Zn3Bi2(PO6)2 crystallizes in the monoclinic Pm space group. There are six inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(15), two equivalent O(10), and two equivalent O(6) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Zn(6)O5 trigonal bipyramid. In the second Zn site, Zn(2) is bonded to one O(16), two equivalent O(12), and two equivalent O(5) atoms to form ZnO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Zn(4)O5 trigonal bipyramids. In the third Zn site, Zn(3) is bonded to one O(13), two equivalent O(3), and two equivalent O(7) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Zn(6)O5 trigonal bipyramids. In the fourth Zn site, Zn(4) is bonded to one O(4), two equivalent O(12), and two equivalent O(2) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent Zn(2)O5 trigonal bipyramids, and  an edgeedge with one Zn(5)O5 square pyramid. In the fifth Zn site, Zn(5) is bonded to one O(8), two equivalent O(1), and two equivalent O(2) atoms to form ZnO5 square pyramids that share  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Zn(4)O5 trigonal bipyramid. In the sixth Zn site, Zn(6) is bonded to one O(11), two equivalent O(3), and two equivalent O(6) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent Zn(3)O5 trigonal bipyramids, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(16), two equivalent O(10), and two equivalent O(3) atoms. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(14), two equivalent O(1), and two equivalent O(12) atoms. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(11), two equivalent O(1), and two equivalent O(12) atoms. In the fourth Bi site, Bi(4) is bonded in a 5-coordinate geometry to one O(8), two equivalent O(10), and two equivalent O(3) atoms. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(13), one O(14), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Zn(5)O5 square pyramids,  a cornercorner with one Zn(3)O5 trigonal bipyramid, and corners with two equivalent Zn(4)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(11), one O(15), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O5 trigonal bipyramid,  a cornercorner with one Zn(6)O5 trigonal bipyramid, and corners with two equivalent Zn(2)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(16), one O(9), and two equivalent O(6) atoms to form PO4 tetrahedra that share  a cornercorner with one Zn(2)O5 trigonal bipyramid, corners with two equivalent Zn(1)O5 trigonal bipyramids, and corners with two equivalent Zn(6)O5 trigonal bipyramids. In the fourth P site, P(4) is bonded to one O(4), one O(8), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Zn(5)O5 square pyramid,  a cornercorner with one Zn(4)O5 trigonal bipyramid, and corners with two equivalent Zn(3)O5 trigonal bipyramids. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Zn(5), one Bi(2), and one Bi(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Zn(4), one Zn(5), and one P(1) atom. In the third O site, O(3) is bonded to one Zn(3), one Zn(6), one Bi(1), and one Bi(4) atom to form edge-sharing OZn2Bi2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Zn(4) and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(6), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Zn(3) and one P(4) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Zn(5), one Bi(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one P(3) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Zn(1), one Bi(1), and one Bi(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Zn(6), one Bi(3), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Zn(2), one Zn(4), one Bi(2), and one Bi(3) atom to form distorted edge-sharing OZn2Bi2 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Zn(3) and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one P(1) atom. In the fifteenth O site, O(15) is bonded in a distorted linear geometry to one Zn(1) and one P(2) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Zn(2), one Bi(1), and one P(3) atom.
Zn3Bi2(PO6)2 crystallizes in the monoclinic Pm space group. There are six inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(15), two equivalent O(10), and two equivalent O(6) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Zn(6)O5 trigonal bipyramid. The Zn(1)-O(15) bond length is 2.15 Å. Both Zn(1)-O(10) bond lengths are 1.99 Å. Both Zn(1)-O(6) bond lengths are 2.07 Å. In the second Zn site, Zn(2) is bonded to one O(16), two equivalent O(12), and two equivalent O(5) atoms to form ZnO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Zn(4)O5 trigonal bipyramids. The Zn(2)-O(16) bond length is 2.10 Å. Both Zn(2)-O(12) bond lengths are 2.04 Å. Both Zn(2)-O(5) bond lengths are 1.99 Å. In the third Zn site, Zn(3) is bonded to one O(13), two equivalent O(3), and two equivalent O(7) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and corners with two equivalent Zn(6)O5 trigonal bipyramids. The Zn(3)-O(13) bond length is 2.30 Å. Both Zn(3)-O(3) bond lengths are 2.02 Å. Both Zn(3)-O(7) bond lengths are 1.98 Å. In the fourth Zn site, Zn(4) is bonded to one O(4), two equivalent O(12), and two equivalent O(2) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent Zn(2)O5 trigonal bipyramids, and  an edgeedge with one Zn(5)O5 square pyramid. The Zn(4)-O(4) bond length is 2.19 Å. Both Zn(4)-O(12) bond lengths are 2.01 Å. Both Zn(4)-O(2) bond lengths are 2.07 Å. In the fifth Zn site, Zn(5) is bonded to one O(8), two equivalent O(1), and two equivalent O(2) atoms to form ZnO5 square pyramids that share  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Zn(4)O5 trigonal bipyramid. The Zn(5)-O(8) bond length is 1.99 Å. Both Zn(5)-O(1) bond lengths are 1.97 Å. Both Zn(5)-O(2) bond lengths are 2.06 Å. In the sixth Zn site, Zn(6) is bonded to one O(11), two equivalent O(3), and two equivalent O(6) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent Zn(3)O5 trigonal bipyramids, and  an edgeedge with one Zn(1)O5 trigonal bipyramid. The Zn(6)-O(11) bond length is 2.03 Å. Both Zn(6)-O(3) bond lengths are 2.02 Å. Both Zn(6)-O(6) bond lengths are 2.11 Å. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(16), two equivalent O(10), and two equivalent O(3) atoms. The Bi(1)-O(16) bond length is 2.58 Å. Both Bi(1)-O(10) bond lengths are 2.19 Å. Both Bi(1)-O(3) bond lengths are 2.40 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(14), two equivalent O(1), and two equivalent O(12) atoms. The Bi(2)-O(14) bond length is 2.43 Å. Both Bi(2)-O(1) bond lengths are 2.37 Å. Both Bi(2)-O(12) bond lengths are 2.24 Å. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(11), two equivalent O(1), and two equivalent O(12) atoms. The Bi(3)-O(11) bond length is 2.54 Å. Both Bi(3)-O(1) bond lengths are 2.19 Å. Both Bi(3)-O(12) bond lengths are 2.46 Å. In the fourth Bi site, Bi(4) is bonded in a 5-coordinate geometry to one O(8), two equivalent O(10), and two equivalent O(3) atoms. The Bi(4)-O(8) bond length is 2.78 Å. Both Bi(4)-O(10) bond lengths are 2.26 Å. Both Bi(4)-O(3) bond lengths are 2.27 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(13), one O(14), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Zn(5)O5 square pyramids,  a cornercorner with one Zn(3)O5 trigonal bipyramid, and corners with two equivalent Zn(4)O5 trigonal bipyramids. The P(1)-O(13) bond length is 1.53 Å. The P(1)-O(14) bond length is 1.53 Å. Both P(1)-O(2) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(11), one O(15), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Zn(1)O5 trigonal bipyramid,  a cornercorner with one Zn(6)O5 trigonal bipyramid, and corners with two equivalent Zn(2)O5 trigonal bipyramids. The P(2)-O(11) bond length is 1.59 Å. The P(2)-O(15) bond length is 1.54 Å. Both P(2)-O(5) bond lengths are 1.53 Å. In the third P site, P(3) is bonded to one O(16), one O(9), and two equivalent O(6) atoms to form PO4 tetrahedra that share  a cornercorner with one Zn(2)O5 trigonal bipyramid, corners with two equivalent Zn(1)O5 trigonal bipyramids, and corners with two equivalent Zn(6)O5 trigonal bipyramids. The P(3)-O(16) bond length is 1.55 Å. The P(3)-O(9) bond length is 1.52 Å. Both P(3)-O(6) bond lengths are 1.58 Å. In the fourth P site, P(4) is bonded to one O(4), one O(8), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Zn(5)O5 square pyramid,  a cornercorner with one Zn(4)O5 trigonal bipyramid, and corners with two equivalent Zn(3)O5 trigonal bipyramids. The P(4)-O(4) bond length is 1.56 Å. The P(4)-O(8) bond length is 1.55 Å. Both P(4)-O(7) bond lengths are 1.55 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Zn(5), one Bi(2), and one Bi(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Zn(4), one Zn(5), and one P(1) atom. In the third O site, O(3) is bonded to one Zn(3), one Zn(6), one Bi(1), and one Bi(4) atom to form edge-sharing OZn2Bi2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Zn(4) and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Zn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(6), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Zn(3) and one P(4) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Zn(5), one Bi(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one P(3) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Zn(1), one Bi(1), and one Bi(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Zn(6), one Bi(3), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Zn(2), one Zn(4), one Bi(2), and one Bi(3) atom to form distorted edge-sharing OZn2Bi2 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Zn(3) and one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one P(1) atom. In the fifteenth O site, O(15) is bonded in a distorted linear geometry to one Zn(1) and one P(2) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Zn(2), one Bi(1), and one P(3) atom.