The structural properties of the iron mixed valence complex (n-C3H7)(4)N[(FeFeIII)-Fe-II(dto)(3)] (dto = dithiooxalato, C2O2S2) have been investigated by single-crystal X-ray diffraction (SCXRD) at low temperatures. (n-C3H7)(4)N-[(FeFeIII)-Fe-II(dto)(3)] has two-dimensional (2D) honeycomb layers consisting of alternating Fe-II and Fe-III arrays bonded by bisbidentate dithiooxalato ligands. Upon cooling, a superlattice structure with q = (1/3, 1/3, 0) was observed below 260 K, which corresponds to an order disorder transition of the (n-C3H7)(4)N+ ions between the honeycomb layers. The charge transfer phase transition (CTPT) occurs at T-C up arrow 1/2 similar to 120 K and T-C down arrow 1/2 similar to 90 K upon heating and cooling, respectively, with an electron transfer between the Fe-II and Fe-III ions, accompanied by a spin-state change, Fe-II (S = 2; HS)-O2C2S2-Fe-III (S = 1/2; LS) <-> Fe-III (S = 5/2; HS)-O2C2S2-Fe-II (S = 0; LS). During the CTPT, the intersheet [(FeFeIII)-Fe-II(dto)(3)] distance decreased monotonously upon cooling, and an abrupt structural contraction was observed in the hexagonal 2D network. The volume contraction during the CTPT was quite small (similar to 0.7%), and differences in the structural distortions at the FeS6 and FeO6 sites were not found in the vicinity of the CTPT. We also calculated the orbital energies and the occupied spin states for the [Fe(O2C2S2)(3)] and [Fe(S2C2O2)(3)] octahedra in the vicinity of the CTPT by density functional theory (DFT). Because the local symmetry around the two coordinating iron ions is already lowered to trigonal symmetry, the CTPT did not cause any further deformation. This symmetry invariance resulted in an absence of orbital contributions to the total entropy change (Delta S) in the CTPT, which is in agreement with the previous heat capacity measurements. [Nakamoto, T; Miyazaki, Y; Itoi, M; Ono, Y; Kojima, N; Sorai, M. Heat Capacity of the Mixed-Valence Complex {[(n-C3H7)(4)N][(FeFeIII)-Fe-II(dto)(3)]}(infinity), Phase Transition because of Electron Transfer, and a Change in Spin-State of the Whole System.