NaSm2C9PNH12O18(CH)2 crystallizes in the triclinic P-1 space group. The structure consists of four 02329_fluka molecules inside a NaSm2C9PNH12O18 framework. In the NaSm2C9PNH12O18 framework, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(17), one O(18), one O(3), and one O(9) atom. The Na(1)-O(1) bond length is 2.75 Å. The Na(1)-O(11) bond length is 2.41 Å. The Na(1)-O(17) bond length is 2.57 Å. The Na(1)-O(18) bond length is 2.43 Å. The Na(1)-O(3) bond length is 2.52 Å. The Na(1)-O(9) bond length is 2.39 Å. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(15), one O(16), one O(2), one O(5), one O(7), and one O(9) atom. The Sm(1)-O(1) bond length is 2.28 Å. The Sm(1)-O(10) bond length is 2.47 Å. The Sm(1)-O(15) bond length is 2.50 Å. The Sm(1)-O(16) bond length is 2.48 Å. The Sm(1)-O(2) bond length is 2.34 Å. The Sm(1)-O(5) bond length is 2.41 Å. The Sm(1)-O(7) bond length is 2.50 Å. The Sm(1)-O(9) bond length is 2.52 Å. In the second Sm site, Sm(2) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(13), one O(14), one O(3), one O(4), one O(6), and one O(8) atom. The Sm(2)-O(11) bond length is 2.51 Å. The Sm(2)-O(12) bond length is 2.47 Å. The Sm(2)-O(13) bond length is 2.40 Å. The Sm(2)-O(14) bond length is 2.47 Å. The Sm(2)-O(3) bond length is 2.29 Å. The Sm(2)-O(4) bond length is 2.33 Å. The Sm(2)-O(6) bond length is 2.40 Å. The Sm(2)-O(8) bond length is 2.51 Å. There are nine inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one C(6), and one N(1) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-C(6) bond length is 1.49 Å. The C(1)-N(1) bond length is 1.37 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1) and one H(1) atom. The C(2)-H(1) bond length is 1.09 Å. In the third C site, C(5) is bonded in a distorted trigonal planar geometry to one N(1) and one H(4) atom. The C(5)-N(1) bond length is 1.36 Å. The C(5)-H(4) bond length is 1.08 Å. In the fourth C site, C(6) is bonded in a distorted water-like geometry to one C(1), one P(1), one H(5), and one H(6) atom. The C(6)-P(1) bond length is 1.85 Å. The C(6)-H(5) bond length is 1.10 Å. The C(6)-H(6) bond length is 1.10 Å. In the fifth C site, C(7) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(7)-O(5) bond length is 1.26 Å. The C(7)-O(6) bond length is 1.27 Å. In the sixth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one O(7) and one O(8) atom. The C(8)-O(7) bond length is 1.26 Å. The C(8)-O(8) bond length is 1.27 Å. In the seventh C site, C(9) is bonded in a distorted bent 120 degrees geometry to one O(10) and one O(9) atom. The C(9)-O(10) bond length is 1.27 Å. The C(9)-O(9) bond length is 1.26 Å. In the eighth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one O(11) and one O(12) atom. The C(10)-O(11) bond length is 1.26 Å. The C(10)-O(12) bond length is 1.27 Å. In the ninth C site, C(11) is bonded in a distorted bent 120 degrees geometry to one O(13) and one O(14) atom. The C(11)-O(13) bond length is 1.26 Å. The C(11)-O(14) bond length is 1.27 Å. P(1) is bonded in a tetrahedral geometry to one C(6), one O(1), one O(2), and one O(3) atom. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.54 Å. N(1) is bonded in a trigonal planar geometry to one C(1), one C(5), and one O(4) atom. The N(1)-O(4) bond length is 1.33 Å. There are twelve inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(4) is bonded in a single-bond geometry to one C(5) atom. In the third H site, H(5) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(6) is bonded in a single-bond geometry to one C(6) atom. In the fifth H site, H(7) is bonded in a single-bond geometry to one O(15) atom. The H(7)-O(15) bond length is 0.98 Å. In the sixth H site, H(8) is bonded in a single-bond geometry to one O(15) atom. The H(8)-O(15) bond length is 1.00 Å. In the seventh H site, H(9) is bonded in a single-bond geometry to one O(16) atom. The H(9)-O(16) bond length is 0.99 Å. In the eighth H site, H(10) is bonded in a single-bond geometry to one O(16) atom. The H(10)-O(16) bond length is 0.99 Å. In the ninth H site, H(11) is bonded in a single-bond geometry to one O(17) atom. The H(11)-O(17) bond length is 0.99 Å. In the tenth H site, H(12) is bonded in a single-bond geometry to one O(17) atom. The H(12)-O(17) bond length is 0.99 Å. In the eleventh H site, H(13) is bonded in a single-bond geometry to one O(18) atom. The H(13)-O(18) bond length is 0.98 Å. In the twelfth H site, H(14) is bonded in a distorted single-bond geometry to one O(18) atom. The H(14)-O(18) bond length is 1.01 Å. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Sm(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Sm(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Sm(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Sm(2) and one N(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Sm(1) and one C(7) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Sm(2) and one C(7) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Sm(1) and one C(8) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one Sm(2) and one C(8) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one Sm(1), and one C(9) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Sm(1) and one C(9) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Na(1), one Sm(2), and one C(10) atom. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Sm(2) and one C(10) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Sm(2) and one C(11) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Sm(2) and one C(11) atom. In the fifteenth O site, O(15) is bonded in a water-like geometry to one Sm(1), one H(7), and one H(8) atom. In the sixteenth O site, O(16) is bonded in a distorted water-like geometry to one Sm(1), one H(10), and one H(9) atom. In the seventeenth O site, O(17) is bonded in a water-like geometry to one Na(1), one H(11), and one H(12) atom. In the eighteenth O site, O(18) is bonded in a distorted water-like geometry to one Na(1), one H(13), and one H(14) atom. Linkers: 5 [O]C(=O)C([O])=O ,2 [O]P([O])(=O)Cc1cccc[n+]1[O-]. Metal clusters: 2 [Na] ,4 [Sm]. The MOF has largest included sphere 2.76 A, density 2.39 g/cm3, surface area 2558.99 m2/g, accessible volume 0.09 cm3/g