Mn3Zn9(PO4)8 crystallizes in the triclinic P-1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent O(14), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent P(4)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(11), two equivalent O(15), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(3)O4 tetrahedra. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(12), and two equivalent O(16) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(4)O4 tetrahedra. There are five inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(3), one O(5), and one O(6) atom. In the second Zn site, Zn(2) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(4), one O(5), and one O(6) atom. In the third Zn site, Zn(3) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(7), one O(8), and one O(9) atom. In the fourth Zn site, Zn(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(2), one O(7), and one O(8) atom. In the fifth Zn site, Zn(5) is bonded to two equivalent O(13), two equivalent O(3), and two equivalent O(9) atoms to form ZnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(3)O6 octahedra and corners with two equivalent Zn(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-57°. In the second P site, P(2) is bonded to one O(10), one O(14), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. In the third P site, P(3) is bonded to one O(11), one O(15), one O(3), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(5)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-57°. In the fourth P site, P(4) is bonded to one O(12), one O(16), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(3), one Zn(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(2), one Zn(4), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(5), and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(1), one Zn(2), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Zn(3), one Zn(4), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Zn(3), one Zn(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Zn(3), one Zn(5), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(1), one Zn(4), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Mn(2), one Zn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Mn(3), one Zn(2), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Zn(3), one Zn(5), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Mn(1), one Zn(4), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Mn(2), one Zn(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Mn(3), one Zn(2), and one P(4) atom.
Mn3Zn9(PO4)8 crystallizes in the triclinic P-1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent O(14), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent P(4)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Mn(1)-O(10) bond lengths are 2.31 Å. Both Mn(1)-O(14) bond lengths are 2.09 Å. Both Mn(1)-O(4) bond lengths are 2.26 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(11), two equivalent O(15), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(3)O4 tetrahedra. Both Mn(2)-O(11) bond lengths are 2.30 Å. Both Mn(2)-O(15) bond lengths are 2.10 Å. Both Mn(2)-O(2) bond lengths are 2.25 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(12), and two equivalent O(16) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(4)O4 tetrahedra. Both Mn(3)-O(1) bond lengths are 2.27 Å. Both Mn(3)-O(12) bond lengths are 2.30 Å. Both Mn(3)-O(16) bond lengths are 2.10 Å. There are five inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 5-coordinate geometry to one O(11), one O(15), one O(3), one O(5), and one O(6) atom. The Zn(1)-O(11) bond length is 1.97 Å. The Zn(1)-O(15) bond length is 2.45 Å. The Zn(1)-O(3) bond length is 2.01 Å. The Zn(1)-O(5) bond length is 2.00 Å. The Zn(1)-O(6) bond length is 2.05 Å. In the second Zn site, Zn(2) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(4), one O(5), and one O(6) atom. The Zn(2)-O(12) bond length is 1.97 Å. The Zn(2)-O(16) bond length is 2.46 Å. The Zn(2)-O(4) bond length is 2.01 Å. The Zn(2)-O(5) bond length is 2.05 Å. The Zn(2)-O(6) bond length is 2.00 Å. In the third Zn site, Zn(3) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(7), one O(8), and one O(9) atom. The Zn(3)-O(1) bond length is 2.01 Å. The Zn(3)-O(13) bond length is 2.46 Å. The Zn(3)-O(7) bond length is 2.05 Å. The Zn(3)-O(8) bond length is 2.01 Å. The Zn(3)-O(9) bond length is 1.97 Å. In the fourth Zn site, Zn(4) is bonded in a 5-coordinate geometry to one O(10), one O(14), one O(2), one O(7), and one O(8) atom. The Zn(4)-O(10) bond length is 1.96 Å. The Zn(4)-O(14) bond length is 2.46 Å. The Zn(4)-O(2) bond length is 2.01 Å. The Zn(4)-O(7) bond length is 2.00 Å. The Zn(4)-O(8) bond length is 2.05 Å. In the fifth Zn site, Zn(5) is bonded to two equivalent O(13), two equivalent O(3), and two equivalent O(9) atoms to form ZnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. Both Zn(5)-O(13) bond lengths are 2.05 Å. Both Zn(5)-O(3) bond lengths are 2.24 Å. Both Zn(5)-O(9) bond lengths are 2.29 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(3)O6 octahedra and corners with two equivalent Zn(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-57°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(13) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(9) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(10), one O(14), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(14) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(11), one O(15), one O(3), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Zn(5)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-57°. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(15) bond length is 1.53 Å. The P(3)-O(3) bond length is 1.58 Å. The P(3)-O(7) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(12), one O(16), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. The P(4)-O(12) bond length is 1.55 Å. The P(4)-O(16) bond length is 1.53 Å. The P(4)-O(4) bond length is 1.57 Å. The P(4)-O(8) bond length is 1.57 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(3), one Zn(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(2), one Zn(4), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(5), and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(1), one Zn(2), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(1), one Zn(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Zn(3), one Zn(4), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Zn(3), one Zn(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Zn(3), one Zn(5), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(1), one Zn(4), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Mn(2), one Zn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Mn(3), one Zn(2), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Zn(3), one Zn(5), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Mn(1), one Zn(4), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Mn(2), one Zn(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Mn(3), one Zn(2), and one P(4) atom.