Ca3B2N4 crystallizes in the orthorhombic Pnnm space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2), one N(4), two equivalent N(1), and two equivalent N(3) atoms to form face-sharing CaN6 octahedra. In the second Ca site, Ca(2) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form a mixture of distorted corner and face-sharing CaN6 octahedra. The corner-sharing octahedral tilt angles are 24°. In the third Ca site, Ca(3) is bonded in a 6-coordinate geometry to one N(2), one N(4), two equivalent N(1), and two equivalent N(3) atoms. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to two equivalent N(4) and four equivalent N(1) atoms. In the fifth Ca site, Ca(5) is bonded to two equivalent N(2) and four equivalent N(3) atoms to form a mixture of distorted corner and face-sharing CaN6 octahedra. The corner-sharing octahedral tilt angles are 24°. There are two inequivalent B sites. In the first B site, B(1) is bonded in a linear geometry to one N(1) and one N(3) atom. In the second B site, B(2) is bonded in a linear geometry to one N(2) and one N(4) atom. There are four inequivalent N sites. In the first N site, N(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(5), two equivalent Ca(3), and one B(1) atom. In the second N site, N(4) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(4), two equivalent Ca(3), and one B(2) atom. In the third N site, N(1) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), two equivalent Ca(3), and one B(1) atom. In the fourth N site, N(2) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), one Ca(5), two equivalent Ca(3), and one B(2) atom.
Ca3B2N4 crystallizes in the orthorhombic Pnnm space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2), one N(4), two equivalent N(1), and two equivalent N(3) atoms to form face-sharing CaN6 octahedra. The Ca(1)-N(2) bond length is 2.41 Å. The Ca(1)-N(4) bond length is 2.34 Å. Both Ca(1)-N(1) bond lengths are 2.41 Å. Both Ca(1)-N(3) bond lengths are 2.34 Å. In the second Ca site, Ca(2) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form a mixture of distorted corner and face-sharing CaN6 octahedra. The corner-sharing octahedral tilt angles are 24°. Both Ca(2)-N(2) bond lengths are 2.66 Å. All Ca(2)-N(1) bond lengths are 2.58 Å. In the third Ca site, Ca(3) is bonded in a 6-coordinate geometry to one N(2), one N(4), two equivalent N(1), and two equivalent N(3) atoms. The Ca(3)-N(2) bond length is 2.66 Å. The Ca(3)-N(4) bond length is 2.61 Å. There is one shorter (2.54 Å) and one longer (2.77 Å) Ca(3)-N(1) bond length. There is one shorter (2.42 Å) and one longer (2.66 Å) Ca(3)-N(3) bond length. In the fourth Ca site, Ca(4) is bonded in a 6-coordinate geometry to two equivalent N(4) and four equivalent N(1) atoms. Both Ca(4)-N(4) bond lengths are 2.43 Å. All Ca(4)-N(1) bond lengths are 2.73 Å. In the fifth Ca site, Ca(5) is bonded to two equivalent N(2) and four equivalent N(3) atoms to form a mixture of distorted corner and face-sharing CaN6 octahedra. The corner-sharing octahedral tilt angles are 24°. Both Ca(5)-N(2) bond lengths are 2.70 Å. All Ca(5)-N(3) bond lengths are 2.62 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a linear geometry to one N(1) and one N(3) atom. The B(1)-N(1) bond length is 1.35 Å. The B(1)-N(3) bond length is 1.34 Å. In the second B site, B(2) is bonded in a linear geometry to one N(2) and one N(4) atom. The B(2)-N(2) bond length is 1.35 Å. The B(2)-N(4) bond length is 1.34 Å. There are four inequivalent N sites. In the first N site, N(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(5), two equivalent Ca(3), and one B(1) atom. In the second N site, N(4) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(4), two equivalent Ca(3), and one B(2) atom. In the third N site, N(1) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), one Ca(4), two equivalent Ca(3), and one B(1) atom. In the fourth N site, N(2) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), one Ca(5), two equivalent Ca(3), and one B(2) atom.