Ni2C18PH19(NO4)2 crystallizes in the triclinic P1 space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one N(3), one O(11), one O(12), one O(13), one O(3), and one O(8) atom to form NiNO5 octahedra that share  a cornercorner with one P(2)CO3 tetrahedra,  an edgeedge with one Ni(2)NO5 octahedra,  an edgeedge with one Ni(3)NO5 octahedra, and  an edgeedge with one Ni(4)NO5 octahedra. The Ni(1)-N(3) bond length is 2.02 Å. The Ni(1)-O(11) bond length is 2.09 Å. The Ni(1)-O(12) bond length is 2.05 Å. The Ni(1)-O(13) bond length is 2.09 Å. The Ni(1)-O(3) bond length is 2.06 Å. The Ni(1)-O(8) bond length is 2.09 Å. In the second Ni site, Ni(2) is bonded to one N(4), one O(11), one O(12), one O(14), one O(4), and one O(7) atom to form NiNO5 octahedra that share  a cornercorner with one P(1)CO3 tetrahedra,  an edgeedge with one Ni(1)NO5 octahedra,  an edgeedge with one Ni(3)NO5 octahedra, and  an edgeedge with one Ni(4)NO5 octahedra. The Ni(2)-N(4) bond length is 1.98 Å. The Ni(2)-O(11) bond length is 2.04 Å. The Ni(2)-O(12) bond length is 2.02 Å. The Ni(2)-O(14) bond length is 2.12 Å. The Ni(2)-O(4) bond length is 2.05 Å. The Ni(2)-O(7) bond length is 2.13 Å. In the third Ni site, Ni(3) is bonded to one N(1), one O(1), one O(11), one O(13), one O(15), and one O(7) atom to form NiNO5 octahedra that share  a cornercorner with one P(1)CO3 tetrahedra,  an edgeedge with one Ni(1)NO5 octahedra, and  an edgeedge with one Ni(2)NO5 octahedra. The Ni(3)-N(1) bond length is 1.95 Å. The Ni(3)-O(1) bond length is 2.10 Å. The Ni(3)-O(11) bond length is 1.98 Å. The Ni(3)-O(13) bond length is 2.09 Å. The Ni(3)-O(15) bond length is 2.04 Å. The Ni(3)-O(7) bond length is 2.31 Å. In the fourth Ni site, Ni(4) is bonded to one N(2), one O(12), one O(14), one O(16), one O(2), and one O(8) atom to form NiNO5 octahedra that share  a cornercorner with one P(2)CO3 tetrahedra,  an edgeedge with one Ni(1)NO5 octahedra, and  an edgeedge with one Ni(2)NO5 octahedra. The Ni(4)-N(2) bond length is 2.00 Å. The Ni(4)-O(12) bond length is 2.01 Å. The Ni(4)-O(14) bond length is 2.10 Å. The Ni(4)-O(16) bond length is 2.09 Å. The Ni(4)-O(2) bond length is 2.03 Å. The Ni(4)-O(8) bond length is 2.22 Å. There are thirty-six inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(1), and one O(3) atom. The C(1)-C(3) bond length is 1.50 Å. The C(1)-O(1) bond length is 1.28 Å. The C(1)-O(3) bond length is 1.28 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(4), one O(2), and one O(4) atom. The C(2)-C(4) bond length is 1.50 Å. The C(2)-O(2) bond length is 1.28 Å. The C(2)-O(4) bond length is 1.28 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(1), one C(13), and one C(5) atom. The C(3)-C(13) bond length is 1.40 Å. The C(3)-C(5) bond length is 1.40 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(14), one C(2), and one C(6) atom. The C(4)-C(14) bond length is 1.40 Å. The C(4)-C(6) bond length is 1.40 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(3), one C(7), and one H(11) atom. The C(5)-C(7) bond length is 1.39 Å. The C(5)-H(11) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(4), one C(8), and one H(12) atom. The C(6)-C(8) bond length is 1.39 Å. The C(6)-H(12) bond length is 1.09 Å. In the seventh C site, C(7) is bonded in a distorted trigonal planar geometry to one C(5), one C(9), and one H(13) atom. The C(7)-C(9) bond length is 1.40 Å. The C(7)-H(13) bond length is 1.09 Å. In the eighth C site, C(8) is bonded in a distorted trigonal planar geometry to one C(10), one C(6), and one H(14) atom. The C(8)-C(10) bond length is 1.40 Å. The C(8)-H(14) bond length is 1.09 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(11), one C(7), and one H(15) atom. The C(9)-C(11) bond length is 1.41 Å. The C(9)-H(15) bond length is 1.09 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(12), one C(8), and one H(16) atom. The C(10)-C(12) bond length is 1.40 Å. The C(10)-H(16) bond length is 1.09 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one C(13), one C(15), and one C(9) atom. The C(11)-C(13) bond length is 1.40 Å. The C(11)-C(15) bond length is 1.51 Å. In the twelfth C site, C(12) is bonded in a trigonal planar geometry to one C(10), one C(14), and one C(16) atom. The C(12)-C(14) bond length is 1.40 Å. The C(12)-C(16) bond length is 1.51 Å. In the thirteenth C site, C(13) is bonded in a distorted trigonal planar geometry to one C(11), one C(3), and one H(17) atom. The C(13)-H(17) bond length is 1.09 Å. In the fourteenth C site, C(14) is bonded in a distorted trigonal planar geometry to one C(12), one C(4), and one H(18) atom. The C(14)-H(18) bond length is 1.09 Å. In the fifteenth C site, C(15) is bonded in a distorted water-like geometry to one C(11), one P(1), one H(19), and one H(21) atom. The C(15)-P(1) bond length is 1.82 Å. The C(15)-H(19) bond length is 1.10 Å. The C(15)-H(21) bond length is 1.10 Å. In the sixteenth C site, C(16) is bonded in a distorted water-like geometry to one C(12), one P(2), one H(20), and one H(22) atom. The C(16)-P(2) bond length is 1.81 Å. The C(16)-H(20) bond length is 1.10 Å. The C(16)-H(22) bond length is 1.10 Å. In the seventeenth C site, C(17) is bonded in a distorted trigonal planar geometry to one C(19), one N(1), and one H(23) atom. The C(17)-C(19) bond length is 1.39 Å. The C(17)-N(1) bond length is 1.35 Å. The C(17)-H(23) bond length is 1.09 Å. In the eighteenth C site, C(18) is bonded in a distorted trigonal planar geometry to one C(20), one N(2), and one H(24) atom. The C(18)-C(20) bond length is 1.39 Å. The C(18)-N(2) bond length is 1.35 Å. The C(18)-H(24) bond length is 1.09 Å. In the nineteenth C site, C(19) is bonded in a distorted trigonal planar geometry to one C(17), one C(21), and one H(25) atom. The C(19)-C(21) bond length is 1.41 Å. The C(19)-H(25) bond length is 1.09 Å. In the twentieth C site, C(20) is bonded in a distorted trigonal planar geometry to one C(18), one C(22), and one H(26) atom. The C(20)-C(22) bond length is 1.41 Å. The C(20)-H(26) bond length is 1.09 Å. In the twenty-first C site, C(21) is bonded in a trigonal planar geometry to one C(19), one C(23), and one C(27) atom. The C(21)-C(23) bond length is 1.41 Å. The C(21)-C(27) bond length is 1.48 Å. In the twenty-second C site, C(22) is bonded in a trigonal planar geometry to one C(20), one C(24), and one C(28) atom. The C(22)-C(24) bond length is 1.41 Å. The C(22)-C(28) bond length is 1.48 Å. In the twenty-third C site, C(23) is bonded in a distorted single-bond geometry to one C(21), one C(25), and one H(27) atom. The C(23)-C(25) bond length is 1.39 Å. The C(23)-H(27) bond length is 1.09 Å. In the twenty-fourth C site, C(24) is bonded in a distorted single-bond geometry to one C(22), one C(26), and one H(28) atom. The C(24)-C(26) bond length is 1.38 Å. The C(24)-H(28) bond length is 1.09 Å. In the twenty-fifth C site, C(25) is bonded in a distorted trigonal planar geometry to one C(23), one N(1), and one H(29) atom. The C(25)-N(1) bond length is 1.35 Å. The C(25)-H(29) bond length is 1.09 Å. In the twenty-sixth C site, C(26) is bonded in a distorted trigonal planar geometry to one C(24), one N(2), and one H(30) atom. The C(26)-N(2) bond length is 1.35 Å. The C(26)-H(30) bond length is 1.09 Å. In the twenty-seventh C site, C(27) is bonded in a trigonal planar geometry to one C(21), one C(29), and one C(35) atom. The C(27)-C(29) bond length is 1.41 Å. The C(27)-C(35) bond length is 1.40 Å. In the twenty-eighth C site, C(28) is bonded in a trigonal planar geometry to one C(22), one C(30), and one C(36) atom. The C(28)-C(30) bond length is 1.41 Å. The C(28)-C(36) bond length is 1.41 Å. In the twenty-ninth C site, C(29) is bonded in a distorted trigonal planar geometry to one C(27), one C(31), and one H(31) atom. The C(29)-C(31) bond length is 1.39 Å. The C(29)-H(31) bond length is 1.09 Å. In the thirtieth C site, C(30) is bonded in a distorted trigonal planar geometry to one C(28), one C(32), and one H(32) atom. The C(30)-C(32) bond length is 1.39 Å. The C(30)-H(32) bond length is 1.09 Å. In the thirty-first C site, C(31) is bonded in a distorted trigonal planar geometry to one C(29), one N(3), and one H(33) atom. The C(31)-N(3) bond length is 1.35 Å. The C(31)-H(33) bond length is 1.09 Å. In the thirty-second C site, C(32) is bonded in a distorted trigonal planar geometry to one C(30), one N(4), and one H(34) atom. The C(32)-N(4) bond length is 1.35 Å. The C(32)-H(34) bond length is 1.09 Å. In the thirty-third C site, C(33) is bonded in a distorted bent 120 degrees geometry to one N(3) and one H(35) atom. The C(33)-N(3) bond length is 1.34 Å. The C(33)-H(35) bond length is 1.09 Å. In the thirty-fourth C site, C(34) is bonded in a distorted bent 120 degrees geometry to one N(4) and one H(36) atom. The C(34)-N(4) bond length is 1.35 Å. The C(34)-H(36) bond length is 1.09 Å. In the thirty-fifth C site, C(35) is bonded in a distorted single-bond geometry to one C(27) and one H(37) atom. The C(35)-H(37) bond length is 1.09 Å. In the thirty-sixth C site, C(36) is bonded in a distorted single-bond geometry to one C(28) and one H(38) atom. The C(36)-H(38) bond length is 1.09 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one C(15), one O(5), one O(7), and one O(9) atom to form PCO3 tetrahedra that share  a cornercorner with one Ni(2)NO5 octahedra and  a cornercorner with one Ni(3)NO5 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to one C(16), one O(10), one O(6), and one O(8) atom to form PCO3 tetrahedra that share  a cornercorner with one Ni(1)NO5 octahedra and  a cornercorner with one Ni(4)NO5 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.57 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Ni(3), one C(17), and one C(25) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Ni(4), one C(18), and one C(26) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Ni(1), one C(31), and one C(33) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one Ni(2), one C(32), and one C(34) atom. There are thirty-eight inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(11) atom. The H(1)-O(11) bond length is 0.98 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 0.99 Å. In the third H site, H(3) is bonded in a distorted single-bond geometry to one O(13) and one O(9) atom. The H(3)-O(13) bond length is 1.02 Å. The H(3)-O(9) bond length is 1.65 Å. In the fourth H site, H(4) is bonded in a distorted single-bond geometry to one O(10) and one O(14) atom. The H(4)-O(10) bond length is 1.66 Å. The H(4)-O(14) bond length is 1.01 Å. In the fifth H site, H(5) is bonded in a distorted linear geometry to one O(13) and one O(6) atom. The H(5)-O(13) bond length is 1.04 Å. The H(5)-O(6) bond length is 1.48 Å. In the sixth H site, H(6) is bonded in a distorted linear geometry to one O(14) and one O(5) atom. The H(6)-O(14) bond length is 1.04 Å. The H(6)-O(5) bond length is 1.46 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(15) and one O(5) atom. The H(7)-O(15) bond length is 1.01 Å. The H(7)-O(5) bond length is 1.70 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(16) and one O(6) atom. The H(8)-O(16) bond length is 1.00 Å. The H(8)-O(6) bond length is 1.70 Å. In the ninth H site, H(9) is bonded in a single-bond geometry to one O(15) atom. The H(9)-O(15) bond length is 1.00 Å. In the tenth H site, H(10) is bonded in a single-bond geometry to one O(16) atom. The H(10)-O(16) bond length is 1.00 Å. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(5) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(6) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(7) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(8) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(9) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(10) atom. In the seventeenth H site, H(17) is bonded in a single-bond geometry to one C(13) atom. In the eighteenth H site, H(18) is bonded in a single-bond geometry to one C(14) atom. In the nineteenth H site, H(19) is bonded in a single-bond geometry to one C(15) atom. In the twentieth H site, H(20) is bonded in a single-bond geometry to one C(16) atom. In the twenty-first H site, H(21) is bonded in a single-bond geometry to one C(15) atom. In the twenty-second H site, H(22) is bonded in a single-bond geometry to one C(16) atom. In the twenty-third H site, H(23) is bonded in a single-bond geometry to one C(17) atom. In the twenty-fourth H site, H(24) is bonded in a single-bond geometry to one C(18) atom. In the twenty-fifth H site, H(25) is bonded in a single-bond geometry to one C(19) atom. In the twenty-sixth H site, H(26) is bonded in a single-bond geometry to one C(20) atom. In the twenty-seventh H site, H(27) is bonded in a single-bond geometry to one C(23) atom. In the twenty-eighth H site, H(28) is bonded in a single-bond geometry to one C(24) atom. In the twenty-ninth H site, H(29) is bonded in a single-bond geometry to one C(25) atom. In the thirtieth H site, H(30) is bonded in a single-bond geometry to one C(26) atom. In the thirty-first H site, H(31) is bonded in a single-bond geometry to one C(29) atom. In the thirty-second H site, H(32) is bonded in a single-bond geometry to one C(30) atom. In the thirty-third H site, H(33) is bonded in a single-bond geometry to one C(31) atom. In the thirty-fourth H site, H(34) is bonded in a single-bond geometry to one C(32) atom. In the thirty-fifth H site, H(35) is bonded in a single-bond geometry to one C(33) atom. In the thirty-sixth H site, H(36) is bonded in a single-bond geometry to one C(34) atom. In the thirty-seventh H site, H(37) is bonded in a single-bond geometry to one C(35) atom. In the thirty-eighth H site, H(38) is bonded in a single-bond geometry to one C(36) atom. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Ni(3) and one C(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Ni(4) and one C(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Ni(1) and one C(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Ni(2) and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one P(1), one H(6), and one H(7) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one P(2), one H(5), and one H(8) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ni(2), one Ni(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Ni(1), one Ni(4), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted L-shaped geometry to one P(1) and one H(3) atom. In the tenth O site, O(10) is bonded in a 2-coordinate geometry to one P(2) and one H(4) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Ni(1), one Ni(2), one Ni(3), and one H(1) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Ni(1), one Ni(2), one Ni(4), and one H(2) atom. In the thirteenth O site, O(13) is bonded in a distorted water-like geometry to one Ni(1), one Ni(3), one H(3), and one H(5) atom. In the fourteenth O site, O(14) is bonded in a distorted water-like geometry to one Ni(2), one Ni(4), one H(4), and one H(6) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Ni(3), one H(7), and one H(9) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Ni(4), one H(10), and one H(8) atom. Linkers: 2 [O]C(=O)c1cccc(CP([O])([O])=O)c1 ,2 c1cc(-c2ccncc2)ccn1. Metal clusters: 1 O.O.O.O.O=P(=O)O[Ni]O[C]O[Ni]O.O=P(=O)O[Ni]O[C]O[Ni]O. The MOF has largest included sphere 4.03 A, density 1.66 g/cm3, surface area 3546.03 m2/g, accessible volume 0.16 cm3/g