Undistorted linear Bi chains with hypervalent bonding in La3TiBi5 from single-crystal X-ray diffraction

The crystal structure of the lanthanum titanium bismuthide La3TiBi5 (Pearson code hP18, Wyckoff sequence b d g2) has been established from single-crystal X-ray diffraction data and analyzed in detail using first-principles calculations. There are no anomalies pertaining to the atomic displacement parameter of the Ti site, previously reported based on a powder X-ray diffraction analysis of this compound. The anionic substructure contains columns of face-sharing TiBi6 octahedra and linear Bi chains. Due to a significant La(5d) and Bi(6p) orbital mixing, a perfectly one-dimensional character of the Bi chains is not realised, while a three-dimensional electronic structure is established instead. The latter fact explains the stability of the polyanionic pnictide units against Peierls distortions. The hypervalent bonding in the Bi chains is reflected in a rather long Bi-Bi distance of 3.2264 (4) angstrom and a typical pattern of bonding and antibonding interactions, as revealed by electronic structure calculations.