Synthesis and characterization of the "metallic salts" A5Pn4 (A = K, Rb, Cs and Pn = As, Sb, Bi) with isolated zigzag tetramers of Pn4(4-) and an extra delocalized electron.

The isostructural title compounds were prepared by direct reactions of the corresponding elements, and their structures were determined from single-crystal X-ray diffraction data in the monoclinic space group C2/m, Z = 2 (K5As4, a = 11.592(2) A, b = 5.2114(5) A, c = 10.383(3) A, beta = 113.42(1) degrees; K5Sb4, a = 12.319(1) A, b = 5.4866(4) A, c = 11.258(1) A, beta = 112.27(7) degrees; Rb5Sb4, a = 12.7803(9) A, b = 5.7518(4) A, c = 11.6310(8) A, beta = 113.701(1) degrees; K5Bi4, a = 12.517(2) A, b = 5.541(1) A, c = 11.625(2) A, beta = 111.46(1) degrees; Rb5Bi4, a = 12.945(4) A, b = 5.7851(9) A, c = 12.018(5) A, beta = 112.78(3) degrees; Cs5Bi4, a = 12.887(3) A, b = 6.323(1) A, c = 12.636(1) A, beta = 122.94(2) degrees). The compounds contain isolated and flat zigzag tetramers of Pn4(4-) (Pnictide (Pn) = As, Sb, Bi) with a conjugated pi-electron system of delocalized electrons. All six compounds are metallic ("metallic salts") and show temperature-independent (Pauli-like) paramagnetism due to a delocalized electron from the extra alkali-metal cation in the formula. At low temperatures (around 9.5 K) and low magnetic fields the bismuthides become superconducting.