BiB3O6 crystallizes in the triclinic P1 space group. There are three inequivalent B sites. In the first B site, B(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form BO4 tetrahedra that share corners with two equivalent Bi(1)O6 pentagonal pyramids. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. Bi(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form distorted BiO6 pentagonal pyramids that share corners with four equivalent Bi(1)O6 pentagonal pyramids and corners with two equivalent B(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one B(1) and one B(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one B(1) and one B(3) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one B(1), one B(3), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one B(1), one B(2), and one Bi(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one B(2) and two equivalent Bi(1) atoms. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one B(3) and two equivalent Bi(1) atoms.
BiB3O6 crystallizes in the triclinic P1 space group. There are three inequivalent B sites. In the first B site, B(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form BO4 tetrahedra that share corners with two equivalent Bi(1)O6 pentagonal pyramids. The B(1)-O(1) bond length is 1.45 Å. The B(1)-O(2) bond length is 1.45 Å. The B(1)-O(3) bond length is 1.51 Å. The B(1)-O(4) bond length is 1.51 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. The B(2)-O(1) bond length is 1.34 Å. The B(2)-O(4) bond length is 1.41 Å. The B(2)-O(5) bond length is 1.38 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. The B(3)-O(2) bond length is 1.35 Å. The B(3)-O(3) bond length is 1.41 Å. The B(3)-O(6) bond length is 1.38 Å. Bi(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form distorted BiO6 pentagonal pyramids that share corners with four equivalent Bi(1)O6 pentagonal pyramids and corners with two equivalent B(1)O4 tetrahedra. The Bi(1)-O(3) bond length is 2.41 Å. The Bi(1)-O(4) bond length is 2.44 Å. There is one shorter (2.17 Å) and one longer (2.62 Å) Bi(1)-O(5) bond length. There is one shorter (2.17 Å) and one longer (2.59 Å) Bi(1)-O(6) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one B(1) and one B(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one B(1) and one B(3) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one B(1), one B(3), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one B(1), one B(2), and one Bi(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one B(2) and two equivalent Bi(1) atoms. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one B(3) and two equivalent Bi(1) atoms.