Na2MnCPO7 crystallizes in the triclinic P1 space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(5) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(15), one O(16), one O(17), one O(20), one O(21), and two equivalent O(18) atoms. In the sixth Na site, Na(6) is bonded in a 7-coordinate geometry to one O(15), one O(16), one O(17), one O(20), one O(21), and two equivalent O(19) atoms. In the seventh Na site, Na(7) is bonded in a 7-coordinate geometry to one O(22), one O(23), one O(26), one O(27), one O(28), and two equivalent O(25) atoms. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to one O(2), one O(24), one O(25), one O(3), and two equivalent O(28) atoms. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(12), one O(13), one O(6), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. In the third Mn site, Mn(3) is bonded to one O(16), one O(17), one O(18), one O(19), one O(21), and one O(23) atom to form distorted MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with two equivalent P(4)O4 tetrahedra. In the fourth Mn site, Mn(4) is bonded to one O(20), one O(22), one O(24), one O(25), one O(26), and one O(27) atom to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with two equivalent P(4)O4 tetrahedra. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(28), and one O(3) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(13), and one O(15) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(14), one O(16), and one O(17) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(1), one O(26), and one O(27) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. In the third P site, P(3) is bonded to one O(18), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-46°. In the fourth P site, P(4) is bonded to one O(21), one O(23), one O(24), and one O(25) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-48°. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(4) atom. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(8), one Mn(1), and one C(1) atom to form a mixture of distorted face and edge-sharing ONa3MnC trigonal bipyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(8), one Mn(1), and one C(1) atom to form a mixture of distorted face and edge-sharing ONa3MnC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(4), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal pyramidal geometry to one Na(3), one Na(4), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one Mn(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Na(3), one Na(4), and one C(3) atom. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Na(5), one Na(6), and one C(2) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Na(5), one Na(6), one Mn(3), and one C(3) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal pyramidal geometry to one Na(5), one Na(6), one Mn(3), and one C(3) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to two equivalent Na(5), one Mn(3), and one P(3) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to two equivalent Na(6), one Mn(3), and one P(3) atom. In the twentieth O site, O(20) is bonded in a 4-coordinate geometry to one Na(5), one Na(6), one Mn(4), and one P(3) atom. In the twenty-first O site, O(21) is bonded in a rectangular see-saw-like geometry to one Na(5), one Na(6), one Mn(3), and one P(4) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(7), one Mn(4), and one P(3) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Na(7), one Mn(3), and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Na(8), one Mn(4), and one P(4) atom. In the twenty-fifth O site, O(25) is bonded in a 5-coordinate geometry to one Na(8), two equivalent Na(7), one Mn(4), and one P(4) atom. In the twenty-sixth O site, O(26) is bonded in a distorted T-shaped geometry to one Na(7), one Mn(4), and one C(4) atom. In the twenty-seventh O site, O(27) is bonded in a 3-coordinate geometry to one Na(7), one Mn(4), and one C(4) atom. In the twenty-eighth O site, O(28) is bonded in a distorted rectangular see-saw-like geometry to one Na(7), two equivalent Na(8), and one C(1) atom.
Na2MnCPO7 crystallizes in the triclinic P1 space group. There are eight inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.30 Å. The Na(1)-O(2) bond length is 2.55 Å. The Na(1)-O(3) bond length is 2.39 Å. The Na(1)-O(6) bond length is 2.56 Å. The Na(1)-O(7) bond length is 2.37 Å. There is one shorter (2.55 Å) and one longer (2.88 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(5) atoms. The Na(2)-O(1) bond length is 2.31 Å. The Na(2)-O(2) bond length is 2.56 Å. The Na(2)-O(3) bond length is 2.39 Å. The Na(2)-O(6) bond length is 2.57 Å. The Na(2)-O(7) bond length is 2.36 Å. There is one shorter (2.57 Å) and one longer (2.87 Å) Na(2)-O(5) bond length. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. The Na(3)-O(10) bond length is 2.56 Å. The Na(3)-O(12) bond length is 2.35 Å. The Na(3)-O(13) bond length is 2.46 Å. The Na(3)-O(14) bond length is 2.25 Å. The Na(3)-O(8) bond length is 2.40 Å. The Na(3)-O(9) bond length is 2.62 Å. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. The Na(4)-O(11) bond length is 2.54 Å. The Na(4)-O(12) bond length is 2.34 Å. The Na(4)-O(13) bond length is 2.46 Å. The Na(4)-O(14) bond length is 2.26 Å. The Na(4)-O(8) bond length is 2.43 Å. The Na(4)-O(9) bond length is 2.60 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(15), one O(16), one O(17), one O(20), one O(21), and two equivalent O(18) atoms. The Na(5)-O(15) bond length is 2.28 Å. The Na(5)-O(16) bond length is 2.48 Å. The Na(5)-O(17) bond length is 2.35 Å. The Na(5)-O(20) bond length is 2.71 Å. The Na(5)-O(21) bond length is 2.43 Å. There is one shorter (2.57 Å) and one longer (2.88 Å) Na(5)-O(18) bond length. In the sixth Na site, Na(6) is bonded in a 7-coordinate geometry to one O(15), one O(16), one O(17), one O(20), one O(21), and two equivalent O(19) atoms. The Na(6)-O(15) bond length is 2.27 Å. The Na(6)-O(16) bond length is 2.47 Å. The Na(6)-O(17) bond length is 2.35 Å. The Na(6)-O(20) bond length is 2.72 Å. The Na(6)-O(21) bond length is 2.43 Å. There is one shorter (2.57 Å) and one longer (2.91 Å) Na(6)-O(19) bond length. In the seventh Na site, Na(7) is bonded in a 7-coordinate geometry to one O(22), one O(23), one O(26), one O(27), one O(28), and two equivalent O(25) atoms. The Na(7)-O(22) bond length is 2.35 Å. The Na(7)-O(23) bond length is 2.54 Å. The Na(7)-O(26) bond length is 2.37 Å. The Na(7)-O(27) bond length is 2.53 Å. The Na(7)-O(28) bond length is 2.27 Å. There is one shorter (2.55 Å) and one longer (2.83 Å) Na(7)-O(25) bond length. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to one O(2), one O(24), one O(25), one O(3), and two equivalent O(28) atoms. The Na(8)-O(2) bond length is 2.54 Å. The Na(8)-O(24) bond length is 2.38 Å. The Na(8)-O(25) bond length is 2.52 Å. The Na(8)-O(3) bond length is 2.60 Å. There is one shorter (2.61 Å) and one longer (2.62 Å) Na(8)-O(28) bond length. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Mn(1)-O(2) bond length is 2.06 Å. The Mn(1)-O(3) bond length is 2.33 Å. The Mn(1)-O(4) bond length is 2.09 Å. The Mn(1)-O(5) bond length is 2.08 Å. The Mn(1)-O(7) bond length is 2.14 Å. The Mn(1)-O(9) bond length is 1.98 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(12), one O(13), one O(6), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Mn(2)-O(10) bond length is 2.09 Å. The Mn(2)-O(11) bond length is 2.09 Å. The Mn(2)-O(12) bond length is 2.18 Å. The Mn(2)-O(13) bond length is 1.98 Å. The Mn(2)-O(6) bond length is 1.97 Å. The Mn(2)-O(8) bond length is 2.10 Å. In the third Mn site, Mn(3) is bonded to one O(16), one O(17), one O(18), one O(19), one O(21), and one O(23) atom to form distorted MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with two equivalent P(4)O4 tetrahedra. The Mn(3)-O(16) bond length is 1.99 Å. The Mn(3)-O(17) bond length is 2.15 Å. The Mn(3)-O(18) bond length is 2.10 Å. The Mn(3)-O(19) bond length is 2.09 Å. The Mn(3)-O(21) bond length is 2.06 Å. The Mn(3)-O(23) bond length is 1.91 Å. In the fourth Mn site, Mn(4) is bonded to one O(20), one O(22), one O(24), one O(25), one O(26), and one O(27) atom to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with two equivalent P(4)O4 tetrahedra. The Mn(4)-O(20) bond length is 1.98 Å. The Mn(4)-O(22) bond length is 1.97 Å. The Mn(4)-O(24) bond length is 2.05 Å. The Mn(4)-O(25) bond length is 2.20 Å. The Mn(4)-O(26) bond length is 2.06 Å. The Mn(4)-O(27) bond length is 2.00 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(28), and one O(3) atom. The C(1)-O(2) bond length is 1.33 Å. The C(1)-O(28) bond length is 1.26 Å. The C(1)-O(3) bond length is 1.30 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(13), and one O(15) atom. The C(2)-O(12) bond length is 1.30 Å. The C(2)-O(13) bond length is 1.33 Å. The C(2)-O(15) bond length is 1.25 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(14), one O(16), and one O(17) atom. The C(3)-O(14) bond length is 1.25 Å. The C(3)-O(16) bond length is 1.33 Å. The C(3)-O(17) bond length is 1.30 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(1), one O(26), and one O(27) atom. The C(4)-O(1) bond length is 1.26 Å. The C(4)-O(26) bond length is 1.31 Å. The C(4)-O(27) bond length is 1.32 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.59 Å. The P(1)-O(8) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(11) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.59 Å. In the third P site, P(3) is bonded to one O(18), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-46°. The P(3)-O(18) bond length is 1.55 Å. The P(3)-O(19) bond length is 1.54 Å. The P(3)-O(20) bond length is 1.58 Å. The P(3)-O(22) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(21), one O(23), one O(24), and one O(25) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-48°. The P(4)-O(21) bond length is 1.54 Å. The P(4)-O(23) bond length is 1.57 Å. The P(4)-O(24) bond length is 1.54 Å. The P(4)-O(25) bond length is 1.55 Å. There are twenty-eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one C(4) atom. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(8), one Mn(1), and one C(1) atom to form a mixture of distorted face and edge-sharing ONa3MnC trigonal bipyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(8), one Mn(1), and one C(1) atom to form a mixture of distorted face and edge-sharing ONa3MnC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(4), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal pyramidal geometry to one Na(3), one Na(4), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one Mn(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Na(3), one Na(4), and one C(3) atom. In the fifteenth O site, O(15) is bonded in a distorted T-shaped geometry to one Na(5), one Na(6), and one C(2) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Na(5), one Na(6), one Mn(3), and one C(3) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal pyramidal geometry to one Na(5), one Na(6), one Mn(3), and one C(3) atom. In the eighteenth O site, O(18) is bonded in a 4-coordinate geometry to two equivalent Na(5), one Mn(3), and one P(3) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to two equivalent Na(6), one Mn(3), and one P(3) atom. In the twentieth O site, O(20) is bonded in a 4-coordinate geometry to one Na(5), one Na(6), one Mn(4), and one P(3) atom. In the twenty-first O site, O(21) is bonded in a rectangular see-saw-like geometry to one Na(5), one Na(6), one Mn(3), and one P(4) atom. In the twenty-second O site, O(22) is bonded in a 3-coordinate geometry to one Na(7), one Mn(4), and one P(3) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Na(7), one Mn(3), and one P(4) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Na(8), one Mn(4), and one P(4) atom. In the twenty-fifth O site, O(25) is bonded in a 5-coordinate geometry to one Na(8), two equivalent Na(7), one Mn(4), and one P(4) atom. In the twenty-sixth O site, O(26) is bonded in a distorted T-shaped geometry to one Na(7), one Mn(4), and one C(4) atom. In the twenty-seventh O site, O(27) is bonded in a 3-coordinate geometry to one Na(7), one Mn(4), and one C(4) atom. In the twenty-eighth O site, O(28) is bonded in a distorted rectangular see-saw-like geometry to one Na(7), two equivalent Na(8), and one C(1) atom.