Preparation and Structures of the 2.2.2-Cryptand(1+) Salts of the [Sb(2)Se(4)](2)(-), [As(2)S(4)](2)(-), [As(10)S(3)](2)(-), and [As(4)Se(6)](2)(-) Anions.

Abstract

2.2.2-Cryptand(1+) salts of the [Sb(2)Se(4)](2)(-), [As(2)S(4)](2)(-), [As(10)S(3)](2)(-), and [As(4)Se(6)](2)(-) anions have been synthesized from the reduction of binary chalcogenide compounds by K in NH(3)(l) in the presence of the alkali-metal-encapsulating ligand 2.2.2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane), followed by recrystallization from CH(3)CN. The [Sb(2)Se(4)](2)(-) anion, which has crystallographically imposed symmetry 2, consists of two discrete edge-sharing SbSe(3) pyramids with terminal Se atoms cis to each other. The Sb-Se(t) bond distance is 2.443(1) Å, whereas the Sb-Se(b) distance is 2.615(1) Å (t = terminal; b = bridge). The Se(b)-Sb-Se(t) angles range from 104.78(4) to 105.18(5) degrees, whereas the Se(b)-Sb-Se(b) angles are 88.09(4) and 88.99(4) degrees. The (77)Se NMR data for this anion in solution are consistent with its X-ray structure (delta 337 and 124 ppm, 1:1 intensity, -30 degrees C, CH(3)CN/CD(3)CN). Similar to this [Sb(2)Se(4)](2)(-) anion, the [As(2)S(4)](2)(-) anion consists of two discrete edge-sharing AsS(3) pyramidal units. The As-S(t) bond distances are 2.136(7) and 2.120(7) Å, whereas the As-S(b) distances range from 2.306(7) to 2.325(7) Å. The S(b)-As-S(t) angles range from 106.2(3) to 108.2(3) degrees, and the S(b)-As-S(b) angles are 88.3(2) and 88.9(2) degrees. The [As(10)S(3)](2)(-) anion has an 11-atom As(10)S center composed of six five-membered edge-sharing rings. One of the three waist positions is occupied by a S atom, and the other two waist positions feature As atoms with exocyclic S atoms attached, making each As atom in the structure three-coordinate. The As-As bond distances range from 2.388(3) to 2.474(3) Å. The As-S(t) bond distances are 2.181(5) and 2.175(4) Å, and the As-S(b) bond distance is 2.284(6) Å. The [As(4)Se(6)](2)(-) anion features two AsSe(3) units joined by Se-Se bonds with the two exocyclic Se atoms trans to each other. The average As-Se(t) bond distance is 2.273(2) Å, whereas the As-Se(b) bond distances range from 2.357(3) to 2.462(2) Å. The Se(b)-As-Se(t) angles range from 101.52(8) to 105.95(9) degrees, and the Se(b)-As-Se(b) angles range from 91.82(7) to 102.97(9) degrees. The (77)Se NMR data for this anion in solution are consistent with its X-ray structure (delta 564 and 317 ppm, 3:1 intensity, 25 degrees C, DMF/CD(3)CN).