NaP2H9(C3O2)3C3H2 crystallizes in the triclinic P-1 space group. The structure consists of one 2,3-dimethyl-1,3-butadiene molecule inside a NaP2H9(C3O2)3 framework. In the NaP2H9(C3O2)3 framework, Na(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with three equivalent P(1)CO3 tetrahedra, corners with three equivalent P(2)CO3 tetrahedra, and  an edgeedge with one Na(1)O6 octahedra. The Na(1)-O(1) bond length is 2.46 Å. The Na(1)-O(2) bond length is 2.46 Å. The Na(1)-O(3) bond length is 2.42 Å. The Na(1)-O(4) bond length is 2.52 Å. There is one shorter (2.27 Å) and one longer (2.33 Å) Na(1)-O(5) bond length. There are nine inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(6), and one P(1) atom. The C(1)-C(2) bond length is 1.40 Å. The C(1)-C(6) bond length is 1.40 Å. The C(1)-P(1) bond length is 1.80 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(3), and one H(2) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-H(2) bond length is 1.09 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one H(4) atom. The C(3)-C(4) bond length is 1.41 Å. The C(3)-H(4) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(3), one C(4), and one C(5) atom. The C(4)-C(4) bond length is 1.49 Å. The C(4)-C(5) bond length is 1.41 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(4), one C(6), and one H(6) atom. The C(5)-C(6) bond length is 1.39 Å. The C(5)-H(6) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(1), one C(5), and one H(7) atom. The C(6)-H(7) bond length is 1.09 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(12), one C(8), and one P(2) atom. The C(7)-C(12) bond length is 1.40 Å. The C(7)-C(8) bond length is 1.40 Å. The C(7)-P(2) bond length is 1.80 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(7) and one H(8) atom. The C(8)-H(8) bond length is 1.09 Å. In the ninth C site, C(12) is bonded in a distorted single-bond geometry to one C(7) and one H(11) atom. The C(12)-H(11) bond length is 1.09 Å. There are two 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 PCO3 tetrahedra that share corners with three equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-51°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.57 Å. In the second P site, P(2) is bonded to one C(7), one O(4), one O(5), and one O(6) atom to form PCO3 tetrahedra that share corners with three equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-59°. The P(2)-O(4) bond length is 1.60 Å. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.55 Å. There are nine inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(2) and one O(6) atom. The H(1)-O(2) bond length is 1.05 Å. The H(1)-O(6) bond length is 1.46 Å. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a linear geometry to one O(3) and one O(6) atom. The H(3)-O(3) bond length is 1.07 Å. The H(3)-O(6) bond length is 1.41 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(3) atom. In the fifth H site, H(5) is bonded in a linear geometry to one O(1) and one O(4) atom. The H(5)-O(1) bond length is 1.51 Å. The H(5)-O(4) bond length is 1.03 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(5) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(6) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(8) atom. In the ninth H site, H(11) is bonded in a single-bond geometry to one C(12) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one H(5) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one H(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one H(3) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Na(1), one P(2), and one H(5) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one P(2), one H(1), and one H(3) atom. Linkers: 1 O=P(O)(O)c1ccc(-c2ccc(P(=O)(O)O)cc2)cc1 ,2 [O]P([O])c1ccc(-c2ccc(P([O])(=O)O)cc2)cc1 ,1 [O]P(=O)(O)c1ccc(-c2ccc(P([O])(=O)O)cc2)cc1. Metal clusters: 2 [Na]. The MOF has largest included sphere 1.58 A, density 1.79 g/cm3, surface area 3631.91 m2/g, accessible volume 0.10 cm3/g