NaC4PNH9SCl crystallizes in the triclinic P-1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one S(1), one Cl(1), and one Cl(2) atom. The Na(1)-S(1) bond length is 2.98 Å. The Na(1)-Cl(1) bond length is 3.05 Å. The Na(1)-Cl(2) bond length is 2.93 Å. In the second Na site, Na(2) is bonded to one S(2), one S(4), one Cl(2), and one Cl(4) atom to form NaS2Cl2 tetrahedra that share corners with two equivalent P(2)SN2Cl tetrahedra and corners with two equivalent P(4)SN2Cl tetrahedra. The Na(2)-S(2) bond length is 2.85 Å. The Na(2)-S(4) bond length is 2.84 Å. The Na(2)-Cl(2) bond length is 2.85 Å. The Na(2)-Cl(4) bond length is 2.83 Å. In the third Na site, Na(3) is bonded to one S(1), one S(3), one Cl(1), and one Cl(3) atom to form distorted NaS2Cl2 tetrahedra that share corners with two equivalent P(1)SN2Cl tetrahedra and corners with two equivalent P(3)SN2Cl tetrahedra. The Na(3)-S(1) bond length is 2.83 Å. The Na(3)-S(3) bond length is 2.83 Å. The Na(3)-Cl(1) bond length is 2.91 Å. The Na(3)-Cl(3) bond length is 2.90 Å. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one S(3), one S(4), one Cl(3), and one Cl(4) atom. The Na(4)-S(3) bond length is 2.92 Å. The Na(4)-S(4) bond length is 3.11 Å. The Na(4)-Cl(3) bond length is 3.14 Å. The Na(4)-Cl(4) bond length is 2.92 Å. There are sixteen inequivalent C sites. In the first C site, C(1) is bonded to one C(4), one C(7), one C(8), and one N(2) atom to form distorted CC3N tetrahedra that share corners with two equivalent P(1)SN2Cl tetrahedra. The C(1)-C(4) bond length is 1.52 Å. The C(1)-C(7) bond length is 1.52 Å. The C(1)-C(8) bond length is 1.55 Å. The C(1)-N(2) bond length is 1.50 Å. In the second C site, C(2) is bonded in a trigonal non-coplanar geometry to one C(6); one H(3); and two equivalent H(1,2,4,5,11,12) atoms. The C(2)-C(6) bond length is 1.53 Å. The C(2)-H(3) bond length is 0.98 Å. Both C(2)-H(1,2,4,5,11,12) bond lengths are 0.98 Å. In the third C site, C(3) is bonded in a trigonal non-coplanar geometry to one C(6); one H(6,10); and two equivalent H(1,2,4,5,11,12) atoms. The C(3)-C(6) bond length is 1.52 Å. The C(3)-H(6,10) bond length is 0.98 Å. Both C(3)-H(1,2,4,5,11,12) bond lengths are 0.98 Å. In the fourth C site, C(4) is bonded in a trigonal non-coplanar geometry to one C(1); one H(8,13,22,34); and two equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. The C(4)-H(8,13,22,34) bond length is 0.98 Å. Both C(4)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. In the fifth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(6); one H(6,10); and two equivalent H(1,2,4,5,11,12) atoms. The C(5)-C(6) bond length is 1.54 Å. The C(5)-H(6,10) bond length is 0.98 Å. Both C(5)-H(1,2,4,5,11,12) bond lengths are 0.98 Å. In the sixth C site, C(6) is bonded to one C(2), one C(3), one C(5), and one N(1) atom to form distorted CC3N tetrahedra that share corners with two equivalent P(2)SN2Cl tetrahedra. The C(6)-N(1) bond length is 1.51 Å. In the seventh C site, C(7) is bonded in a trigonal non-coplanar geometry to one C(1); one H(8,13,22,34); and two equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. The C(7)-H(8,13,22,34) bond length is 0.98 Å. Both C(7)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. In the eighth C site, C(8) is bonded in a trigonal non-coplanar geometry to one C(1) and three equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. All C(8)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. In the ninth C site, C(9) is bonded in a trigonal non-coplanar geometry to one C(10) and three equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. The C(9)-C(10) bond length is 1.54 Å. All C(9)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. In the tenth C site, C(10) is bonded to one C(11), one C(12), one C(9), and one N(3) atom to form distorted CC3N tetrahedra that share corners with two equivalent P(3)SN2Cl tetrahedra. The C(10)-C(11) bond length is 1.54 Å. The C(10)-C(12) bond length is 1.51 Å. The C(10)-N(3) bond length is 1.50 Å. In the eleventh C site, C(11) is bonded in a trigonal non-coplanar geometry to one C(10); one H(8,13,22,34); and two equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. The C(11)-H(8,13,22,34) bond length is 0.98 Å. Both C(11)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. In the twelfth C site, C(12) is bonded in a trigonal non-coplanar geometry to one C(10) and three equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. All C(12)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. In the thirteenth C site, C(13) is bonded to one C(14), one C(15), one C(16), and one N(4) atom to form distorted CC3N tetrahedra that share corners with two equivalent P(4)SN2Cl tetrahedra. The C(13)-C(14) bond length is 1.54 Å. The C(13)-C(15) bond length is 1.53 Å. The C(13)-C(16) bond length is 1.52 Å. The C(13)-N(4) bond length is 1.49 Å. In the fourteenth C site, C(14) is bonded in a trigonal non-coplanar geometry to one C(13); one H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36); and two equivalent H(28,30) atoms. The C(14)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond length is 0.98 Å. Both C(14)-H(28,30) bond lengths are 0.98 Å. In the fifteenth C site, C(15) is bonded in a trigonal non-coplanar geometry to one C(13) and three equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. All C(15)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. In the sixteenth C site, C(16) is bonded in a trigonal non-coplanar geometry to one C(13); one H(8,13,22,34); and two equivalent H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) atoms. The C(16)-H(8,13,22,34) bond length is 0.98 Å. Both C(16)-H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) bond lengths are 0.98 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to two equivalent N(2), one S(1), and one Cl(1) atom to form PSN2Cl tetrahedra that share corners with two equivalent Na(3)S2Cl2 tetrahedra, corners with two equivalent C(1)C3N tetrahedra, and  an edgeedge with one P(1)SN2Cl tetrahedra. Both P(1)-N(2) bond lengths are 1.70 Å. The P(1)-S(1) bond length is 1.99 Å. The P(1)-Cl(1) bond length is 1.98 Å. In the second P site, P(2) is bonded to two equivalent N(1), one S(2), and one Cl(2) atom to form PSN2Cl tetrahedra that share corners with two equivalent Na(2)S2Cl2 tetrahedra, corners with two equivalent C(6)C3N tetrahedra, and  an edgeedge with one P(2)SN2Cl tetrahedra. There is one shorter (1.70 Å) and one longer (1.71 Å) P(2)-N(1) bond length. The P(2)-S(2) bond length is 1.98 Å. The P(2)-Cl(2) bond length is 1.98 Å. In the third P site, P(3) is bonded to two equivalent N(3), one S(3), and one Cl(3) atom to form PSN2Cl tetrahedra that share corners with two equivalent Na(3)S2Cl2 tetrahedra, corners with two equivalent C(10)C3N tetrahedra, and  an edgeedge with one P(3)SN2Cl tetrahedra. Both P(3)-N(3) bond lengths are 1.70 Å. The P(3)-S(3) bond length is 1.99 Å. The P(3)-Cl(3) bond length is 1.98 Å. In the fourth P site, P(4) is bonded to two equivalent N(4), one S(4), and one Cl(4) atom to form PSN2Cl tetrahedra that share corners with two equivalent Na(2)S2Cl2 tetrahedra, corners with two equivalent C(13)C3N tetrahedra, and  an edgeedge with one P(4)SN2Cl tetrahedra. There is one shorter (1.69 Å) and one longer (1.71 Å) P(4)-N(4) bond length. The P(4)-S(4) bond length is 1.98 Å. The P(4)-Cl(4) bond length is 1.99 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one C(6) and two equivalent P(2) atoms. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one C(1) and two equivalent P(1) atoms. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one C(10) and two equivalent P(3) atoms. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one C(13) and two equivalent P(4) atoms. There are six inequivalent H sites. In the first H site, H(1,2,4,5,11,12) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(3) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(6,10) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(7,9,14,15,16,17,18,19,20,21,23,24,25,26,27,29,31,32,33,35,36) is bonded in a single-bond geometry to one C(4) atom. In the fifth H site, H(8,13,22,34) is bonded in a single-bond geometry to one C(4) atom. In the sixth H site, H(28,30) is bonded in a single-bond geometry to one C(14) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a T-shaped geometry to one Na(1), one Na(3), and one P(1) atom. In the second S site, S(2) is bonded in an L-shaped geometry to one Na(2) and one P(2) atom. In the third S site, S(3) is bonded in a T-shaped geometry to one Na(3), one Na(4), and one P(3) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Na(2), one Na(4), and one P(4) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to one Na(1), one Na(3), and one P(1) atom. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one P(2) atom. In the third Cl site, Cl(3) is bonded in a distorted T-shaped geometry to one Na(3), one Na(4), and one P(3) atom. In the fourth Cl site, Cl(4) is bonded in a distorted T-shaped geometry to one Na(2), one Na(4), and one P(4) atom. Linkers: 5 CC(C)(C)N1[P@]([S])(Cl)N(C(C)(C)C)[P@@]1([S])Cl. Metal clusters: 8 [Na]. The MOF has largest included sphere 5.28 A, density 0.99 g/cm3, surface area 4436.74 m2/g, accessible volume 0.49 cm3/g