Bi(PO3)3 crystallizes in the monoclinic P2_1/c space group. Bi(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and two equivalent O(2) atoms to form distorted BiO7 pentagonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O7 pentagonal bipyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with three equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. In the second P site, P(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. In the third P site, P(3) is bonded to one O(5), one O(7), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. There are nine inequivalent O sites. In the first O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(3) atom. In the second O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(7) is bonded in a distorted single-bond geometry to one Bi(1) and one P(3) atom. In the fourth O site, O(8) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the fifth O site, O(1) is bonded in a distorted linear geometry to one Bi(1) and one P(1) atom. In the sixth O site, O(9) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Bi(1) and one P(1) atom. In the eighth O site, O(3) is bonded in a distorted single-bond geometry to one Bi(1) and one P(2) atom. In the ninth O site, O(4) is bonded in a distorted linear geometry to one Bi(1) and one P(2) atom.
Bi(PO3)3 crystallizes in the monoclinic P2_1/c space group. Bi(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and two equivalent O(2) atoms to form distorted BiO7 pentagonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Bi(1)O7 pentagonal bipyramid. The Bi(1)-O(1) bond length is 2.36 Å. The Bi(1)-O(3) bond length is 2.33 Å. The Bi(1)-O(4) bond length is 2.41 Å. The Bi(1)-O(5) bond length is 2.26 Å. The Bi(1)-O(7) bond length is 2.39 Å. There is one shorter (2.38 Å) and one longer (2.71 Å) Bi(1)-O(2) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with three equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The P(1)-O(1) bond length is 1.49 Å. The P(1)-O(2) bond length is 1.50 Å. The P(1)-O(6) bond length is 1.58 Å. The P(1)-O(9) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The P(2)-O(3) bond length is 1.49 Å. The P(2)-O(4) bond length is 1.48 Å. The P(2)-O(6) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.60 Å. In the third P site, P(3) is bonded to one O(5), one O(7), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The P(3)-O(5) bond length is 1.49 Å. The P(3)-O(7) bond length is 1.47 Å. The P(3)-O(8) bond length is 1.59 Å. The P(3)-O(9) bond length is 1.59 Å. There are nine inequivalent O sites. In the first O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Bi(1) and one P(3) atom. In the second O site, O(6) is bonded in a distorted bent 120 degrees geometry to one P(1) and one P(2) atom. In the third O site, O(7) is bonded in a distorted single-bond geometry to one Bi(1) and one P(3) atom. In the fourth O site, O(8) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the fifth O site, O(1) is bonded in a distorted linear geometry to one Bi(1) and one P(1) atom. In the sixth O site, O(9) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Bi(1) and one P(1) atom. In the eighth O site, O(3) is bonded in a distorted single-bond geometry to one Bi(1) and one P(2) atom. In the ninth O site, O(4) is bonded in a distorted linear geometry to one Bi(1) and one P(2) atom.