Nb5(NO)2 crystallizes in the monoclinic Cm space group. There are five inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one N(1), one N(2), one O(1), and two equivalent O(2) atoms to form distorted NbN2O3 square pyramids that share corners with two equivalent Nb(1)N2O3 square pyramids, corners with two equivalent Nb(5)N2O3 square pyramids, corners with two equivalent Nb(4)N3O2 square pyramids, edges with two equivalent Nb(5)N2O3 square pyramids, edges with two equivalent Nb(4)N3O2 square pyramids, and edges with three equivalent Nb(3)N3O2 square pyramids. In the second Nb site, Nb(2) is bonded in a distorted rectangular see-saw-like geometry to one N(1), one N(2), one O(1), and one O(2) atom. In the third Nb site, Nb(3) is bonded to one N(2), two equivalent N(1), one O(1), and one O(2) atom to form NbN3O2 square pyramids that share corners with two equivalent Nb(5)N2O3 square pyramids, corners with two equivalent Nb(3)N3O2 square pyramids, corners with two equivalent Nb(4)N3O2 square pyramids, edges with two equivalent Nb(5)N2O3 square pyramids, edges with two equivalent Nb(4)N3O2 square pyramids, and edges with three equivalent Nb(1)N2O3 square pyramids. In the fourth Nb site, Nb(4) is bonded to one N(1), two equivalent N(2), one O(1), and one O(2) atom to form NbN3O2 square pyramids that share corners with two equivalent Nb(1)N2O3 square pyramids, corners with two equivalent Nb(3)N3O2 square pyramids, corners with two equivalent Nb(4)N3O2 square pyramids, edges with two equivalent Nb(1)N2O3 square pyramids, edges with two equivalent Nb(3)N3O2 square pyramids, and edges with three equivalent Nb(5)N2O3 square pyramids. In the fifth Nb site, Nb(5) is bonded to one N(1), one N(2), one O(2), and two equivalent O(1) atoms to form distorted NbN2O3 square pyramids that share corners with two equivalent Nb(1)N2O3 square pyramids, corners with two equivalent Nb(5)N2O3 square pyramids, corners with two equivalent Nb(3)N3O2 square pyramids, edges with two equivalent Nb(1)N2O3 square pyramids, edges with two equivalent Nb(3)N3O2 square pyramids, and edges with three equivalent Nb(4)N3O2 square pyramids. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Nb(1), one Nb(2), one Nb(4), one Nb(5), and two equivalent Nb(3) atoms to form NNb6 octahedra that share  a cornercorner with one N(2)Nb6 octahedra,  a cornercorner with one O(1)Nb6 octahedra,  a cornercorner with one O(2)Nb6 octahedra, corners with two equivalent N(1)Nb6 octahedra, edges with three equivalent N(2)Nb6 octahedra, edges with three equivalent O(1)Nb6 octahedra, and edges with three equivalent O(2)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 1-18°. In the second N site, N(2) is bonded to one Nb(1), one Nb(2), one Nb(3), one Nb(5), and two equivalent Nb(4) atoms to form NNb6 octahedra that share  a cornercorner with one N(1)Nb6 octahedra,  a cornercorner with one O(1)Nb6 octahedra,  a cornercorner with one O(2)Nb6 octahedra, corners with two equivalent N(2)Nb6 octahedra, edges with three equivalent N(1)Nb6 octahedra, edges with three equivalent O(1)Nb6 octahedra, and edges with three equivalent O(2)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 4-21°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Nb(1), one Nb(2), one Nb(3), one Nb(4), and two equivalent Nb(5) atoms to form ONb6 octahedra that share  a cornercorner with one N(1)Nb6 octahedra,  a cornercorner with one N(2)Nb6 octahedra,  a cornercorner with one O(2)Nb6 octahedra, corners with two equivalent O(1)Nb6 octahedra, edges with three equivalent N(1)Nb6 octahedra, edges with three equivalent N(2)Nb6 octahedra, and edges with three equivalent O(2)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 9-22°. In the second O site, O(2) is bonded to one Nb(2), one Nb(3), one Nb(4), one Nb(5), and two equivalent Nb(1) atoms to form distorted ONb6 octahedra that share  a cornercorner with one N(1)Nb6 octahedra,  a cornercorner with one N(2)Nb6 octahedra,  a cornercorner with one O(1)Nb6 octahedra, corners with two equivalent O(2)Nb6 octahedra, edges with three equivalent N(1)Nb6 octahedra, edges with three equivalent N(2)Nb6 octahedra, and edges with three equivalent O(1)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 1-21°.
Nb5(NO)2 crystallizes in the monoclinic Cm space group. There are five inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one N(1), one N(2), one O(1), and two equivalent O(2) atoms to form distorted NbN2O3 square pyramids that share corners with two equivalent Nb(1)N2O3 square pyramids, corners with two equivalent Nb(5)N2O3 square pyramids, corners with two equivalent Nb(4)N3O2 square pyramids, edges with two equivalent Nb(5)N2O3 square pyramids, edges with two equivalent Nb(4)N3O2 square pyramids, and edges with three equivalent Nb(3)N3O2 square pyramids. The Nb(1)-N(1) bond length is 2.32 Å. The Nb(1)-N(2) bond length is 2.21 Å. The Nb(1)-O(1) bond length is 2.41 Å. Both Nb(1)-O(2) bond lengths are 2.23 Å. In the second Nb site, Nb(2) is bonded in a distorted rectangular see-saw-like geometry to one N(1), one N(2), one O(1), and one O(2) atom. The Nb(2)-N(1) bond length is 2.13 Å. The Nb(2)-N(2) bond length is 2.21 Å. The Nb(2)-O(1) bond length is 2.30 Å. The Nb(2)-O(2) bond length is 2.72 Å. In the third Nb site, Nb(3) is bonded to one N(2), two equivalent N(1), one O(1), and one O(2) atom to form NbN3O2 square pyramids that share corners with two equivalent Nb(5)N2O3 square pyramids, corners with two equivalent Nb(3)N3O2 square pyramids, corners with two equivalent Nb(4)N3O2 square pyramids, edges with two equivalent Nb(5)N2O3 square pyramids, edges with two equivalent Nb(4)N3O2 square pyramids, and edges with three equivalent Nb(1)N2O3 square pyramids. The Nb(3)-N(2) bond length is 2.25 Å. Both Nb(3)-N(1) bond lengths are 2.21 Å. The Nb(3)-O(1) bond length is 2.26 Å. The Nb(3)-O(2) bond length is 2.24 Å. In the fourth Nb site, Nb(4) is bonded to one N(1), two equivalent N(2), one O(1), and one O(2) atom to form NbN3O2 square pyramids that share corners with two equivalent Nb(1)N2O3 square pyramids, corners with two equivalent Nb(3)N3O2 square pyramids, corners with two equivalent Nb(4)N3O2 square pyramids, edges with two equivalent Nb(1)N2O3 square pyramids, edges with two equivalent Nb(3)N3O2 square pyramids, and edges with three equivalent Nb(5)N2O3 square pyramids. The Nb(4)-N(1) bond length is 2.22 Å. Both Nb(4)-N(2) bond lengths are 2.22 Å. The Nb(4)-O(1) bond length is 2.35 Å. The Nb(4)-O(2) bond length is 2.33 Å. In the fifth Nb site, Nb(5) is bonded to one N(1), one N(2), one O(2), and two equivalent O(1) atoms to form distorted NbN2O3 square pyramids that share corners with two equivalent Nb(1)N2O3 square pyramids, corners with two equivalent Nb(5)N2O3 square pyramids, corners with two equivalent Nb(3)N3O2 square pyramids, edges with two equivalent Nb(1)N2O3 square pyramids, edges with two equivalent Nb(3)N3O2 square pyramids, and edges with three equivalent Nb(4)N3O2 square pyramids. The Nb(5)-N(1) bond length is 2.33 Å. The Nb(5)-N(2) bond length is 2.18 Å. The Nb(5)-O(2) bond length is 2.22 Å. Both Nb(5)-O(1) bond lengths are 2.23 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Nb(1), one Nb(2), one Nb(4), one Nb(5), and two equivalent Nb(3) atoms to form NNb6 octahedra that share  a cornercorner with one N(2)Nb6 octahedra,  a cornercorner with one O(1)Nb6 octahedra,  a cornercorner with one O(2)Nb6 octahedra, corners with two equivalent N(1)Nb6 octahedra, edges with three equivalent N(2)Nb6 octahedra, edges with three equivalent O(1)Nb6 octahedra, and edges with three equivalent O(2)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 1-18°. In the second N site, N(2) is bonded to one Nb(1), one Nb(2), one Nb(3), one Nb(5), and two equivalent Nb(4) atoms to form NNb6 octahedra that share  a cornercorner with one N(1)Nb6 octahedra,  a cornercorner with one O(1)Nb6 octahedra,  a cornercorner with one O(2)Nb6 octahedra, corners with two equivalent N(2)Nb6 octahedra, edges with three equivalent N(1)Nb6 octahedra, edges with three equivalent O(1)Nb6 octahedra, and edges with three equivalent O(2)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 4-21°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Nb(1), one Nb(2), one Nb(3), one Nb(4), and two equivalent Nb(5) atoms to form ONb6 octahedra that share  a cornercorner with one N(1)Nb6 octahedra,  a cornercorner with one N(2)Nb6 octahedra,  a cornercorner with one O(2)Nb6 octahedra, corners with two equivalent O(1)Nb6 octahedra, edges with three equivalent N(1)Nb6 octahedra, edges with three equivalent N(2)Nb6 octahedra, and edges with three equivalent O(2)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 9-22°. In the second O site, O(2) is bonded to one Nb(2), one Nb(3), one Nb(4), one Nb(5), and two equivalent Nb(1) atoms to form distorted ONb6 octahedra that share  a cornercorner with one N(1)Nb6 octahedra,  a cornercorner with one N(2)Nb6 octahedra,  a cornercorner with one O(1)Nb6 octahedra, corners with two equivalent O(2)Nb6 octahedra, edges with three equivalent N(1)Nb6 octahedra, edges with three equivalent N(2)Nb6 octahedra, and edges with three equivalent O(1)Nb6 octahedra. The corner-sharing octahedral tilt angles range from 1-21°.