Na3Ga(HCOO)6 crystallizes in the orthorhombic Pccn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form distorted NaO6 pentagonal pyramids that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one Ga(1)O6 octahedra, and edges with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 49-68°. The Na(1)-O(2) bond length is 2.68 Å. The Na(1)-O(5) bond length is 2.49 Å. There is one shorter (2.28 Å) and one longer (2.47 Å) Na(1)-O(4) bond length. There is one shorter (2.26 Å) and one longer (2.43 Å) Na(1)-O(6) bond length. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids and edges with two equivalent Ga(1)O6 octahedra. Both Na(2)-O(1) bond lengths are 2.50 Å. Both Na(2)-O(3) bond lengths are 2.43 Å. Both Na(2)-O(5) bond lengths are 2.46 Å. Ga(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form GaO6 octahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids and edges with two equivalent Na(2)O6 octahedra. Both Ga(1)-O(1) bond lengths are 2.01 Å. Both Ga(1)-O(2) bond lengths are 2.02 Å. Both Ga(1)-O(3) bond lengths are 2.04 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one H(1), one O(1), and one O(4) atom. The C(1)-H(1) bond length is 1.10 Å. The C(1)-O(1) bond length is 1.29 Å. The C(1)-O(4) bond length is 1.25 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one H(2), one O(2), and one O(5) atom. The C(2)-H(2) bond length is 1.11 Å. The C(2)-O(2) bond length is 1.29 Å. The C(2)-O(5) bond length is 1.25 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one H(3), one O(3), and one O(6) atom. The C(3)-H(3) bond length is 1.11 Å. The C(3)-O(3) bond length is 1.29 Å. The C(3)-O(6) bond length is 1.24 Å. There are three inequivalent H sites. In the first H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the third H site, H(2) is bonded in a single-bond geometry to one C(2) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one Ga(1), and one C(1) atom. In the second O site, O(5) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one C(2) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ga(1), and one C(2) atom. In the fourth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(3) atom. In the fifth O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(2), one Ga(1), and one C(3) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(1) atom. Linkers: 24 [O]C=O. Metal clusters: 12 [Na] ,4 [Ga]. The MOF has largest included sphere 1.27 A, density 2.15 g/cm3, surface area 2086.98 m2/g, accessible volume 0.04 cm3/g