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Bi8La10O27 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are ten inequivalent La3+ sites. In the first La3+ site, La3+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of La–O bond distances ranging from 2.32–2.65 Å. In the second La3+ site, La3+ is bonded to seven O2- atoms to form distorted edge-sharing LaO7 hexagonal pyramids. There are a spread of La–O bond distances ranging from 2.33–2.66 Å. In the third La3+ site, La3+ is bonded to seven O2- atoms to form distorted edge-sharing LaO7 hexagonal pyramids. There are a spread of La–O bond distances ranging from 2.43–2.51 Å. In the fourth La3+ site, La3+ is bonded to seven O2- atoms to form distorted edge-sharing LaO7 hexagonal pyramids. There are a spread of La–O bond distances ranging from 2.45–2.54 Å. In the fifth La3+ site, La3+ is bonded in a distorted body-centered cubic geometry to eight O2- atoms. There are a spread of La–O bond distances ranging from 2.52–3.06 Å. In the sixth La3+ site, La3+ is bonded in a distorted body-centered cubic geometry to eight O2- atoms. There are a spread of La–O bond distances ranging from 2.52–3.02 Å. In the seventh La3+ site, La3+ is bonded to seven O2- atoms to form distorted LaO7 pentagonal bipyramids that share corners with two BiO4 trigonal pyramids and edges with two LaO7 hexagonal pyramids. There are a spread of La–O bond distances ranging from 2.42–2.54 Å. In the eighth La3+ site, La3+ is bonded in a distorted body-centered cubic geometry to eight O2- atoms. There are a spread of La–O bond distances ranging from 2.37–2.76 Å. In the ninth La3+ site, La3+ is bonded in a body-centered cubic geometry to eight O2- atoms. There are a spread of La–O bond distances ranging from 2.40–2.72 Å. In the tenth La3+ site, La3+ is bonded to seven O2- atoms to form distorted LaO7 pentagonal bipyramids that share corners with two BiO4 trigonal pyramids and edges with two LaO7 hexagonal pyramids. There are a spread of La–O bond distances ranging from 2.42–2.54 Å. There are eight inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to four O2- atoms to form distorted BiO4 trigonal pyramids that share corners with two LaO7 pentagonal bipyramids and corners with two equivalent BiO4 trigonal pyramids. There are a spread of Bi–O bond distances ranging from 2.13–2.33 Å. In the second Bi3+ site, Bi3+ is bonded to four O2- atoms to form distorted BiO4 trigonal pyramids that share corners with two LaO7 pentagonal bipyramids and corners with two equivalent BiO4 trigonal pyramids. There are a spread of Bi–O bond distances ranging from 2.13–2.33 Å. In the third Bi3+ site, Bi3+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Bi–O bond distances ranging from 2.16–2.24 Å. In the fourth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Bi–O bond distances ranging from 2.16–2.73 Å. In the fifth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Bi–O bond distances ranging from 2.16–2.73 Å. In the sixth Bi3+ site, Bi3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Bi–O bond distances ranging from 2.17–3.02 Å. In the seventh Bi3+ site, Bi3+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are two shorter (2.07 Å) and one longer (2.13 Å) Bi–O bond lengths. In the eighth Bi3+ site, Bi3+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are two shorter (2.07 Å) and one longer (2.13 Å) Bi–O bond lengths. There are twenty-seven inequivalent O2- sites. In the first O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form distorted OLa3Bi tetrahedra that share corners with eleven OLa4 tetrahedra, edges with four OLa4 tetrahedra, and an edgeedge with one OLaBi3 trigonal pyramid. In the second O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form distorted OLa3Bi tetrahedra that share corners with ten OLa4 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa4 tetrahedra. In the third O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form distorted OLa3Bi tetrahedra that share corners with ten OLa4 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa4 tetrahedra. In the fourth O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form distorted OLa3Bi tetrahedra that share corners with eleven OLa4 tetrahedra, edges with four OLa4 tetrahedra, and an edgeedge with one OLaBi3 trigonal pyramid. In the fifth O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with nine OLa4 tetrahedra and edges with four OLa3Bi tetrahedra. In the sixth O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with nine OLa4 tetrahedra, edges with four OLa2Bi2 tetrahedra, and an edgeedge with one OLaBi3 trigonal pyramid. In the seventh O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with nine OLa4 tetrahedra and edges with four OLa2Bi2 tetrahedra. In the eighth O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with nine OLa4 tetrahedra and edges with five OLa3Bi tetrahedra. In the ninth O2- site, O2- is bonded to one La3+ and three Bi3+ atoms to form distorted OLaBi3 tetrahedra that share corners with nine OLa4 tetrahedra, corners with two equivalent OLaBi3 trigonal pyramids, and edges with three OLa3Bi tetrahedra. In the tenth O2- site, O2- is bonded to one La3+ and three Bi3+ atoms to form distorted OLaBi3 trigonal pyramids that share corners with eleven OLa4 tetrahedra and edges with three OLa3Bi tetrahedra. In the eleventh O2- site, O2- is bonded to four La3+ atoms to form a mixture of edge and corner-sharing OLa4 tetrahedra. In the twelfth O2- site, O2- is bonded to two La3+ and two Bi3+ atoms to form a mixture of distorted edge and corner-sharing OLa2Bi2 tetrahedra. In the thirteenth O2- site, O2- is bonded to two La3+ and two Bi3+ atoms to form distorted OLa2Bi2 tetrahedra that share corners with seven OLa3Bi tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa4 tetrahedra. In the fourteenth O2- site, O2- is bonded to four La3+ atoms to form a mixture of edge and corner-sharing OLa4 tetrahedra. In the fifteenth O2- site, O2- is bonded to four La3+ atoms to form OLa4 tetrahedra that share corners with twelve OLa4 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with four OLa3Bi tetrahedra. In the sixteenth O2- site, O2- is bonded to four La3+ atoms to form OLa4 tetrahedra that share corners with thirteen OLa4 tetrahedra and edges with four OLa2Bi2 tetrahedra. In the seventeenth O2- site, O2- is bonded to two La3+ and two Bi3+ atoms to form distorted OLa2Bi2 tetrahedra that share corners with seven OLa2Bi2 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa4 tetrahedra. In the eighteenth O2- site, O2- is bonded to two La3+ and two Bi3+ atoms to form distorted OLa2Bi2 tetrahedra that share corners with six OLa2Bi2 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa3Bi tetrahedra. In the nineteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to three Bi3+ atoms. In the twentieth O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with nine OLa4 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa3Bi tetrahedra. In the twenty-first O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with ten OLa4 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa2Bi2 tetrahedra. In the twenty-second O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with ten OLa4 tetrahedra, a cornercorner with one OLaBi3 trigonal pyramid, and edges with five OLa3Bi tetrahedra. In the twenty-third O2- site, O2- is bonded to three La3+ and one Bi3+ atom to form OLa3Bi tetrahedra that share corners with ten OLa4 tetrahedra and edges with five OLa2Bi2 tetrahedra. In the twenty-fourth O2- site, O2- is bonded in a 4-coordinate geometry to three La3+ and one Bi3+ atom. In the twenty-fifth O2- site, O2- is bonded in a 3-coordinate geometry to three La3+ and one Bi3+ atom. In the twenty-sixth O2- site, O2- is bonded in a 4-coordinate geometry to three La3+ and one Bi3+ atom. In the twenty-seventh O2- site, O2- is bonded in a 4-coordinate geometry to three La3+ and one Bi3+ atom.

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