The role of solid-state nuclear magnetic resonance in crystal engineering

Abstract

This Highlight article discusses the role of solid-state NMR spectroscopy in crystal engineering with the aid of several examples from the literature.

NMR Crystallography: Evaluation of Hydrogen Positions in Hydromagnesite by 13C{1H} REDOR Solid‐State NMR and Density Functional Theory Calculation of Chemical Shielding Tensors

“…NMR crystallography, combines NMR, XRD, and computational chemistry, to resolve atomic positions within crystals. A strength of this scheme is using NMR chemical shifts and dipolar couplings between nuclei to validate ab initio quantum calculations for refining atom positions that are invisible to XRD …”

“…[19] XRD suffers,h owever, from being insensitive to low atomic number (Z) nuclei, such as hydrogen;h ence,i ns ome cases,t he structural models produced by XRD are not sufficiently accurate for understanding how the resulting chemistry is directed by coordination. [20] Creative efforts in the emerging field of NMR crystallography [21][22][23][24][25] have pushed the use of NMR as ac omplementary tool for the elucidation of precise atomic coordinates,especially protons,int he unit cell.NMR crystallography,c ombines NMR, XRD,a nd computational chemistry, [26][27][28][29][30][31][32][33] to resolve atomic positions within crystals.Astrength of this scheme is using NMR chemical shifts and dipolar couplings between nuclei to validate ab initio quantum calculations for refining atom positions that are invisible to XRD. [34][35][36] Generally,i sotropic chemical shifts (d iso )a re used to identify spin-1/2 (nuclear spin, I = 1/2) NMR active species in structures,b ecause they are the most readily observed in NMR spectra.…”

“…NMR crystallography,c ombines NMR, XRD,a nd computational chemistry, [26][27][28][29][30][31][32][33] to resolve atomic positions within crystals.Astrength of this scheme is using NMR chemical shifts and dipolar couplings between nuclei to validate ab initio quantum calculations for refining atom positions that are invisible to XRD. [34][35][36] Generally,i sotropic chemical shifts (d iso )a re used to identify spin-1/2 (nuclear spin, I = 1/2) NMR active species in structures,b ecause they are the most readily observed in NMR spectra.…”

Growth, structure, Hirshfeld surface and spectroscopic properties of 2-amino-4-hydroxy-6-methylpyrimidinium-2,3-pyrazinedicorboxylate single crystal

“…The NMR is the versatile technique that provides information on the molecular structure as a fingerprint and identification of the non-equivalency of hydrogen and carbon atoms being affected by intermolecular interaction in the crystal [63]. The observed 1 H and 13 C NMR spectra of PDCA À .AHMP þ crystal are depicted in Fig.…”

Unexpected Crystallization Patterns of Zinc Boron Imidazolate Framework ZBIF‐1: NMR Crystallography of Integrated Metal–Organic Frameworks

“…describing crystalline ZIF analogues can be used as references for the peak assignments for the ZIFzni (IMIDZB01) framework (see Figure S2). Generally, 13 C chemical shifts of crystalline compounds are easily reproducible to within about 0.1 ppm under appropriate conditions, and similarities between the two systems are expected. Finally, the presence of the ZIFzni analogue is also supported by the DFT results (Figure and Supporting Information).…”