DOE OSTI2020
MoCl5 crystallizes in the monoclinic C2/m space group. The structure is zero-dimensional and consists of six MoCl5 clusters. In two of the MoCl5 clusters, Mo5+ is bonded to six Cl1- atoms to form edge-sharing MoCl6 octahedra. There are a spread of Mo–Cl bond distances ranging from 2.28–2.54 Å. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a water-like geometry to two equivalent Mo5+ atoms. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Mo5+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Mo5+ atom. In four of the MoCl5 clusters, Mo5+ is bonded to six Cl1- atoms to form edge-sharing MoCl6 octahedra. There are a spread of Mo–Cl bond distances ranging from 2.27–2.55 Å. There are six inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Mo5+ atom. In the second Cl1- site, Cl1- is bonded in a water-like geometry to two equivalent Mo5+ atoms. In the third Cl1- site, Cl1- is bonded in a water-like geometry to two equivalent Mo5+ atoms. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Mo5+ atom. In the fifth Cl1- site, Cl1- is bonded in a single-bond geometry to one Mo5+ atom. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one Mo5+ atom.