Pr4B3O10F crystallizes in the triclinic P-1 space group. There are four inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(6), one O(7), one O(8), and one O(9) atom. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(6), one O(8), one O(9), two equivalent O(5), and two equivalent F(1) atoms. In the third Pr site, Pr(3) is bonded in a 9-coordinate geometry to one O(2), one O(3), one O(6), one O(7), one O(8), one O(9), two equivalent O(4), and one F(1) atom. In the fourth Pr site, Pr(4) is bonded in a 10-coordinate geometry to one O(10), one O(2), one O(3), one O(5), one O(6), one O(7), one O(8), two equivalent O(1), and one F(1) atom. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(10), one O(6), and one O(7) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(8) atom. In the third B site, B(3) is bonded in a tetrahedral geometry to one O(2), one O(4), one O(5), and one O(9) atom. There are ten inequivalent O sites. In the first O site, O(10) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(4), and one B(1) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), two equivalent Pr(4), and one B(2) atom. In the third O site, O(2) is bonded in a 1-coordinate geometry to one Pr(1), one Pr(3), one Pr(4), and one B(3) atom. In the fourth O site, O(3) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(3), one Pr(4), and one B(2) atom. In the fifth O site, O(4) is bonded to one Pr(1), two equivalent Pr(3), and one B(3) atom to form distorted OPr3B tetrahedra that share corners with two equivalent F(1)Pr4 tetrahedra and  an edgeedge with one O(4)Pr3B tetrahedra. In the sixth O site, O(5) is bonded in a distorted single-bond geometry to one Pr(4), two equivalent Pr(2), and one B(3) atom. In the seventh O site, O(6) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(3), one Pr(4), and one B(1) atom. In the eighth O site, O(7) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(3), one Pr(4), and one B(1) atom. In the ninth O site, O(8) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(3), one Pr(4), and one B(2) atom. In the tenth O site, O(9) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(3), and one B(3) atom. F(1) is bonded to one Pr(3), one Pr(4), and two equivalent Pr(2) atoms to form FPr4 tetrahedra that share corners with two equivalent O(4)Pr3B tetrahedra and  an edgeedge with one F(1)Pr4 tetrahedra.
Pr4B3O10F crystallizes in the triclinic P-1 space group. There are four inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(6), one O(7), one O(8), and one O(9) atom. The Pr(1)-O(1) bond length is 2.51 Å. The Pr(1)-O(10) bond length is 2.55 Å. The Pr(1)-O(2) bond length is 2.35 Å. The Pr(1)-O(3) bond length is 2.45 Å. The Pr(1)-O(4) bond length is 2.45 Å. The Pr(1)-O(6) bond length is 2.79 Å. The Pr(1)-O(7) bond length is 2.65 Å. The Pr(1)-O(8) bond length is 2.85 Å. The Pr(1)-O(9) bond length is 2.42 Å. In the second Pr site, Pr(2) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(6), one O(8), one O(9), two equivalent O(5), and two equivalent F(1) atoms. The Pr(2)-O(1) bond length is 2.94 Å. The Pr(2)-O(10) bond length is 2.44 Å. The Pr(2)-O(6) bond length is 2.55 Å. The Pr(2)-O(8) bond length is 2.54 Å. The Pr(2)-O(9) bond length is 2.42 Å. There is one shorter (2.41 Å) and one longer (2.44 Å) Pr(2)-O(5) bond length. There is one shorter (2.54 Å) and one longer (2.63 Å) Pr(2)-F(1) bond length. In the third Pr site, Pr(3) is bonded in a 9-coordinate geometry to one O(2), one O(3), one O(6), one O(7), one O(8), one O(9), two equivalent O(4), and one F(1) atom. The Pr(3)-O(2) bond length is 2.83 Å. The Pr(3)-O(3) bond length is 2.53 Å. The Pr(3)-O(6) bond length is 2.81 Å. The Pr(3)-O(7) bond length is 2.43 Å. The Pr(3)-O(8) bond length is 3.09 Å. The Pr(3)-O(9) bond length is 2.43 Å. There is one shorter (2.37 Å) and one longer (2.43 Å) Pr(3)-O(4) bond length. The Pr(3)-F(1) bond length is 2.59 Å. In the fourth Pr site, Pr(4) is bonded in a 10-coordinate geometry to one O(10), one O(2), one O(3), one O(5), one O(6), one O(7), one O(8), two equivalent O(1), and one F(1) atom. The Pr(4)-O(10) bond length is 2.95 Å. The Pr(4)-O(2) bond length is 2.44 Å. The Pr(4)-O(3) bond length is 2.55 Å. The Pr(4)-O(5) bond length is 2.54 Å. The Pr(4)-O(6) bond length is 2.93 Å. The Pr(4)-O(7) bond length is 2.51 Å. The Pr(4)-O(8) bond length is 2.76 Å. There is one shorter (2.51 Å) and one longer (3.03 Å) Pr(4)-O(1) bond length. The Pr(4)-F(1) bond length is 2.51 Å. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(10), one O(6), and one O(7) atom. The B(1)-O(10) bond length is 1.38 Å. The B(1)-O(6) bond length is 1.39 Å. The B(1)-O(7) bond length is 1.39 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(8) atom. The B(2)-O(1) bond length is 1.39 Å. The B(2)-O(3) bond length is 1.39 Å. The B(2)-O(8) bond length is 1.40 Å. In the third B site, B(3) is bonded in a tetrahedral geometry to one O(2), one O(4), one O(5), and one O(9) atom. The B(3)-O(2) bond length is 1.47 Å. The B(3)-O(4) bond length is 1.49 Å. The B(3)-O(5) bond length is 1.51 Å. The B(3)-O(9) bond length is 1.52 Å. There are ten inequivalent O sites. In the first O site, O(10) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(4), and one B(1) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), two equivalent Pr(4), and one B(2) atom. In the third O site, O(2) is bonded in a 1-coordinate geometry to one Pr(1), one Pr(3), one Pr(4), and one B(3) atom. In the fourth O site, O(3) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(3), one Pr(4), and one B(2) atom. In the fifth O site, O(4) is bonded to one Pr(1), two equivalent Pr(3), and one B(3) atom to form distorted OPr3B tetrahedra that share corners with two equivalent F(1)Pr4 tetrahedra and  an edgeedge with one O(4)Pr3B tetrahedra. In the sixth O site, O(5) is bonded in a distorted single-bond geometry to one Pr(4), two equivalent Pr(2), and one B(3) atom. In the seventh O site, O(6) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(3), one Pr(4), and one B(1) atom. In the eighth O site, O(7) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(3), one Pr(4), and one B(1) atom. In the ninth O site, O(8) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(3), one Pr(4), and one B(2) atom. In the tenth O site, O(9) is bonded in a distorted single-bond geometry to one Pr(1), one Pr(2), one Pr(3), and one B(3) atom. F(1) is bonded to one Pr(3), one Pr(4), and two equivalent Pr(2) atoms to form FPr4 tetrahedra that share corners with two equivalent O(4)Pr3B tetrahedra and  an edgeedge with one F(1)Pr4 tetrahedra.