Treatment of an aryl-sec-alkyl unsymmetrical thiourea (Tu) with (CuX2)-X-II (X = I, Br) transform the thiourea (Tu) into a thioamidoguanidino (Tag) moiety with concomitant reduction of Cu-II to Cu-I, which forms a [Cu-2(I)(mu(2)-X)(2)Tag(2)) (X = I (for A) and X = Br (for B)) complex. Meanwhile, the treatment of same unsymmetrical thiourea (Tu) with (CuX)-X-I (X = Br) forms a stable cluster with a [Cu-3(I)(mu(2)-S)(4)Tu(4)X(3)] core (C). Single crystal X-ray diffraction revealed that compounds A and B exhibit ID chain with a Cu-2(mu(2)-X)(2) core, whereas compound C is a (Cu3S4Br3)-S-I cluster. Compound A is centrosymmetric due to the trans orientation of two Tag units whereas compound B is ascentric due to the cis orientation of two Tag units. In compound A, the Cu2I2 core is perfectly rhomboidal where the iodine atoms are trans oriented. However in compound B, the Cu2Br2 core is not perfectly rhomboidal (bowl shaped) and the bromine atoms are cis oriented. It is interesting to note that although the Tag moiety in compounds A and B contain two morpholine-O atoms; only one of the morpholine-O atoms (02) is involved in the generation of three-dimensional network. The (Cu3S4Br3)-S-I cluster in compound C contains one tri- and two tetra-coordinated Cu-I centers. The Cu-I cluster in C contains a Cu-2(mu(2)-S)(2) rhomboidal plane exhibiting a chair and a boat form containing the (Cu3S3)-S-I unit. In compounds A and B, the two Cu-I centers are mu(2)-X bridged and have a mu(1)-S linkage, whereas in compound C the linkages are opposite having four mu(2)-S bridges and three mu(1)-Br linkages.