CsNa2Fe3P4O14Cl crystallizes in the monoclinic C2/c space group. Cs(1) is bonded in a 14-coordinate geometry to two equivalent O(3), two equivalent O(5), four equivalent O(1), four equivalent O(2), and two equivalent Cl(1) atoms. Na(1) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(3), and two equivalent O(6) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), one O(7), and one Cl(1) atom. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent Cl(1) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form corner-sharing PO4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form corner-sharing PO4 tetrahedra. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Fe(1), and one P(2) atom. In the second O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Fe(1), and one P(1) atom. In the third O site, O(1) is bonded in a 2-coordinate geometry to two equivalent Cs(1), one Fe(2), and one P(2) atom. In the fourth O site, O(5) is bonded in a 3-coordinate geometry to one Cs(1), one Na(1), one Fe(1), and one P(1) atom. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Cs(1), one P(1), and one P(2) atom. In the sixth O site, O(3) is bonded in a 1-coordinate geometry to one Cs(1), two equivalent Na(1), one Fe(1), and one P(2) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(1) atom. Cl(1) is bonded to two equivalent Cs(1), two equivalent Fe(1), and two equivalent Fe(2) atoms to form distorted corner-sharing ClCs2Fe4 octahedra. The corner-sharing octahedra are not tilted.
CsNa2Fe3P4O14Cl crystallizes in the monoclinic C2/c space group. Cs(1) is bonded in a 14-coordinate geometry to two equivalent O(3), two equivalent O(5), four equivalent O(1), four equivalent O(2), and two equivalent Cl(1) atoms. Both Cs(1)-O(3) bond lengths are 3.47 Å. Both Cs(1)-O(5) bond lengths are 3.65 Å. There are two shorter (3.21 Å) and two longer (3.27 Å) Cs(1)-O(1) bond lengths. There are two shorter (3.22 Å) and two longer (3.48 Å) Cs(1)-O(2) bond lengths. Both Cs(1)-Cl(1) bond lengths are 3.49 Å. Na(1) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(3), and two equivalent O(6) atoms. The Na(1)-O(5) bond length is 2.48 Å. The Na(1)-O(7) bond length is 2.40 Å. There is one shorter (2.40 Å) and one longer (2.68 Å) Na(1)-O(3) bond length. There is one shorter (2.47 Å) and one longer (2.54 Å) Na(1)-O(6) bond length. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), one O(7), and one Cl(1) atom. The Fe(1)-O(3) bond length is 2.16 Å. The Fe(1)-O(4) bond length is 2.21 Å. The Fe(1)-O(5) bond length is 2.09 Å. The Fe(1)-O(6) bond length is 2.20 Å. The Fe(1)-O(7) bond length is 2.13 Å. The Fe(1)-Cl(1) bond length is 2.91 Å. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent Cl(1) atoms. Both Fe(2)-O(1) bond lengths are 1.97 Å. Both Fe(2)-O(4) bond lengths are 2.36 Å. There is one shorter (2.52 Å) and one longer (2.78 Å) Fe(2)-Cl(1) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form corner-sharing PO4 tetrahedra. The P(1)-O(2) bond length is 1.64 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form corner-sharing PO4 tetrahedra. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.63 Å. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.54 Å. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Fe(1), and one P(2) atom. In the second O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Fe(1), and one P(1) atom. In the third O site, O(1) is bonded in a 2-coordinate geometry to two equivalent Cs(1), one Fe(2), and one P(2) atom. In the fourth O site, O(5) is bonded in a 3-coordinate geometry to one Cs(1), one Na(1), one Fe(1), and one P(1) atom. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Cs(1), one P(1), and one P(2) atom. In the sixth O site, O(3) is bonded in a 1-coordinate geometry to one Cs(1), two equivalent Na(1), one Fe(1), and one P(2) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(1) atom. Cl(1) is bonded to two equivalent Cs(1), two equivalent Fe(1), and two equivalent Fe(2) atoms to form distorted corner-sharing ClCs2Fe4 octahedra. The corner-sharing octahedra are not tilted.