LiCN4H crystallizes in the orthorhombic C222_1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a tetrahedral geometry to two equivalent N(12) and two equivalent N(7) atoms. Both Li(1)-N(12) bond lengths are 2.05 Å. Both Li(1)-N(7) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded in a tetrahedral geometry to two equivalent N(13) and two equivalent N(5) atoms. Both Li(2)-N(13) bond lengths are 2.04 Å. Both Li(2)-N(5) bond lengths are 2.06 Å. In the third Li site, Li(3) is bonded in a tetrahedral geometry to two equivalent N(16) and two equivalent N(6) atoms. Both Li(3)-N(16) bond lengths are 2.04 Å. Both Li(3)-N(6) bond lengths are 2.04 Å. In the fourth Li site, Li(4) is bonded in a tetrahedral geometry to one N(11), one N(14), one N(4), and one N(8) atom. The Li(4)-N(11) bond length is 2.06 Å. The Li(4)-N(14) bond length is 2.04 Å. The Li(4)-N(4) bond length is 2.04 Å. The Li(4)-N(8) bond length is 2.05 Å. In the fifth Li site, Li(5) is bonded in a tetrahedral geometry to two equivalent N(1) and two equivalent N(3) atoms. Both Li(5)-N(1) bond lengths are 2.05 Å. Both Li(5)-N(3) bond lengths are 2.04 Å. In the sixth Li site, Li(6) is bonded in a tetrahedral geometry to one N(10), one N(15), one N(2), and one N(9) atom. The Li(6)-N(10) bond length is 2.05 Å. The Li(6)-N(15) bond length is 2.04 Å. The Li(6)-N(2) bond length is 2.05 Å. The Li(6)-N(9) bond length is 2.04 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(2), one N(5), and one H(2) atom. The C(1)-N(2) bond length is 1.34 Å. The C(1)-N(5) bond length is 1.34 Å. The C(1)-H(2) bond length is 1.08 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(10), one N(7), and one H(3) atom. The C(2)-N(10) bond length is 1.34 Å. The C(2)-N(7) bond length is 1.34 Å. The C(2)-H(3) bond length is 1.08 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(1), one N(11), and one H(1) atom. The C(3)-N(1) bond length is 1.34 Å. The C(3)-N(11) bond length is 1.34 Å. The C(3)-H(1) bond length is 1.08 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one N(16), one N(8), and one H(4) atom. The C(4)-N(16) bond length is 1.34 Å. The C(4)-N(8) bond length is 1.34 Å. The C(4)-H(4) bond length is 1.08 Å. There are sixteen inequivalent N sites. In the first N site, N(9) is bonded in a distorted trigonal planar geometry to one Li(6), one N(13), and one N(8) atom. The N(9)-N(13) bond length is 1.32 Å. The N(9)-N(8) bond length is 1.34 Å. In the second N site, N(10) is bonded in a distorted trigonal planar geometry to one Li(6), one C(2), and one N(14) atom. The N(10)-N(14) bond length is 1.34 Å. In the third N site, N(11) is bonded in a distorted trigonal planar geometry to one Li(4), one C(3), and one N(15) atom. The N(11)-N(15) bond length is 1.35 Å. In the fourth N site, N(12) is bonded in a distorted single-bond geometry to one Li(1), one N(1), and one N(15) atom. The N(12)-N(1) bond length is 1.34 Å. The N(12)-N(15) bond length is 1.32 Å. In the fifth N site, N(13) is bonded in a distorted trigonal planar geometry to one Li(2), one N(16), and one N(9) atom. The N(13)-N(16) bond length is 1.35 Å. In the sixth N site, N(14) is bonded in a distorted trigonal planar geometry to one Li(4), one N(10), and one N(3) atom. The N(14)-N(3) bond length is 1.32 Å. In the seventh N site, N(15) is bonded in a distorted trigonal planar geometry to one Li(6), one N(11), and one N(12) atom. In the eighth N site, N(16) is bonded in a distorted trigonal planar geometry to one Li(3), one C(4), and one N(13) atom. In the ninth N site, N(1) is bonded in a distorted bent 120 degrees geometry to one Li(5), one C(3), and one N(12) atom. In the tenth N site, N(2) is bonded in a distorted trigonal planar geometry to one Li(6), one C(1), and one N(4) atom. The N(2)-N(4) bond length is 1.35 Å. In the eleventh N site, N(3) is bonded in a distorted trigonal planar geometry to one Li(5), one N(14), and one N(7) atom. The N(3)-N(7) bond length is 1.35 Å. In the twelfth N site, N(4) is bonded in a distorted trigonal planar geometry to one Li(4), one N(2), and one N(6) atom. The N(4)-N(6) bond length is 1.32 Å. In the thirteenth N site, N(5) is bonded in a distorted trigonal planar geometry to one Li(2), one C(1), and one N(6) atom. The N(5)-N(6) bond length is 1.34 Å. In the fourteenth N site, N(6) is bonded in a distorted single-bond geometry to one Li(3), one N(4), and one N(5) atom. In the fifteenth N site, N(7) is bonded in a distorted trigonal planar geometry to one Li(1), one C(2), and one N(3) atom. In the sixteenth N site, N(8) is bonded in a distorted trigonal planar geometry to one Li(4), one C(4), and one N(9) atom. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(1) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(2) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. Linkers: 16 C1=NN=N[N]1. Metal clusters: 16 [Li]. The MOF has largest included sphere 3.09 A, density 1.48 g/cm3, surface area 4292.73 m2/g, accessible volume 0.16 cm3/g