Ca3Bi2(AsO6)2 crystallizes in the triclinic P1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), one O(10), one O(11), one O(2), one O(5), one O(8), and one O(9) atom to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one As(2)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra, edges with two equivalent Ca(3)O7 pentagonal bipyramids,  an edgeedge with one As(2)O4 tetrahedra, and  a faceface with one Ca(2)O7 pentagonal bipyramid. In the second Ca site, Ca(2) is bonded to one O(11), one O(12), one O(3), one O(4), one O(5), one O(6), and one O(9) atom to form distorted CaO7 pentagonal bipyramids that share corners with four equivalent Ca(3)O7 pentagonal bipyramids,  a cornercorner with one As(2)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra,  an edgeedge with one As(2)O4 tetrahedra, and  a faceface with one Ca(1)O7 pentagonal bipyramid. In the third Ca site, Ca(3) is bonded to one O(1), one O(11), one O(12), one O(3), one O(7), one O(8), and one O(9) atom to form distorted CaO7 pentagonal bipyramids that share corners with four equivalent Ca(2)O7 pentagonal bipyramids,  a cornercorner with one As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, edges with two equivalent Ca(1)O7 pentagonal bipyramids, and  an edgeedge with one As(1)O4 tetrahedra. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(4), one O(6), and one O(8) atom. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(11), one O(12), one O(2), and one O(7) atom to form AsO4 tetrahedra that share  a cornercorner with one Ca(3)O7 pentagonal bipyramid, corners with two equivalent Ca(1)O7 pentagonal bipyramids, corners with two equivalent Ca(2)O7 pentagonal bipyramids, and  an edgeedge with one Ca(3)O7 pentagonal bipyramid. In the second As site, As(2) is bonded to one O(10), one O(3), one O(5), and one O(9) atom to form AsO4 tetrahedra that share  a cornercorner with one Ca(1)O7 pentagonal bipyramid,  a cornercorner with one Ca(2)O7 pentagonal bipyramid, corners with two equivalent Ca(3)O7 pentagonal bipyramids,  an edgeedge with one Ca(1)O7 pentagonal bipyramid, and  an edgeedge with one Ca(2)O7 pentagonal bipyramid. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(3), one Bi(1), and one Bi(2) atom to form edge-sharing OCa2Bi2 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Bi(1), and one As(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(3), and one As(2) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Ca(2), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one As(2) atom. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Ca(2), one Bi(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ca(3), one Bi(1), and one As(1) atom. In the eighth O site, O(8) is bonded to one Ca(1), one Ca(3), one Bi(1), and one Bi(2) atom to form edge-sharing OCa2Bi2 tetrahedra. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Ca(2), one Ca(3), and one As(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Bi(2), and one As(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), and one As(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Ca(2), one Ca(3), and one As(1) atom.
Ca3Bi2(AsO6)2 crystallizes in the triclinic P1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one O(1), one O(10), one O(11), one O(2), one O(5), one O(8), and one O(9) atom to form distorted CaO7 pentagonal bipyramids that share  a cornercorner with one As(2)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra, edges with two equivalent Ca(3)O7 pentagonal bipyramids,  an edgeedge with one As(2)O4 tetrahedra, and  a faceface with one Ca(2)O7 pentagonal bipyramid. The Ca(1)-O(1) bond length is 2.31 Å. The Ca(1)-O(10) bond length is 2.50 Å. The Ca(1)-O(11) bond length is 2.76 Å. The Ca(1)-O(2) bond length is 2.35 Å. The Ca(1)-O(5) bond length is 2.38 Å. The Ca(1)-O(8) bond length is 2.39 Å. The Ca(1)-O(9) bond length is 2.50 Å. In the second Ca site, Ca(2) is bonded to one O(11), one O(12), one O(3), one O(4), one O(5), one O(6), and one O(9) atom to form distorted CaO7 pentagonal bipyramids that share corners with four equivalent Ca(3)O7 pentagonal bipyramids,  a cornercorner with one As(2)O4 tetrahedra, corners with two equivalent As(1)O4 tetrahedra,  an edgeedge with one As(2)O4 tetrahedra, and  a faceface with one Ca(1)O7 pentagonal bipyramid. The Ca(2)-O(11) bond length is 2.49 Å. The Ca(2)-O(12) bond length is 2.39 Å. The Ca(2)-O(3) bond length is 2.57 Å. The Ca(2)-O(4) bond length is 2.30 Å. The Ca(2)-O(5) bond length is 2.51 Å. The Ca(2)-O(6) bond length is 2.40 Å. The Ca(2)-O(9) bond length is 2.72 Å. In the third Ca site, Ca(3) is bonded to one O(1), one O(11), one O(12), one O(3), one O(7), one O(8), and one O(9) atom to form distorted CaO7 pentagonal bipyramids that share corners with four equivalent Ca(2)O7 pentagonal bipyramids,  a cornercorner with one As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, edges with two equivalent Ca(1)O7 pentagonal bipyramids, and  an edgeedge with one As(1)O4 tetrahedra. The Ca(3)-O(1) bond length is 2.48 Å. The Ca(3)-O(11) bond length is 2.74 Å. The Ca(3)-O(12) bond length is 2.40 Å. The Ca(3)-O(3) bond length is 2.41 Å. The Ca(3)-O(7) bond length is 2.46 Å. The Ca(3)-O(8) bond length is 2.44 Å. The Ca(3)-O(9) bond length is 2.44 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Bi(1)-O(1) bond length is 2.20 Å. The Bi(1)-O(2) bond length is 2.64 Å. The Bi(1)-O(4) bond length is 2.14 Å. The Bi(1)-O(6) bond length is 2.14 Å. The Bi(1)-O(7) bond length is 2.52 Å. The Bi(1)-O(8) bond length is 2.24 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(4), one O(6), and one O(8) atom. The Bi(2)-O(1) bond length is 2.21 Å. The Bi(2)-O(10) bond length is 2.47 Å. The Bi(2)-O(4) bond length is 2.17 Å. The Bi(2)-O(6) bond length is 2.17 Å. The Bi(2)-O(8) bond length is 2.26 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(11), one O(12), one O(2), and one O(7) atom to form AsO4 tetrahedra that share  a cornercorner with one Ca(3)O7 pentagonal bipyramid, corners with two equivalent Ca(1)O7 pentagonal bipyramids, corners with two equivalent Ca(2)O7 pentagonal bipyramids, and  an edgeedge with one Ca(3)O7 pentagonal bipyramid. The As(1)-O(11) bond length is 1.72 Å. The As(1)-O(12) bond length is 1.74 Å. The As(1)-O(2) bond length is 1.73 Å. The As(1)-O(7) bond length is 1.74 Å. In the second As site, As(2) is bonded to one O(10), one O(3), one O(5), and one O(9) atom to form AsO4 tetrahedra that share  a cornercorner with one Ca(1)O7 pentagonal bipyramid,  a cornercorner with one Ca(2)O7 pentagonal bipyramid, corners with two equivalent Ca(3)O7 pentagonal bipyramids,  an edgeedge with one Ca(1)O7 pentagonal bipyramid, and  an edgeedge with one Ca(2)O7 pentagonal bipyramid. The As(2)-O(10) bond length is 1.75 Å. The As(2)-O(3) bond length is 1.72 Å. The As(2)-O(5) bond length is 1.73 Å. The As(2)-O(9) bond length is 1.72 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Ca(1), one Ca(3), one Bi(1), and one Bi(2) atom to form edge-sharing OCa2Bi2 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Bi(1), and one As(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(2), one Ca(3), and one As(2) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Ca(2), one Bi(1), and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ca(1), one Ca(2), and one As(2) atom. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Ca(2), one Bi(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ca(3), one Bi(1), and one As(1) atom. In the eighth O site, O(8) is bonded to one Ca(1), one Ca(3), one Bi(1), and one Bi(2) atom to form edge-sharing OCa2Bi2 tetrahedra. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Ca(1), one Ca(2), one Ca(3), and one As(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1), one Bi(2), and one As(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), and one As(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Ca(2), one Ca(3), and one As(1) atom.