Zr(MnN)4 crystallizes in the triclinic P-1 space group. Zr(1) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(4), and two equivalent N(2) atoms. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form a mixture of distorted edge and corner-sharing MnN4 trigonal pyramids. In the second Mn site, Mn(2) is bonded in a distorted T-shaped geometry to one N(3) and two equivalent N(2) atoms. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to one N(3), one N(4), and two equivalent N(1) atoms. In the fourth Mn site, Mn(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form MnN5 square pyramids that share corners with three equivalent Mn(1)N4 trigonal pyramids, edges with two equivalent Mn(4)N5 square pyramids, and  an edgeedge with one Mn(1)N4 trigonal pyramid. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Zr(1), one Mn(1), two equivalent Mn(3), and two equivalent Mn(4) atoms to form NZrMn5 octahedra that share corners with two equivalent N(3)ZrMn4 square pyramids,  a cornercorner with one N(2)Zr2Mn3 trigonal bipyramid, edges with two equivalent N(1)ZrMn5 octahedra, edges with two equivalent N(3)ZrMn4 square pyramids, and  an edgeedge with one N(2)Zr2Mn3 trigonal bipyramid. In the second N site, N(2) is bonded to two equivalent Zr(1), one Mn(1), and two equivalent Mn(2) atoms to form NZr2Mn3 trigonal bipyramids that share  a cornercorner with one N(1)ZrMn5 octahedra, corners with three equivalent N(3)ZrMn4 square pyramids,  an edgeedge with one N(1)ZrMn5 octahedra,  an edgeedge with one N(3)ZrMn4 square pyramid, and edges with two equivalent N(2)Zr2Mn3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. In the third N site, N(3) is bonded to one Zr(1), one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom to form distorted NZrMn4 square pyramids that share corners with two equivalent N(1)ZrMn5 octahedra, corners with three equivalent N(2)Zr2Mn3 trigonal bipyramids, edges with two equivalent N(1)ZrMn5 octahedra, and  an edgeedge with one N(2)Zr2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-17°. In the fourth N site, N(4) is bonded in a 5-coordinate geometry to one Zr(1), one Mn(1), one Mn(3), and two equivalent Mn(4) atoms.
Zr(MnN)4 crystallizes in the triclinic P-1 space group. Zr(1) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(4), and two equivalent N(2) atoms. The Zr(1)-N(1) bond length is 2.27 Å. The Zr(1)-N(3) bond length is 2.24 Å. The Zr(1)-N(4) bond length is 2.21 Å. There is one shorter (2.20 Å) and one longer (2.26 Å) Zr(1)-N(2) bond length. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form a mixture of distorted edge and corner-sharing MnN4 trigonal pyramids. The Mn(1)-N(1) bond length is 1.97 Å. The Mn(1)-N(2) bond length is 1.97 Å. The Mn(1)-N(3) bond length is 1.92 Å. The Mn(1)-N(4) bond length is 1.90 Å. In the second Mn site, Mn(2) is bonded in a distorted T-shaped geometry to one N(3) and two equivalent N(2) atoms. The Mn(2)-N(3) bond length is 1.90 Å. There is one shorter (1.86 Å) and one longer (1.89 Å) Mn(2)-N(2) bond length. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to one N(3), one N(4), and two equivalent N(1) atoms. The Mn(3)-N(3) bond length is 2.04 Å. The Mn(3)-N(4) bond length is 2.01 Å. There is one shorter (2.05 Å) and one longer (2.11 Å) Mn(3)-N(1) bond length. In the fourth Mn site, Mn(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form MnN5 square pyramids that share corners with three equivalent Mn(1)N4 trigonal pyramids, edges with two equivalent Mn(4)N5 square pyramids, and  an edgeedge with one Mn(1)N4 trigonal pyramid. The Mn(4)-N(3) bond length is 2.06 Å. There is one shorter (2.06 Å) and one longer (2.11 Å) Mn(4)-N(1) bond length. There is one shorter (2.01 Å) and one longer (2.12 Å) Mn(4)-N(4) bond length. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Zr(1), one Mn(1), two equivalent Mn(3), and two equivalent Mn(4) atoms to form NZrMn5 octahedra that share corners with two equivalent N(3)ZrMn4 square pyramids,  a cornercorner with one N(2)Zr2Mn3 trigonal bipyramid, edges with two equivalent N(1)ZrMn5 octahedra, edges with two equivalent N(3)ZrMn4 square pyramids, and  an edgeedge with one N(2)Zr2Mn3 trigonal bipyramid. In the second N site, N(2) is bonded to two equivalent Zr(1), one Mn(1), and two equivalent Mn(2) atoms to form NZr2Mn3 trigonal bipyramids that share  a cornercorner with one N(1)ZrMn5 octahedra, corners with three equivalent N(3)ZrMn4 square pyramids,  an edgeedge with one N(1)ZrMn5 octahedra,  an edgeedge with one N(3)ZrMn4 square pyramid, and edges with two equivalent N(2)Zr2Mn3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. In the third N site, N(3) is bonded to one Zr(1), one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom to form distorted NZrMn4 square pyramids that share corners with two equivalent N(1)ZrMn5 octahedra, corners with three equivalent N(2)Zr2Mn3 trigonal bipyramids, edges with two equivalent N(1)ZrMn5 octahedra, and  an edgeedge with one N(2)Zr2Mn3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-17°. In the fourth N site, N(4) is bonded in a 5-coordinate geometry to one Zr(1), one Mn(1), one Mn(3), and two equivalent Mn(4) atoms.