Ba3V2H4(C5O12)2 crystallizes in the monoclinic C2/c space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one O(10), one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), one O(9), and two equivalent O(12) atoms. The Ba(1)-O(10) bond length is 2.85 Å. The Ba(1)-O(2) bond length is 2.78 Å. The Ba(1)-O(3) bond length is 3.06 Å. The Ba(1)-O(4) bond length is 2.87 Å. The Ba(1)-O(5) bond length is 2.74 Å. The Ba(1)-O(6) bond length is 3.24 Å. The Ba(1)-O(7) bond length is 3.03 Å. The Ba(1)-O(9) bond length is 2.75 Å. There is one shorter (2.81 Å) and one longer (3.08 Å) Ba(1)-O(12) bond length. In the second Ba site, Ba(2) is bonded in a distorted q6 geometry to two equivalent O(1), two equivalent O(10), two equivalent O(11), two equivalent O(5), and two equivalent O(7) atoms. Both Ba(2)-O(1) bond lengths are 2.84 Å. Both Ba(2)-O(10) bond lengths are 3.06 Å. Both Ba(2)-O(11) bond lengths are 2.85 Å. Both Ba(2)-O(5) bond lengths are 2.72 Å. Both Ba(2)-O(7) bond lengths are 2.90 Å. V(1) is bonded in a distorted octahedral geometry to one O(1), one O(11), one O(3), one O(6), one O(8), and one O(9) atom. The V(1)-O(1) bond length is 2.01 Å. The V(1)-O(11) bond length is 1.62 Å. The V(1)-O(3) bond length is 2.18 Å. The V(1)-O(6) bond length is 1.98 Å. The V(1)-O(8) bond length is 2.02 Å. The V(1)-O(9) bond length is 2.01 Å. There are five inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The C(1)-O(1) bond length is 1.28 Å. The C(1)-O(2) bond length is 1.23 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. The C(2)-O(3) bond length is 1.27 Å. The C(2)-O(4) bond length is 1.23 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(3)-O(5) bond length is 1.23 Å. The C(3)-O(6) bond length is 1.29 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(7) and one O(8) atom. The C(4)-O(7) bond length is 1.23 Å. The C(4)-O(8) bond length is 1.27 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one O(10) and one O(9) atom. The C(5)-O(10) bond length is 1.23 Å. The C(5)-O(9) bond length is 1.28 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(12) atom. The H(1)-O(12) bond length is 0.81 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(12) atom. The H(2)-O(12) bond length is 0.75 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Ba(2), one V(1), and one C(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ba(1) and one C(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Ba(1), one V(1), and one C(2) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Ba(1) and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one C(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Ba(1), one V(1), and one C(3) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one C(4) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(1) and one C(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Ba(1), one V(1), and one C(5) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one Ba(1), one Ba(2), and one C(5) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one Ba(2) and one V(1) atom. In the twelfth O site, O(12) is bonded in a water-like geometry to two equivalent Ba(1), one H(1), and one H(2) atom. Linkers: 20 [O]C(=O)C([O])=O. Metal clusters: 12 [Ba] ,8 [V]. The MOF has largest included sphere 4.26 A, density 2.43 g/cm3, surface area 2003.17 m2/g, accessible volume 0.14 cm3/g