V4NiC12H32(NO2)6 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(1)N4O2 octahedra and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 14°. The V(1)-O(1) bond length is 1.65 Å. The V(1)-O(2) bond length is 1.67 Å. The V(1)-O(4) bond length is 1.80 Å. The V(1)-O(5) bond length is 1.80 Å. In the second V site, V(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form corner-sharing VO4 tetrahedra. The V(2)-O(3) bond length is 1.67 Å. The V(2)-O(4) bond length is 1.82 Å. The V(2)-O(5) bond length is 1.81 Å. The V(2)-O(6) bond length is 1.64 Å. Ni(1) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent O(1) atoms to form NiN4O2 octahedra that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent C(6)H2CN tetrahedra. Both Ni(1)-N(1) bond lengths are 2.15 Å. Both Ni(1)-N(2) bond lengths are 1.98 Å. Both Ni(1)-O(1) bond lengths are 2.22 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal non-coplanar geometry to one N(1), one H(5), and one H(6) atom. The C(1)-N(1) bond length is 1.49 Å. The C(1)-H(5) bond length is 1.10 Å. The C(1)-H(6) bond length is 1.09 Å. In the second C site, C(2) is bonded in a 3-coordinate geometry to one C(6), one N(2), one H(7), and one H(8) atom. The C(2)-C(6) bond length is 1.51 Å. The C(2)-N(2) bond length is 1.48 Å. The C(2)-H(7) bond length is 1.10 Å. The C(2)-H(8) bond length is 1.10 Å. In the third C site, C(3) is bonded in a distorted trigonal non-coplanar geometry to one N(3), one H(10), and one H(9) atom. The C(3)-N(3) bond length is 1.49 Å. The C(3)-H(10) bond length is 1.10 Å. The C(3)-H(9) bond length is 1.10 Å. In the fourth C site, C(4) is bonded in a distorted trigonal non-coplanar geometry to one N(1) and two equivalent H(11,12) atoms. The C(4)-N(1) bond length is 1.49 Å. There is one shorter (1.09 Å) and one longer (1.10 Å) C(4)-H(11,12) bond length. In the fifth C site, C(5) is bonded in a distorted trigonal non-coplanar geometry to one N(3), one H(13), and one H(14) atom. The C(5)-N(3) bond length is 1.49 Å. The C(5)-H(13) bond length is 1.10 Å. The C(5)-H(14) bond length is 1.09 Å. In the sixth C site, C(6) is bonded to one C(2), one N(1), one H(15), and one H(16) atom to form distorted CH2CN tetrahedra that share  a cornercorner with one Ni(1)N4O2 octahedra and  a cornercorner with one N(2)NiH2C tetrahedra. The corner-sharing octahedral tilt angles are 76°. The C(6)-N(1) bond length is 1.50 Å. The C(6)-H(15) bond length is 1.10 Å. The C(6)-H(16) bond length is 1.10 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded to one Ni(1), one C(1), one C(4), and one C(6) atom to form NNiC3 tetrahedra that share  a cornercorner with one N(1)NiC3 tetrahedra and corners with two equivalent N(2)NiH2C tetrahedra. In the second N site, N(2) is bonded to one Ni(1), one C(2), one H(1), and one H(2) atom to form distorted NNiH2C tetrahedra that share  a cornercorner with one C(6)H2CN tetrahedra,  a cornercorner with one N(2)NiH2C tetrahedra, and corners with two equivalent N(1)NiC3 tetrahedra. The N(2)-H(1) bond length is 1.03 Å. The N(2)-H(2) bond length is 1.03 Å. In the third N site, N(3) is bonded in a tetrahedral geometry to one C(3), one C(5), one H(3), and one H(4) atom. The N(3)-H(3) bond length is 1.07 Å. The N(3)-H(4) bond length is 1.06 Å. There are fifteen inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one N(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one N(2) atom. In the third H site, H(3) is bonded in a distorted linear geometry to one N(3) and one O(2) atom. The H(3)-O(2) bond length is 1.55 Å. In the fourth H site, H(4) is bonded in a distorted single-bond geometry to one N(3) and one O(3) atom. The H(4)-O(3) bond length is 1.67 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(1) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(1) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(2) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(2) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(3) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(3) atom. In the eleventh H site, H(11,12) is bonded in a single-bond geometry to one C(4) atom. In the twelfth H site, H(13) is bonded in a single-bond geometry to one C(5) atom. In the thirteenth H site, H(14) is bonded in a single-bond geometry to one C(5) atom. In the fourteenth H site, H(15) is bonded in a single-bond geometry to one C(6) atom. In the fifteenth H site, H(16) is bonded in a single-bond geometry to one C(6) atom. There are six inequivalent O sites. In the first O site, O(6) is bonded in a single-bond geometry to one V(2) atom. In the second O site, O(1) is bonded in a distorted linear geometry to one V(1) and one Ni(1) atom. In the third O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one H(3) atom. In the fourth O site, O(3) is bonded in a water-like geometry to one V(2) and one H(4) atom. In the fifth O site, O(4) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. Linkers: 2 NCCN1CC[NH2]CC1. Metal clusters: 8 [V] ,2 [Ni]. The MOF has largest included sphere 1.88 A, density 1.97 g/cm3, surface area 3342.49 m2/g, accessible volume 0.11 cm3/g