Inge, A. KenKöppen, MilanSu, JieFeyand, MarkXu, HongyiZou, XiaodongO'Keeffe, MichaelStock, Norbert2025-06-302025-06-300002-7863ORCID:/0000-0002-8271-3906/work/162953343http://www.scopus.com/inward/record.url?scp=84959017481&partnerID=8YFLogxKhttps://hdl.handle.net/1885/733765553A bismuth-based metal-organic framework (MOF), [Bi(BTC)(H2O)]·2H2O·MeOH denoted CAU-17, was synthesized and found to have an exceptionally complicated structure with helical Bi-O rods cross-linked by 1,3,5-benzenetricarboxylate (BTC3-) ligands. Five crystallographically independent 1D channels including two hexagonal channels, two rectangular channels, and one triangular channel have accessible diameters of 9.6, 9.6, 3.6, 3.6, and 3.4 Å, respectively. The structure is further complicated by twinning. Rod-incorporated MOF structures typically have underlying nets with only one unique node and three or four unique edges. In contrast, topological analysis of CAU-17 revealed unprecedented complexity for a MOF structure with 54 unique nodes and 135 edges. The complexity originates from the rod packing and the rods themselves, which are related to aperiodic helices.This work has been supported by the DFG (SPP 1415) and MATsynCELL. A.K.I. is supported by the Knut and Alice Wallenberg Foundation (KAW) through the MAX IV postdoctoral scholarship. M.O.K. is supported by the US National Science Foundation grant number 1104798. H. Xu acknowledges the post-doctoral grant from the Wenner-Gren Foundations. We thank KAW for the project grant 3DEMNATUR and a grant for purchasing the TEMs. We thank Diamond Light Source and the staff of Beamline I19 for the opportunity to collect X-ray diffraction data and particularly Dr. Sarah A. Barnett for the assistance in data processing. We thank Dr. Helge Reinsch and Prof. Junliang Sun for the fruitful discussions. We also thank Bart Bueken for the scanning electron micrographs.7enPublisher Copyright: © 2016 American Chemical Society.2016-02-1710.1021/jacs.5b1248484959017481