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Five new compounds in the Cu/P/Se phase diagram have been synthesized, and their crystal structures have been determined. The crystal structures of these compounds comprise four previously unreported zero-, one-, and two-dimensional selenidophosphate anions containing low-valent phosphorus. In addition to two new modifications of Cu4P2Se6 featuring the well-known hexaselenidohypodiphosphate(IV) ion, there are three copper selenidophosphates with low-valent P: Cu4P3Se4 contains two different new anions, (i) a monomeric (zero-dimensional) selenidophosphate anion [P2Se4](4-) and (ii) a one-dimensional selenidophosphate anion [Formula: see text], which is related to the well-known gray-Se-like [Formula: see text] Zintl anion. Cu4P4Se3 contains one-dimensional [Formula: see text] polyanions, whereas CuP2Se contains the 2D selenidophosphate [Formula: see text] polyanion. It consists of charge-neutral CuP2Se layers separated by a van der Waals gap which is very rare for a Zintl-type phase. Hence, besides black P, CuP2Se constitutes a new possible source of 2D oxidized phosphorus containing layers for intercalation or exfoliation experiments. Additionally, the electronic structures and some fundamental physical properties of the new compounds are reported. All compounds are semiconducting with indirect band gaps of the orders of around 1 eV. The phases reported here add to the structural diversity of chalcogenido phosphates. The structural variety of this family of compounds may translate into a variety of tunable physical properties.

Two intermetallic phases in the Sr-Li system have been synthesized and structurally characterized. According to single-crystal X-ray diffraction data, Sr(19)Li(44) and Sr(3)Li(2) crystallize with tetragonal unit cells (Sr(19)Li(44), I-42d, a = 15.9122(7) Å, c = 31.831(2) Å, Z = 4, V = 8059(2) Å(3); Sr(3)Li(2), P42/mnm, a = 9.803(1) Å, c = 8.784(2) Å, Z = 4, V = 844.2(2) Å(3)). The first compound is isostructural with the recently discovered Ba(19)Li(44). Sr in Sr(19)Li(44) can be fully replaced by Ba with no changes to the crystal structure, whereas the substitution of Sr by Ca is only possible within a limited concentration range. Sr(3)Li(2) can be assigned to the Al(2)Zr(3) structure type. The crystal structure determination of Sr(19)Li(44) was complicated by multiple twinning. As an experimental highlight, an electron microscopy investigation of the highly moisture- and electron-beam-sensitive crystals was performed, enabling high-resolution imaging of the defect structure.

The topochemical deintercalation of Na(+) ions from solid NaFeAs at room temperature in THF with iodine yields the superconducting phase Na(1-y)Fe(2-x)As(2) (T(c) ≈ 11 K). This metastable iron arsenide decomposes at 120 °C and is not accessible by high-temperature solid-state synthesis. X-ray powder diffraction confirms the ThCr(2)Si(2)-type structure, but reveals very small coherently scattering domains with a mean composition Na(0.9(2))Fe(1.7(1))As(2). HRTEM investigations show crystalline as well as strongly distorted areas with planar defects. The latter are probably due to sodium loss and disorder which is also detected by (23)Na solid state NMR. The (57)Fe-Mossbauer spectrum of Na(1-y)Fe(2-x)As(2) shows one type of iron atoms in tetrahedral coordination. All results point to one crystallographic phase with very small domains due to fluctuations of the chemical composition. From electronic reasons we suggest the superconducting phase is presumably NaFe(2)As(2) in the ordered fractions of the sample.

The new compound Y(21)I(18)C(14)B(7) was prepared from YI(3), Y, C, and B at 1450 K. The average crystal structure was determined from single-crystal X-ray data. The structure consists of pseudoorthorhombic twisted metal atom double layers containing quasi-molecular CBC units. These are sandwiched by pseudohexagonal iodine layers. Owing to the symmetry and metric misfit the structure must be described with a large triclinic unit cell (space group Ponemacr;, a = 10.660(2) Å, b = 15.546(3) Å, c = 18.416(3) Å, alpha = 82.49(2) degrees, beta = 85.01(2) degrees, gamma = 82.92(2) degrees, Z = 2), which is probably only a good space-averaged approximation. Significant deviations from the averaged structure are indicated by unusual displacement parameters and the results of high-resolution electron microscopy.