Ni3C10P4H22(N2O9)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(6) atoms. Both Ni(1)-O(1) bond lengths are 1.86 Å. Both Ni(1)-O(6) bond lengths are 1.88 Å. In the second Ni site, Ni(2) is bonded to one O(4), one O(7), one O(8), one O(9), and two equivalent O(3) atoms to form NiO6 octahedra that share  a cornercorner with one C(5)P2CO tetrahedra, corners with two equivalent P(1)CO3 tetrahedra, corners with two equivalent P(2)CO3 tetrahedra, and  an edgeedge with one Ni(2)O6 octahedra. The Ni(2)-O(4) bond length is 2.03 Å. The Ni(2)-O(7) bond length is 2.23 Å. The Ni(2)-O(8) bond length is 2.05 Å. The Ni(2)-O(9) bond length is 2.06 Å. There is one shorter (2.04 Å) and one longer (2.09 Å) Ni(2)-O(3) bond length. There are five inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(7) atom. The C(1)-N(1) bond length is 1.34 Å. The C(1)-N(2) bond length is 1.34 Å. The C(1)-H(7) bond length is 1.08 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(3), one N(2), and one H(8) atom. The C(2)-C(3) bond length is 1.37 Å. The C(2)-N(2) bond length is 1.38 Å. The C(2)-H(8) bond length is 1.08 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(1), and one H(9) atom. The C(3)-N(1) bond length is 1.39 Å. The C(3)-H(9) bond length is 1.08 Å. In the fourth C site, C(4) is bonded in a distorted trigonal non-coplanar geometry to one C(5), one N(1), one H(10), and one H(11) atom. The C(4)-C(5) bond length is 1.53 Å. The C(4)-N(1) bond length is 1.46 Å. The C(4)-H(10) bond length is 1.10 Å. The C(4)-H(11) bond length is 1.10 Å. In the fifth C site, C(5) is bonded to one C(4), one P(1), one P(2), and one O(9) atom to form distorted CP2CO tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles are 74°. The C(5)-P(1) bond length is 1.88 Å. The C(5)-P(2) bond length is 1.87 Å. The C(5)-O(9) bond length is 1.45 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one C(5), one O(1), one O(3), and one O(5) atom to form distorted PCO3 tetrahedra that share corners with two equivalent Ni(2)O6 octahedra and  a cornercorner with one P(2)CO3 tetrahedra. The corner-sharing octahedral tilt angles range from 23-68°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.49 Å. In the second P site, P(2) is bonded to one C(5), one O(6), one O(7), and one O(8) atom to form PCO3 tetrahedra that share corners with two equivalent Ni(2)O6 octahedra and  a cornercorner with one P(1)CO3 tetrahedra. The corner-sharing octahedral tilt angles range from 55-69°. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.54 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(4) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one C(1), one C(2), and one H(6) atom. The N(2)-H(6) bond length is 1.05 Å. There are eleven inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(2) and one O(8) atom. The H(1)-O(2) bond length is 1.00 Å. The H(1)-O(8) bond length is 1.75 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(2) atom. The H(2)-O(2) bond length is 0.98 Å. In the third H site, H(3) is bonded in a distorted single-bond geometry to one O(4) atom. The H(3)-O(4) bond length is 1.00 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(4) atom. The H(4)-O(4) bond length is 0.99 Å. In the fifth H site, H(5) is bonded in a distorted linear geometry to one O(7) and one O(9) atom. The H(5)-O(7) bond length is 1.53 Å. The H(5)-O(9) bond length is 1.03 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one N(2) and one O(1) atom. The H(6)-O(1) bond length is 1.73 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(1) 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(4) atom. In the eleventh H site, H(11) 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 3-coordinate geometry to one Ni(1), one P(1), and one H(6) atom. In the second O site, O(2) is bonded in a water-like geometry to one H(1) and one H(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Ni(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Ni(2), one H(3), and one H(4) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ni(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Ni(2), one P(2), and one H(5) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Ni(2), one P(2), and one H(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Ni(2), one C(5), and one H(5) atom. Linkers: 2 [O]P([O])(=O)C(O)(CN1[CH]NC=C1)P([O])([O])=O. Metal clusters: 3 [Ni]. The MOF has largest included sphere 2.75 A, density 2.18 g/cm3, surface area 2882.90 m2/g, accessible volume 0.09 cm3/g