Na5LiCo2P2(CO7)2 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(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 to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Na(2)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, edges with two equivalent Li(1)O5 trigonal bipyramids, and  a faceface with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 72°. 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(11) atoms. In the fourth Na site, Na(4) 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 fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and two equivalent O(14) atoms. Li(1) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and edges with two equivalent Na(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 68-89°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(11), one O(12), one O(13), one O(7), and one O(9) atom to form distorted CoO6 octahedra that share  a cornercorner with one Na(2)O7 pentagonal bipyramid, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. In the second Co site, Co(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  an edgeedge with one Na(2)O7 pentagonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  a faceface with one Na(2)O7 pentagonal bipyramid. 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(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Na(2)O7 pentagonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-56°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Na(2)O7 pentagonal bipyramid, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-55°. 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 4-coordinate geometry to one Na(2), one Na(5), one Co(2), and one C(1) atom. In the third O site, O(3) is bonded to one Na(2), one Na(5), one Li(1), one Co(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing ONa2LiCoC trigonal bipyramids. In the fourth O site, O(4) is bonded to one Na(1), one Li(1), one Co(2), and one P(1) atom to form distorted ONaLiCoP trigonal pyramids that share  a cornercorner with one O(12)Na3CoC trigonal bipyramid, corners with two equivalent O(3)Na2LiCoC trigonal bipyramids, and  an edgeedge with one O(6)NaLiCoP trigonal pyramid. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Co(2), and one P(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Co(2), and one P(2) atom to form distorted ONaLiCoP trigonal pyramids that share  a cornercorner with one O(3)Na2LiCoC trigonal bipyramid,  an edgeedge with one O(3)Na2LiCoC trigonal bipyramid, and  an edgeedge with one O(4)NaLiCoP trigonal pyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Co(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Co(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(3), one Na(4), one Co(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(4), one Co(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(3), one Co(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 Co(1), and one C(2) atom to form distorted corner-sharing ONa3CoC trigonal bipyramids. 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 Co(1), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), two equivalent Na(5), and one C(1) atom.
Na5LiCo2P2(CO7)2 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(12), one O(13), one O(4), one O(5), and two equivalent O(1) atoms. The Na(1)-O(12) bond length is 2.53 Å. The Na(1)-O(13) bond length is 2.31 Å. The Na(1)-O(4) bond length is 2.38 Å. The Na(1)-O(5) bond length is 2.49 Å. There is one shorter (2.45 Å) and one longer (2.75 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Na(2)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, edges with two equivalent Li(1)O5 trigonal bipyramids, and  a faceface with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 72°. The Na(2)-O(1) bond length is 2.38 Å. The Na(2)-O(2) bond length is 2.73 Å. The Na(2)-O(3) bond length is 2.43 Å. The Na(2)-O(6) bond length is 2.34 Å. The Na(2)-O(7) bond length is 2.49 Å. There is one shorter (2.55 Å) and one longer (2.77 Å) Na(2)-O(5) bond length. 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(11) atoms. The Na(3)-O(12) bond length is 2.41 Å. The Na(3)-O(13) bond length is 2.71 Å. The Na(3)-O(14) bond length is 2.33 Å. The Na(3)-O(8) bond length is 2.40 Å. The Na(3)-O(9) bond length is 2.30 Å. There is one shorter (2.51 Å) and one longer (2.82 Å) Na(3)-O(11) bond length. In the fourth Na site, Na(4) 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(4)-O(12) bond length is 2.44 Å. The Na(4)-O(13) bond length is 2.72 Å. The Na(4)-O(14) bond length is 2.32 Å. The Na(4)-O(8) bond length is 2.43 Å. The Na(4)-O(9) bond length is 2.29 Å. There is one shorter (2.52 Å) and one longer (2.83 Å) Na(4)-O(10) bond length. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and two equivalent O(14) atoms. The Na(5)-O(10) bond length is 2.53 Å. The Na(5)-O(11) bond length is 2.40 Å. The Na(5)-O(2) bond length is 2.29 Å. The Na(5)-O(3) bond length is 2.60 Å. There is one shorter (2.37 Å) and one longer (2.83 Å) Na(5)-O(14) bond length. Li(1) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and edges with two equivalent Na(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 68-89°. The Li(1)-O(1) bond length is 2.29 Å. The Li(1)-O(3) bond length is 2.55 Å. The Li(1)-O(4) bond length is 2.13 Å. The Li(1)-O(6) bond length is 2.08 Å. The Li(1)-O(7) bond length is 2.14 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(11), one O(12), one O(13), one O(7), and one O(9) atom to form distorted CoO6 octahedra that share  a cornercorner with one Na(2)O7 pentagonal bipyramid, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The Co(1)-O(10) bond length is 2.10 Å. The Co(1)-O(11) bond length is 2.10 Å. The Co(1)-O(12) bond length is 2.29 Å. The Co(1)-O(13) bond length is 2.18 Å. The Co(1)-O(7) bond length is 2.13 Å. The Co(1)-O(9) bond length is 2.11 Å. In the second Co site, Co(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  an edgeedge with one Na(2)O7 pentagonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  a faceface with one Na(2)O7 pentagonal bipyramid. The Co(2)-O(2) bond length is 2.15 Å. The Co(2)-O(3) bond length is 2.23 Å. The Co(2)-O(4) bond length is 2.11 Å. The Co(2)-O(5) bond length is 2.11 Å. The Co(2)-O(6) bond length is 2.13 Å. The Co(2)-O(8) bond length is 2.06 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 1.29 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 1.29 Å. The C(2)-O(12) bond length is 1.31 Å. The C(2)-O(13) bond length is 1.31 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(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Na(2)O7 pentagonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-56°. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.57 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  a cornercorner with one Na(2)O7 pentagonal bipyramid, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-55°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) 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 4-coordinate geometry to one Na(2), one Na(5), one Co(2), and one C(1) atom. In the third O site, O(3) is bonded to one Na(2), one Na(5), one Li(1), one Co(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing ONa2LiCoC trigonal bipyramids. In the fourth O site, O(4) is bonded to one Na(1), one Li(1), one Co(2), and one P(1) atom to form distorted ONaLiCoP trigonal pyramids that share  a cornercorner with one O(12)Na3CoC trigonal bipyramid, corners with two equivalent O(3)Na2LiCoC trigonal bipyramids, and  an edgeedge with one O(6)NaLiCoP trigonal pyramid. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Co(2), and one P(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Co(2), and one P(2) atom to form distorted ONaLiCoP trigonal pyramids that share  a cornercorner with one O(3)Na2LiCoC trigonal bipyramid,  an edgeedge with one O(3)Na2LiCoC trigonal bipyramid, and  an edgeedge with one O(4)NaLiCoP trigonal pyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Co(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Co(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(3), one Na(4), one Co(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(4), one Co(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(3), one Co(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 Co(1), and one C(2) atom to form distorted corner-sharing ONa3CoC trigonal bipyramids. 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 Co(1), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), two equivalent Na(5), and one C(1) atom.