Tuning the coordination sites of two isomeric semirigid ligands, 5-(4-pyridin-3-yl-benzoylamino)isophthalic acid (3-H2PBI) and 5(4-pyridin-4-yl-benzoylamino)isophthalic acid (4-H2PBI), afforded six new coordination polymers (CPs), [Zn(3-PBI)(H2O)](n) (1), {[Mn-2(3-PBI)(2)(H2O)]center dot DMF-2H(2)O}(n) (2), {[Gd-2(3-PBI)(3)(H2O)(3)]center dot DMF center dot 3H(2)O}(n) (3), {[Zn-2(4-PBI)(2)]center dot H2O}(n) (4), {[Mn-2(4-PBI)(2)(H2O)(2)]center dot 4H(2)O}(n) (5), and {(Me2NH2)[Gd(4-PBI)(2)]center dot H2O}(n) (6). Structural analysis shows that 1 consists of 2D honeycomb (6,3) net, three sets of networks interlace mutually, generating an unexpected 2D + 2D + 2D -> 3D polycatenating interesting system. 2 exhibits a 3D pcu topology. 3 presents a unique 3D with 3,3,6T13 network topology. 4 possesses 3D 2-fold interpenetrated structure with rutile topology. 5 presents an alluring 2D architecture comprising two distinct topologies (kgd and hcb), stacked arrangement in an unexpected ABBABB mode. 6 displays 2D (4,4)-grid network. A differentiation of these structural features indicate that coordination connectivity of metals, together with binding modes of two ligands are accountable for the fascinating structural contrast. In addition, 2 and 5 were then transformed into Mn2O3 via a simple heat treatment. Electrochemical test results show that both of the obtained Mn2O3 moieties exhibit stable lithium storage properties and excellent rate capabilities.