NaLi5Mn2P2(CO7)2 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(4), one O(5), and one O(8) atom. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(4), one O(5), and one O(9) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(12), one O(5), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(13), one O(14), one O(2), one O(6), and one O(7) atom. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(13), one O(14), one O(2), one O(6), and one O(8) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(13), one O(14), one O(3), one O(5), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(4), one O(6), and one O(9) atom. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(5) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(6) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(14), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. In the second P site, P(2) is bonded to one O(10), one O(12), one O(13), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Li(1), one Li(3), and one C(2) atom to form distorted ONaLi2C tetrahedra that share  a cornercorner with one O(7)Li2MnP trigonal pyramid,  a cornercorner with one O(9)Li2MnP trigonal pyramid, and  an edgeedge with one O(11)NaLiMnP tetrahedra. In the second O site, O(2) is bonded to one Li(2), one Li(4), one Li(5), and one C(1) atom to form a mixture of edge and corner-sharing OLi3C tetrahedra. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Li(2), one Mn(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Li(2), one Li(3), one Mn(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one Mn(2), and one C(2) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(4), one Mn(1), and one P(1) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(2)Li3C tetrahedra,  a cornercorner with one O(1)NaLi2C tetrahedra,  a cornercorner with one O(11)NaLiMnP tetrahedra, and corners with two equivalent O(13)Li2MnP tetrahedra. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Li(1), one Li(5), one Mn(1), and one P(1) atom. In the ninth O site, O(9) is bonded to one Li(2), one Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(13)Li2MnP tetrahedra,  a cornercorner with one O(2)Li3C tetrahedra,  a cornercorner with one O(1)NaLi2C tetrahedra, and corners with two equivalent O(11)NaLiMnP tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Li(2), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Li(3), one Mn(2), and one P(1) atom to form distorted ONaLiMnP tetrahedra that share  a cornercorner with one O(7)Li2MnP trigonal pyramid, corners with two equivalent O(9)Li2MnP trigonal pyramids, and  an edgeedge with one O(1)NaLi2C tetrahedra. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Li(3), one Mn(2), and one P(2) atom. In the thirteenth O site, O(13) is bonded to one Li(4), one Li(5), one Mn(1), and one P(2) atom to form OLi2MnP tetrahedra that share  a cornercorner with one O(9)Li2MnP trigonal pyramid, corners with two equivalent O(7)Li2MnP trigonal pyramids, and  an edgeedge with one O(2)Li3C tetrahedra. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one Mn(1), and one P(1) atom.
NaLi5Mn2P2(CO7)2 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(4), one O(5), and one O(8) atom. The Na(1)-O(1) bond length is 2.32 Å. The Na(1)-O(10) bond length is 2.35 Å. The Na(1)-O(11) bond length is 2.46 Å. The Na(1)-O(12) bond length is 2.40 Å. The Na(1)-O(4) bond length is 2.64 Å. The Na(1)-O(5) bond length is 2.36 Å. The Na(1)-O(8) bond length is 2.89 Å. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(7), and one O(8) atom. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(6) bond length is 2.55 Å. The Li(1)-O(7) bond length is 2.27 Å. The Li(1)-O(8) bond length is 2.39 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(4), one O(5), and one O(9) atom. The Li(2)-O(10) bond length is 2.50 Å. The Li(2)-O(2) bond length is 2.06 Å. The Li(2)-O(4) bond length is 1.99 Å. The Li(2)-O(5) bond length is 2.47 Å. The Li(2)-O(9) bond length is 2.17 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(12), one O(5), and one O(9) atom. The Li(3)-O(1) bond length is 2.02 Å. The Li(3)-O(11) bond length is 2.09 Å. The Li(3)-O(12) bond length is 2.17 Å. The Li(3)-O(5) bond length is 2.62 Å. The Li(3)-O(9) bond length is 2.11 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(13), one O(14), one O(2), one O(6), and one O(7) atom. The Li(4)-O(13) bond length is 2.12 Å. The Li(4)-O(14) bond length is 2.29 Å. The Li(4)-O(2) bond length is 2.07 Å. The Li(4)-O(6) bond length is 2.57 Å. The Li(4)-O(7) bond length is 2.04 Å. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(13), one O(14), one O(2), one O(6), and one O(8) atom. The Li(5)-O(13) bond length is 2.20 Å. The Li(5)-O(14) bond length is 2.31 Å. The Li(5)-O(2) bond length is 2.06 Å. The Li(5)-O(6) bond length is 2.55 Å. The Li(5)-O(8) bond length is 2.19 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(13), one O(14), one O(3), one O(5), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The Mn(1)-O(13) bond length is 2.13 Å. The Mn(1)-O(14) bond length is 2.16 Å. The Mn(1)-O(3) bond length is 2.50 Å. The Mn(1)-O(5) bond length is 2.21 Å. The Mn(1)-O(7) bond length is 2.15 Å. The Mn(1)-O(8) bond length is 2.16 Å. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(4), one O(6), and one O(9) atom. The Mn(2)-O(10) bond length is 2.14 Å. The Mn(2)-O(11) bond length is 2.12 Å. The Mn(2)-O(12) bond length is 2.20 Å. The Mn(2)-O(4) bond length is 2.54 Å. The Mn(2)-O(6) bond length is 2.17 Å. The Mn(2)-O(9) bond length is 2.18 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(5) atom. The C(1)-O(2) bond length is 1.31 Å. The C(1)-O(3) bond length is 1.29 Å. The C(1)-O(5) 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(4), and one O(6) atom. The C(2)-O(1) bond length is 1.30 Å. The C(2)-O(4) bond length is 1.30 Å. The C(2)-O(6) bond length is 1.30 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(14), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. The P(1)-O(11) bond length is 1.56 Å. The P(1)-O(14) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.56 Å. The P(1)-O(8) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(10), one O(12), one O(13), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(12) bond length is 1.55 Å. The P(2)-O(13) bond length is 1.57 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 to one Na(1), one Li(1), one Li(3), and one C(2) atom to form distorted ONaLi2C tetrahedra that share  a cornercorner with one O(7)Li2MnP trigonal pyramid,  a cornercorner with one O(9)Li2MnP trigonal pyramid, and  an edgeedge with one O(11)NaLiMnP tetrahedra. In the second O site, O(2) is bonded to one Li(2), one Li(4), one Li(5), and one C(1) atom to form a mixture of edge and corner-sharing OLi3C tetrahedra. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Li(2), one Mn(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Li(2), one Li(3), one Mn(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one Mn(2), and one C(2) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(4), one Mn(1), and one P(1) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(2)Li3C tetrahedra,  a cornercorner with one O(1)NaLi2C tetrahedra,  a cornercorner with one O(11)NaLiMnP tetrahedra, and corners with two equivalent O(13)Li2MnP tetrahedra. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Li(1), one Li(5), one Mn(1), and one P(1) atom. In the ninth O site, O(9) is bonded to one Li(2), one Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(13)Li2MnP tetrahedra,  a cornercorner with one O(2)Li3C tetrahedra,  a cornercorner with one O(1)NaLi2C tetrahedra, and corners with two equivalent O(11)NaLiMnP tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Li(2), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Li(3), one Mn(2), and one P(1) atom to form distorted ONaLiMnP tetrahedra that share  a cornercorner with one O(7)Li2MnP trigonal pyramid, corners with two equivalent O(9)Li2MnP trigonal pyramids, and  an edgeedge with one O(1)NaLi2C tetrahedra. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Li(3), one Mn(2), and one P(2) atom. In the thirteenth O site, O(13) is bonded to one Li(4), one Li(5), one Mn(1), and one P(2) atom to form OLi2MnP tetrahedra that share  a cornercorner with one O(9)Li2MnP trigonal pyramid, corners with two equivalent O(7)Li2MnP trigonal pyramids, and  an edgeedge with one O(2)Li3C tetrahedra. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one Mn(1), and one P(1) atom.