DOE OSTI2020
V8Ga3(MoS6)4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eight inequivalent V+3.88+ sites. In the first V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, an edgeedge with one MoS6 octahedra, edges with four VS6 octahedra, and an edgeedge with one MoS6 pentagonal pyramid. There are a spread of V–S bond distances ranging from 2.27–2.58 Å. In the second V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, an edgeedge with one MoS6 octahedra, edges with four VS6 octahedra, and an edgeedge with one MoS6 pentagonal pyramid. There are a spread of V–S bond distances ranging from 2.28–2.58 Å. In the third V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, edges with two MoS6 octahedra, edges with three VS6 octahedra, and an edgeedge with one MoS6 pentagonal pyramid. There are three shorter (2.30 Å) and three longer (2.56 Å) V–S bond lengths. In the fourth V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, edges with two MoS6 octahedra, edges with three VS6 octahedra, and an edgeedge with one MoS6 pentagonal pyramid. There are a spread of V–S bond distances ranging from 2.28–2.58 Å. In the fifth V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, edges with two MoS6 octahedra, and edges with four VS6 octahedra. There are a spread of V–S bond distances ranging from 2.28–2.57 Å. In the sixth V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, edges with three VS6 octahedra, and edges with three MoS6 octahedra. There are a spread of V–S bond distances ranging from 2.30–2.56 Å. In the seventh V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, edges with four VS6 octahedra, and edges with two equivalent MoS6 pentagonal pyramids. There are a spread of V–S bond distances ranging from 2.28–2.58 Å. In the eighth V+3.88+ site, V+3.88+ is bonded to six S2- atoms to form distorted VS6 octahedra that share corners with three GaS4 tetrahedra, edges with three VS6 octahedra, and edges with three MoS6 octahedra. There are a spread of V–S bond distances ranging from 2.28–2.59 Å. There are four inequivalent Mo2+ sites. In the first Mo2+ site, Mo2+ is bonded to six S2- atoms to form distorted MoS6 octahedra that share corners with three GaS4 tetrahedra, an edgeedge with one MoS6 octahedra, and edges with five VS6 octahedra. There are a spread of Mo–S bond distances ranging from 2.33–2.60 Å. In the second Mo2+ site, Mo2+ is bonded to six S2- atoms to form distorted MoS6 pentagonal pyramids that share corners with three GaS4 tetrahedra and edges with six VS6 octahedra. There are three shorter (2.35 Å) and three longer (2.63 Å) Mo–S bond lengths. In the third Mo2+ site, Mo2+ is bonded to six S2- atoms to form distorted MoS6 octahedra that share corners with three GaS4 tetrahedra, an edgeedge with one MoS6 octahedra, and edges with five VS6 octahedra. There are three shorter (2.35 Å) and three longer (2.63 Å) Mo–S bond lengths. In the fourth Mo2+ site, Mo2+ is bonded to six S2- atoms to form distorted MoS6 octahedra that share corners with three GaS4 tetrahedra, edges with two MoS6 octahedra, and edges with four VS6 octahedra. There are a spread of Mo–S bond distances ranging from 2.34–2.62 Å. There are three inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with three MoS6 octahedra, corners with eight VS6 octahedra, and a cornercorner with one MoS6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 64–66°. There are one shorter (2.30 Å) and three longer (2.31 Å) Ga–S bond lengths. In the second Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with two MoS6 octahedra, corners with nine VS6 octahedra, and a cornercorner with one MoS6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 64–66°. All Ga–S bond lengths are 2.31 Å. In the third Ga3+ site, Ga3+ is bonded to four S2- atoms to form GaS4 tetrahedra that share corners with four MoS6 octahedra, corners with seven VS6 octahedra, and a cornercorner with one MoS6 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 64–66°. There are one shorter (2.30 Å) and three longer (2.31 Å) Ga–S bond lengths. There are twenty-four inequivalent S2- sites. In the first S2- site, S2- is bonded to three V+3.88+ and one Ga3+ atom to form a mixture of edge and corner-sharing SV3Ga tetrahedra. In the second S2- site, S2- is bonded to three V+3.88+ and one Ga3+ atom to form a mixture of edge and corner-sharing SV3Ga tetrahedra. In the third S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form distorted SV2GaMo tetrahedra that share corners with three SV2GaMo tetrahedra and edges with three SVGaMo2 tetrahedra. In the fourth S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form a mixture of distorted edge and corner-sharing SV2GaMo tetrahedra. In the fifth S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form a mixture of distorted edge and corner-sharing SV2GaMo tetrahedra. In the sixth S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form distorted SV2GaMo tetrahedra that share corners with three SV3Ga tetrahedra and edges with three SV2GaMo tetrahedra. In the seventh S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form distorted SV2GaMo tetrahedra that share corners with three SV3Ga tetrahedra and edges with three SV2GaMo tetrahedra. In the eighth S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form distorted SV2GaMo tetrahedra that share corners with three SV2GaMo tetrahedra and edges with three SV3Ga tetrahedra. In the ninth S2- site, S2- is bonded to one V+3.88+, two Mo2+, and one Ga3+ atom to form distorted SVGaMo2 tetrahedra that share corners with three SV3Ga tetrahedra and edges with three SV2GaMo tetrahedra. In the tenth S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form distorted SV2GaMo tetrahedra that share corners with three SV3Ga tetrahedra and edges with three SV2GaMo tetrahedra. In the eleventh S2- site, S2- is bonded to two V+3.88+, one Mo2+, and one Ga3+ atom to form a mixture of distorted edge and corner-sharing SV2GaMo tetrahedra. In the twelfth S2- site, S2- is bonded to one V+3.88+, two Mo2+, and one Ga3+ atom to form a mixture of distorted edge and corner-sharing SVGaMo2 tetrahedra. In the thirteenth S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom. In the fourteenth S2- site, S2- is bonded in a 3-coordinate geometry to three V+3.88+ atoms. In the fifteenth S2- site, S2- is bonded in a 3-coordinate geometry to three V+3.88+ atoms. In the sixteenth S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom. In the seventeenth S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom. In the eighteenth S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom. In the nineteenth S2- site, S2- is bonded in a 3-coordinate geometry to one V+3.88+ and two Mo2+ atoms. In the twentieth S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom. In the twenty-first S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom. In the twenty-second S2- site, S2- is bonded in a 3-coordinate geometry to one V+3.88+ and two Mo2+ atoms. In the twenty-third S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom. In the twenty-fourth S2- site, S2- is bonded in a 3-coordinate geometry to two V+3.88+ and one Mo2+ atom.