Compound 3 is unique. Its structure was unambiguously confirmed from a fractional crystallisation and manual separation from the components in the mixture (Figure ). In the solid state, 3 exhibits a ternary spirocyclic array with a central 7-membered ring-system that incorporates two aluminium, one sulfur and four carbon atoms. This ring system is derived from the double C-S activation of thiophene by two equiv. of 1. The 7-membered ring system is non-planar and puckers into a distorted twist-boat structure. The Al-S bond lengths of 2.2054(18) and 2.2147(17) Å are consistent with known aluminium(III) sulfide derivatives containing the -diketiminate ligand system, while Al-C bond lengths of 1.957( ) and 1.977 (6) Å are similar to related 5-membered aluminocycles derived from 1. Within the hydrocarbon unit, C-C and C=C bonds alternate, consistent with a localised butadiene structure. In C6D6 solution, 3 demonstrates 1 H resonances at  = 6.14 (d, 2H, J = 16.9 Hz) and 7.00 (d, 2H, J = 16.9