On the dissolution of gold in K2Qx and Na2Qx fluxes (Q=S, Se). Formation of KAuS5, KAuSe5, CsAuSe3, KAuSe2 and NaAuSe2: low-dimensional Au+ and Au3+ compounds with poly- and mono-chalcogenide ligands

Abstract Five compounds of gold, KAuS 5 , KAuSe 5 , CsAuSe 3 , KAuSe 2 and NaAuSe 2 are reported. Their preparation was accomplished by dissolving gold in molten alkali polychalcogenide salts in the temperature range of 250–350 °C. KAuS 5 and KAuSe 5 crystallize in the space group Ibam with a =8.310(2) A, b =10.758(3) A, c =15.468(4) A, V =1383 A 3 , and a =8.625(6) A, b =11.293(9) A, c =16.425(11) A, V =1600 A 3 , respectively. CsAuSe 3 , crystallizes in the space group C2/c with a =6.483(3) A, b =13.789(5) A, c =7.651(3) A, β =112.17(3)°, V =633 A 3 . KAuSe 2 crystallizes in the space group P4/mbm with a = b =7.699(3) A, c =3.665(1) A, V =217 A 3 . Finally NaAuSe 2 crystallizes in the space group P2 1 /c with a =6.991(8) A, b =8.374(9) A, c =6.724(8) A, β =105.23(9)°, V =379.8 A 3 . KAuS 5 and KAuSe 5 have one-dimensional infinite [AuQ 5 ] − chains with linear Au + atoms connected with Q 5 2− ligands. There are close Au-Au interactions between the chains. CsAuSe 3 has a similar one-dimensional structure but the [AuSe 3 ] − chains are helical and there are no Au-Au interactions between the chains. KAuSe 2 and NaAuSe 2 are Au 3+ compounds where the gold atoms are in square planar geometry. The K + salt has infinite ribbons of [AuSe 2 ] − but the Na salt has corrugated layers of [AuSe 2 ] − . Spectroscopic characterization of the compounds is reported.

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