From the reaction between a dinuclear paddle-wheel carboxylate, namely [Cu(2)mu-(O2CCH2C4H3S)(4)] (1), and the flexible ligand 1,3-bis(4-pyridyl) propane (BPP) a neutral 2-D coordination polymer {[Cu-2(O2CCH2C4H3S)(4)mu-(BPP)(2)]}(n) (2) was obtained. Compounds 1 and 2 were characterized by means of elemental analysis, thermal analysis (TG/DSC), vibrational spectroscopy, and electron paramagnetic resonance (EPR). The crystal structure of 2 reveals that each Cu-II is coordinated by two nitrogen atoms from different BPP ligands and two 3-thiopheneacetate groups within a distorted square planar geometry in a trans-{N, N, O, O} arrangement. The BPP ligand adopts a TG conformation bridging two copper centers giving rise to a 1-D sinusoidal polymeric chain along the crystallographic c axis. Adjacent 1-D chains are extended into a 2-D coordination network through pairs of monatomic carboxylate bridges in direction of the b axis. This bridging mode affords centrosymmetric dimeric units Cu2O2, and therefore, the copper ions are involved in a CuN2O2O' chromophore displaying a (4 + 1) square pyramidal coordination in the resultant 2-D polymeric network. The polycrystalline X-band EPR spectrum of 2 at room temperature is characteristic of a triplet state with nonnegligible zero-field splitting in agreement with the crystal structure. Crystal data for 2: monoclinic, space group P2(1)/c, a = 9.4253(10) Angstrom, b = 10.9373(10) Angstrom, c = 23.6378(10) Angstrom, beta = 98.733(4)degrees, Z = 2.