Pr4PO8Cl crystallizes in the orthorhombic Pmn2_1 space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), two equivalent O(2), and one Cl(1) atom. In the second Pr site, Pr(2) is bonded in a 6-coordinate geometry to one O(4), one O(5), two equivalent O(1), two equivalent O(2), and one Cl(1) atom. P(1) is bonded in a tetrahedral geometry to one O(3), one O(5), and two equivalent O(4) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Pr(1) and two equivalent Pr(2) atoms to form a mixture of corner and edge-sharing OPr4 tetrahedra. In the second O site, O(2) is bonded to two equivalent Pr(1) and two equivalent Pr(2) atoms to form a mixture of corner and edge-sharing OPr4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to two equivalent Pr(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to two equivalent Pr(2) and one P(1) atom. Cl(1) is bonded in a 4-coordinate geometry to two equivalent Pr(1) and two equivalent Pr(2) atoms.
Pr4PO8Cl crystallizes in the orthorhombic Pmn2_1 space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 6-coordinate geometry to one O(3), one O(4), two equivalent O(1), two equivalent O(2), and one Cl(1) atom. The Pr(1)-O(3) bond length is 2.49 Å. The Pr(1)-O(4) bond length is 2.63 Å. There is one shorter (2.36 Å) and one longer (2.38 Å) Pr(1)-O(1) bond length. There is one shorter (2.37 Å) and one longer (2.39 Å) Pr(1)-O(2) bond length. The Pr(1)-Cl(1) bond length is 3.32 Å. In the second Pr site, Pr(2) is bonded in a 6-coordinate geometry to one O(4), one O(5), two equivalent O(1), two equivalent O(2), and one Cl(1) atom. The Pr(2)-O(4) bond length is 2.66 Å. The Pr(2)-O(5) bond length is 2.54 Å. There is one shorter (2.37 Å) and one longer (2.39 Å) Pr(2)-O(1) bond length. There is one shorter (2.39 Å) and one longer (2.40 Å) Pr(2)-O(2) bond length. The Pr(2)-Cl(1) bond length is 3.38 Å. P(1) is bonded in a tetrahedral geometry to one O(3), one O(5), and two equivalent O(4) atoms. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.56 Å. Both P(1)-O(4) bond lengths are 1.55 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Pr(1) and two equivalent Pr(2) atoms to form a mixture of corner and edge-sharing OPr4 tetrahedra. In the second O site, O(2) is bonded to two equivalent Pr(1) and two equivalent Pr(2) atoms to form a mixture of corner and edge-sharing OPr4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to two equivalent Pr(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to two equivalent Pr(2) and one P(1) atom. Cl(1) is bonded in a 4-coordinate geometry to two equivalent Pr(1) and two equivalent Pr(2) atoms.