Preparation of heterometallic single cubes [W(3)MS(4)(H2O)(12)](n+) (M=In, Ge or Sn) and the first corner-share double cubes [W6SnS8(H2O)(18)](8+) and [W3Mo3SnS8(H2O)(18)](8+) as derivatives of [W3S4(H2O)(9)](4+)

Conversion of the purple trinuclear W-3(IV) incomplete cuboidal cluster [W3S4(H2O)(9)](4+) into heterometallic single cubes of the kind [W(3)MS(4)(H2O)(12)](n+) has been achieved with M = In, Ge or Sn. The indigo blue [W3InS4(H2O)(12)](5+) product was obtained by reaction of [W3S4(H2O)(9)](4+) with aquaindium(I), or indium metal, or In-III in the presence of BH4-. Red-brown [W3GeS4(H2O)](6+) was obtained by reaction with GeO, which can also be regarded as addition of Ge-II. An alternative route is provided by the reaction with GeO2 and a reducing agent (here H3PO2). Although a crystal structure of [W-3(SnCl3)S-4(NCS)(9)](6-) has been reported previously, isolation of the yellow-brown aqua ion [W3SnS4(H2O)(12)](6+) as the chloro product [W-3(SnCl3)S-4(H2O)(9)](3+) by addition of Sn-II to [W3S4(H2O)(9)](4+) in 2 M HCl is described for the first time. The same product was obtained by treating [W3S4(H2O)(9)](4+) with tin metal. Charges applying to the core of the cube were determined from the stoichiometry of its reaction with [Fe(H2O)(6)](3+). In the case of [Mo3S4(H2O)(9)](4+), reaction with tin metal gave the corner-shared double cube [Mo6SnS8(H2O)(18)](8+). The W-6 analogue was only obtained by the reaction of [W3S4(H2O)(9)](4+) with [W3SnS4(H2O)(12)](6+) in the presence of a reducing agent (BH4-). The corresponding reaction of [MoSnS4(H2O)(12)](6+) gave the mixed corner-shared double cube [W3Mo3SnS8(H2O)(18)](8+). Near-quantitative transfer of the heterometal atom was observed on treating [W3InS4(H2O)(12)](5+) or [W3SnS4(H2O)(12)](6+) with [Mo3S4(H2O)(9)](4+), indicating a much stronger affinity of the heterometal atom for [Mo3S4(H2O)(9)](4+).