Abstract: | Crystal structures of (Et4N)2Mo3S7Br6] (I) and (Et4N)(H9O4)Mo3S7Cl6] (II) clusters belonging to the class of Mo3S 7 4+ were determined by X-ray diffraction analysis. Crystals I are orthorhombic a=19.106(3), b=12.930(2), c=29.887(5) Å, V=7383(2) Å3, space group Pbca, Z=8, dcalc=2.253 g/cm3, R(F)=0.0402, wR(F2)=0.0587 for 2493 Fhkl>4σ. Crystals II are monoclinic, a=17.106(3), b=18.882(4), c=11.006(2), Å, β=126.13(3)°, V=2871.2(9) Å3, space group Cc, Z=4, dcalc=2.147 g/cm3, R(F)=0.0181, wR(F2)=0.0445 for 2307 Fhkl>4σ. Structure I has an anion dimer with 3Sax…Cl=3.258(4)–3.404(4) Å; the dimer is similar to that observed in the structures of A2M3X7Hal6], A=Ph4P+, Ph3EtP+, and PPN+. In structure II, infinite chains of anions bonded by 3Sax…Cl contacts of 3.183(3)–3.394(3) Å were found. A similar phenomenon was established earlier for the structure of (Et4N)(H9O4)Mo3S7Br6] (III), which is not isostructural to II. Compounds II and III also differ in the structure of the H9O4 + cation: infinite helix in II and pyramid in III. |