Li2BaC10H4(NO2)4 crystallizes in the orthorhombic P2_12_12 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one N(2), one O(1), and one O(4) atom. The Li(1)-N(2) bond length is 2.14 Å. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(4) bond length is 2.04 Å. In the second Li site, Li(2) is bonded in a trigonal pyramidal geometry to one O(2), one O(3), one O(5), and one O(8) atom. The Li(2)-O(2) bond length is 1.91 Å. The Li(2)-O(3) bond length is 1.90 Å. The Li(2)-O(5) bond length is 2.03 Å. The Li(2)-O(8) bond length is 1.94 Å. In the third Li site, Li(3) is bonded in a tetrahedral geometry to one O(11), one O(4), one O(6), and one O(9) atom. The Li(3)-O(11) bond length is 1.91 Å. The Li(3)-O(4) bond length is 1.93 Å. The Li(3)-O(6) bond length is 1.93 Å. The Li(3)-O(9) bond length is 1.96 Å. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one N(3), one O(1), one O(11), one O(12), one O(2), one O(5), one O(7), one O(9), and two equivalent O(10) atoms. The Ba(1)-N(3) bond length is 2.84 Å. The Ba(1)-O(1) bond length is 2.96 Å. The Ba(1)-O(11) bond length is 2.78 Å. The Ba(1)-O(12) bond length is 2.76 Å. The Ba(1)-O(2) bond length is 2.81 Å. The Ba(1)-O(5) bond length is 3.07 Å. The Ba(1)-O(7) bond length is 2.90 Å. The Ba(1)-O(9) bond length is 2.92 Å. There is one shorter (2.72 Å) and one longer (3.20 Å) Ba(1)-O(10) bond length. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent N(5), two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms. Both Ba(2)-N(5) bond lengths are 3.12 Å. Both Ba(2)-O(5) bond lengths are 2.82 Å. Both Ba(2)-O(8) bond lengths are 2.68 Å. Both Ba(2)-O(9) bond lengths are 2.68 Å. There are fifteen inequivalent C sites. In the first C site, C(1) is bonded in a bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.50 Å. The C(1)-O(1) bond length is 1.26 Å. The C(1)-O(2) bond length is 1.24 Å. In the second C site, C(2) is bonded in a 3-coordinate geometry to one C(1), one C(3), and one N(1) atom. The C(2)-C(3) bond length is 1.38 Å. The C(2)-N(1) bond length is 1.35 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one H(4) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-H(4) bond length is 0.95 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3), one C(5), and one N(2) atom. The C(4)-C(5) bond length is 1.50 Å. The C(4)-N(2) bond length is 1.34 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one C(4), one O(3), and one O(4) atom. The C(5)-O(3) bond length is 1.25 Å. The C(5)-O(4) bond length is 1.27 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(6)-O(5) bond length is 1.26 Å. The C(6)-O(6) bond length is 1.25 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one N(3) atom. The C(7)-N(3) bond length is 1.34 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(9) and one H(5) atom. The C(8)-C(9) bond length is 1.38 Å. The C(8)-H(5) bond length is 0.95 Å. In the ninth C site, C(9) is bonded in a distorted trigonal planar geometry to one C(10), one C(8), and one N(4) atom. The C(9)-C(10) bond length is 1.48 Å. The C(9)-N(4) bond length is 1.36 Å. In the tenth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one C(9), one O(7), and one O(8) atom. The C(10)-O(7) bond length is 1.24 Å. The C(10)-O(8) bond length is 1.27 Å. In the eleventh C site, C(11) is bonded in a bent 120 degrees geometry to one C(12), one O(10), and one O(9) atom. The C(11)-C(12) bond length is 1.48 Å. The C(11)-O(10) bond length is 1.23 Å. The C(11)-O(9) bond length is 1.27 Å. In the twelfth C site, C(12) is bonded in a distorted single-bond geometry to one C(11), one C(13), and one N(5) atom. The C(12)-C(13) bond length is 1.39 Å. The C(12)-N(5) bond length is 1.35 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one C(12), one C(14), and one H(6) atom. The C(13)-C(14) bond length is 1.37 Å. The C(13)-H(6) bond length is 0.95 Å. In the fourteenth C site, C(14) is bonded in a distorted trigonal planar geometry to one C(13), one C(15), and one N(6) atom. The C(14)-C(15) bond length is 1.48 Å. The C(14)-N(6) bond length is 1.36 Å. In the fifteenth C site, C(15) is bonded in a distorted bent 120 degrees geometry to one C(14), one O(11), and one O(12) atom. The C(15)-O(11) bond length is 1.26 Å. The C(15)-O(12) bond length is 1.24 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a 1-coordinate geometry to one C(2), one N(2), and one H(1) atom. The N(1)-N(2) bond length is 1.34 Å. The N(1)-H(1) bond length is 0.88 Å. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Li(1), one C(4), and one N(1) atom. In the third N site, N(3) is bonded in a distorted single-bond geometry to one Ba(1), one C(7), and one N(4) atom. The N(3)-N(4) bond length is 1.34 Å. In the fourth N site, N(4) is bonded in a 3-coordinate geometry to one C(9), one N(3), and one H(2) atom. The N(4)-H(2) bond length is 0.88 Å. In the fifth N site, N(5) is bonded in a 3-coordinate geometry to one Ba(2), one C(12), and one N(6) atom. The N(5)-N(6) bond length is 1.34 Å. In the sixth N site, N(6) is bonded in a distorted single-bond geometry to one C(14), one N(5), and one H(3) atom. The N(6)-H(3) bond length is 0.88 Å. There are six 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(4) atom. In the third H site, H(3) is bonded in a single-bond geometry to one N(6) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(3) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(8) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(13) atom. There are twelve inequivalent O sites. In the first O site, O(3) is bonded in a bent 150 degrees geometry to one Li(2) and one C(5) atom. In the second O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Li(3), and one C(5) atom. In the third O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Li(2), one Ba(1), one Ba(2), and one C(6) atom. In the fourth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(3) and one C(6) atom. In the fifth O site, O(7) is bonded in a distorted single-bond geometry to one Ba(1) and one C(10) atom. In the sixth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one Ba(2), and one C(10) atom. In the seventh O site, O(9) is bonded in a 2-coordinate geometry to one Li(3), one Ba(1), one Ba(2), and one C(11) atom. In the eighth O site, O(10) is bonded in a distorted single-bond geometry to two equivalent Ba(1) and one C(11) atom. In the ninth O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Li(3), one Ba(1), and one C(15) atom. In the tenth O site, O(12) is bonded in a distorted single-bond geometry to one Ba(1) and one C(15) atom. In the eleventh O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Li(1), one Ba(1), and one C(1) atom. In the twelfth O site, O(2) is bonded in a 2-coordinate geometry to one Li(2), one Ba(1), and one C(1) atom. Linkers: 12 [O]C(=O)c1cc(C([O])=O)[nH]n1. Metal clusters: 6 [Ba] ,12 [Li]. The MOF has largest included sphere 6.16 A, density 1.61 g/cm3, surface area 2834.08 m2/g, accessible volume 0.25 cm3/g