Na2MnFeCd(PO4)3 crystallizes in the monoclinic C2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted NaO8 hexagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Cd(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and edges with two equivalent P(2)O4 tetrahedra. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(9), two equivalent O(7), and two equivalent O(8) atoms. Mn(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(1)O8 hexagonal bipyramid,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Cd(1)O6 octahedra. Fe(1) is bonded to one O(10), one O(11), one O(12), one O(2), one O(4), and one O(6) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(1)O8 hexagonal bipyramid, and  an edgeedge with one Mn(1)O6 octahedra. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form distorted CdO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Na(1)O8 hexagonal bipyramid, and edges with two equivalent Mn(1)O6 octahedra. In the second Cd site, Cd(2) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid,  a cornercorner with one Cd(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-60°. In the second P site, P(2) is bonded to one O(12), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cd(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-59°. In the third P site, P(3) is bonded to two equivalent O(4) and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles are 50°. In the fourth P site, P(4) is bonded to two equivalent O(10) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-63°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(1), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Mn(1), one Cd(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Fe(1), one Cd(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Mn(1), one Cd(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Fe(1), one Cd(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Cd(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Cd(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(3), one Mn(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(3), one Fe(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(2) atom.
Na2MnFeCd(PO4)3 crystallizes in the monoclinic C2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted NaO8 hexagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Cd(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and edges with two equivalent P(2)O4 tetrahedra. Both Na(1)-O(1) bond lengths are 2.58 Å. Both Na(1)-O(2) bond lengths are 2.56 Å. Both Na(1)-O(4) bond lengths are 2.72 Å. Both Na(1)-O(5) bond lengths are 2.89 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(2)-O(1) bond lengths are 2.35 Å. Both Na(2)-O(2) bond lengths are 2.69 Å. Both Na(2)-O(3) bond lengths are 2.75 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(9), two equivalent O(7), and two equivalent O(8) atoms. The Na(3)-O(10) bond length is 2.43 Å. The Na(3)-O(9) bond length is 2.35 Å. There is one shorter (2.37 Å) and one longer (2.63 Å) Na(3)-O(7) bond length. There is one shorter (2.39 Å) and one longer (2.60 Å) Na(3)-O(8) bond length. Mn(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(1)O8 hexagonal bipyramid,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Cd(1)O6 octahedra. The Mn(1)-O(1) bond length is 2.15 Å. The Mn(1)-O(11) bond length is 2.35 Å. The Mn(1)-O(12) bond length is 2.22 Å. The Mn(1)-O(3) bond length is 2.20 Å. The Mn(1)-O(5) bond length is 2.15 Å. The Mn(1)-O(9) bond length is 2.08 Å. Fe(1) is bonded to one O(10), one O(11), one O(12), one O(2), one O(4), and one O(6) atom to form FeO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(1)O8 hexagonal bipyramid, and  an edgeedge with one Mn(1)O6 octahedra. The Fe(1)-O(10) bond length is 1.97 Å. The Fe(1)-O(11) bond length is 2.11 Å. The Fe(1)-O(12) bond length is 2.21 Å. The Fe(1)-O(2) bond length is 2.03 Å. The Fe(1)-O(4) bond length is 2.04 Å. The Fe(1)-O(6) bond length is 2.09 Å. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form distorted CdO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Na(1)O8 hexagonal bipyramid, and edges with two equivalent Mn(1)O6 octahedra. Both Cd(1)-O(3) bond lengths are 2.32 Å. Both Cd(1)-O(5) bond lengths are 2.36 Å. Both Cd(1)-O(7) bond lengths are 2.35 Å. In the second Cd site, Cd(2) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms. Both Cd(2)-O(4) bond lengths are 2.42 Å. Both Cd(2)-O(6) bond lengths are 2.37 Å. Both Cd(2)-O(8) bond lengths are 2.30 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid,  a cornercorner with one Cd(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-60°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(11) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.59 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(12), one O(2), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Cd(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-59°. The P(2)-O(12) bond length is 1.56 Å. The P(2)-O(2) bond length is 1.58 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to two equivalent O(4) and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles are 50°. Both P(3)-O(4) bond lengths are 1.58 Å. Both P(3)-O(9) bond lengths are 1.53 Å. In the fourth P site, P(4) is bonded to two equivalent O(10) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-63°. Both P(4)-O(10) bond lengths are 1.56 Å. Both P(4)-O(3) bond lengths are 1.55 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(1), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Mn(1), one Cd(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Fe(1), one Cd(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Mn(1), one Cd(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Fe(1), one Cd(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Cd(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Cd(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(3), one Mn(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(3), one Fe(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(2) atom.