Na2LiMnCPO7 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(12), one O(13), one O(4), one O(5), and two equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms. 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. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted see-saw-like geometry to one O(1), one O(5), one O(6), and one O(7) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(14), and one O(2) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) 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 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(3), one O(4), one O(5), one O(7), and one O(9) atom to form distorted MnO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(14), one O(2), and one O(3) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(12), and one O(13) atom. There are two 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)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 52-61°. 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)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 43-50°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Li(1), and one C(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Li(2), and one C(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one Mn(2), and one C(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), one Mn(2), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Mn(2), and one P(1) atom to form distorted ONaLiMnP trigonal pyramids that share  a cornercorner with one O(9)Na2MnP tetrahedra,  a cornercorner with one O(12)Na3MnC trigonal bipyramid, and  an edgeedge with one O(7)NaLiMnP trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded to one Na(2), one Li(1), one Mn(2), and one P(2) atom to form distorted ONaLiMnP trigonal pyramids that share corners with two equivalent O(9)Na2MnP tetrahedra and  an edgeedge with one O(5)NaLiMnP trigonal pyramid. 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(1), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(3), one Na(4), one Mn(2), and one P(2) atom to form distorted ONa2MnP tetrahedra that share corners with two equivalent O(12)Na3MnC trigonal bipyramids,  a cornercorner with one O(5)NaLiMnP trigonal pyramid, corners with two equivalent O(7)NaLiMnP trigonal pyramids, and  an edgeedge with one O(14)Na2LiC tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Li(2), one Mn(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(4), one Li(2), one Mn(1), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(3), one Na(4), one Mn(1), and one C(2) atom to form distorted ONa3MnC trigonal bipyramids that share corners with two equivalent O(14)Na2LiC tetrahedra, corners with two equivalent O(9)Na2MnP tetrahedra, and  a cornercorner with one O(5)NaLiMnP trigonal pyramid. In the thirteenth O site, O(13) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Mn(1), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Na(3), one Na(4), one Li(2), and one C(1) atom to form distorted ONa2LiC tetrahedra that share corners with two equivalent O(12)Na3MnC trigonal bipyramids and  an edgeedge with one O(9)Na2MnP tetrahedra.
Na2LiMnCPO7 crystallizes in the triclinic P1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(12), one O(13), one O(4), one O(5), and two equivalent O(1) atoms. The Na(1)-O(12) bond length is 2.52 Å. The Na(1)-O(13) bond length is 2.28 Å. The Na(1)-O(4) bond length is 2.60 Å. The Na(1)-O(5) bond length is 2.37 Å. There is one shorter (2.42 Å) and one longer (2.76 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom. The Na(2)-O(1) bond length is 2.39 Å. The Na(2)-O(2) bond length is 2.69 Å. The Na(2)-O(3) bond length is 2.42 Å. The Na(2)-O(4) bond length is 2.48 Å. The Na(2)-O(6) bond length is 2.61 Å. The Na(2)-O(7) bond length is 2.44 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms. The Na(3)-O(12) bond length is 2.44 Å. The Na(3)-O(13) bond length is 2.64 Å. The Na(3)-O(14) bond length is 2.32 Å. The Na(3)-O(8) bond length is 2.32 Å. The Na(3)-O(9) bond length is 2.43 Å. There is one shorter (2.47 Å) and one longer (2.89 Å) Na(3)-O(10) bond length. 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 2.45 Å. The Na(4)-O(12) bond length is 2.45 Å. The Na(4)-O(13) bond length is 2.65 Å. The Na(4)-O(14) bond length is 2.33 Å. The Na(4)-O(8) bond length is 2.35 Å. The Na(4)-O(9) bond length is 2.44 Å. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted see-saw-like geometry to one O(1), one O(5), one O(6), and one O(7) atom. The Li(1)-O(1) bond length is 2.13 Å. The Li(1)-O(5) bond length is 2.05 Å. The Li(1)-O(6) bond length is 2.05 Å. The Li(1)-O(7) bond length is 2.20 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(14), and one O(2) atom. The Li(2)-O(10) bond length is 2.11 Å. The Li(2)-O(11) bond length is 2.46 Å. The Li(2)-O(14) bond length is 1.98 Å. The Li(2)-O(2) bond length is 2.00 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) 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 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(10) bond length is 2.21 Å. The Mn(1)-O(11) bond length is 2.17 Å. The Mn(1)-O(12) bond length is 2.34 Å. The Mn(1)-O(13) bond length is 2.34 Å. The Mn(1)-O(6) bond length is 2.17 Å. The Mn(1)-O(8) bond length is 2.18 Å. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form distorted MnO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Mn(2)-O(3) bond length is 2.14 Å. The Mn(2)-O(4) bond length is 2.20 Å. The Mn(2)-O(5) bond length is 2.19 Å. The Mn(2)-O(7) bond length is 2.16 Å. The Mn(2)-O(9) bond length is 2.09 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(14), one O(2), and one O(3) atom. The C(1)-O(14) bond length is 1.30 Å. The C(1)-O(2) bond length is 1.30 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(1), one O(12), and one O(13) atom. The C(2)-O(1) bond length is 1.30 Å. The C(2)-O(12) bond length is 1.31 Å. The C(2)-O(13) bond length is 1.30 Å. There are two 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)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 52-61°. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.57 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)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 43-50°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(9) bond length is 1.56 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Li(1), and one C(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Li(2), and one C(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one Mn(2), and one C(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), one Mn(2), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Mn(2), and one P(1) atom to form distorted ONaLiMnP trigonal pyramids that share  a cornercorner with one O(9)Na2MnP tetrahedra,  a cornercorner with one O(12)Na3MnC trigonal bipyramid, and  an edgeedge with one O(7)NaLiMnP trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded to one Na(2), one Li(1), one Mn(2), and one P(2) atom to form distorted ONaLiMnP trigonal pyramids that share corners with two equivalent O(9)Na2MnP tetrahedra and  an edgeedge with one O(5)NaLiMnP trigonal pyramid. 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(1), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(3), one Na(4), one Mn(2), and one P(2) atom to form distorted ONa2MnP tetrahedra that share corners with two equivalent O(12)Na3MnC trigonal bipyramids,  a cornercorner with one O(5)NaLiMnP trigonal pyramid, corners with two equivalent O(7)NaLiMnP trigonal pyramids, and  an edgeedge with one O(14)Na2LiC tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Li(2), one Mn(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(4), one Li(2), one Mn(1), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(3), one Na(4), one Mn(1), and one C(2) atom to form distorted ONa3MnC trigonal bipyramids that share corners with two equivalent O(14)Na2LiC tetrahedra, corners with two equivalent O(9)Na2MnP tetrahedra, and  a cornercorner with one O(5)NaLiMnP trigonal pyramid. In the thirteenth O site, O(13) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Mn(1), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Na(3), one Na(4), one Li(2), and one C(1) atom to form distorted ONa2LiC tetrahedra that share corners with two equivalent O(12)Na3MnC trigonal bipyramids and  an edgeedge with one O(9)Na2MnP tetrahedra.