By the reaction of Nb(6)Cl(14)6CH(3)OH with sodium methoxide in methan
ol at 254 K, the triclinic cluster compound Na-4[Nb6Cl12(OCH3)(6)] nCH
(3)OH 1 with a = 1125.2(11), b = 1156.9(11), c = 1294.9(13) pm, a = 89
.66(8)degrees, beta = 71.46(8)degrees, gamma = 68.19(8)degrees and V =
1471.7 x 10(6) pm(3) has been prepared. Reacting 1 with 222-cryptand
yields triclinic crystals (cryptNa)(2)Na-2[Nb6Cl12(OCH3)(6)]. 15CH(3)O
H 2 with space group <P(1)over bar>(No. 2), a = 1325.6(4), b = 1669.2(
6), c = 2442.1(9) pm, alpha = 81.70(3)degrees, beta = 77.09(3)degrees,
gamma = 77.95(3)degrees; V = 5123.8(31) x 10(6) pm(3) Z = 2, Dc = 1.6
17 g/cm(3) The structure of 2 is built from (C18H36N2O6Na)(+) and [Na-
2(CH3OH)(8)](2+) cations and [Nb6Cl12(OCH3)(6)](4-) anions. The Nb-Nb
and Nb-Cli distances in the range of 295.2 to 298.0 pm and 246.6 to 24
9.8 pm, respectively, being longer than expected for [Nb6Cl12](2+) uni
ts, are not fully understood.