VFe3(PO4)4 crystallizes in the monoclinic Pm space group. V(1) is bonded to one O(1), one O(9), two equivalent O(5), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Fe(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(10), one O(2), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with four equivalent Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second Fe site, Fe(2) is bonded to one O(11), one O(3), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the third Fe site, Fe(3) is bonded to one O(12), one O(4), two equivalent O(5), and two equivalent O(8) atoms to form FeO6 octahedra that share corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. In the second P site, P(2) is bonded to one O(2), one O(9), and two equivalent O(6) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-57°. In the third P site, P(3) is bonded to one O(12), one O(3), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. In the fourth P site, P(4) is bonded to one O(11), one O(4), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-58°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(3) atom.
VFe3(PO4)4 crystallizes in the monoclinic Pm space group. V(1) is bonded to one O(1), one O(9), two equivalent O(5), and two equivalent O(8) atoms to form VO6 octahedra that share corners with four equivalent Fe(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(9) bond length is 1.97 Å. Both V(1)-O(5) bond lengths are 2.11 Å. Both V(1)-O(8) bond lengths are 2.13 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(10), one O(2), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with four equivalent Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Fe(1)-O(10) bond length is 1.96 Å. The Fe(1)-O(2) bond length is 1.93 Å. Both Fe(1)-O(6) bond lengths are 2.16 Å. Both Fe(1)-O(7) bond lengths are 2.08 Å. In the second Fe site, Fe(2) is bonded to one O(11), one O(3), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Fe(2)-O(11) bond length is 1.95 Å. The Fe(2)-O(3) bond length is 1.93 Å. Both Fe(2)-O(6) bond lengths are 2.07 Å. Both Fe(2)-O(7) bond lengths are 2.17 Å. In the third Fe site, Fe(3) is bonded to one O(12), one O(4), two equivalent O(5), and two equivalent O(8) atoms to form FeO6 octahedra that share corners with four equivalent V(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Fe(3)-O(12) bond length is 1.96 Å. The Fe(3)-O(4) bond length is 1.93 Å. Both Fe(3)-O(5) bond lengths are 2.09 Å. Both Fe(3)-O(8) bond lengths are 2.15 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(3)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(10) bond length is 1.52 Å. Both P(1)-O(5) bond lengths are 1.59 Å. In the second P site, P(2) is bonded to one O(2), one O(9), and two equivalent O(6) atoms to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-57°. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.52 Å. Both P(2)-O(6) bond lengths are 1.58 Å. In the third P site, P(3) is bonded to one O(12), one O(3), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-57°. The P(3)-O(12) bond length is 1.52 Å. The P(3)-O(3) bond length is 1.53 Å. Both P(3)-O(7) bond lengths are 1.58 Å. In the fourth P site, P(4) is bonded to one O(11), one O(4), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Fe(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-58°. The P(4)-O(11) bond length is 1.53 Å. The P(4)-O(4) bond length is 1.53 Å. Both P(4)-O(8) bond lengths are 1.58 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(3) atom.