The novel iron selenidostannates [Fe(bipy)3]- Sn4Se9.2H(2)O (1) and [Fe(bipy)(3)](2)[ Sn3Se7](2).bipy.2H(2)O (2) (bipy = bipyridine) were prepared by the reactions of Sn, Se, FeCl2.4H(2)O, bipy, and then with/without KSCN under hydrothermal conditions (dien = diethylenetriamine). In 1, four SnSe5 units condense via edge sharing to form the novel 3-D framework selenidostannate (3)(infinity)[Sn4Se92-] containing an interpenetrating channel system. The [Fe(bipy)(3)](2+) cations are accommodated in the different channels according to the conformation of the [Fe(bipy)(3)](2+) cation. In 2, three SnSe5 units share edges to form a 2-D (2)(infinity)[Sn3Se72-] layered anion, while two SnSe5 units and one SnSe4 unit are connected via edge sharing, forming a 1-D (1)(infinity)[Sn3Se72-] chainlike anion. The (1)(infinity)[Sn3Se72-], [Fe(bipy)(3)](2+), bipy, and H2O species are embedded between the (2)(infinity)[Sn3Se72-] layers. 2 is the first example of a selenidostannate constructed by both (2)(infinity)[Sn3Se72-]and (1)(infinity)[Sn3Se72-] anions. The coexistence of 1-D (1)(infinity)[Sn3Se72-] and 2-D (2)(infinity)[Sn3Se72-] anions in 2 might support the possible reaction mechanism that the (2)(infinity)[Sn3Se72-] anions are formed by condensation of the (1)(infinity) [Sn3Se72-] chains. 1 and 2 exhibit band gaps at 1.43 and 2.01 eV, respectively.