Na3C20P8H45(NO4)8 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(15), two equivalent O(4), and two equivalent O(7) atoms. Both Na(1)-O(15) bond lengths are 2.46 Å. Both Na(1)-O(4) bond lengths are 2.32 Å. Both Na(1)-O(7) bond lengths are 2.44 Å. In the second Na site, Na(2) is bonded to one O(13), one O(16), one O(2), one O(8), and two equivalent O(10) atoms to form NaO6 octahedra that share  a cornercorner with one C(1)P2CO tetrahedra,  a cornercorner with one P(1)CO3 tetrahedra,  a cornercorner with one P(3)CO3 tetrahedra, corners with two equivalent P(4)CO3 tetrahedra, and  an edgeedge with one Na(2)O6 octahedra. The Na(2)-O(13) bond length is 2.51 Å. The Na(2)-O(16) bond length is 2.56 Å. The Na(2)-O(2) bond length is 2.45 Å. The Na(2)-O(8) bond length is 2.36 Å. There is one shorter (2.30 Å) and one longer (2.39 Å) Na(2)-O(10) bond length. There are ten inequivalent C sites. In the first C site, C(1) is bonded to one C(2), one P(1), one P(2), and one O(13) atom to form distorted CP2CO tetrahedra that share  a cornercorner with one Na(2)O6 octahedra. The corner-sharing octahedral tilt angles are 46°. The C(1)-C(2) bond length is 1.53 Å. The C(1)-P(1) bond length is 1.87 Å. The C(1)-P(2) bond length is 1.88 Å. The C(1)-O(13) bond length is 1.42 Å. In the second C site, C(2) is bonded in a distorted trigonal non-coplanar geometry to one C(1), one N(1), one H(8), and one H(9) atom. The C(2)-N(1) bond length is 1.46 Å. The C(2)-H(8) bond length is 1.09 Å. The C(2)-H(9) bond length is 1.10 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(10) atom. The C(3)-N(1) bond length is 1.34 Å. The C(3)-N(2) bond length is 1.34 Å. The C(3)-H(10) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(5), one N(2), and one H(12) atom. The C(4)-C(5) bond length is 1.37 Å. The C(4)-N(2) bond length is 1.38 Å. The C(4)-H(12) bond length is 1.08 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one C(4), one N(1), and one H(13) atom. The C(5)-N(1) bond length is 1.38 Å. The C(5)-H(13) bond length is 1.08 Å. In the sixth C site, C(6) is bonded in a distorted tetrahedral geometry to one C(7), one P(3), one P(4), and one O(14) atom. The C(6)-C(7) bond length is 1.54 Å. The C(6)-P(3) bond length is 1.86 Å. The C(6)-P(4) bond length is 1.89 Å. The C(6)-O(14) bond length is 1.42 Å. In the seventh C site, C(7) is bonded in a distorted trigonal non-coplanar geometry to one C(6), one N(3), one H(14), and one H(15) atom. The C(7)-N(3) bond length is 1.46 Å. The C(7)-H(14) bond length is 1.09 Å. The C(7)-H(15) bond length is 1.09 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(9), one N(3), and one H(17) atom. The C(8)-C(9) bond length is 1.37 Å. The C(8)-N(3) bond length is 1.38 Å. The C(8)-H(17) bond length is 1.08 Å. In the ninth C site, C(9) is bonded in a distorted bent 120 degrees geometry to one C(8), one N(4), and one H(18) atom. The C(9)-N(4) bond length is 1.38 Å. The C(9)-H(18) bond length is 1.08 Å. In the tenth C site, C(10) is bonded in a trigonal planar geometry to one N(3), one N(4), and one H(19) atom. The C(10)-N(3) bond length is 1.35 Å. The C(10)-N(4) bond length is 1.34 Å. The C(10)-H(19) bond length is 1.09 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one C(1), one O(1), one O(2), and one O(3) atom to form distorted PCO3 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra and  a cornercorner with one P(2)CO3 tetrahedra. The corner-sharing octahedral tilt angles are 38°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.59 Å. The P(1)-O(3) bond length is 1.51 Å. In the second P site, P(2) is bonded to one C(1), one O(4), one O(5), and one O(6) atom to form distorted corner-sharing PCO3 tetrahedra. The P(2)-O(4) bond length is 1.49 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.65 Å. In the third P site, P(3) is bonded to one C(6), one O(7), one O(8), and one O(9) atom to form PCO3 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra and  a cornercorner with one P(4)CO3 tetrahedra. The corner-sharing octahedral tilt angles are 57°. The P(3)-O(7) bond length is 1.51 Å. The P(3)-O(8) bond length is 1.59 Å. The P(3)-O(9) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one C(6), one O(10), one O(11), and one O(12) atom to form distorted PCO3 tetrahedra that share corners with two equivalent Na(2)O6 octahedra and  a cornercorner with one P(3)CO3 tetrahedra. The corner-sharing octahedral tilt angles range from 33-54°. The P(4)-O(10) bond length is 1.51 Å. The P(4)-O(11) bond length is 1.61 Å. The P(4)-O(12) bond length is 1.51 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one C(5) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one C(3), one C(4), and one H(11) atom. The N(2)-H(11) bond length is 1.06 Å. In the third N site, N(3) is bonded in a trigonal planar geometry to one C(10), one C(7), and one C(8) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one C(10), one C(9), and one H(16) atom. The N(4)-H(16) bond length is 1.08 Å. There are twenty-three inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(1) and one O(2) atom. The H(1)-O(1) bond length is 1.48 Å. The H(1)-O(2) bond length is 1.04 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. The H(2)-O(6) bond length is 0.98 Å. In the third H site, H(3) is bonded in a distorted linear geometry to one O(5) and one O(8) atom. The H(3)-O(5) bond length is 1.55 Å. The H(3)-O(8) bond length is 1.03 Å. In the fourth H site, H(4) is bonded in a linear geometry to two equivalent O(9) atoms. Both H(4)-O(9) bond lengths are 1.20 Å. In the fifth H site, H(5) is bonded in a linear geometry to one O(11) and one O(3) atom. The H(5)-O(11) bond length is 1.03 Å. The H(5)-O(3) bond length is 1.53 Å. In the sixth H site, H(6) is bonded in a linear geometry to one O(13) and one O(7) atom. The H(6)-O(13) bond length is 1.02 Å. The H(6)-O(7) bond length is 1.53 Å. In the seventh H site, H(7) is bonded in a distorted linear geometry to one O(1) and one O(14) atom. The H(7)-O(1) bond length is 1.63 Å. The H(7)-O(14) bond length is 1.00 Å. 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(2) 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) is bonded in a linear geometry to one N(2) and one O(5) atom. The H(11)-O(5) bond length is 1.59 Å. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(4) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(5) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(7) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(7) atom. In the sixteenth H site, H(16) is bonded in a linear geometry to one N(4) and one O(12) atom. The H(16)-O(12) bond length is 1.52 Å. In the seventeenth H site, H(17) is bonded in a single-bond geometry to one C(8) atom. In the eighteenth H site, H(18) is bonded in a single-bond geometry to one C(9) atom. In the nineteenth H site, H(19) is bonded in a single-bond geometry to one C(10) atom. In the twentieth H site, H(20) is bonded in a single-bond geometry to one O(15) atom. The H(20)-O(15) bond length is 0.98 Å. In the twenty-first H site, H(21) is bonded in a single-bond geometry to one O(15) atom. The H(21)-O(15) bond length is 0.99 Å. In the twenty-second H site, H(22) is bonded in a single-bond geometry to one O(16) atom. The H(22)-O(16) bond length is 0.98 Å. In the twenty-third H site, H(23) is bonded in a single-bond geometry to one O(16) atom. The H(23)-O(16) bond length is 0.98 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one P(1), one H(1), and one H(7) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one P(1), and one H(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one P(1) and one H(5) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Na(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one P(2), one H(11), and one H(3) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one P(2) and one H(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(1), one P(3), and one H(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(2), one P(3), and one H(3) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one P(3) and one H(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to two equivalent Na(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one P(4) and one H(5) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one P(4) and one H(16) atom. In the thirteenth O site, O(13) is bonded in a 2-coordinate geometry to one Na(2), one C(1), and one H(6) atom. In the fourteenth O site, O(14) is bonded in a water-like geometry to one C(6) and one H(7) atom. In the fifteenth O site, O(15) is bonded in a water-like geometry to one Na(1), one H(20), and one H(21) atom. In the sixteenth O site, O(16) is bonded in a water-like geometry to one Na(2), one H(22), and one H(23) atom. Linkers: 1 [O]P(=O)(O)C(O)(CN1[CH]NC=C1)P(=O)(O)O.[O]P(O)[C@](O)(CN1[CH]N[C]=C1)P([O])(=O)O ,1 [O]P(=O)(O)C(O)(CN1[CH]NC=C1)P(=O)(O)O.[O]P(=O)(O)C(O)(CN1[CH]NC=C1)P([O])(=O)O ,1 [O]P(=O)(O)C(O)(CN1[CH]NC=C1)P([O])(=O)O.[O]P(O)[C@@](O)(CN1[CH]N[C]=C1)P(=O)(O)O. Metal clusters: 3 [Na]. The MOF has largest included sphere 2.46 A, density 1.88 g/cm3, surface area 3255.56 m2/g, accessible volume 0.04 cm3/g