Na3Li3Fe2P2(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 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 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 third Na site, Na(3) 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. There are three 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 distorted see-saw-like geometry to one O(10), one O(14), one O(8), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(11), one O(12), one O(14), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 71-91°. There are two inequivalent Fe sites. In the first Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. In the second Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal 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(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-62°. 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Li(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 43-63°. 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(3), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Fe(1), and one P(1) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(9)Li2FeP tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(8)Li2FeP trigonal pyramid, and  an edgeedge with one O(7)NaLiFeP trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Fe(2), and one P(1) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(10)NaLiFeP trigonal pyramid, corners with two equivalent O(8)Li2FeP trigonal pyramids, corners with two equivalent O(5)NaLiFeP trigonal pyramids, and corners with two equivalent O(7)NaLiFeP trigonal pyramids. In the seventh O site, O(7) is bonded to one Na(2), one Li(1), one Fe(1), and one P(2) atom to form distorted ONaLiFeP trigonal pyramids that share corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(10)NaLiFeP trigonal pyramid, and  an edgeedge with one O(5)NaLiFeP trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(2), one Li(3), one Fe(2), and one P(1) atom to form distorted OLi2FeP trigonal pyramids that share corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(5)NaLiFeP trigonal pyramid, and  an edgeedge with one O(10)NaLiFeP trigonal pyramid. In the ninth O site, O(9) is bonded to one Li(2), one Li(3), one Fe(1), and one P(2) atom to form distorted OLi2FeP tetrahedra that share  a cornercorner with one O(5)NaLiFeP trigonal pyramid, corners with two equivalent O(8)Li2FeP trigonal pyramids, corners with two equivalent O(10)NaLiFeP trigonal pyramids, and corners with two equivalent O(7)NaLiFeP trigonal pyramids. In the tenth O site, O(10) is bonded to one Na(3), one Li(2), one Fe(2), and one P(2) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(6)NaLiFeP tetrahedra, corners with two equivalent O(9)Li2FeP tetrahedra,  a cornercorner with one O(7)NaLiFeP trigonal pyramid, and  an edgeedge with one O(8)Li2FeP trigonal pyramid. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(3), one Li(3), one Fe(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Na(1), one Li(3), one Fe(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(1), one Fe(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to two equivalent Na(3), one Li(2), one Li(3), and one C(1) atom.
Na3Li3Fe2P2(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 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 2.43 Å. The Na(1)-O(13) bond length is 2.26 Å. The Na(1)-O(4) bond length is 2.59 Å. The Na(1)-O(5) bond length is 2.41 Å. There is one shorter (2.40 Å) and one longer (2.80 Å) Na(1)-O(1) 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(4) atoms. The Na(2)-O(1) bond length is 2.31 Å. The Na(2)-O(2) bond length is 2.59 Å. The Na(2)-O(3) bond length is 2.39 Å. The Na(2)-O(6) bond length is 2.49 Å. The Na(2)-O(7) bond length is 2.30 Å. There is one shorter (2.56 Å) and one longer (2.84 Å) Na(2)-O(4) bond length. In the third Na site, Na(3) 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(3)-O(10) bond length is 2.38 Å. The Na(3)-O(11) bond length is 2.54 Å. The Na(3)-O(2) bond length is 2.28 Å. The Na(3)-O(3) bond length is 2.38 Å. There is one shorter (2.50 Å) and one longer (2.71 Å) Na(3)-O(14) bond length. There are three 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 2.05 Å. The Li(1)-O(5) bond length is 2.16 Å. The Li(1)-O(6) bond length is 2.06 Å. The Li(1)-O(7) bond length is 2.06 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(10), one O(14), one O(8), and one O(9) atom. The Li(2)-O(10) bond length is 2.17 Å. The Li(2)-O(14) bond length is 2.11 Å. The Li(2)-O(8) bond length is 2.13 Å. The Li(2)-O(9) bond length is 2.18 Å. In the third Li site, Li(3) is bonded to one O(11), one O(12), one O(14), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 71-91°. The Li(3)-O(11) bond length is 2.20 Å. The Li(3)-O(12) bond length is 2.53 Å. The Li(3)-O(14) bond length is 2.14 Å. The Li(3)-O(8) bond length is 2.16 Å. The Li(3)-O(9) bond length is 2.20 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. The Fe(1)-O(2) bond length is 2.23 Å. The Fe(1)-O(3) bond length is 2.43 Å. The Fe(1)-O(4) bond length is 2.05 Å. The Fe(1)-O(5) bond length is 2.05 Å. The Fe(1)-O(7) bond length is 2.20 Å. The Fe(1)-O(9) bond length is 2.20 Å. In the second Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Fe(2)-O(10) bond length is 2.06 Å. The Fe(2)-O(11) bond length is 2.05 Å. The Fe(2)-O(12) bond length is 2.35 Å. The Fe(2)-O(13) bond length is 2.20 Å. The Fe(2)-O(6) bond length is 2.15 Å. The Fe(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 1.30 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 1.30 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-62°. 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(6) bond length is 1.56 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Li(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 43-63°. 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(7) bond length is 1.55 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 4-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Fe(1), and one P(1) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(9)Li2FeP tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(8)Li2FeP trigonal pyramid, and  an edgeedge with one O(7)NaLiFeP trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Fe(2), and one P(1) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(10)NaLiFeP trigonal pyramid, corners with two equivalent O(8)Li2FeP trigonal pyramids, corners with two equivalent O(5)NaLiFeP trigonal pyramids, and corners with two equivalent O(7)NaLiFeP trigonal pyramids. In the seventh O site, O(7) is bonded to one Na(2), one Li(1), one Fe(1), and one P(2) atom to form distorted ONaLiFeP trigonal pyramids that share corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(10)NaLiFeP trigonal pyramid, and  an edgeedge with one O(5)NaLiFeP trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(2), one Li(3), one Fe(2), and one P(1) atom to form distorted OLi2FeP trigonal pyramids that share corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(5)NaLiFeP trigonal pyramid, and  an edgeedge with one O(10)NaLiFeP trigonal pyramid. In the ninth O site, O(9) is bonded to one Li(2), one Li(3), one Fe(1), and one P(2) atom to form distorted OLi2FeP tetrahedra that share  a cornercorner with one O(5)NaLiFeP trigonal pyramid, corners with two equivalent O(8)Li2FeP trigonal pyramids, corners with two equivalent O(10)NaLiFeP trigonal pyramids, and corners with two equivalent O(7)NaLiFeP trigonal pyramids. In the tenth O site, O(10) is bonded to one Na(3), one Li(2), one Fe(2), and one P(2) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(6)NaLiFeP tetrahedra, corners with two equivalent O(9)Li2FeP tetrahedra,  a cornercorner with one O(7)NaLiFeP trigonal pyramid, and  an edgeedge with one O(8)Li2FeP trigonal pyramid. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(3), one Li(3), one Fe(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Na(1), one Li(3), one Fe(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(1), one Fe(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to two equivalent Na(3), one Li(2), one Li(3), and one C(1) atom.