The series of compounds V1+xMo2−xS4 (0 ≤
x
≤ 2) has been prepared and characterised by powder X-ray and neutron diffraction, thermogravimetry, SQUID magnetometry and electrical transport measurements. Materials with x
≤ 0.50 adopt a distorted variant of the Cr3S4 structure (space group Cca
≈ 11.8, b
≈ 6.5, c
≈ 12.8 Å, β
≈ 114.8°) in which there are triangular clusters of cations within a dichalcogenide unit. At higher levels of vanadium incorporation, the phases crystallise in the space group C2/m (a
≈ 12.8, b
≈ 3.3, c
≈ 5.9 Å, β
≈ 114.9°) and the cations within the dichalcogenide slab form zigzag chains, with an intrachain cation–cation separation of ca 2.8Å. The change in the nature of the cation clustering occurs at a composition where there is a transition from semiconducting (x
≤ 0.50) to metallic (x > 0.50) behaviour. Magnetic measurements reveal that paramagnetism is observed over the whole composition range. The measured Curie constants suggest a magnetic moment associated with the cations in the ordered defect layer only and indicate a significant degree of electron delocalisation.
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