Na2BBiAsO7 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. Bi(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form distorted BiO6 pentagonal pyramids that share corners with four equivalent As(1)O4 tetrahedra. As(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form AsO4 tetrahedra that share corners with four equivalent Bi(1)O6 pentagonal pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one B(1) atom. In the second O site, O(2) is bonded to two equivalent Na(1), one B(1), and one Bi(1) atom to form distorted corner-sharing ONa2BiB trigonal pyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one B(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Bi(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Bi(1), and one As(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(1), one Bi(1), and one As(1) atom to form distorted corner-sharing ONa2BiAs tetrahedra.
Na2BBiAsO7 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.34 Å. The Na(1)-O(2) bond length is 2.43 Å. The Na(1)-O(3) bond length is 2.47 Å. The Na(1)-O(4) bond length is 2.47 Å. The Na(1)-O(5) bond length is 2.76 Å. The Na(1)-O(6) bond length is 2.72 Å. B(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The B(1)-O(1) bond length is 1.36 Å. The B(1)-O(2) bond length is 1.38 Å. The B(1)-O(3) bond length is 1.40 Å. Bi(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form distorted BiO6 pentagonal pyramids that share corners with four equivalent As(1)O4 tetrahedra. The Bi(1)-O(2) bond length is 2.24 Å. The Bi(1)-O(3) bond length is 2.40 Å. The Bi(1)-O(5) bond length is 2.29 Å. The Bi(1)-O(6) bond length is 2.67 Å. Both Bi(1)-O(4) bond lengths are 2.31 Å. As(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form AsO4 tetrahedra that share corners with four equivalent Bi(1)O6 pentagonal pyramids. The As(1)-O(5) bond length is 1.76 Å. The As(1)-O(6) bond length is 1.71 Å. Both As(1)-O(4) bond lengths are 1.72 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one B(1) atom. In the second O site, O(2) is bonded to two equivalent Na(1), one B(1), and one Bi(1) atom to form distorted corner-sharing ONa2BiB trigonal pyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(1), one B(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Bi(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Bi(1), and one As(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(1), one Bi(1), and one As(1) atom to form distorted corner-sharing ONa2BiAs tetrahedra.