DOE OSTI2020
Bi5(S2Cl)3 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twenty inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to six S2- and two Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.36 Å. There are one shorter (3.21 Å) and one longer (3.29 Å) Bi–Cl bond lengths. In the second Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to five S2- and three Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–3.19 Å. There are a spread of Bi–Cl bond distances ranging from 2.80–3.41 Å. In the third Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to five S2- and three Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.49 Å. There are a spread of Bi–Cl bond distances ranging from 3.19–3.43 Å. In the fourth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to seven S2- and one Cl1- atom. There are a spread of Bi–S bond distances ranging from 2.64–3.55 Å. The Bi–Cl bond length is 3.30 Å. In the fifth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to seven S2- and one Cl1- atom. There are a spread of Bi–S bond distances ranging from 2.76–3.25 Å. The Bi–Cl bond length is 3.14 Å. In the sixth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to five S2- and three Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.61–3.34 Å. There are a spread of Bi–Cl bond distances ranging from 3.15–3.29 Å. In the seventh Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to five S2- and three Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.71–3.41 Å. There are a spread of Bi–Cl bond distances ranging from 2.94–3.21 Å. In the eighth Bi3+ site, Bi3+ is bonded in a distorted hexagonal planar geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.79–2.99 Å. In the ninth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to seven S2- and one Cl1- atom. There are a spread of Bi–S bond distances ranging from 2.65–3.44 Å. The Bi–Cl bond length is 3.31 Å. In the tenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.68–3.24 Å. There are one shorter (2.95 Å) and one longer (3.04 Å) Bi–Cl bond lengths. In the eleventh Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Bi–S bond distances ranging from 2.67–3.48 Å. In the twelfth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to six S2- and two Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.67–3.40 Å. There are one shorter (2.95 Å) and one longer (3.01 Å) Bi–Cl bond lengths. In the thirteenth Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to five S2- and one Cl1- atom. There are a spread of Bi–S bond distances ranging from 2.70–3.13 Å. The Bi–Cl bond length is 3.21 Å. In the fourteenth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to five S2- and three Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.25 Å. There are a spread of Bi–Cl bond distances ranging from 2.99–3.50 Å. In the fifteenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to three S2- and four Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.66–3.12 Å. There are a spread of Bi–Cl bond distances ranging from 2.66–3.18 Å. In the sixteenth Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to three S2- and five Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.64–2.76 Å. There are a spread of Bi–Cl bond distances ranging from 3.04–3.51 Å. In the seventeenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to four S2- and three Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.60–3.42 Å. There are a spread of Bi–Cl bond distances ranging from 2.93–3.42 Å. In the eighteenth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to four S2- and three Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.57–3.41 Å. There are a spread of Bi–Cl bond distances ranging from 3.05–3.52 Å. In the nineteenth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to four S2- and four Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–3.21 Å. There are a spread of Bi–Cl bond distances ranging from 2.77–3.50 Å. In the twentieth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to three S2- and five Cl1- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.26 Å. There are a spread of Bi–Cl bond distances ranging from 2.85–3.23 Å. There are twenty-four inequivalent S2- sites. In the first S2- site, S2- is bonded in a 3-coordinate geometry to three Bi3+ atoms. In the second S2- site, S2- is bonded in a 2-coordinate geometry to five Bi3+ atoms. In the third S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the fourth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Bi3+ atoms. In the fifth S2- site, S2- is bonded in a 4-coordinate geometry to five Bi3+ atoms. In the sixth S2- site, S2- is bonded in a 3-coordinate geometry to three Bi3+ atoms. In the seventh S2- site, S2- is bonded in a 6-coordinate geometry to five Bi3+ and one Cl1- atom. The S–Cl bond length is 3.33 Å. In the eighth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the ninth S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the tenth S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the eleventh S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the twelfth S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the thirteenth S2- site, S2- is bonded in a 2-coordinate geometry to five Bi3+ atoms. In the fourteenth S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms. In the fifteenth S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the sixteenth S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the seventeenth S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the eighteenth S2- site, S2- is bonded in a 5-coordinate geometry to four Bi3+ and one Cl1- atom. The S–Cl bond length is 3.36 Å. In the nineteenth S2- site, S2- is bonded in a 4-coordinate geometry to five Bi3+ and one Cl1- atom. The S–Cl bond length is 3.39 Å. In the twentieth S2- site, S2- is bonded in a 2-coordinate geometry to five Bi3+ atoms. In the twenty-first S2- site, S2- is bonded in a 2-coordinate geometry to four Bi3+ atoms. In the twenty-second S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the twenty-third S2- site, S2- is bonded in a 2-coordinate geometry to four Bi3+ atoms. In the twenty-fourth S2- site, S2- is bonded in a 2-coordinate geometry to five Bi3+ atoms. There are twelve inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 5-coordinate geometry to five Bi3+ and one S2- atom. In the second Cl1- site, Cl1- is bonded in a 1-coordinate geometry to five Bi3+ and one S2- atom. In the third Cl1- site, Cl1- is bonded in a 4-coordinate geometry to four Bi3+ and one S2- atom. In the fourth Cl1- site, Cl1- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the fifth Cl1- site, Cl1- is bonded in a 4-coordinate geometry to five Bi3+ atoms. In the sixth Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Bi3+ atoms. In the seventh Cl1- site, Cl1- is bonded in a distorted single-bond geometry to four Bi3+ atoms. In the eighth Cl1- site, Cl1- is bonded in a 3-coordinate geometry to three Bi3+ atoms. In the ninth Cl1- site, Cl1- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the tenth Cl1- site, Cl1- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the eleventh Cl1- site, Cl1- is bonded in a 2-coordinate geometry to five Bi3+ atoms. In the twelfth Cl1- site, Cl1- is bonded in a 1-coordinate geometry to three Bi3+ atoms.