Bi3NF6 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent F(1), and two equivalent F(4) atoms. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to two equivalent F(2), two equivalent F(4), and four equivalent F(3) atoms. N(1) is bonded to four equivalent Bi(1) atoms to form NBi4 tetrahedra that share corners with four equivalent F(1)Bi4 tetrahedra, edges with two equivalent N(1)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. There are four inequivalent F sites. In the first F site, F(4) is bonded in a 2-coordinate geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second F site, F(1) is bonded to four equivalent Bi(1) atoms to form distorted FBi4 tetrahedra that share corners with four equivalent N(1)Bi4 tetrahedra, edges with two equivalent N(1)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. In the third F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Bi(2) atoms. In the fourth F site, F(3) is bonded in a water-like geometry to two equivalent Bi(2) atoms.
Bi3NF6 crystallizes in the orthorhombic Pbcm space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent F(1), and two equivalent F(4) atoms. There is one shorter (2.27 Å) and one longer (2.28 Å) Bi(1)-N(1) bond length. There is one shorter (2.51 Å) and one longer (2.68 Å) Bi(1)-F(1) bond length. There is one shorter (2.26 Å) and one longer (2.79 Å) Bi(1)-F(4) bond length. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to two equivalent F(2), two equivalent F(4), and four equivalent F(3) atoms. There is one shorter (2.28 Å) and one longer (2.36 Å) Bi(2)-F(2) bond length. Both Bi(2)-F(4) bond lengths are 2.46 Å. There are two shorter (2.35 Å) and two longer (2.40 Å) Bi(2)-F(3) bond lengths. N(1) is bonded to four equivalent Bi(1) atoms to form NBi4 tetrahedra that share corners with four equivalent F(1)Bi4 tetrahedra, edges with two equivalent N(1)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. There are four inequivalent F sites. In the first F site, F(4) is bonded in a 2-coordinate geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second F site, F(1) is bonded to four equivalent Bi(1) atoms to form distorted FBi4 tetrahedra that share corners with four equivalent N(1)Bi4 tetrahedra, edges with two equivalent N(1)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. In the third F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Bi(2) atoms. In the fourth F site, F(3) is bonded in a water-like geometry to two equivalent Bi(2) atoms.