To identify the material, we turned to continuous rotation electron diffraction (cRED, Figure , SI Section S3), which revealed a new 2D layered Zr MOF, denoted GUF-14, with trigonal space group R3 ! m and unit cell dimensions a = 21.007(3) and c = 14.647(3) Å. In contrast to the 18-and 12-connected dodecanuclear Zr12 clusters observed in the hcp and hxl topology Zr-dicarboxylate systems, 20 GUF-14 is comprised of 6-connected Zr6 SBUs, with 8-coordinate Zr 4+ ions linking EDB 2-ligands into a network with hxl topology (Figure ). The two-dimensional, hexagonal sheets adopt an ABC layer stacking arrangement, where individual layers shift 1/3 of unit cell along the ab direction, and 2/3 along the a+1/2b direction (Figure ).