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LaPtIn was attempted hydrogenated at a hydrogen pressure of 182 bar and temperatures from room temperature to 673 K. The crystal structure of the resulting LaPtInH 0.53 hydride was determined from powder neutron diffraction data. The structure was indexed on an expanded LaPtIn intermetallic unit cell with space group P 6 ¯ 2 m and dimensions a = 7.8229(2) A and c = 4.1647(2) A. Hydrogen occupies tetrahedral 4h sites in such a way that tetrahedral voids sharing a common face are not simultaneously populated. The result could not support previous density-functional theory calculations regarding the hydrogen absorption capacity of LaPtIn [P. Ravindran, P. Vajeeston, R. Vidya, A. Kjekshus, H. Fjellvag, Phys. Rev. Lett. 89 (2002) 106403].

First-principles modeling, experimental, and thermodynamic methodologies were integrated to facilitate a fundamentally guided investigation of quaternary complex hydride compounds within the bialkali Na-Li-Al-H hydrogen storage system. The integrated approach has broad utility for the discovery, understanding, and optimization of solid-state chemical systems. Density functional theory ground-state minimizations, low-temperature powder neutron diffraction, and low-temperature synchrotron X-ray diffraction were coupled to refine the crystallographic structures for various low-temperature distorted Na 2LiAlH6 allotropes. Direct method lattice dynamics were used to identify a stable Na2- LiAlH 6 allotrope for thermodynamic property predictions. The results were interpreted to propose transformation pathways between this allotrope and the less stable cubic allotrope observed at room temperature. The calculated bialkali dissociation pressure relationships were compared with those determined from pressure-composition-isotherm experiments to validate the predicted thermodynamic properties. These predictions enabled computational thermodynamic modeling of Na 2LiAlH6 and competing lower order phases within the Na-Li-Al-H system over a wide of temperature and pressure conditions. The predictions were substantiated by experimental observations of varying Na 2LiAlH6 dehydrogenation behavior with temperature. The modeling was used to identify the most favorable reaction pathways and equilibrium products for H discharge/recharge in the Na-Li-Al-H system, and to design conditions that maximize the theoretical hydrogen reversibility within the Na -Li-Al-H system.

KAlD 4 was synthesized from LiAlD 4 , AlEt 3 and KF in Et 2 O. The crystal structure was determined from powder neutron diffraction data at 8 and 295 K. KAlD 4 takes the same structure as BaSO 4 and KGaD 4 with space group Pnma and unit-cell dimensions a = 885.15 (14) pm, b = 581.19 pm (8), c = 734.57 (11) pm at 295 K. The crystal structure consists of isolated, nearly ideal, AlD 4 − tetrahedra with K + in 10-coordinated sites in-between. The average Al–D distance is 161.8 pm.

Two hydrogenated intermetallics with the highest Al/Zr ratio among the hydrogen-absorbing Zr–Al compounds, Zr 4 Al 3 and Zr 3 Al 2 , have been studied by synchrotron X-ray, powder neutron diffraction and thermal desorption spectroscopy. Initial intermetallic compounds are quite different with respect to Al–Al interactions and contain plain Kagome Al nets (Zr 4 Al 3 ) or Al–Al pairs (Zr 3 Al 2 ). In hexagonal Zr 4 Al 3 D 2.68 (space group (s.g.) P 6 3 22; a =11.0017(4); c =11.1694(5) A) a 2 a ×2 a ×2 c superstructure is formed as a result of deuterium ordering in half of the available Zr 4 tetrahedra. These tetrahedra share common corners and edges and form layers separated by 6363 Al-nets. In tetragonal Zr 3 Al 2 D 2.26 (s.g. P 4 2 / mnm ; a =7.5970(3); c =7.2613(3) A) in addition to the completely filled Zr 4 tetrahedra hydrogen partially occupies Zr 3 triangular sites. Thermal stability of the studied deuterides and Zr–D bonding characteristics can be related to the size of the occupied Zr 4 tetrahedra. Higher thermal stability of Zr 3 Al 2 D 2.26 agrees well with the existence of large Zr 4 sites and contrasts to the behavior of Zr 4 Al 3 D 2.68 containing ‘contracted’ Zr 4 tetrahedra and having weaker Zr–D bonds.

The recent powder neutron diffraction study of the crystal structure of LaNiInD 1.22 [J. Alloys Comp. 330–322 (2002) 132] concluded on the formation of a D…D pair with an unusually short interatomic distance of 1.63 A. Hydrogen atoms in LaNiInD 1.22 occupy a single crystallographic site and are coordinated by face-sharing La 3 Ni tetrahedra (92% occupancy). PCT measurements show that hydrogen storage capacity of LaNiIn, 1.63 at.H/formula unit, exceeds the limit of 1.33 at.H/LaNiIn when the La 3 Ni sites are completely occupied. In the present work, in situ powder neutron diffraction data were collected under D 2 pressure of 4.6 bar in order to study the deuteride with a maximum D content in the metal matrix. In the hexagonal structure of LaNiInD 1.63 (space group P 6 2 m ; a =7.3874(4); c =4.6816(2) A) Rietveld refinements showed that deuterium atoms occupy 36% of the available distorted La 3 NiIn 2 octahedra, in addition to the 96% filled La 3 Ni sites. The structure of LaNiInD 1.63 represents the first example of a deuteride containing direct In–D bonds (2.346(2) A). H bonding to the La 3 NiIn 2 sites is rather weak and a desorption from these sites takes place at room temperature and hydrogen pressures below 1 bar.

The structure of Li 3 AlD 6 has been determined by combined synchrotron X-ray and neutron diffraction. The space group is R 3 with unit-cell dimensions a =8.07117(10) and c =9.5130(2) A. The structure consists of isolated and close to regular AlD 6 3− octahedra, which are connected via six-coordinated Li. The Al–D distances are 1.734–1.754 A, and the Li–D distances are 1.892–2.120 A. The shortest D–D distance of 2.395 A is found within the octahedra. The structure can be described as a distorted bcc structure of AlD 6 3− units with all tetrahedral sites filled with Li.

The crystal structure of rhombohedral PbNb2O6 is re-examined by powder XRD and powder neutron diffraction in combination with ab initio DFT calculations.

Mechanochemical milling of LnCl3 (Ln: La—Tb, Er, Yb, Lu) with LiBH4 in the molar ratio of 1:6 for 5 h and additional annealing at 100 °C for 50 h leads to the new compounds LiLn(BH4)3Cl (Ln: La, Ce, Pr, Nd, Sm, Gd), Ln(BH4)3 (Ln: Sm, Gd, Tb, Er, Yb), and/or LiLn(BH4)4 (Ln: Yb, Lu).

The deuterides Zr 3 V 3 B 0.24 O 0.36 D 8.0 and Zr 3 V 3 B 0.40 O 0.60 D 6.4 with cubic structures [space group Fd 3 m (No. 227)] related to η 1 - (Fe 3 W 3 C) type have been studied by powder X-ray and neutron diffraction. The transition from the alloys to the corresponding deuterides gives a redistribution of the O/B atoms between two available types of zirconium octahedra, from 16 d (1/2, 1/2, 1/2) into the 8 b (7/8, 3/8, 7/8) sites. A correlation between occupancy/vacancy of the Zr 6 octahedra and the structure of the deuterium sublattice has been established. This explains the significant differences between the deuterides studied in this work and the previously reported, chemically similar Zr 3 V 3 OD 4.93 .

Compositions in the range Zr3V3B0.12–0.40O0.18–0.60 from the Zr–V–B2O3 system have been subjected to metallographic characterisation, microprobe analysis and powder neutron diffraction. On melting, boron was found to be reduced from its oxide and in the annealed condition, it was identified as a constituent of two phases, η-oxyboride Zr3V3(B,O) and vanadium boride V3B2. Hydrogen absorption–desorption properties were studied and related to the phase and structural composition of the alloys. A redistribution of the light atoms (oxygen, boron) within the η-oxyboride Zr3V3(B,O) matrix and, also, between the constituent phases of the alloys takes place during high temperature cycling in hydrogen which could indicate increased lattice mobility of these non-metallic elements in the hydride material.

The crystal structure of hexa(phenylthio)-l,3-butadiene, C40H30S6, was studied by X-ray diffraction at 87 K. The space group is monoclinic, Ia, a = 13.947(2) Å, b = 22.254(4) Å, c = 11.610(2) Å, β = 106.54(1)° and Z = 4. Intensity data were collected with MoKα radiation to (sin θ)/λ < 0.705 Å−1. The structure was solved by direct methods. Refinement based on 4920 |F o| converged at Rw = 0.032. The central bond of the butadienyl core, 1.472(4) Å, is comparable to the single bond of unconjugated 1,3-butadiene, whereas the two double bonds, 1.353(5) Å and 1.371(5) Å, are longer than expected for a C(sp 2) = C(sp 2) bond. This may be attributed in part to hybridization changes caused by the S atoms. The large torsion angle over the central bond C1–C2–C3–C4 = −66.8(4)°, reflects the accommodation of this fragment to a highly crowded intramolecular environment. All phenyl rings have intramolecular contacts within van der Waals radii with at least one other ring and one of the butadiene carbon atoms. The sulfur atoms are engaged in an inner loop of short 1,n S···S contacts in the range 3.070(3) Å −3.429(4) Å for n ≥ 3. Averaged deviations from 120° in the ipso, 0.5(1)°, and ortho, −0.5(1)°, positions of the six phenyl rings show that the S atoms serve as electronegative substituents attracting electron density from the rings.

The crystal structure of bis(phenylthio)acetylene, C14H10S2, was studied by X-ray diffraction at 87 K. The space group is P21/c, a = 14.6790(8) Å, b = 5.6481(3) Å, c= 14.7115(11) Å, β= 105.60(1)° from repeated centrings on resolved MoK α 1 peaks, Z = 4. Intensity data were collected with MoKα radiation on three different crystals, LO data with (sinθ)/λ < 0.714 Å−1 on one crystal, and HO data in the (sinθ)/λ range 0.682–0.857 Å−1 on two different crystals. The standard corrections were applied to the data, including corrections for absorption, before merging. Structure solution was by direct methods, refinement based on the full data set, 5757 F o converged at Rw = 0.036, a separate refinement including only non-hydrogen atoms and based on 3206 F o with (sin θ/λ > 0.65 Å−1 gave a final Rw = 0.031. The atomic sequence –S–C≡C–S– is distinctly nonlinear, the S–C (acetylene) bonds, average 1.6647(9) Å, have significant double bond character, and the central C≡C bond, 1.2224(12) Å, is about 0.04 Å longer than expected for a vicinally substituted carbon-carbon triple bond. The pattern of angular deviations from 120° in the phenyl rings shows that the S atoms are electronegative substituents combining σ-electron withdrawal with some π-electron donation. Both phenyl groups are nearly eclipsed with the acetylenic moiety which gives rise to two short intramolecular H(phenyl)…C(acetylene) contacts, 2.49 Å and 2.59 Å.

C4H10O2S2, Mr = 154.25, monoclinic, T = 87(1) K. (α) P21/n, a = 10.520(2), b = 5.818(1), c = 12.029(2) Å, β = 92.86(1)°, V = 735.3(2) Å3, Z = 4, Dx = 1.3934(4) Mgm−3, λ(MoKᾱ) = 0.71073 Å, μ = 0.617 mm−1, F(000) = 328, R = 0.023 for 2080 reflections. (β) P21/c, a = 10.413(1), b = 6.706(1), c = 10.229(1) Å, β = 94.32(2)°, V = 712.3(2) Å3, Z = 4, Dx = 1.4384(8) Mgm−3, λ(MoKᾱ) = 0.71073 Å, μ = 0.637 mm−1, F(000) = 328, R = 0.021 for 2007 reflections. The main conformational distinction between the two forms is the −synclinal and +synclinal orientation of the C(Me)–S–C–C in the thio end of the α and β forms, respectively. The bond lengths and angles are very similar in the two forms, and in good agreement with some related sulfone and sulfide structures.

The ferromagnetic ordering of the Heusler-related alloy AuMnSn has been verified by powder neutron diffraction. The cubic AlLiSi-type crystal structure of AuMnSn [a=634.12(11) pm at 298 K, Au in 4c, Mn in 4b, Sn in 4a of F43m] has been confirmed. Contrary to the indications from the preceding single-crystal X-ray diffraction study of AuMnSn the powder neutron diffraction data gave no evidence for intermixing of Mn and Sn on the 4b and 4a sites. The ordered magnetic moments are confined to the Mn atoms and their size at 298 K is μF,Mn=3.62(7) μB.

The structure of Li 3 AlD 6 has been determined by combined synchrotron X-ray and neutron diffraction. The space group is R 3 with unit-cell dimensions a =8.07117(10) and c =9.5130(2) A. The structure consists of isolated and close to regular AlD 6 3− octahedra, which are connected via six-coordinated Li. The Al–D distances are 1.734–1.754 A, and the Li–D distances are 1.892–2.120 A. The shortest D–D distance of 2.395 A is found within the octahedra. The structure can be described as a distorted bcc structure of AlD 6 3− units with all tetrahedral sites filled with Li.