Pb2In4P6O23 crystallizes in the triclinic P1 space group. There are four inequivalent In sites. In the first In site, In(1) is bonded to one O(13), one O(2), one O(5), one O(7), one O(8), and one O(9) atom to form distorted InO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the second In site, In(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(14), one O(6), one O(7), and one O(8) atom. In the third In site, In(3) is bonded to one O(12), one O(16), one O(17), one O(19), one O(22), and one O(3) atom to form InO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and corners with two equivalent P(6)O4 tetrahedra. In the fourth In site, In(4) is bonded to one O(11), one O(15), one O(18), one O(20), one O(21), and one O(4) atom to form InO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and corners with two equivalent P(5)O4 tetrahedra. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(13), one O(15), and one O(9) atom. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(14), one O(16), and one O(2) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(15), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(3)O6 octahedra, and  a cornercorner with one In(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. In the second P site, P(2) is bonded to one O(14), one O(16), one O(2), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(3)O6 octahedra, and  a cornercorner with one In(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-52°. In the third P site, P(3) is bonded to one O(19), one O(23), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one In(3)O6 octahedra, corners with two equivalent In(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-59°. In the fourth P site, P(4) is bonded to one O(10), one O(20), one O(23), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one In(4)O6 octahedra and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. In the fifth P site, P(5) is bonded to one O(11), one O(17), one O(21), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(3)O6 octahedra, and corners with two equivalent In(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. In the sixth P site, P(6) is bonded to one O(12), one O(18), one O(22), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(4)O6 octahedra, and corners with two equivalent In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-63°. There are twenty-three inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one In(2), one Pb(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one In(1), one Pb(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one In(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one In(4) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one In(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one In(2) and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one In(1), one In(2), and one P(5) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one In(1), one In(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one In(1), one Pb(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one In(2), one Pb(2), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one In(4), one Pb(1), and one P(5) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one In(3), one Pb(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one In(1), one Pb(1), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one In(2), one Pb(2), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one In(4), one Pb(1), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one In(3), one Pb(2), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one In(3) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one In(4) and one P(6) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one In(3) and one P(3) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one In(4) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 120 degrees geometry to one In(4) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 120 degrees geometry to one In(3) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a linear geometry to one P(3) and one P(4) atom.
Pb2In4P6O23 crystallizes in the triclinic P1 space group. There are four inequivalent In sites. In the first In site, In(1) is bonded to one O(13), one O(2), one O(5), one O(7), one O(8), and one O(9) atom to form distorted InO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The In(1)-O(13) bond length is 2.11 Å. The In(1)-O(2) bond length is 2.14 Å. The In(1)-O(5) bond length is 2.13 Å. The In(1)-O(7) bond length is 2.57 Å. The In(1)-O(8) bond length is 2.12 Å. The In(1)-O(9) bond length is 2.20 Å. In the second In site, In(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(14), one O(6), one O(7), and one O(8) atom. The In(2)-O(1) bond length is 2.14 Å. The In(2)-O(10) bond length is 2.22 Å. The In(2)-O(14) bond length is 2.12 Å. The In(2)-O(6) bond length is 2.16 Å. The In(2)-O(7) bond length is 2.12 Å. The In(2)-O(8) bond length is 2.59 Å. In the third In site, In(3) is bonded to one O(12), one O(16), one O(17), one O(19), one O(22), and one O(3) atom to form InO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and corners with two equivalent P(6)O4 tetrahedra. The In(3)-O(12) bond length is 2.28 Å. The In(3)-O(16) bond length is 2.21 Å. The In(3)-O(17) bond length is 2.13 Å. The In(3)-O(19) bond length is 2.16 Å. The In(3)-O(22) bond length is 2.17 Å. The In(3)-O(3) bond length is 2.17 Å. In the fourth In site, In(4) is bonded to one O(11), one O(15), one O(18), one O(20), one O(21), and one O(4) atom to form InO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and corners with two equivalent P(5)O4 tetrahedra. The In(4)-O(11) bond length is 2.28 Å. The In(4)-O(15) bond length is 2.20 Å. The In(4)-O(18) bond length is 2.13 Å. The In(4)-O(20) bond length is 2.14 Å. The In(4)-O(21) bond length is 2.17 Å. The In(4)-O(4) bond length is 2.17 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(13), one O(15), and one O(9) atom. The Pb(1)-O(1) bond length is 2.75 Å. The Pb(1)-O(11) bond length is 2.49 Å. The Pb(1)-O(13) bond length is 2.52 Å. The Pb(1)-O(15) bond length is 2.44 Å. The Pb(1)-O(9) bond length is 2.69 Å. In the second Pb site, Pb(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(14), one O(16), and one O(2) atom. The Pb(2)-O(10) bond length is 2.68 Å. The Pb(2)-O(12) bond length is 2.49 Å. The Pb(2)-O(14) bond length is 2.52 Å. The Pb(2)-O(16) bond length is 2.44 Å. The Pb(2)-O(2) bond length is 2.76 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(15), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(3)O6 octahedra, and  a cornercorner with one In(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(13) bond length is 1.56 Å. The P(1)-O(15) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(14), one O(16), one O(2), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(3)O6 octahedra, and  a cornercorner with one In(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-52°. The P(2)-O(14) bond length is 1.56 Å. The P(2)-O(16) bond length is 1.56 Å. The P(2)-O(2) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(19), one O(23), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one In(3)O6 octahedra, corners with two equivalent In(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-59°. The P(3)-O(19) bond length is 1.53 Å. The P(3)-O(23) bond length is 1.59 Å. The P(3)-O(5) bond length is 1.52 Å. The P(3)-O(9) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(10), one O(20), one O(23), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one In(4)O6 octahedra and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 35°. The P(4)-O(10) bond length is 1.55 Å. The P(4)-O(20) bond length is 1.52 Å. The P(4)-O(23) bond length is 1.59 Å. The P(4)-O(6) bond length is 1.53 Å. In the fifth P site, P(5) is bonded to one O(11), one O(17), one O(21), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(3)O6 octahedra, and corners with two equivalent In(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. The P(5)-O(11) bond length is 1.57 Å. The P(5)-O(17) bond length is 1.54 Å. The P(5)-O(21) bond length is 1.54 Å. The P(5)-O(7) bond length is 1.60 Å. In the sixth P site, P(6) is bonded to one O(12), one O(18), one O(22), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra,  a cornercorner with one In(4)O6 octahedra, and corners with two equivalent In(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-63°. The P(6)-O(12) bond length is 1.57 Å. The P(6)-O(18) bond length is 1.54 Å. The P(6)-O(22) bond length is 1.54 Å. The P(6)-O(8) bond length is 1.59 Å. There are twenty-three inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one In(2), one Pb(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one In(1), one Pb(2), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one In(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one In(4) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one In(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one In(2) and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one In(1), one In(2), and one P(5) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one In(1), one In(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one In(1), one Pb(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one In(2), one Pb(2), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one In(4), one Pb(1), and one P(5) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one In(3), one Pb(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one In(1), one Pb(1), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one In(2), one Pb(2), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one In(4), one Pb(1), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one In(3), one Pb(2), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one In(3) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one In(4) and one P(6) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one In(3) and one P(3) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one In(4) and one P(4) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 120 degrees geometry to one In(4) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 120 degrees geometry to one In(3) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a linear geometry to one P(3) and one P(4) atom.