NaFeBr4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one Br(1), one Br(3), and four equivalent Br(2) atoms to form distorted NaBr6 pentagonal pyramids that share corners with four equivalent Na(1)Br6 pentagonal pyramids, corners with two equivalent Fe(1)Br4 tetrahedra, and edges with two equivalent Fe(1)Br4 tetrahedra. Fe(1) is bonded to one Br(1), one Br(3), and two equivalent Br(2) atoms to form FeBr4 tetrahedra that share corners with two equivalent Na(1)Br6 pentagonal pyramids and edges with two equivalent Na(1)Br6 pentagonal pyramids. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in an L-shaped geometry to one Na(1) and one Fe(1) atom. In the second Br site, Br(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one Fe(1) atom. In the third Br site, Br(3) is bonded in an L-shaped geometry to one Na(1) and one Fe(1) atom.
NaFeBr4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one Br(1), one Br(3), and four equivalent Br(2) atoms to form distorted NaBr6 pentagonal pyramids that share corners with four equivalent Na(1)Br6 pentagonal pyramids, corners with two equivalent Fe(1)Br4 tetrahedra, and edges with two equivalent Fe(1)Br4 tetrahedra. The Na(1)-Br(1) bond length is 3.04 Å. The Na(1)-Br(3) bond length is 2.97 Å. There are two shorter (3.05 Å) and two longer (3.09 Å) Na(1)-Br(2) bond lengths. Fe(1) is bonded to one Br(1), one Br(3), and two equivalent Br(2) atoms to form FeBr4 tetrahedra that share corners with two equivalent Na(1)Br6 pentagonal pyramids and edges with two equivalent Na(1)Br6 pentagonal pyramids. The Fe(1)-Br(1) bond length is 2.34 Å. The Fe(1)-Br(3) bond length is 2.33 Å. Both Fe(1)-Br(2) bond lengths are 2.36 Å. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in an L-shaped geometry to one Na(1) and one Fe(1) atom. In the second Br site, Br(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one Fe(1) atom. In the third Br site, Br(3) is bonded in an L-shaped geometry to one Na(1) and one Fe(1) atom.