Na5Ca2Fe3(PO4)6 crystallizes in the triclinic P1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(21), one O(22), one O(23), and one O(24) atom. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(21), one O(22), one O(23), one O(24), one O(3), and one O(4) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(17), one O(18), one O(19), and one O(20) atom. In the fourth Na site, Na(4) is bonded to one O(13), one O(15), one O(17), one O(18), one O(19), and one O(20) atom to form distorted NaO6 octahedra that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(10), one O(15), one O(19), one O(20), one O(3), one O(4), and one O(9) atom. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(15), one O(20), one O(21), one O(6), and one O(8) atom. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(17), one O(18), and one O(2) atom. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(16), one O(2), one O(22), one O(5), and one O(7) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(5)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. In the second Fe site, Fe(2) is bonded to one O(10), one O(13), one O(23), one O(3), one O(6), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. In the third Fe site, Fe(3) is bonded to one O(14), one O(24), one O(4), one O(5), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(14), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-70°. In the second P site, P(2) is bonded to one O(15), one O(16), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. In the third P site, P(3) is bonded to one O(17), one O(21), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and corners with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the fourth P site, P(4) is bonded to one O(10), one O(18), one O(22), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-51°. In the fifth P site, P(5) is bonded to one O(11), one O(19), one O(23), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. In the sixth P site, P(6) is bonded to one O(12), one O(20), one O(24), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ca(2), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Ca(2), one Fe(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one Fe(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one P(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ca(1), one Fe(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(5), one Fe(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(5), one Fe(2), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Ca(2), one Fe(1), and one P(5) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Ca(1), one Ca(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(4), one Fe(2), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(3), one Fe(3), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Na(4), one Na(5), one Ca(1), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(3), one Fe(1), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Ca(2), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Ca(2), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one Na(5), and one P(5) atom. In the twentieth O site, O(20) is bonded in a 1-coordinate geometry to one Na(3), one Na(4), one Na(5), one Ca(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a distorted tetrahedral geometry to one Na(1), one Na(2), one Ca(1), and one P(3) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(1), and one P(4) atom. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(2), and one P(5) atom. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(3), and one P(6) atom.
Na5Ca2Fe3(PO4)6 crystallizes in the triclinic P1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(21), one O(22), one O(23), and one O(24) atom. The Na(1)-O(1) bond length is 2.67 Å. The Na(1)-O(2) bond length is 2.72 Å. The Na(1)-O(21) bond length is 2.38 Å. The Na(1)-O(22) bond length is 2.47 Å. The Na(1)-O(23) bond length is 2.65 Å. The Na(1)-O(24) bond length is 2.67 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(21), one O(22), one O(23), one O(24), one O(3), and one O(4) atom. The Na(2)-O(11) bond length is 3.00 Å. The Na(2)-O(12) bond length is 2.85 Å. The Na(2)-O(21) bond length is 2.41 Å. The Na(2)-O(22) bond length is 2.88 Å. The Na(2)-O(23) bond length is 2.52 Å. The Na(2)-O(24) bond length is 2.67 Å. The Na(2)-O(3) bond length is 2.63 Å. The Na(2)-O(4) bond length is 2.48 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(14), one O(16), one O(17), one O(18), one O(19), and one O(20) atom. The Na(3)-O(14) bond length is 2.48 Å. The Na(3)-O(16) bond length is 2.43 Å. The Na(3)-O(17) bond length is 2.79 Å. The Na(3)-O(18) bond length is 2.33 Å. The Na(3)-O(19) bond length is 2.52 Å. The Na(3)-O(20) bond length is 2.47 Å. In the fourth Na site, Na(4) is bonded to one O(13), one O(15), one O(17), one O(18), one O(19), and one O(20) atom to form distorted NaO6 octahedra that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. The Na(4)-O(13) bond length is 2.44 Å. The Na(4)-O(15) bond length is 2.32 Å. The Na(4)-O(17) bond length is 2.34 Å. The Na(4)-O(18) bond length is 2.62 Å. The Na(4)-O(19) bond length is 2.28 Å. The Na(4)-O(20) bond length is 2.47 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(10), one O(15), one O(19), one O(20), one O(3), one O(4), and one O(9) atom. The Na(5)-O(10) bond length is 2.50 Å. The Na(5)-O(15) bond length is 2.79 Å. The Na(5)-O(19) bond length is 2.37 Å. The Na(5)-O(20) bond length is 2.47 Å. The Na(5)-O(3) bond length is 2.44 Å. The Na(5)-O(4) bond length is 2.56 Å. The Na(5)-O(9) bond length is 2.50 Å. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(15), one O(20), one O(21), one O(6), and one O(8) atom. The Ca(1)-O(1) bond length is 2.38 Å. The Ca(1)-O(12) bond length is 2.30 Å. The Ca(1)-O(15) bond length is 2.22 Å. The Ca(1)-O(20) bond length is 2.82 Å. The Ca(1)-O(21) bond length is 2.32 Å. The Ca(1)-O(6) bond length is 2.50 Å. The Ca(1)-O(8) bond length is 2.33 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(17), one O(18), and one O(2) atom. The Ca(2)-O(1) bond length is 2.37 Å. The Ca(2)-O(11) bond length is 2.46 Å. The Ca(2)-O(12) bond length is 2.29 Å. The Ca(2)-O(17) bond length is 2.41 Å. The Ca(2)-O(18) bond length is 2.39 Å. The Ca(2)-O(2) bond length is 2.42 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(16), one O(2), one O(22), one O(5), and one O(7) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(5)O4 tetrahedra, and  an edgeedge with one Fe(3)O6 octahedra. The Fe(1)-O(11) bond length is 2.05 Å. The Fe(1)-O(16) bond length is 1.95 Å. The Fe(1)-O(2) bond length is 2.05 Å. The Fe(1)-O(22) bond length is 1.99 Å. The Fe(1)-O(5) bond length is 2.10 Å. The Fe(1)-O(7) bond length is 2.17 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(13), one O(23), one O(3), one O(6), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. The Fe(2)-O(10) bond length is 2.04 Å. The Fe(2)-O(13) bond length is 2.09 Å. The Fe(2)-O(23) bond length is 2.08 Å. The Fe(2)-O(3) bond length is 2.04 Å. The Fe(2)-O(6) bond length is 2.09 Å. The Fe(2)-O(8) bond length is 2.11 Å. In the third Fe site, Fe(3) is bonded to one O(14), one O(24), one O(4), one O(5), one O(7), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. The Fe(3)-O(14) bond length is 2.02 Å. The Fe(3)-O(24) bond length is 2.02 Å. The Fe(3)-O(4) bond length is 1.99 Å. The Fe(3)-O(5) bond length is 2.19 Å. The Fe(3)-O(7) bond length is 2.24 Å. The Fe(3)-O(9) bond length is 1.99 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(14), and one O(2) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-70°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(13) bond length is 1.56 Å. The P(1)-O(14) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(15), one O(16), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The P(2)-O(15) bond length is 1.52 Å. The P(2)-O(16) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(17), one O(21), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and corners with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The P(3)-O(17) bond length is 1.54 Å. The P(3)-O(21) bond length is 1.54 Å. The P(3)-O(5) bond length is 1.58 Å. The P(3)-O(9) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(10), one O(18), one O(22), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-51°. The P(4)-O(10) bond length is 1.56 Å. The P(4)-O(18) bond length is 1.54 Å. The P(4)-O(22) bond length is 1.57 Å. The P(4)-O(6) bond length is 1.56 Å. In the fifth P site, P(5) is bonded to one O(11), one O(19), one O(23), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-56°. The P(5)-O(11) bond length is 1.58 Å. The P(5)-O(19) bond length is 1.52 Å. The P(5)-O(23) bond length is 1.57 Å. The P(5)-O(7) bond length is 1.59 Å. In the sixth P site, P(6) is bonded to one O(12), one O(20), one O(24), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. The P(6)-O(12) bond length is 1.55 Å. The P(6)-O(20) bond length is 1.53 Å. The P(6)-O(24) bond length is 1.58 Å. The P(6)-O(8) bond length is 1.56 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Ca(1), one Ca(2), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Ca(2), one Fe(1), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ca(1), one Fe(2), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Fe(1), one Fe(3), and one P(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ca(1), one Fe(2), and one P(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(5), one Fe(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(5), one Fe(2), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Ca(2), one Fe(1), and one P(5) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Ca(1), one Ca(2), and one P(6) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(4), one Fe(2), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(3), one Fe(3), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Na(4), one Na(5), one Ca(1), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(3), one Fe(1), and one P(2) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Ca(2), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Ca(2), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one Na(5), and one P(5) atom. In the twentieth O site, O(20) is bonded in a 1-coordinate geometry to one Na(3), one Na(4), one Na(5), one Ca(1), and one P(6) atom. In the twenty-first O site, O(21) is bonded in a distorted tetrahedral geometry to one Na(1), one Na(2), one Ca(1), and one P(3) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(1), and one P(4) atom. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(2), and one P(5) atom. In the twenty-fourth O site, O(24) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Fe(3), and one P(6) atom.