Fe4W2N crystallizes in the monoclinic Cm space group. There are five inequivalent W sites. In the first W site, W(1) is bonded in a 2-coordinate geometry to one Fe(1), one Fe(2), one Fe(5), one Fe(6), one Fe(7), one Fe(8), one N(2), and one N(3) atom. In the second W site, W(2) is bonded in a 2-coordinate geometry to one Fe(7), one Fe(9), two equivalent Fe(2), two equivalent Fe(5), one N(1), and one N(3) atom. In the third W site, W(3) is bonded in a 2-coordinate geometry to one Fe(2), one Fe(3), one Fe(5), one Fe(6), one Fe(7), one Fe(8), one N(1), and one N(2) atom. In the fourth W site, W(4) is bonded in a 2-coordinate geometry to one Fe(1), one Fe(3), one Fe(4), one Fe(6), two equivalent Fe(8), and two equivalent N(2) atoms. In the fifth W site, W(5) is bonded in a 2-coordinate geometry to one Fe(1), one Fe(2), one Fe(4), one Fe(5), one Fe(8), one Fe(9), one N(2), and one N(3) atom. There are twelve inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one W(4), two equivalent W(1), two equivalent W(5), one Fe(12), one Fe(6), one Fe(9), two equivalent Fe(5), and two equivalent Fe(8) atoms to form distorted FeFe7W5 cuboctahedra that share edges with two equivalent N(3)FeW5 octahedra, edges with four equivalent N(2)Fe2W4 octahedra, faces with two equivalent Fe(3)Fe9W3 cuboctahedra, and faces with four equivalent Fe(2)Fe8W4 cuboctahedra. In the second Fe site, Fe(2) is bonded to one W(1), one W(2), one W(3), one W(5), one Fe(10), one Fe(11), one Fe(4), one Fe(5), one Fe(6), one Fe(7), one Fe(8), and one Fe(9) atom to form distorted FeFe8W4 cuboctahedra that share edges with two equivalent N(2)Fe2W4 octahedra, edges with two equivalent N(1)Fe3W3 octahedra, edges with two equivalent N(3)FeW5 octahedra, faces with two equivalent Fe(1)Fe7W5 cuboctahedra, faces with two equivalent Fe(2)Fe8W4 cuboctahedra, and faces with two equivalent Fe(3)Fe9W3 cuboctahedra. In the third Fe site, Fe(3) is bonded to one W(4), two equivalent W(3), one Fe(12), one Fe(4), one Fe(7), two equivalent Fe(11), two equivalent Fe(5), and two equivalent Fe(8) atoms to form distorted FeFe9W3 cuboctahedra that share edges with two equivalent N(1)Fe3W3 octahedra, edges with four equivalent N(2)Fe2W4 octahedra, faces with two equivalent Fe(1)Fe7W5 cuboctahedra, and faces with four equivalent Fe(2)Fe8W4 cuboctahedra. In the fourth Fe site, Fe(4) is bonded in a 12-coordinate geometry to one W(4), two equivalent W(5), one Fe(10), one Fe(3), one Fe(6), two equivalent Fe(11), two equivalent Fe(2), and two equivalent Fe(5) atoms. In the fifth Fe site, Fe(5) is bonded in a 12-coordinate geometry to one W(1), one W(2), one W(3), one W(5), one Fe(1), one Fe(11), one Fe(12), one Fe(2), one Fe(3), one Fe(4), one Fe(5), and one Fe(6) atom. In the sixth Fe site, Fe(6) is bonded in a 12-coordinate geometry to one W(4), two equivalent W(1), two equivalent W(3), one Fe(1), one Fe(10), one Fe(4), two equivalent Fe(2), and two equivalent Fe(5) atoms. In the seventh Fe site, Fe(7) is bonded in a 12-coordinate geometry to one W(2), two equivalent W(1), two equivalent W(3), one Fe(12), one Fe(3), one Fe(9), two equivalent Fe(2), and two equivalent Fe(8) atoms. In the eighth Fe site, Fe(8) is bonded in a 12-coordinate geometry to one W(1), one W(3), one W(4), one W(5), one Fe(1), one Fe(10), one Fe(11), one Fe(2), one Fe(3), one Fe(7), one Fe(8), and one Fe(9) atom. In the ninth Fe site, Fe(9) is bonded in a 12-coordinate geometry to one W(2), two equivalent W(5), one Fe(1), one Fe(12), one Fe(7), two equivalent Fe(11), two equivalent Fe(2), and two equivalent Fe(8) atoms. In the tenth Fe site, Fe(10) is bonded in a distorted bent 120 degrees geometry to one Fe(4), one Fe(6), two equivalent Fe(2), two equivalent Fe(8), one N(1), and one N(3) atom. In the eleventh Fe site, Fe(11) is bonded in a distorted bent 120 degrees geometry to one Fe(2), one Fe(3), one Fe(4), one Fe(5), one Fe(8), one Fe(9), one N(1), and one N(2) atom. In the twelfth Fe site, Fe(12) is bonded in a distorted bent 120 degrees geometry to one Fe(1), one Fe(3), one Fe(7), one Fe(9), two equivalent Fe(5), and two equivalent N(2) atoms. There are three inequivalent N sites. In the first N site, N(1) is bonded to one W(2), two equivalent W(3), one Fe(10), and two equivalent Fe(11) atoms to form NFe3W3 octahedra that share corners with two equivalent N(3)FeW5 octahedra, corners with four equivalent N(2)Fe2W4 octahedra, edges with two equivalent Fe(3)Fe9W3 cuboctahedra, and edges with four equivalent Fe(2)Fe8W4 cuboctahedra. The corner-sharing octahedral tilt angles range from 44-49°. In the second N site, N(2) is bonded to one W(1), one W(3), one W(4), one W(5), one Fe(11), and one Fe(12) atom to form NFe2W4 octahedra that share corners with two equivalent N(2)Fe2W4 octahedra, corners with two equivalent N(1)Fe3W3 octahedra, corners with two equivalent N(3)FeW5 octahedra, edges with two equivalent Fe(1)Fe7W5 cuboctahedra, edges with two equivalent Fe(2)Fe8W4 cuboctahedra, and edges with two equivalent Fe(3)Fe9W3 cuboctahedra. The corner-sharing octahedral tilt angles range from 44-49°. In the third N site, N(3) is bonded to one W(2), two equivalent W(1), two equivalent W(5), and one Fe(10) atom to form NFeW5 octahedra that share corners with two equivalent N(1)Fe3W3 octahedra, corners with four equivalent N(2)Fe2W4 octahedra, edges with two equivalent Fe(1)Fe7W5 cuboctahedra, and edges with four equivalent Fe(2)Fe8W4 cuboctahedra. The corner-sharing octahedral tilt angles range from 44-47°.
Fe4W2N crystallizes in the monoclinic Cm space group. There are five inequivalent W sites. In the first W site, W(1) is bonded in a 2-coordinate geometry to one Fe(1), one Fe(2), one Fe(5), one Fe(6), one Fe(7), one Fe(8), one N(2), and one N(3) atom. The W(1)-Fe(1) bond length is 2.74 Å. The W(1)-Fe(2) bond length is 2.77 Å. The W(1)-Fe(5) bond length is 2.75 Å. The W(1)-Fe(6) bond length is 2.71 Å. The W(1)-Fe(7) bond length is 2.66 Å. The W(1)-Fe(8) bond length is 2.63 Å. The W(1)-N(2) bond length is 2.06 Å. The W(1)-N(3) bond length is 2.11 Å. In the second W site, W(2) is bonded in a 2-coordinate geometry to one Fe(7), one Fe(9), two equivalent Fe(2), two equivalent Fe(5), one N(1), and one N(3) atom. The W(2)-Fe(7) bond length is 2.74 Å. The W(2)-Fe(9) bond length is 2.64 Å. Both W(2)-Fe(2) bond lengths are 2.71 Å. Both W(2)-Fe(5) bond lengths are 2.64 Å. The W(2)-N(1) bond length is 2.11 Å. The W(2)-N(3) bond length is 2.21 Å. In the third W site, W(3) is bonded in a 2-coordinate geometry to one Fe(2), one Fe(3), one Fe(5), one Fe(6), one Fe(7), one Fe(8), one N(1), and one N(2) atom. The W(3)-Fe(2) bond length is 2.75 Å. The W(3)-Fe(3) bond length is 2.67 Å. The W(3)-Fe(5) bond length is 2.61 Å. The W(3)-Fe(6) bond length is 2.67 Å. The W(3)-Fe(7) bond length is 2.68 Å. The W(3)-Fe(8) bond length is 2.62 Å. The W(3)-N(1) bond length is 2.11 Å. The W(3)-N(2) bond length is 2.17 Å. In the fourth W site, W(4) is bonded in a 2-coordinate geometry to one Fe(1), one Fe(3), one Fe(4), one Fe(6), two equivalent Fe(8), and two equivalent N(2) atoms. The W(4)-Fe(1) bond length is 2.80 Å. The W(4)-Fe(3) bond length is 2.62 Å. The W(4)-Fe(4) bond length is 2.59 Å. The W(4)-Fe(6) bond length is 2.67 Å. Both W(4)-Fe(8) bond lengths are 2.69 Å. Both W(4)-N(2) bond lengths are 2.14 Å. In the fifth W site, W(5) is bonded in a 2-coordinate geometry to one Fe(1), one Fe(2), one Fe(4), one Fe(5), one Fe(8), one Fe(9), one N(2), and one N(3) atom. The W(5)-Fe(1) bond length is 2.73 Å. The W(5)-Fe(2) bond length is 2.66 Å. The W(5)-Fe(4) bond length is 2.65 Å. The W(5)-Fe(5) bond length is 2.66 Å. The W(5)-Fe(8) bond length is 2.76 Å. The W(5)-Fe(9) bond length is 2.67 Å. The W(5)-N(2) bond length is 2.08 Å. The W(5)-N(3) bond length is 2.12 Å. There are twelve inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one W(4), two equivalent W(1), two equivalent W(5), one Fe(12), one Fe(6), one Fe(9), two equivalent Fe(5), and two equivalent Fe(8) atoms to form distorted FeFe7W5 cuboctahedra that share edges with two equivalent N(3)FeW5 octahedra, edges with four equivalent N(2)Fe2W4 octahedra, faces with two equivalent Fe(3)Fe9W3 cuboctahedra, and faces with four equivalent Fe(2)Fe8W4 cuboctahedra. The Fe(1)-Fe(12) bond length is 2.69 Å. The Fe(1)-Fe(6) bond length is 2.35 Å. The Fe(1)-Fe(9) bond length is 2.33 Å. Both Fe(1)-Fe(5) bond lengths are 2.31 Å. Both Fe(1)-Fe(8) bond lengths are 2.37 Å. In the second Fe site, Fe(2) is bonded to one W(1), one W(2), one W(3), one W(5), one Fe(10), one Fe(11), one Fe(4), one Fe(5), one Fe(6), one Fe(7), one Fe(8), and one Fe(9) atom to form distorted FeFe8W4 cuboctahedra that share edges with two equivalent N(2)Fe2W4 octahedra, edges with two equivalent N(1)Fe3W3 octahedra, edges with two equivalent N(3)FeW5 octahedra, faces with two equivalent Fe(1)Fe7W5 cuboctahedra, faces with two equivalent Fe(2)Fe8W4 cuboctahedra, and faces with two equivalent Fe(3)Fe9W3 cuboctahedra. The Fe(2)-Fe(10) bond length is 2.72 Å. The Fe(2)-Fe(11) bond length is 2.72 Å. The Fe(2)-Fe(4) bond length is 2.30 Å. The Fe(2)-Fe(5) bond length is 2.34 Å. The Fe(2)-Fe(6) bond length is 2.36 Å. The Fe(2)-Fe(7) bond length is 2.38 Å. The Fe(2)-Fe(8) bond length is 2.36 Å. The Fe(2)-Fe(9) bond length is 2.34 Å. In the third Fe site, Fe(3) is bonded to one W(4), two equivalent W(3), one Fe(12), one Fe(4), one Fe(7), two equivalent Fe(11), two equivalent Fe(5), and two equivalent Fe(8) atoms to form distorted FeFe9W3 cuboctahedra that share edges with two equivalent N(1)Fe3W3 octahedra, edges with four equivalent N(2)Fe2W4 octahedra, faces with two equivalent Fe(1)Fe7W5 cuboctahedra, and faces with four equivalent Fe(2)Fe8W4 cuboctahedra. The Fe(3)-Fe(12) bond length is 2.72 Å. The Fe(3)-Fe(4) bond length is 2.29 Å. The Fe(3)-Fe(7) bond length is 2.37 Å. Both Fe(3)-Fe(11) bond lengths are 2.71 Å. Both Fe(3)-Fe(5) bond lengths are 2.32 Å. Both Fe(3)-Fe(8) bond lengths are 2.33 Å. In the fourth Fe site, Fe(4) is bonded in a 12-coordinate geometry to one W(4), two equivalent W(5), one Fe(10), one Fe(3), one Fe(6), two equivalent Fe(11), two equivalent Fe(2), and two equivalent Fe(5) atoms. The Fe(4)-Fe(10) bond length is 2.78 Å. The Fe(4)-Fe(6) bond length is 2.49 Å. Both Fe(4)-Fe(11) bond lengths are 2.72 Å. Both Fe(4)-Fe(5) bond lengths are 2.43 Å. In the fifth Fe site, Fe(5) is bonded in a 12-coordinate geometry to one W(1), one W(2), one W(3), one W(5), one Fe(1), one Fe(11), one Fe(12), one Fe(2), one Fe(3), one Fe(4), one Fe(5), and one Fe(6) atom. The Fe(5)-Fe(11) bond length is 2.70 Å. The Fe(5)-Fe(12) bond length is 2.70 Å. The Fe(5)-Fe(5) bond length is 2.47 Å. The Fe(5)-Fe(6) bond length is 2.52 Å. In the sixth Fe site, Fe(6) is bonded in a 12-coordinate geometry to one W(4), two equivalent W(1), two equivalent W(3), one Fe(1), one Fe(10), one Fe(4), two equivalent Fe(2), and two equivalent Fe(5) atoms. The Fe(6)-Fe(10) bond length is 2.71 Å. In the seventh Fe site, Fe(7) is bonded in a 12-coordinate geometry to one W(2), two equivalent W(1), two equivalent W(3), one Fe(12), one Fe(3), one Fe(9), two equivalent Fe(2), and two equivalent Fe(8) atoms. The Fe(7)-Fe(12) bond length is 2.65 Å. The Fe(7)-Fe(9) bond length is 2.47 Å. Both Fe(7)-Fe(8) bond lengths are 2.43 Å. In the eighth Fe site, Fe(8) is bonded in a 12-coordinate geometry to one W(1), one W(3), one W(4), one W(5), one Fe(1), one Fe(10), one Fe(11), one Fe(2), one Fe(3), one Fe(7), one Fe(8), and one Fe(9) atom. The Fe(8)-Fe(10) bond length is 2.64 Å. The Fe(8)-Fe(11) bond length is 2.65 Å. The Fe(8)-Fe(8) bond length is 2.44 Å. The Fe(8)-Fe(9) bond length is 2.48 Å. In the ninth Fe site, Fe(9) is bonded in a 12-coordinate geometry to one W(2), two equivalent W(5), one Fe(1), one Fe(12), one Fe(7), two equivalent Fe(11), two equivalent Fe(2), and two equivalent Fe(8) atoms. The Fe(9)-Fe(12) bond length is 2.62 Å. Both Fe(9)-Fe(11) bond lengths are 2.65 Å. In the tenth Fe site, Fe(10) is bonded in a distorted bent 120 degrees geometry to one Fe(4), one Fe(6), two equivalent Fe(2), two equivalent Fe(8), one N(1), and one N(3) atom. The Fe(10)-N(1) bond length is 1.98 Å. The Fe(10)-N(3) bond length is 2.08 Å. In the eleventh Fe site, Fe(11) is bonded in a distorted bent 120 degrees geometry to one Fe(2), one Fe(3), one Fe(4), one Fe(5), one Fe(8), one Fe(9), one N(1), and one N(2) atom. The Fe(11)-N(1) bond length is 2.02 Å. The Fe(11)-N(2) bond length is 2.07 Å. In the twelfth Fe site, Fe(12) is bonded in a distorted bent 120 degrees geometry to one Fe(1), one Fe(3), one Fe(7), one Fe(9), two equivalent Fe(5), and two equivalent N(2) atoms. Both Fe(12)-N(2) bond lengths are 2.06 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded to one W(2), two equivalent W(3), one Fe(10), and two equivalent Fe(11) atoms to form NFe3W3 octahedra that share corners with two equivalent N(3)FeW5 octahedra, corners with four equivalent N(2)Fe2W4 octahedra, edges with two equivalent Fe(3)Fe9W3 cuboctahedra, and edges with four equivalent Fe(2)Fe8W4 cuboctahedra. The corner-sharing octahedral tilt angles range from 44-49°. In the second N site, N(2) is bonded to one W(1), one W(3), one W(4), one W(5), one Fe(11), and one Fe(12) atom to form NFe2W4 octahedra that share corners with two equivalent N(2)Fe2W4 octahedra, corners with two equivalent N(1)Fe3W3 octahedra, corners with two equivalent N(3)FeW5 octahedra, edges with two equivalent Fe(1)Fe7W5 cuboctahedra, edges with two equivalent Fe(2)Fe8W4 cuboctahedra, and edges with two equivalent Fe(3)Fe9W3 cuboctahedra. The corner-sharing octahedral tilt angles range from 44-49°. In the third N site, N(3) is bonded to one W(2), two equivalent W(1), two equivalent W(5), and one Fe(10) atom to form NFeW5 octahedra that share corners with two equivalent N(1)Fe3W3 octahedra, corners with four equivalent N(2)Fe2W4 octahedra, edges with two equivalent Fe(1)Fe7W5 cuboctahedra, and edges with four equivalent Fe(2)Fe8W4 cuboctahedra. The corner-sharing octahedral tilt angles range from 44-47°.