NaFe2(MoO4)3 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(12), one O(4), one O(5), one O(7), and two equivalent O(9) atoms. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form MoO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-52°. In the second Mo site, Mo(2) is bonded to one O(11), one O(5), one O(7), and one O(9) atom to form MoO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-49°. In the third Mo site, Mo(3) is bonded to one O(10), one O(12), one O(4), and one O(8) atom to form MoO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra and corners with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-56°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(10), one O(3), one O(7), and two equivalent O(2) atoms to form FeO6 octahedra that share  a cornercorner with one Mo(2)O4 tetrahedra,  a cornercorner with one Mo(3)O4 tetrahedra, corners with four equivalent Mo(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. In the second Fe site, Fe(2) is bonded to one O(11), one O(12), one O(4), one O(6), one O(8), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one Mo(1)O4 tetrahedra, corners with two equivalent Mo(2)O4 tetrahedra, and corners with three equivalent Mo(3)O4 tetrahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mo(1) and one Fe(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mo(1) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mo(1) and one Fe(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one Mo(3), and one Fe(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Na(1) and one Mo(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Mo(1) and one Fe(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Mo(2), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mo(3) and one Fe(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent Na(1), one Mo(2), and one Fe(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(3) and one Fe(1) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Mo(2) and one Fe(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Na(1), one Mo(3), and one Fe(2) atom.
NaFe2(MoO4)3 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(12), one O(4), one O(5), one O(7), and two equivalent O(9) atoms. The Na(1)-O(12) bond length is 2.35 Å. The Na(1)-O(4) bond length is 2.34 Å. The Na(1)-O(5) bond length is 2.31 Å. The Na(1)-O(7) bond length is 2.88 Å. There is one shorter (2.64 Å) and one longer (3.00 Å) Na(1)-O(9) bond length. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form MoO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-52°. The Mo(1)-O(1) bond length is 1.78 Å. The Mo(1)-O(2) bond length is 1.83 Å. The Mo(1)-O(3) bond length is 1.76 Å. The Mo(1)-O(6) bond length is 1.81 Å. In the second Mo site, Mo(2) is bonded to one O(11), one O(5), one O(7), and one O(9) atom to form MoO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-49°. The Mo(2)-O(11) bond length is 1.83 Å. The Mo(2)-O(5) bond length is 1.75 Å. The Mo(2)-O(7) bond length is 1.78 Å. The Mo(2)-O(9) bond length is 1.84 Å. In the third Mo site, Mo(3) is bonded to one O(10), one O(12), one O(4), and one O(8) atom to form MoO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra and corners with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-56°. The Mo(3)-O(10) bond length is 1.76 Å. The Mo(3)-O(12) bond length is 1.82 Å. The Mo(3)-O(4) bond length is 1.83 Å. The Mo(3)-O(8) bond length is 1.80 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(10), one O(3), one O(7), and two equivalent O(2) atoms to form FeO6 octahedra that share  a cornercorner with one Mo(2)O4 tetrahedra,  a cornercorner with one Mo(3)O4 tetrahedra, corners with four equivalent Mo(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. The Fe(1)-O(1) bond length is 2.11 Å. The Fe(1)-O(10) bond length is 2.14 Å. The Fe(1)-O(3) bond length is 2.09 Å. The Fe(1)-O(7) bond length is 2.14 Å. There is one shorter (2.14 Å) and one longer (2.17 Å) Fe(1)-O(2) bond length. In the second Fe site, Fe(2) is bonded to one O(11), one O(12), one O(4), one O(6), one O(8), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one Mo(1)O4 tetrahedra, corners with two equivalent Mo(2)O4 tetrahedra, and corners with three equivalent Mo(3)O4 tetrahedra. The Fe(2)-O(11) bond length is 2.03 Å. The Fe(2)-O(12) bond length is 2.08 Å. The Fe(2)-O(4) bond length is 2.05 Å. The Fe(2)-O(6) bond length is 1.97 Å. The Fe(2)-O(8) bond length is 2.03 Å. The Fe(2)-O(9) bond length is 2.04 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mo(1) and one Fe(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mo(1) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mo(1) and one Fe(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one Mo(3), and one Fe(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Na(1) and one Mo(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Mo(1) and one Fe(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Mo(2), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mo(3) and one Fe(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent Na(1), one Mo(2), and one Fe(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(3) and one Fe(1) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Mo(2) and one Fe(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Na(1), one Mo(3), and one Fe(2) atom.