DOE OSTI2020
Mo3S7Cl4 crystallizes in the monoclinic P2_1/c space group. The structure is two-dimensional and consists of one Mo3S7Cl4 sheet oriented in the (1, 0, 0) direction. there are three inequivalent Mo6+ sites. In the first Mo6+ site, Mo6+ is bonded to five S2- and two Cl1- atoms to form distorted face-sharing MoS5Cl2 pentagonal bipyramids. There are a spread of Mo–S bond distances ranging from 2.38–2.50 Å. There are one shorter (2.45 Å) and one longer (2.50 Å) Mo–Cl bond lengths. In the second Mo6+ site, Mo6+ is bonded to five S2- and two Cl1- atoms to form a mixture of distorted edge and face-sharing MoS5Cl2 pentagonal bipyramids. There are a spread of Mo–S bond distances ranging from 2.36–2.51 Å. There are one shorter (2.50 Å) and one longer (2.59 Å) Mo–Cl bond lengths. In the third Mo6+ site, Mo6+ is bonded to five S2- and two Cl1- atoms to form a mixture of distorted edge and face-sharing MoS5Cl2 pentagonal bipyramids. There are a spread of Mo–S bond distances ranging from 2.36–2.51 Å. There are one shorter (2.52 Å) and one longer (2.58 Å) Mo–Cl bond lengths. There are seven inequivalent S2- sites. In the first S2- site, S2- is bonded in a 3-coordinate geometry to three Mo6+ atoms. In the second S2- site, S2- is bonded in a 3-coordinate geometry to two Mo6+ and one S2- atom. The S–S bond length is 2.03 Å. In the third S2- site, S2- is bonded in a 4-coordinate geometry to two Mo6+, one S2-, and one Cl1- atom. The S–S bond length is 2.02 Å. The S–Cl bond length is 3.32 Å. In the fourth S2- site, S2- is bonded in a 4-coordinate geometry to two Mo6+, one S2-, and one Cl1- atom. The S–S bond length is 2.03 Å. The S–Cl bond length is 3.22 Å. In the fifth S2- site, S2- is bonded in a 7-coordinate geometry to two Mo6+ and one S2- atom. In the sixth S2- site, S2- is bonded in a 5-coordinate geometry to two Mo6+ and one S2- atom. In the seventh S2- site, S2- is bonded in a 6-coordinate geometry to two Mo6+, one S2-, and three Cl1- atoms. There are a spread of S–Cl bond distances ranging from 3.24–3.37 Å. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a water-like geometry to two Mo6+ atoms. In the second Cl1- site, Cl1- is bonded in a distorted single-bond geometry to one Mo6+ and three S2- atoms. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Mo6+ and one S2- atom. In the fourth Cl1- site, Cl1- is bonded in a water-like geometry to two Mo6+ and one S2- atom.