title: A structure refinement strategy for NMR crystallography: an improved crystal structure of silica-ZSM-12 zeolite from 29Si chemical shift tensors.
abstract: A strategy for performing crystal structure refinements with NMR chemical shift tensors is described in detail and implemented for the zeolite silica-ZSM-12 (framework type code MTW). The 29Si chemical shift tensors were determined from a slow magic-angle spinning spectrum obtained at an ultrahigh magnetic field of 21.1T. The Si and O atomic coordinate parameters were optimized to give the best agreement between experimentally measured and ab initio calculated principal components of the 29Si chemical shift tensors, with the closest Si-O, O-O, and Si-Si distances restrained to correspond with the distributions of the distances found in a set of single-crystal X-ray diffraction (XRD) structures of high-silica zeolites. An improved structure for the silica-ZSM-12 zeolite, compared to a prior structure derived from powder XRD data, is obtained in which the agreement between the experimental and calculated 29Si chemical shift tensors is dramatically improved, the Si-O, O-O, and Si-Si distances correspond to the expected distributions, while the calculated powder XRD pattern remains in good agreement with the experimental powder XRD data. It is anticipated that this "NMR crystallography" structure refinement strategy will be an important tool for the accurate structure determination of materials that are difficult to fully characterize by traditional diffraction methods.
authors.affiliation: Steacie Institute for Molecular Science, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ont., Canada. Darren.Brouwer@nrc-cnrc.gc.ca
authors.forename: Darren H
authors.initials: DH
authors.lastname: Brouwer
mesh_terms: D000465:Algorithms; D003461:Crystallography / Q000379:methods*; D007554:Isotopes / Q000032:analysis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008968:Molecular Conformation; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D012825:Silicon / Q000032:analysis / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*; D017641:Zeolites / Q000737:chemistry*
chemical_list: D007554:Isotopes; D017641:Zeolites; D012822:Silicon Dioxide; D012825:Silicon