LiCH3(N2O)3 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one N(3), one O(1), one O(2), and two equivalent O(3) atoms to form corner-sharing LiNO4 trigonal bipyramids. The Li(1)-N(3) bond length is 2.13 Å. The Li(1)-O(1) bond length is 2.05 Å. The Li(1)-O(2) bond length is 2.17 Å. There is one shorter (2.00 Å) and one longer (2.03 Å) Li(1)-O(3) bond length. C(1) is bonded in a trigonal planar geometry to one N(1), one N(4), and one N(5) atom. The C(1)-N(1) bond length is 1.36 Å. The C(1)-N(4) bond length is 1.35 Å. The C(1)-N(5) bond length is 1.36 Å. There are six inequivalent N sites. In the first N site, N(4) is bonded in a distorted water-like geometry to one C(1) and one N(3) atom. The N(4)-N(3) bond length is 1.35 Å. In the second N site, N(5) is bonded in a distorted trigonal planar geometry to one C(1), one N(6), and one H(2) atom. The N(5)-N(6) bond length is 1.32 Å. The N(5)-H(2) bond length is 1.73 Å. In the third N site, N(6) is bonded in a distorted trigonal planar geometry to one N(5), one O(1), and one O(2) atom. The N(6)-O(1) bond length is 1.26 Å. The N(6)-O(2) bond length is 1.27 Å. In the fourth N site, N(1) is bonded in a 3-coordinate geometry to one C(1), one N(2), and one H(1) atom. The N(1)-N(2) bond length is 1.35 Å. The N(1)-H(1) bond length is 1.05 Å. In the fifth N site, N(2) is bonded in a water-like geometry to one N(1) and one N(3) atom. The N(2)-N(3) bond length is 1.30 Å. In the sixth N site, N(3) is bonded in a trigonal planar geometry to one Li(1), one N(2), and one N(4) atom. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one N(5) and one O(3) atom. The H(2)-O(3) bond length is 1.00 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(3) atom. The H(3)-O(3) bond length is 0.98 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one N(6) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(1) and one N(6) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one H(2), and one H(3) atom to form distorted corner-sharing OLi2H2 tetrahedra. Linkers: 4 O=[N+]([O-])[N]c1nnn[nH]1. Metal clusters: 4 [Li]. The MOF has largest included sphere 1.67 A, density 1.90 g/cm3, surface area 3285.83 m2/g, accessible volume 0.06 cm3/g