Li5C20H20(N4O)4 crystallizes in the tetragonal I4_1/a space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal non-coplanar geometry to one N(1), one H(4), and one O(1) atom. The Li(1)-N(1) bond length is 2.06 Å. The Li(1)-H(4) bond length is 1.39 Å. The Li(1)-O(1) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a tetrahedral geometry to four equivalent O(1) atoms. All Li(2)-O(1) bond lengths are 1.93 Å. There are five inequivalent C sites. In the first C site, C(1) is bonded in a 4-coordinate geometry to one N(1), one N(2), one H(1), and one H(3) atom. The C(1)-N(1) bond length is 1.34 Å. The C(1)-N(2) bond length is 1.32 Å. The C(1)-H(1) bond length is 0.93 Å. The C(1)-H(3) bond length is 1.40 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(3), one N(2), and one N(3) atom. The C(2)-C(3) bond length is 1.38 Å. The C(2)-N(2) bond length is 1.36 Å. The C(2)-N(3) bond length is 1.37 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(2), one C(4), and one N(4) atom. The C(3)-C(4) bond length is 1.41 Å. The C(3)-N(4) bond length is 1.38 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(3), one N(1), and one O(1) atom. The C(4)-N(1) bond length is 1.37 Å. The C(4)-O(1) bond length is 1.26 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one N(3), one N(4), and one H(2) atom. The C(5)-N(3) bond length is 1.33 Å. The C(5)-N(4) bond length is 1.33 Å. The C(5)-H(2) bond length is 0.93 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a distorted single-bond geometry to one Li(1), one C(1), one C(4), and one H(3) atom. The N(1)-H(3) bond length is 0.88 Å. In the second N site, N(2) is bonded in a bent 120 degrees geometry to one C(1) and one C(2) atom. In the third N site, N(3) is bonded in a 3-coordinate geometry to one C(2), one C(5), and one H(4) atom. The N(3)-H(4) bond length is 0.96 Å. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one C(3), one C(5), and one H(5) atom. The N(4)-H(5) bond length is 0.92 Å. There are five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(5) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(1) and one N(1) atom. In the fourth H site, H(4) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one N(3) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one N(4) atom. O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one C(4) atom. Linkers: 15 O=c1[nH]cnc2c1N[CH]N2. Metal clusters: 20 [Li]. The MOF has largest included sphere 6.32 A, density 1.03 g/cm3, surface area 4603.49 m2/g, accessible volume 0.42 cm3/g