Ba3(GeN)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 5-coordinate geometry to one Ge(2), two equivalent N(2), and three equivalent N(1) atoms. In the second Ba site, Ba(2) is bonded in a 2-coordinate geometry to three equivalent Ge(2) and two equivalent N(1) atoms. In the third Ba site, Ba(3) is bonded in a 3-coordinate geometry to three equivalent Ge(2) and three equivalent N(2) atoms. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a water-like geometry to one N(1) and one N(2) atom. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to one Ba(1), three equivalent Ba(2), three equivalent Ba(3), and two equivalent Ge(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Ba(2), three equivalent Ba(1), and one Ge(1) atom to form a mixture of distorted corner, face, and edge-sharing NBa5Ge octahedra. The corner-sharing octahedral tilt angles range from 44-60°. In the second N site, N(2) is bonded to two equivalent Ba(1), three equivalent Ba(3), and one Ge(1) atom to form a mixture of distorted corner, face, and edge-sharing NBa5Ge octahedra. The corner-sharing octahedral tilt angles range from 44-60°.
Ba3(GeN)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 5-coordinate geometry to one Ge(2), two equivalent N(2), and three equivalent N(1) atoms. The Ba(1)-Ge(2) bond length is 3.72 Å. Both Ba(1)-N(2) bond lengths are 2.93 Å. There is one shorter (2.75 Å) and two longer (2.91 Å) Ba(1)-N(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 2-coordinate geometry to three equivalent Ge(2) and two equivalent N(1) atoms. There are two shorter (3.59 Å) and one longer (3.84 Å) Ba(2)-Ge(2) bond length. Both Ba(2)-N(1) bond lengths are 2.82 Å. In the third Ba site, Ba(3) is bonded in a 3-coordinate geometry to three equivalent Ge(2) and three equivalent N(2) atoms. There are two shorter (3.58 Å) and one longer (3.79 Å) Ba(3)-Ge(2) bond length. There is one shorter (2.69 Å) and two longer (2.82 Å) Ba(3)-N(2) bond lengths. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a water-like geometry to one N(1) and one N(2) atom. The Ge(1)-N(1) bond length is 1.88 Å. The Ge(1)-N(2) bond length is 1.88 Å. In the second Ge site, Ge(2) is bonded in a 9-coordinate geometry to one Ba(1), three equivalent Ba(2), three equivalent Ba(3), and two equivalent Ge(2) atoms. Both Ge(2)-Ge(2) bond lengths are 2.51 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Ba(2), three equivalent Ba(1), and one Ge(1) atom to form a mixture of distorted corner, face, and edge-sharing NBa5Ge octahedra. The corner-sharing octahedral tilt angles range from 44-60°. In the second N site, N(2) is bonded to two equivalent Ba(1), three equivalent Ba(3), and one Ge(1) atom to form a mixture of distorted corner, face, and edge-sharing NBa5Ge octahedra. The corner-sharing octahedral tilt angles range from 44-60°.