Crystal and Electronic Structures of the New Antimonides TiGeSb and HfGeSb

Ternary arsenides Zr(Si As1−)As with PbCl2-type (0 ≤x≤ 0.4) and PbFCl-type (x= 0.6) structures

“…A key motivation for examining these systems is to understand mixed-anion compounds that may adopt structures different from the parent binaries because of stabilization through differential fractional site occupancy (DFSO) [1][2][3]. The most well-studied of these systems are the silicon-and germanium-containing antimonides, which comprise the following phases (for Tt = Si, Ge): MTt x Sb 2−x (PbCl 2 -or PbFCl-types) [4][5][6], TiTt x Sb 1−x (NiAs-type) [7], Ti 5 TtSb 2 (W 5 Si 3 -type) [7][8][9], Ti 5 Tt 3−x Sb x (Mn 5 Si 3 -type) [8,9], and Zr 5 TtSb 3 (stuffed Mn 5 Si 3 -type) [10,11]. The tin-containing antimonides tend to be distinct, as exemplified by ZrSn x Sb 2−x (CrSi 2 -or PbCl 2 -types) [4,12], TiSnSb (Mg 2 Cu-type) [13,14], and Ti 11 Sn x Sb 8−x (Cr 11 Ge 8 -type) [15].…”

Crystal Structure and Physical Properties of the New Antimonide Hf3Cu2Ge3.58Sb1.42

“…55 Finally, an Sb3-Sb3 distance of 3.31 Å across neighboring Sb3 layers may be bonding as well, similar to the Sb-Sb contact in HfGeSb of also 3.31 Å . 35 Electronic Structure. Because of the numerous long but likely significant Hf-Hf and Sb-Sb contacts in addition to undistorted square nets with mixed Ge/Sb occupancies, we expected the title compound to be metallic.…”

“…The crystal structure of Hf 3 Cu 2 Ge 3.58 Sb 1.42 (Figure ) may be regarded as an intergrowth of the ZrSiS type, adopted by, e.g., ZrGeSb and HfGeSb (fragment A), and the (ordered) NdTe 3 type, adopted by PrSeTe 2 (fragment B), comprising square nets of the E1 site (88% Ge, 12% Sb) within fragment A as well as square nets of the Cu atoms within fragment B.…”

“…Only the reaction with the 3.58:1.42 afforded the target compound without noticeable side products. The samples with the 3.7:1.4 and 3.4:1.6 ratios included smaller amounts of HfGeSb (ZrSiS type) and HfCuGe 2 in addition to the target, whereass the target was not formed at all in the remaining two reactions. One can thus conclude that the phase width of the title compound has to be very small, possibly negligibly so.…”

HfSb2–xTex: The Second New Compound on the Quasi‐Binary Section HfSb2‐HfTe2 with Different Sb–Sb Interactions

“…Representatives include the Chimney ladder phases Ti 5 Sb 8 14 and Zr 11 Sb 18 15 with a multitude of intermediate Sb–Sb bonds between 3.1 Å and 3.4 Å, TiSb 2 with Sb 2 4– dumbbells,16 ZrSb 2 and HfSb 2 with antimony ribbons and pairs,17,18 and Hf 5 Sb 9 with a planar T‐shaped net of antimony atoms 19,20. Different structures were obtained when replacing part of the antimony atoms with tellurium and with E = Si, Ge, Sn, namely ZrSbTe and HfSbTe21 with planar rectangular antimony layers (NbPS type), Zr E x Sb 2– x and Hf E x Sb 2– x 22 (Co 2 Si type), and ZrSi 0.7 Sb 1.3 , ZrGeSb23 and HfGeSb24 (with square planar layers formed by the Si/Ge atoms with some antimony content (ZrSiS type)). Square nets of > 80 % antimony atoms were observed in the structure of Hf 3 Cu 2 Ge 3.58 Sb 1.42 25.…”