^?7s. The magnetic structure is characterized by an exchange narrowing ω_e = 3 × 10¹⁰rad/s which corresponds to a transition temperature of about 0.5 K. Static susceptibility measurements at high magnetic field show a paramagnetic behaviour with an antiferromagnetic interaction which is interpreted in the magnetic space group P_2c4bm as the interaction between V⁴⁺ ions from consecutive planes parallel to (001).     

Loss of ferromagnetism in YNi3 after H2 absorption

The compound YNi₃ ($\text{PuNi}{}_3\text{-}\text{type}\text{,}\text{a}\text{= 4.973}\text{A}\text{?}\text{,}\text{c}\text{= 24.42}\text{A}\text{?}$) is ferromagnetic below T_c = 35 K. After hydrogen absorption it loses its ferromagnetic character and becomes Pauli paramagnetic. The composition of the ternary hydride is approximately YNi₃H₄. The lattice constants are $\text{a}\text{= 5.267}\text{A}\text{?}$, $\text{c}\text{= 26.57}\text{A}\text{?}$.     

Thermoelectric power of (Me4N)2Ag13I15 and (Et4N)2Ag13I15

Thermoelectric power using reversible silver electrodes and electrical conductivity on the compressed pellets of (Me₄N)₂Ag₁₃I₁₅, and (Et₄N)₂Ag₁₃I₁₅ have been measured between room temperature and below 160°C. The results of θ can be expressed by the equations:?θ = 0.115 (10³/T)+0.2905VK^?1 and ?θ = 0.150 (10³/T) + 0.305mV K^?1; and those of conductivity by the equations; σ = 28.7 exp (?0.17eV/kT) ohm^?1cm^?1 and $\text{σ = 216.6 exp (?0.24e}\text{V}\text{kT}\text{)}$ ohm^?1cm^?1; respectively for Me- and Et-electrolytes. The results are discussed and compared with those of previous authors.