GENERATING STRUCTURAL MOTIFS BETWEEN 3-DIMENSIONAL SOLIDS AND DISCRETE SPECIES BASED ON THE (CUNCS) UNIT - (PPH4)[(RES4)CU-2(NCS)(2)], (NET4)(2)[(RES4)CU-3(NCS)(4)], AND (PPH4)(2)[(RES4)(2)CU-2(NCS)(2)]

The reaction of (PPh4)ReS4 or (NEt4)ReS4 with CuNCS (in different solv ents and with different relative amounts of reactants) yielded black c rystals of (PPh4)[(ReS4)Cu-2(NCS)(2)] (1), (NEt4)(2)[(ReS4)Cu-3(NCS)(4 )] (2) and (PPh4)(2)[(ReS4)(2)Cu-2 (NCS)(2)] (3). Compound 1 crystalli zes in the monoclinic space group P2(1)/n [a = 21.488(6) Angstrom, b = 11.142(4) Angstrom, c = 12.860(5) Angstrom, beta = 90.66(3)degrees, V = 3079(2) Angstrom(3), Z = 4, R = 0.058 and R-w = 0.063 for 5802 refl ections with F>4 sigma(F)], compound 2 in the monoclinic space group P 2(1)n [a = 10.551(4) Angstrom, b = 14.849(6) Angstrom, c = 22.782(11) Angstrom, beta = 92.35(4)degrees, V = 3566(3) Angstrom(3), Z = 4, R = 0.078 and R-w = 0.056 for 3006 reflections with F > 4.5 sigma(F)] and compound 3 in the triclinic space group P (1) over bar [a = 10.901(3) Angstrom, b = 10.981(3) Angstrom, c = 12.296(3) Angstrom, alpha = 109. 20(2), beta = 96.40(2), gamma = 98.17(2)degrees, V = 1356.0(6) Angstro m(3), Z = 1, R = 0.056 and R-w = 0.061 for 5016 reflections with F > 4 sigma(F)]. The structure of the anion in 1 consists of pairs of infin ite CuNCS zigzag chains connected by ReS4- groups, thus generating twe lve-membered rings running almost parallel to the b axis. In 2, one Cu (NCS)(2) and two Cu(NCS) units are linked by ReS4- groups leading to t welve-membered and novel, unusual sixteen-membered rings alternately a rranged in a linear strand. In the discrete complex of 3, two terminal ReS4- groups stabilize one eight-membered (CuNCS)(2) ring. An interes ting aspect of the present chemistry is the possibility of excision or linking of fragments from a solid-state structure (CuNCS) in which ro bust entities are interlinked in different ways.