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Bi19S27Br3 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are thirty-eight inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.96 Å. There are one shorter (3.52 Å) and one longer (3.57 Å) Bi–Br bond lengths. In the second Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. There are one shorter (3.51 Å) and one longer (3.53 Å) Bi–Br bond lengths. In the third Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.94 Å. Both Bi–Br bond lengths are 3.54 Å. In the fourth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. There are one shorter (3.52 Å) and one longer (3.54 Å) Bi–Br bond lengths. In the fifth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.93 Å. Both Bi–Br bond lengths are 3.54 Å. In the sixth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.96 Å. There are one shorter (3.52 Å) and one longer (3.57 Å) Bi–Br bond lengths. In the seventh Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.93 Å. Both Bi–Br bond lengths are 3.54 Å. In the eighth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.95 Å. There are one shorter (3.52 Å) and one longer (3.57 Å) Bi–Br bond lengths. In the ninth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. There are one shorter (3.52 Å) and one longer (3.54 Å) Bi–Br bond lengths. In the tenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.97 Å. There are one shorter (3.52 Å) and one longer (3.56 Å) Bi–Br bond lengths. In the eleventh Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.92 Å. There are one shorter (3.54 Å) and one longer (3.55 Å) Bi–Br bond lengths. In the twelfth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. There are one shorter (3.51 Å) and one longer (3.54 Å) Bi–Br bond lengths. In the thirteenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. There are one shorter (3.52 Å) and one longer (3.54 Å) Bi–Br bond lengths. In the fourteenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.97 Å. There are one shorter (3.52 Å) and one longer (3.56 Å) Bi–Br bond lengths. In the fifteenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.93 Å. There are one shorter (3.54 Å) and one longer (3.55 Å) Bi–Br bond lengths. In the sixteenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.92 Å. There are one shorter (3.54 Å) and one longer (3.56 Å) Bi–Br bond lengths. In the seventeenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. There are one shorter (3.51 Å) and one longer (3.55 Å) Bi–Br bond lengths. In the eighteenth Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to five S2- and two Br1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.97 Å. There are one shorter (3.52 Å) and one longer (3.55 Å) Bi–Br bond lengths. In the nineteenth 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 2.88–2.92 Å. In the twentieth 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 2.87–2.94 Å. In the twenty-first Bi3+ site, Bi3+ is bonded in a 7-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.56 Å. In the twenty-second Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.69–3.48 Å. In the twenty-third Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.14 Å. In the twenty-fourth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.69–3.48 Å. In the twenty-fifth Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.14 Å. In the twenty-sixth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.56 Å. In the twenty-seventh Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.14 Å. In the twenty-eighth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.55 Å. In the twenty-ninth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.69–3.48 Å. In the thirtieth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.70–3.48 Å. In the thirty-first Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.15 Å. In the thirty-second Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.66–3.55 Å. In the thirty-third Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.66–3.55 Å. In the thirty-fourth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.69–3.49 Å. In the thirty-fifth Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.16 Å. In the thirty-sixth Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.64–3.16 Å. In the thirty-seventh Bi3+ site, Bi3+ is bonded in a 6-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.66–3.55 Å. In the thirty-eighth Bi3+ site, Bi3+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Bi–S bond distances ranging from 2.69–3.47 Å. There are fifty-four inequivalent S2- sites. In the first S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the second S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the third S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms. In the fourth S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the fifth S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms. In the sixth S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the seventh S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms. In the eighth S2- site, S2- is bonded in a 3-coordinate geometry to four 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 3-coordinate geometry to four Bi3+ atoms. In the eleventh S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the twelfth S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms. In the thirteenth S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms. In the fourteenth S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the fifteenth S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the sixteenth S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the seventeenth S2- site, S2- is bonded in a 3-coordinate geometry to five Bi3+ atoms. In the eighteenth S2- site, S2- is bonded in a 3-coordinate geometry to four Bi3+ atoms. In the nineteenth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the twentieth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the twenty-first S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with three SBi4 tetrahedra and an edgeedge with one SBi5 square pyramid. In the twenty-second S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with four SBi4 tetrahedra and an edgeedge with one SBi5 square pyramid. In the twenty-third S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the twenty-fourth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the twenty-fifth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the twenty-sixth S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with four SBi4 tetrahedra and an edgeedge with one SBi5 square pyramid. In the twenty-seventh S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the twenty-eighth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the twenty-ninth S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with four SBi4 tetrahedra and an edgeedge with one SBi5 square pyramid. In the thirtieth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the thirty-first S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with four SBi4 tetrahedra and an edgeedge with one SBi5 square pyramid. In the thirty-second S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the thirty-third S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the thirty-fourth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the thirty-fifth S2- site, S2- is bonded in a 5-coordinate geometry to five Bi3+ atoms. In the thirty-sixth S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with three SBi4 tetrahedra and an edgeedge with one SBi5 square pyramid. In the thirty-seventh S2- site, S2- is bonded to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with two SBi5 square pyramids, corners with four SBi4 tetrahedra, and edges with two SBi4 tetrahedra. In the thirty-eighth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Bi3+ atoms. In the thirty-ninth S2- site, S2- is bonded to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with two SBi5 square pyramids, corners with four SBi4 tetrahedra

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