Structural Characterization of Thermochromic and Spin Equilibria in Solid-State Ni(detu)4Cl2 (detu = N,N′‑Diethylthiourea)

Consecutive thermochromic lattice distortional and spin crossover equilibria in solid-state Ni­(detu)4Cl2 (detu = N,N′-diethylthiourea) are investigated by variable-temperature X-ray crystallography (173–333 K), DFT calculations, and differential scanning calorimetry. Thermochromism and anomalous magnetism were reported previously (S. L. Holt, Jr., et al. J. Am. Chem. Soc. 1964, 86, 519–520); the latter was attributed to equilibration of a singlet ground state and a thermally accessible triplet state, but structural data were not obtained. A crystal structure at 173(2) K revealed [Ni­(detu)4]2+ centers with distorted planar ligation of nickel­(II) to the four sulfur atoms, with an average Ni–S bond length of 2.226(3) Å. The nickel ion was displaced out-of-plane by 0.334 Å toward a proximal apical chloride at a nonbonding distance of 3.134(1) Å. Asymmetry in the trans S–Ni–S angles was coupled to a monoclinic ↔ tetragonal lattice distortion (T1/2 = 254 ± 11 K), resulting in thermochromism. Spin crossover occurs by tetragonal modulation of nickel­(II) with approach of the proximal chloride at higher temperatures (T1/2 = 383 ± 18 K), which is consistent with a contraction of −0.096(4) Å in the Ni···Cl separation observed at 293 K. A high-spin (S = 1) square-pyramidal [Ni­(dmtu)4Cl]+ model (dmtu = N,N′-dimethylthiourea) was optimized by DFT calculations, which estimated limiting equatorial Ni–S bond lengths of 2.45 Å and an apical Ni–Cl bond of 2.43 Å. Electronic spectra of the spin isomers were calculated by TD-DFT methods. Assignment of the FTIR spectrum was assisted by frequency calculations and isotope substitution.