A Further Extension of Pnictide Oxide Chemistry – Synthesis and Structure of La2AuP2O

The phosphide oxide La₂AuP₂O was synthesized from lanthanum filings, dried La₂O₃, gold pieces, and ground red phosphorus in the ideal 1.33:0.33:1:2 ratio in an evacuated silica tube at 1473 K. Small single crystals were obtained by recrystallization in a NaCl/KCl flux. The structure was determined on the basis of single‐crystal X‐ray diffractometer data: new type, C2/m, a = 1537.3(3), b = 427.39(8), c = 1009.2(2) pm, β = 131.02(1) °, wR₂ = 0.046, 1102 F² values, 38 variables. La₂AuP₂O contains two striking structural motifs: The oxygen atoms are located in La₄ tetrahedra. The latter are cis‐edge‐shared forming polymeric cationic [La₂O]⁴⁺ chains. These cationic units are separated and charge‐balanced by [AuP₂]^4– polyanions which have monovalent gold in distorted trigonal planar phosphorus coordination. Two crystallographically independent phosphorus sites occur in the polyanion, i.e. isolated P^3– besides dumb‐bells P₂^4– (P2–P2 223 pm). La₂AuP₂O, which crystallizes in the form of ruby red transparent crystals, is an electron precise phosphide oxide (4La³⁺)(2Au⁺)(2P^3–)(P₂^4–)(2O^2–).