An experimental electron density (ED) analysis of the spin crossover coordination complex Fe(btr)(2)(NCS)(2).H(2)O has been performed in the ground low-spin (LS) state and in the metastable thermally quenched high-spin (HS) state at 15 K by fitting a multipolar model to high-resolution X-ray diffraction measurements. The ED has been quantitatively analyzed using the quantum theory of atoms in molecules. This is the first time the ED distribution of a molecular metastable state has been experimentally investigated. The electron deformation densities and derived Fe 3d orbital populations are characteristic of LS (t(2g)(6) e(g)(0)) and HS (t(2g)(4) e(g)(2)) electron configurations and indicate significant sigma donation to the Fe d(x)2(-)(y)2 and d(z)2 atomic orbitals. The Fe-N(NCS) and Fe-N(btr) coordination interactions are characterized using the laplacian distribution of the ED, the molecular electrostatic potential, and the fragment charges obtained by integration over the topological atomic basins. A combination of electrostatic and covalent contributions to these interactions is pointed out. Interlayer interactions are evidenced by the presence of bond critical points in N...H hydrogen bonds involving the non-coordinated water molecule. Systematic differences in the atomic displacement parameters between the LS and HS states have been described and rationalized in terms of modifications of bond force constants.