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Bi19S27I3 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 6-coordinate geometry to six S2- atoms. There are a spread of Bi–S bond distances ranging from 2.65–3.19 Å. In the 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 2.70–3.50 Å. In the 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 2.66–3.57 Å. In the fourth 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 2.65–3.58 Å. In the 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 2.65–3.18 Å. In the 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 2.69–3.48 Å. In the seventh 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 2.70–3.50 Å. In the eighth 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 2.65–3.58 Å. In the ninth 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 2.65–3.18 Å. In the tenth 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 2.66–3.57 Å. In the eleventh 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 2.65–3.20 Å. In the twelfth 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 thirteenth 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 2.64–3.20 Å. In the fourteenth 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 2.70–3.50 Å. In the fifteenth 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 2.66–3.56 Å. In the sixteenth 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 2.70–3.50 Å. In the seventeenth 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 2.67–3.57 Å. In the eighteenth 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 2.64–3.21 Å. 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 2.90–2.93 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 2.88–2.95 Å. In the twenty-first Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.93 Å. Both Bi–I bond lengths are 3.63 Å. In the twenty-second Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.96 Å. There are one shorter (3.61 Å) and one longer (3.63 Å) Bi–I bond lengths. In the twenty-third Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.96 Å. There are one shorter (3.61 Å) and one longer (3.66 Å) Bi–I bond lengths. In the twenty-fourth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.97 Å. There are one shorter (3.60 Å) and one longer (3.66 Å) Bi–I bond lengths. In the twenty-fifth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. Both Bi–I bond lengths are 3.63 Å. In the twenty-sixth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.96 Å. There are one shorter (3.60 Å) and one longer (3.62 Å) Bi–I bond lengths. In the twenty-seventh Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.96 Å. There are one shorter (3.60 Å) and one longer (3.63 Å) Bi–I bond lengths. In the twenty-eighth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.97 Å. There are one shorter (3.60 Å) and one longer (3.66 Å) Bi–I bond lengths. In the twenty-ninth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.93 Å. There are one shorter (3.62 Å) and one longer (3.63 Å) Bi–I bond lengths. In the thirtieth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.95 Å. There are one shorter (3.60 Å) and one longer (3.64 Å) Bi–I bond lengths. In the thirty-first Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.93 Å. There are one shorter (3.63 Å) and one longer (3.65 Å) Bi–I bond lengths. In the thirty-second Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.98 Å. There are one shorter (3.62 Å) and one longer (3.64 Å) Bi–I bond lengths. In the thirty-third Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.93 Å. There are one shorter (3.63 Å) and one longer (3.64 Å) Bi–I bond lengths. In the thirty-fourth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.99 Å. There are one shorter (3.61 Å) and one longer (3.65 Å) Bi–I bond lengths. In the thirty-fifth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.96 Å. There are one shorter (3.60 Å) and one longer (3.63 Å) Bi–I bond lengths. In the thirty-sixth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.98 Å. There are one shorter (3.61 Å) and one longer (3.64 Å) Bi–I bond lengths. In the thirty-seventh Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.63–2.96 Å. There are one shorter (3.60 Å) and one longer (3.63 Å) Bi–I bond lengths. In the thirty-eighth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five S2- and two I1- atoms. There are a spread of Bi–S bond distances ranging from 2.62–2.93 Å. There are one shorter (3.63 Å) and one longer (3.64 Å) Bi–I bond lengths. There are fifty-four inequivalent S2- sites. In the first S2- site, S2- is bonded to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with four SBi5 square pyramids, corners with two SBi4 tetrahedra, an edgeedge with one SBi5 square pyramid, and edges with two SBi4 tetrahedra. In the second S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three 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 to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with three SBi5 square pyramids, a cornercorner with one SBi4 tetrahedra, and an edgeedge with one SBi5 square pyramid. In the sixth S2- site, S2- is bonded to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with four SBi5 square pyramids, corners with four SBi4 tetrahedra, and an edgeedge with one SBi4 tetrahedra. In the seventh S2- site, S2- is bonded in a 4-coordinate geometry to four Bi3+ atoms. In the eighth S2- site, S2- is bonded to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with four SBi5 square pyramids, corners with three SBi4 tetrahedra, an edgeedge with one SBi5 square pyramid, and an edgeedge with one SBi4 tetrahedra. In the ninth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three 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 distorted trigonal non-coplanar geometry to three Bi3+ atoms. In the thirteenth S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Bi3+ atoms. In the fourteenth S2- site, S2- is bonded to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with three SBi5 square pyramids, corners with two SBi4 tetrahedra, an edgeedge with one SBi5 square pyramid, and edges with two SBi4 tetrahedra. 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 distorted trigonal non-coplanar geometry to three Bi3+ atoms. In the eighteenth S2- site, S2- is bonded to four Bi3+ atoms to form distorted SBi4 tetrahedra that share corners with four SBi5 square pyramids, corners with two SBi4 tetrahedra, an edgeedge with one SBi5 square pyramid, and edges with two SBi4 tetrahedra. In the nineteenth S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share a cornercorner with one SBi4 tetrahedra and edges with four SBi5 square pyramids. In the twentieth S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share a cornercorner with one SBi4 tetrahedra, edges with four SBi5 square pyramids, and an edgeedge with one SBi4 tetrahedra. In the twenty-first S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with two SBi4 tetrahedra and edges with four SBi5 square pyramids. In the twenty-second S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with two SBi4 tetrahedra and edges with three SBi5 square pyramids. In the twenty-third S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share a cornercorner with one SBi4 tetrahedra, edges with two SBi5 square pyramids, and an edgeedge with one SBi4 tetrahedra. 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 to five Bi3+ atoms to form distorted SBi5 square pyramids that share a cornercorner with one SBi4 tetrahedra, edges with four SBi5 square pyramids, and an edgeedge with one SBi4 tetrahedra. In the twenty-sixth S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share corners with two SBi4 tetrahedra and edges with four SBi5 square pyramids. In the twenty-seventh S2- site, S2- is bonded to five Bi3+ atoms to form distorted SBi5 square pyramids that share a c

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