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Pb4Sb6S13 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eight inequivalent Pb2+ sites. In the first Pb2+ site, Pb2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Pb–S bond distances ranging from 2.78–3.55 Å. In the second Pb2+ site, Pb2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Pb–S bond distances ranging from 2.76–3.43 Å. In the third Pb2+ site, Pb2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Pb–S bond distances ranging from 2.79–3.49 Å. In the fourth Pb2+ site, Pb2+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Pb–S bond distances ranging from 2.81–3.53 Å. In the fifth Pb2+ site, Pb2+ is bonded in a 5-coordinate geometry to eight S2- atoms. There are a spread of Pb–S bond distances ranging from 2.79–3.66 Å. In the sixth Pb2+ site, Pb2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Pb–S bond distances ranging from 2.80–3.33 Å. In the seventh Pb2+ site, Pb2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Pb–S bond distances ranging from 2.89–3.27 Å. In the eighth Pb2+ site, Pb2+ is bonded in a 7-coordinate geometry to seven S2- atoms. There are a spread of Pb–S bond distances ranging from 2.81–3.45 Å. There are twelve inequivalent Sb3+ sites. In the first Sb3+ site, Sb3+ is bonded to five S2- atoms to form SbS5 square pyramids that share corners with two equivalent SbS5 square pyramids, edges with two equivalent SbS6 octahedra, and edges with three SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.47–3.05 Å. In the second Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.49–2.92 Å. In the third Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of distorted corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.44–3.23 Å. In the fourth Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.46–2.81 Å. In the fifth Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of distorted corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.51–3.12 Å. In the sixth Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.46–3.01 Å. In the seventh Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.48–2.93 Å. In the eighth Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.50–2.91 Å. In the ninth Sb3+ site, Sb3+ is bonded to six S2- atoms to form distorted SbS6 octahedra that share edges with two equivalent SbS6 octahedra and edges with two equivalent SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.58–3.16 Å. In the tenth Sb3+ site, Sb3+ is bonded to five S2- atoms to form a mixture of distorted corner and edge-sharing SbS5 square pyramids. There are a spread of Sb–S bond distances ranging from 2.49–3.18 Å. In the eleventh Sb3+ site, Sb3+ is bonded in a 5-coordinate geometry to five S2- atoms. There are a spread of Sb–S bond distances ranging from 2.51–3.29 Å. In the twelfth Sb3+ site, Sb3+ is bonded in a 5-coordinate geometry to seven S2- atoms. There are a spread of Sb–S bond distances ranging from 2.55–3.31 Å. There are twenty-six inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to three Sb3+ atoms. In the second S2- site, S2- is bonded to five Sb3+ atoms to form distorted edge-sharing SSb5 square pyramids. In the third S2- site, S2- is bonded in a distorted water-like geometry to three Pb2+ and two equivalent Sb3+ atoms. In the fourth S2- site, S2- is bonded in a distorted water-like geometry to two equivalent Pb2+ and two equivalent Sb3+ atoms. In the fifth S2- site, S2- is bonded in a 4-coordinate geometry to two equivalent Pb2+ and three Sb3+ atoms. In the sixth S2- site, S2- is bonded in a 4-coordinate geometry to two Pb2+ and two equivalent Sb3+ atoms. In the seventh S2- site, S2- is bonded in a distorted water-like geometry to two equivalent Pb2+ and two equivalent Sb3+ atoms. In the eighth S2- site, S2- is bonded in a distorted water-like geometry to three Pb2+ and two equivalent Sb3+ atoms. In the ninth S2- site, S2- is bonded in a 2-coordinate geometry to three Pb2+ and two equivalent Sb3+ atoms. In the tenth S2- site, S2- is bonded in a 4-coordinate geometry to two Pb2+ and two equivalent Sb3+ atoms. In the eleventh S2- site, S2- is bonded to one Pb2+ and four Sb3+ atoms to form a mixture of distorted corner and edge-sharing SSb4Pb square pyramids. In the twelfth S2- site, S2- is bonded to one Pb2+ and four Sb3+ atoms to form a mixture of distorted corner and edge-sharing SSb4Pb square pyramids. In the thirteenth S2- site, S2- is bonded to one Pb2+ and four Sb3+ atoms to form edge-sharing SSb4Pb square pyramids. In the fourteenth S2- site, S2- is bonded in a 5-coordinate geometry to one Pb2+ and four Sb3+ atoms. In the fifteenth S2- site, S2- is bonded to one Pb2+ and four Sb3+ atoms to form edge-sharing SSb4Pb square pyramids. In the sixteenth S2- site, S2- is bonded in a 1-coordinate geometry to four Pb2+ and one Sb3+ atom. In the seventeenth S2- site, S2- is bonded in a 4-coordinate geometry to two Pb2+ and two equivalent Sb3+ atoms. In the eighteenth S2- site, S2- is bonded in a 3-coordinate geometry to one Pb2+ and three Sb3+ atoms. In the nineteenth S2- site, S2- is bonded in a 1-coordinate geometry to four Pb2+ and one Sb3+ atom. In the twentieth S2- site, S2- is bonded in a 5-coordinate geometry to four Pb2+ and one Sb3+ atom. In the twenty-first S2- site, S2- is bonded in a 1-coordinate geometry to three Pb2+ and one Sb3+ atom. In the twenty-second S2- site, S2- is bonded to two equivalent Pb2+ and three Sb3+ atoms to form distorted edge-sharing SSb3Pb2 square pyramids. In the twenty-third S2- site, S2- is bonded in a 5-coordinate geometry to four Pb2+ and one Sb3+ atom. In the twenty-fourth S2- site, S2- is bonded in a 1-coordinate geometry to four Pb2+ and one Sb3+ atom. In the twenty-fifth S2- site, S2- is bonded to two equivalent Pb2+ and three Sb3+ atoms to form distorted edge-sharing SSb3Pb2 square pyramids. In the twenty-sixth S2- site, S2- is bonded in a 1-coordinate geometry to four Pb2+ and one Sb3+ atom.

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