Na3Li3Mn2P2(CO7)2 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(12), one O(13), one O(4), 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(5), one O(6), and one O(7) atom. 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. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 68°. In the second Li site, Li(2) is bonded to one O(11), one O(14), one O(8), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, and  an edgeedge with one Mn(2)O6 octahedra. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to 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(3), one O(4), one O(5), one O(7), and one O(9) atom to form distorted MnO5 trigonal bipyramids that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(1)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 distorted MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(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(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Mn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 55-63°. 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(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with two equivalent Mn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-53°. 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(3), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Mn(2), and one P(1) atom to form distorted corner-sharing ONaLiMnP tetrahedra. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Li(2), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(3), one Li(2), one Mn(1), and one P(2) atom to form distorted ONaLiMnP tetrahedra that share corners with two equivalent O(11)Li2MnP tetrahedra and  an edgeedge with one O(14)NaLi2C tetrahedra. 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 to one Li(2), one Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP tetrahedra that share  a cornercorner with one O(6)NaLiMnP tetrahedra, corners with two equivalent O(14)NaLi2C tetrahedra, and corners with two equivalent O(9)NaLiMnP tetrahedra. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Na(3), one Li(2), one Li(3), and one C(1) atom to form distorted ONaLi2C tetrahedra that share corners with two equivalent O(11)Li2MnP tetrahedra and  an edgeedge with one O(9)NaLiMnP tetrahedra.
Na3Li3Mn2P2(CO7)2 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(12), one O(13), one O(4), and two equivalent O(1) atoms. The Na(1)-O(12) bond length is 2.42 Å. The Na(1)-O(13) bond length is 2.25 Å. The Na(1)-O(4) bond length is 2.30 Å. There is one shorter (2.40 Å) and one longer (2.79 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(5), one O(6), and one O(7) atom. The Na(2)-O(1) bond length is 2.37 Å. The Na(2)-O(2) bond length is 2.60 Å. The Na(2)-O(3) bond length is 2.44 Å. The Na(2)-O(5) bond length is 2.47 Å. The Na(2)-O(6) bond length is 2.59 Å. The Na(2)-O(7) bond length is 2.46 Å. 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 2.45 Å. The Na(3)-O(12) bond length is 2.41 Å. The Na(3)-O(13) bond length is 2.54 Å. The Na(3)-O(14) bond length is 2.42 Å. The Na(3)-O(8) bond length is 2.43 Å. The Na(3)-O(9) bond length is 2.50 Å. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 68°. The Li(1)-O(1) bond length is 2.05 Å. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(6) bond length is 2.00 Å. The Li(1)-O(7) bond length is 2.08 Å. In the second Li site, Li(2) is bonded to one O(11), one O(14), one O(8), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Mn(1)O5 trigonal bipyramid, and  an edgeedge with one Mn(2)O6 octahedra. The Li(2)-O(11) bond length is 2.11 Å. The Li(2)-O(14) bond length is 2.05 Å. The Li(2)-O(8) bond length is 2.07 Å. The Li(2)-O(9) bond length is 2.05 Å. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to one O(11), one O(14), and one O(2) atom. The Li(3)-O(11) bond length is 2.05 Å. The Li(3)-O(14) bond length is 2.02 Å. The Li(3)-O(2) bond length is 1.98 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) 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  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The Mn(1)-O(3) bond length is 2.17 Å. The Mn(1)-O(4) bond length is 2.17 Å. The Mn(1)-O(5) bond length is 2.15 Å. The Mn(1)-O(7) bond length is 2.19 Å. The Mn(1)-O(9) bond length is 2.13 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 distorted MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The Mn(2)-O(10) bond length is 2.13 Å. The Mn(2)-O(11) bond length is 2.20 Å. The Mn(2)-O(12) bond length is 2.31 Å. The Mn(2)-O(13) bond length is 2.32 Å. The Mn(2)-O(6) bond length is 2.16 Å. The Mn(2)-O(8) bond length is 2.21 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 1.31 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 1.30 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(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent Mn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 55-63°. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.55 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(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and corners with two equivalent Mn(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 35-53°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(11) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(9) bond length is 1.57 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(3), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Mn(2), and one P(1) atom to form distorted corner-sharing ONaLiMnP tetrahedra. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Li(2), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(3), one Li(2), one Mn(1), and one P(2) atom to form distorted ONaLiMnP tetrahedra that share corners with two equivalent O(11)Li2MnP tetrahedra and  an edgeedge with one O(14)NaLi2C tetrahedra. 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 to one Li(2), one Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP tetrahedra that share  a cornercorner with one O(6)NaLiMnP tetrahedra, corners with two equivalent O(14)NaLi2C tetrahedra, and corners with two equivalent O(9)NaLiMnP tetrahedra. In the twelfth O site, O(12) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Na(3), one Li(2), one Li(3), and one C(1) atom to form distorted ONaLi2C tetrahedra that share corners with two equivalent O(11)Li2MnP tetrahedra and  an edgeedge with one O(9)NaLiMnP tetrahedra.