The reaction of Mn and Cd in alkali metal polythioarsenate fluxes afforded four new compounds featuring molecular anions. K-8[Mn-2(AsS4)(4)] (I) crystallizes in the monoclinic space group P2/n with a = 9.1818(8) Angstrom, b = 8.5867(8) Angstrom, c = 20.3802(19) Angstrom, and beta = 95.095(2)degrees. Rb-8[Mn-2(AsS4)(4)] (II) and Cs-8[Mn-2(AsS4)(4)] (III) both crystallize in the triclinic space group P (1) over bar with a = 9.079(3) Angstrom, b = 9.197(3) Angstrom, c = 11.219(4) Angstrom, alpha = 105.958(7)degrees, beta = 103.950(5)degrees, and gamma = 92,612(6)degrees for II and a = 9.420(5) Angstrom, b = 9.559(5) Angstrom, c = 11,496(7) Angstrom, alpha = 105.606(14)degrees, beta = 102.999(12)degrees, and gamma = 92.423(14)degrees for III. The discrete dimeric [Mn-2(AsS4)(4)](8-) clusters in these compounds are composed of two octahedral Mn2+ ions bridged by two [AsS4](3-) units and chelated each by a [AsS4](3-) unit. Rb-8[Cd-2(AsS4)(2)(AsS5)(2)] (IV) crystallizes in P (1) over bar with a = 9.122(2) Angstrom, b = 9,285(2) Angstrom, c = 12.400(3) Angstrom, alpha = 111.700(6)degrees, beta = 108.744degrees, and gamma = 90.163(5)degrees. Owing to the greater size of Cd compared to Mn, the Cd centers in this compound are bridged by [AsS5](3-) units. The [Cd-2(AsS4)(4)](8-) cluster is a minor component cocrystallized in the lattice. These compounds are yellow in color and soluble in water.