In extension of earlier work on complexes of p-tert-butyltetrathiacalix[4]arene, LH₄, with late transition-metal M^II species, we report studies of complexes modelled on the basis of single-crystal X-ray studies as derivatives of V^V, W^VI, Mn^II, Fe^III, Ni^II, Cu^II and Pd^II, the last as a trio of heteronuclear species also involving Ca^II. In complexes [VO(OH)(LH₂)·2.5dmf·2H₂O] (×2) (1), Cl₂W(L)·3.5C₆H₆ (2) and [Mn(LH₂)·3.5CH₂Cl₂] (×2) (3) included dmf is found only in the partially deprotonated calixarene cavities of 1 and 3. In oligonuclear OFe₃(HCO₂)(LH)₂·2H₂O·6dmf (4) and 2Cuac₂·Cu₂(L)·dmf·4.5CH₂Cl₂ (6) (ac = acetate) included dmf is found in both. Ni^II provides several species, including 5a, binuclear (Et₃NH)Ni₂(LH)(LH₂)·2dmf·2Me₂CO·H₂O, 5b, a remarkable hexanuclear (binuclear + tetranuclear) aggregate, Ni₆(L)(LH)₂(LH₂)·4MeCN·6H₂O, and 5c, an even more remarkable Ni₃₂ aggregate modelled as (centrosymmetric) Ni₃₂(OH)₄₀(L)₆·8dmso·10dmf, in which there are two sets of nickel atoms, one disposed at the corners of a cube (Ni₈), the other (Ni₂₄) at the vertices of a cuboctahedron (the Ni₈ vertices at the centres of the hexagonal faces); the hydroxy groups comprise two sets: one, (OH)₂₄, disposed outside the spheroidal shell of nickel atoms, the other, (OH)₁₆, disordered within, the thiacalixarene ligands L₆ being disposed about the axes of the octahedron. Heteronuclear species have been found as Ca^II/Pd^II combinations CaPd₂(LH)₂·1.5CH₂Cl₂ (7a), CaPd(LH₂)·3dmso·H₂O·4.5MeCN (7b), Ca₂Pd(LH)₂·3.5dmso·1.5H₂O·4MeCN (7c), all with included solvent.