Mn12Rh4N crystallizes in the monoclinic P2/m space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted single-bond geometry to two equivalent Rh(1), two equivalent Rh(2), and one N(1) atom. In the second Mn site, Mn(2) is bonded to two equivalent Mn(4), six equivalent Mn(3), two equivalent Rh(1), and two equivalent Rh(2) atoms to form distorted MnMn8Rh4 cuboctahedra that share corners with two equivalent Mn(2)Mn8Rh4 cuboctahedra, corners with four equivalent Rh(2)Mn12 cuboctahedra, corners with two equivalent N(1)Mn6 octahedra, edges with two equivalent Rh(1)Mn12 cuboctahedra, edges with four equivalent Rh(2)Mn12 cuboctahedra, faces with two equivalent Rh(1)Mn12 cuboctahedra, faces with two equivalent Rh(2)Mn12 cuboctahedra, and faces with four equivalent Mn(2)Mn8Rh4 cuboctahedra. The corner-sharing octahedral tilt angles are 46°. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to three equivalent Mn(2), one Rh(1), and three equivalent Rh(2) atoms. In the fourth Mn site, Mn(4) is bonded in a distorted single-bond geometry to one Mn(2), one Rh(2), three equivalent Rh(1), and one N(1) atom. There are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to two equivalent Mn(1), two equivalent Mn(2), two equivalent Mn(3), and six equivalent Mn(4) atoms to form RhMn12 cuboctahedra that share corners with two equivalent Rh(1)Mn12 cuboctahedra, corners with four equivalent Rh(2)Mn12 cuboctahedra, corners with two equivalent N(1)Mn6 octahedra, edges with two equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with two equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with four equivalent Rh(1)Mn12 cuboctahedra, faces with four equivalent Rh(2)Mn12 cuboctahedra, and faces with two equivalent N(1)Mn6 octahedra. The corner-sharing octahedral tilt angles are 19°. In the second Rh site, Rh(2) is bonded to two equivalent Mn(1), two equivalent Mn(2), two equivalent Mn(4), and six equivalent Mn(3) atoms to form RhMn12 cuboctahedra that share corners with two equivalent Rh(2)Mn12 cuboctahedra, corners with four equivalent Mn(2)Mn8Rh4 cuboctahedra, corners with four equivalent Rh(1)Mn12 cuboctahedra,  a cornercorner with one N(1)Mn6 octahedra, edges with four equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with two equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with four equivalent Rh(1)Mn12 cuboctahedra, faces with four equivalent Rh(2)Mn12 cuboctahedra, and  a faceface with one N(1)Mn6 octahedra. The corner-sharing octahedral tilt angles are 18°. N(1) is bonded to two equivalent Mn(1) and four equivalent Mn(4) atoms to form NMn6 octahedra that share corners with two equivalent Rh(2)Mn12 cuboctahedra, corners with four equivalent Mn(2)Mn8Rh4 cuboctahedra, corners with four equivalent Rh(1)Mn12 cuboctahedra, faces with two equivalent Rh(2)Mn12 cuboctahedra, and faces with four equivalent Rh(1)Mn12 cuboctahedra.
Mn12Rh4N crystallizes in the monoclinic P2/m space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted single-bond geometry to two equivalent Rh(1), two equivalent Rh(2), and one N(1) atom. Both Mn(1)-Rh(1) bond lengths are 2.61 Å. There is one shorter (2.52 Å) and one longer (2.60 Å) Mn(1)-Rh(2) bond length. The Mn(1)-N(1) bond length is 1.88 Å. In the second Mn site, Mn(2) is bonded to two equivalent Mn(4), six equivalent Mn(3), two equivalent Rh(1), and two equivalent Rh(2) atoms to form distorted MnMn8Rh4 cuboctahedra that share corners with two equivalent Mn(2)Mn8Rh4 cuboctahedra, corners with four equivalent Rh(2)Mn12 cuboctahedra, corners with two equivalent N(1)Mn6 octahedra, edges with two equivalent Rh(1)Mn12 cuboctahedra, edges with four equivalent Rh(2)Mn12 cuboctahedra, faces with two equivalent Rh(1)Mn12 cuboctahedra, faces with two equivalent Rh(2)Mn12 cuboctahedra, and faces with four equivalent Mn(2)Mn8Rh4 cuboctahedra. The corner-sharing octahedral tilt angles are 46°. Both Mn(2)-Mn(4) bond lengths are 2.63 Å. There are a spread of Mn(2)-Mn(3) bond distances ranging from 2.46-2.51 Å. There is one shorter (2.56 Å) and one longer (2.58 Å) Mn(2)-Rh(1) bond length. Both Mn(2)-Rh(2) bond lengths are 2.61 Å. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to three equivalent Mn(2), one Rh(1), and three equivalent Rh(2) atoms. The Mn(3)-Rh(1) bond length is 2.57 Å. There are a spread of Mn(3)-Rh(2) bond distances ranging from 2.58-2.60 Å. In the fourth Mn site, Mn(4) is bonded in a distorted single-bond geometry to one Mn(2), one Rh(2), three equivalent Rh(1), and one N(1) atom. The Mn(4)-Rh(2) bond length is 2.64 Å. There are a spread of Mn(4)-Rh(1) bond distances ranging from 2.51-2.66 Å. The Mn(4)-N(1) bond length is 1.90 Å. There are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to two equivalent Mn(1), two equivalent Mn(2), two equivalent Mn(3), and six equivalent Mn(4) atoms to form RhMn12 cuboctahedra that share corners with two equivalent Rh(1)Mn12 cuboctahedra, corners with four equivalent Rh(2)Mn12 cuboctahedra, corners with two equivalent N(1)Mn6 octahedra, edges with two equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with two equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with four equivalent Rh(1)Mn12 cuboctahedra, faces with four equivalent Rh(2)Mn12 cuboctahedra, and faces with two equivalent N(1)Mn6 octahedra. The corner-sharing octahedral tilt angles are 19°. In the second Rh site, Rh(2) is bonded to two equivalent Mn(1), two equivalent Mn(2), two equivalent Mn(4), and six equivalent Mn(3) atoms to form RhMn12 cuboctahedra that share corners with two equivalent Rh(2)Mn12 cuboctahedra, corners with four equivalent Mn(2)Mn8Rh4 cuboctahedra, corners with four equivalent Rh(1)Mn12 cuboctahedra,  a cornercorner with one N(1)Mn6 octahedra, edges with four equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with two equivalent Mn(2)Mn8Rh4 cuboctahedra, faces with four equivalent Rh(1)Mn12 cuboctahedra, faces with four equivalent Rh(2)Mn12 cuboctahedra, and  a faceface with one N(1)Mn6 octahedra. The corner-sharing octahedral tilt angles are 18°. N(1) is bonded to two equivalent Mn(1) and four equivalent Mn(4) atoms to form NMn6 octahedra that share corners with two equivalent Rh(2)Mn12 cuboctahedra, corners with four equivalent Mn(2)Mn8Rh4 cuboctahedra, corners with four equivalent Rh(1)Mn12 cuboctahedra, faces with two equivalent Rh(2)Mn12 cuboctahedra, and faces with four equivalent Rh(1)Mn12 cuboctahedra.