Whereas stable octanuclear clusters of the type M-8(I)((EE)-E-boolean AND)(6) (M = Cu, Ag; (EE)-E-boolean AND = dithio or diseleno ligand) are known for being able to encapsulate a hydride or main-group anion under some circumstances, only the related hydride-containing heptanuclear [M-I](7)(H)((EE)-E-boolean AND)(6) and empty hexanuclear [M-I](6)((EE)-E-boolean AND)(6) species have been characterized so far. In this paper we investigate by the means of theoretical calculations and experiments the viability of empty and anion-centered clusters of the type [Cu-I](7)(X)((EE)-E-boolean AND)(6) and [Cu-I](6)(X)((EE)-E-boolean AND)(6) (X = vacancy, H or a main-group atom). The theoretical prediction for the existence of anion-containing heptanuclear species, the shape of which is modulated by the anion nature and size, have been fully confirmed by the synthesis and characterization of [Cu-7(X){S2P((OPr)-Pr-i)(2)}(6)] (X = H, Br). This consistency between experiment and theory allows us to predict the stability and shape-modulated structure of a whole series of [Cu-I](7)(X)((EE)-E-boolean AND)(6) (X = vacancy, H, O, S, halogen) and [Cu-I](6)(X)((EE)-E-boolean AND)(6) (X = H, halogen) clusters.