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The self-assembly reactions of [MOS3]2– (M = W, Mo) with CuS2COCH3 in DMF produced two novel dodecanuclear Mo(W)/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- (CuS2COCH3)3]·H2O (1: M = W; 2: M = Mo). Cluster 1 crystallizes in hexagonal, space g