We report the synthesis and structure and discuss in substantial detail the bonding of a remarkable family of compounds spanning most of the transition series. All members of the MTSi (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni; T = Co, Ni) series have now been prepared, and their crystal structures have been determined accurately using X-ray diffraction and, for MnNiSi and FeNiSi, neutron diffraction. Each of these compounds, four of which were previously unknown, crystallizes in the TiNiSi structure type. In contrast, for T = Cu, one has only representatives with M = Sc and Ti. A simple Zintl picture, which works so well for the three-dimensional four-connected indium net of the related BaIn2 structure, is not applicable to these intermetallics; there is substantial M−T and M−Si bonding, and the “extra” electrons in the MTSi structure enter orbitals essentially nonbonding within the TSi network. A structural change observed for M = Fe and higher d-electron counts, distorting the six-rings in the structure, is traced to the formation of M−M bonds. The instability of the corresponding Cu phases is discussed in terms of Miedema's ideas about electronegativity and electron density.

The alpha-beta phase transition in the novel energetic material 1,1-diamino-2,2-dinitroethylene, C2H4N4O4 (FOX-7), has been studied by single-crystal X-ray investigations at five different temperatures over the 200-393 K range. In these investigations, the positions of the hydrogen atoms were experimentally determined without any geometric constraints. In addition, X-ray powder investigations using the Guinier technique have been performed to characterize the beta-phase up to 423 K. The alpha-beta phase transition at 389 K is first order, shows a discontinuous increase of the molar volume and entropy (DeltaV = 1.75 cm3/mol, X-ray investigation; DeltaS = 1.5 cal/K mol, DSC analysis), and can be classified as displacive. The hitherto unknown structure of beta-FOX-7 was solved at 393 K and showed simple structural relations to the alpha-polymorph. The characteristic bonding in wave-shaped layers is now found for beta-FOX-7 (P2(1)2(1)2(1), z = 4, a= 6.9738(7) A, b = 6.635(1) A, c = 11.648(2) A, 393 K), as well as for alpha-FOX-7 (P2(1)/n, z = 4, a = 6.9467(7) A, b = 6.6887(9) A, c = 11.350(1) A, beta = 90.143(13) degrees , 373 K). Interestingly, whereas the intramolecular C-C, C-N, N-O, and N-H bond distances remain nearly unchanged for both polymorphs over the whole temperature range from 200 to 393 K, the two nitro groups deviate strongly from the molecular plane formed by the two carbon and two amino nitrogen atoms. In alpha-FOX-7 at 373 K, the nitro groups are twisted -47 and +6 degrees with respect to the carbon-carbon bond, but in beta-FOX-7 at 393 K, these twist angles are changed to -36 and +20 degrees . Within the layers, the FOX-7 molecules show strong pi-conjugation and extensive intra- and intermolecular hydrogen bonding. In this investigation, we have been able to show that alpha- and beta-FOX-7 build up different nets of intermolecular hydrogen bonds. In alpha-FOX-7, each oxygen atom of the nitro groups is involved in two hydrogen bonds resulting in two intramolecular and six intermolecular hydrogen bonds. But in beta-FOX-7 this coordination changes, and half of the oxygen atoms build up two and the other half build up three hydrogen bonds leading to two intramolecular and eight intermolecular hydrogen bonds. The average intermolecular hydrogen bond distance increases slightly from 2.31 A in alpha-FOX-7 to 2.52 A in beta-FOX-7. The C-NO2 bonds are of particular interest because they are referred to as the detonation trigger. It has been suggested that these bonds could be strengthened by the extensive intermolecular hydrogen bonding within the layers in both polymorphs. Such bond strengthening via cooperative effects was proposed in earlier DFT calculations on FOX-7 and may be one key to understanding its low sensitivity and high activation energy to impact.

The crystallochemistry of and the bonding in the orthorhombic four-connected nets of BaIn(2) (CeCu(2) structure) and of CaPtSn (TiNiSi structure, a derivative of the CeCu(2) structure) are analyzed with approximate molecular orbital calculations. Following the Zintl concept, in BaIn(2) the In(-) ions are isoelectronic with group IV tin and should adopt a four-connected structure. In contrast to alpha-tin, which has a cubic diamond structure, the indium ions in BaIn(2) build up an orthorhombic three-dimensional four-connected net containing distorted tetrahedra and ladder polymers of four-membered rings. In the CeCu(2) structure (space group Imma) two bond angles in these distorted tetrahedra are fixed at 90 degrees. The four-connected net in the CeCu(2) structure is topologically related to the layers in black phosphorus (space group Cmca). In CaPtSn (TiNiSi structure) the orthorhombic four-connected net is formed by (PtSn)(2)(-) ions in an ordered arrangement. Calculations on BaIn(2) and CaPtSn show that the four-connected nets are increasingly stabilized as the valence electron count is increased from 16 to 30 valence electrons per 4 formula units. For more than 30e, the nets are destabilized due to filling of M-E antibonding states. Structural data obtained by precise single crystal investigations for the TiNiSi series CaPdIn (20e), CaPdSn (24e), CaPdSb (28e), and CaAgSb (32e), confirm the results of the extended Hückel calculations. We find an interesting and understandable angular asymmetry of the tetrahedral sites in these ternary compounds.

Abstract1,1‐Diamino‐2,2‐dinitroethene, C2H4N4O4 (FOX‐7), is a novel high energy density material with low friction and impact sensitivity and a high activation barrier to detonation. In this study, the previously unknown crystal structure of the γ‐polymorph of trimorphic FOX‐7 is reported. γ‐FOX‐7 is stable from ∼435 K until the compound decomposes just above 504 K. A single crystal of α‐FOX‐7 (P21/n, Z=4, a=694.67(7) pm, b=668.87(9) pm, c=1135.1(1) pm, β=90.14(1)°, T=373 K) was first transformed into a single crystal of β‐FOX‐7 (P212121, Z=4, a=698.6(1) pm, b=668.6(2) pm, c=1168.7(3) pm, T=423 K) and then into a single crystal of γ‐FOX‐7 at 450 K. The γ‐FOX‐7 crystal was then subsequently quenched to 200 K. The structure of γ‐FOX‐7 (P21/n, Z=8, a=1335.4(3) pm, b=689.5(1) pm, c=1205.0(2) pm, β=111.102(8)°, T=200 K) consists of four planar layers, each containing two crystallographically independent FOX‐7 molecules found in the asymmetric unit.

We studied lithium azide (LiN(3)) by x-ray diffraction and Raman spectroscopy at hydrostatic compression up to pressures above 60 GPa at room temperature. The results of x-ray diffraction analyses reveal the stability of the ambient-pressure C 2/m crystal structure up to the highest pressure. The pressure dependence of librational modes provides evidence for an order-disorder transition at low pressures (below 3 GPa), similar to the transition observed previously at low temperatures. The observed structure stability indicates that this transition is not associated with structural changes. The phase stability of LiN(3) is in contrast to that of sodium azide (which is isostructural at ambient pressure), for which a set of phase transitions has been reported at pressures below 50 GPa.