V9Si4C6H12(N2O9)2(CH2)2 crystallizes in the tetragonal P-42_1c space group. The structure consists of eight 02329_fluka molecules inside a V9Si4C6H12(N2O9)2 framework. In the V9Si4C6H12(N2O9)2 framework, there are five inequivalent V sites. In the first V site, V(1) is bonded in a distorted see-saw-like geometry to one O(1), one O(6), one O(7), and one O(8) atom. The V(1)-O(1) bond length is 1.89 Å. The V(1)-O(6) bond length is 1.97 Å. The V(1)-O(7) bond length is 2.03 Å. The V(1)-O(8) bond length is 1.93 Å. In the second V site, V(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(8) atom. The V(2)-O(1) bond length is 1.95 Å. The V(2)-O(4) bond length is 1.98 Å. The V(2)-O(5) bond length is 2.00 Å. The V(2)-O(8) bond length is 1.95 Å. In the third V site, V(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(8) atom. The V(3)-O(1) bond length is 1.97 Å. The V(3)-O(4) bond length is 2.01 Å. The V(3)-O(5) bond length is 2.02 Å. The V(3)-O(8) bond length is 1.89 Å. In the fourth V site, V(4) is bonded in a distorted see-saw-like geometry to one N(1), one N(2), one O(3), and one O(9) atom. The V(4)-N(1) bond length is 2.16 Å. The V(4)-N(2) bond length is 2.22 Å. The V(4)-O(3) bond length is 1.87 Å. The V(4)-O(9) bond length is 1.81 Å. In the fifth V site, V(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(6) and two equivalent O(7) atoms. Both V(5)-O(6) bond lengths are 2.01 Å. Both V(5)-O(7) bond lengths are 1.95 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form corner-sharing SiO4 tetrahedra. The Si(1)-O(2) bond length is 1.66 Å. The Si(1)-O(3) bond length is 1.55 Å. The Si(1)-O(5) bond length is 1.61 Å. The Si(1)-O(7) bond length is 1.67 Å. In the second Si site, Si(2) is bonded to one O(2), one O(4), one O(6), and one O(9) atom to form corner-sharing SiO4 tetrahedra. The Si(2)-O(2) bond length is 1.61 Å. The Si(2)-O(4) bond length is 1.65 Å. The Si(2)-O(6) bond length is 1.65 Å. The Si(2)-O(9) bond length is 1.61 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a 3-coordinate geometry to one N(1) and two equivalent H(1,2) atoms. The C(1)-N(1) bond length is 1.49 Å. Both C(1)-H(1,2) bond lengths are 0.97 Å. In the second C site, C(3) is bonded in a distorted water-like geometry to one C(4), one H(5), and one H(6) atom. The C(3)-C(4) bond length is 1.27 Å. The C(3)-H(5) bond length is 0.97 Å. The C(3)-H(6) bond length is 0.97 Å. In the third C site, C(4) is bonded in a 4-coordinate geometry to one C(3), one N(2), one H(7), and one H(8) atom. The C(4)-N(2) bond length is 1.41 Å. The C(4)-H(7) bond length is 0.96 Å. The C(4)-H(8) bond length is 0.97 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one V(4) and one C(1) atom. In the second N site, N(2) is bonded in a distorted bent 120 degrees geometry to one V(4) and one C(4) atom. There are five inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(5) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(6) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(7) is bonded in a single-bond geometry to one C(4) atom. In the fifth H site, H(8) is bonded in a single-bond geometry to one C(4) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(4) and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one Si(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one Si(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(5), and one Si(1) atom. In the eighth O site, O(8) is bonded in a T-shaped geometry to one V(1), one V(2), and one V(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(4) and one Si(2) atom. Linkers: 8 [O][Si]([O])([O])O[Si]([O])([O])[O] ,8 [N]CCCC[N]. Metal clusters: 36 [V]. The MOF has largest included sphere 6.91 A, density 1.43 g/cm3, surface area 2572.57 m2/g, accessible volume 0.29 cm3/g