Add time:07/31/2019         Source:sciencedirect.com

The first quaternary nitride telluride with trivalent gadolinium, Cs2Gd6N2Te7, was obtained by the reaction of metallic gadolinium with cesium azide, elemental tellurium, and gadolinium trichloride as well as cesium chloride as flux at 900 °C for 7 days in evacuated silica tubes. Single crystals occur as long black needles and crystallize in the monoclinic space group C2/m (a = 2403.1(2) pm, b = 424.03(3) pm, c = 1142.91(7) pm, β = 103.709(4)°, Z = 2). Three crystallographically different Gd3+ cations constitute the structure, two are coordinated by one N3− (d(Gd(1/2)–N) = 217 pm) and five Te2− anions (d(Gd(1/2)–Te) = 305–326 pm), and the third Gd3+ by two N3− (d(Gd(3)–N) = 244 pm) and four Te2− anions (d(Gd(3)–Te) = 316–317 pm), all forming distorted octahedra about Gd3+. The Cs+ cation shows a perfect bicapped trigonal prism (C.N. = 8, d(Cs–Te) = 383–431 pm) as coordination sphere. Two of these polyhedra are condensed via a common (non-capped) rectangular face building up double prisms [Cs2Te12]22−. Further linkage via triangular faces (along [0 1 0]) and two of the four caps (along [0 0 1]) results in corrugated layers [Cs2Te7]12− running parallel to (1 0 0). However, the main feature of the crystal structure comprises N3−-centered (Gd3+)4 tetrahedra (d(N–Gd) = 217 pm (2×) and 244 pm (2×); ∡(Gd–N–Gd) = 107° (2 + 2 + 1×) and 121° (1×)), which are connected via two vertices each to build up one-dimensional infinite chains {∞1[N(Gd1)1/1t(Gd2)1/1t(Gd3)2/2v]6+} (t = terminal, v = vertex-shared) along [0 1 0] like in the structure of the M3NCh3-type nitride chalcogenides with M = La–Nd, Sm, Gd–Dy, and Ch = S, Se.

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