Patrick M. J. Szell

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

An overview of the role of solid-state nuclear magnetic resonance (SSNMR) spectroscopy in the field of crystal engineering is provided. NMR methodologies often provide insights into the structure and dynamics of solid materials which would otherwise be unavailable by X-ray diffraction. More generally, NMR crystallographic structure solutions or refinement approaches seek to incorporate available data from all sources, including the results of density functional theory calculations and diffraction data. This Highlight article discusses the state of the field through a recapitulation of relevant theory and selected applications from the literature. Specific topics covered include NMR structure refinement, polymorph identification and differentiation, non-covalent interactions, and the role of dynamics.

Interaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) with CoX2 (X = Cl, Br) in water: trapping of new self-assembled water–chloride/bromide clusters in a [Co(bpca)2]+ host (bpca = bis(2-pyrimidylcarbonyl)amidate anion)

2D polymeric water–chloride/bromide sheets comprising a unique pentagon-like dichloride/dibromide-trihydrate cluster in the solid state have been observed as [Co(bpca)2]+ (bpca = bis(2-pyrimidylcarbonyl)amidate anion) counterions. Both compounds were obtained by the reaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) with CoX2 (X = Cl, Br) in water. Solid-state multinuclear magnetic resonance spectroscopy and XRD provide insight into the structures.

13C and 19F solid‐state NMR and X‐ray crystallographic study of halogen‐bonded frameworks featuring nitrogen‐containing heterocycles

Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P21/c space group: acridine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C13H9N, 1,10-phenanthroline-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C12H8N2, and 2,3,5,6-tetramethylpyrazine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C8H12N2. 13C and 19F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from 19F to 13C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional 1H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental 13C and 19F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

1,3,5-Tri(iodoethynyl)-2,4,6-trifluorobenzene: halogen-bonded frameworks and NMR spectroscopic analysis

Halogen bonding is the non-covalent interaction between the region of positive electrostatic potential associated with a covalently bonded halogen atom, named the σ-hole, and a Lewis base. Single-crystal X-ray diffraction structures are reported for a series of seven halogen-bonded cocrystals featuring 1,3,5-tris(iodoethynyl)-2,4,6-trifluorobenzene (1) as the halogen-bond donor, and bromide ions (as ammonium or phosphonium salts) as the halogen-bond acceptors: (1)·MePh3PBr, (1)·EtPh3PBr, (1)·acetonyl-Ph3PBr, (1)·Ph4PBr, (1)·[bis(4-fluorophenyl)methyl]triphenylphosphonium bromide, and two new polymorphs of (1)·Et3BuNBr. The cocrystals all feature moderately strong iodine-bromide halogen bonds. The crystal structure of pure [bis(4-fluorophenyl)methyl]triphenylphosphonium bromide is also reported. The results of a crystal engineering strategy of varying the size of the counter-cation are explored, and the features of the resulting framework materials are discussed. Given the potential utility of (1) in future crystal engineering applications, detailed NMR analyses (in solution and in the solid state) of this halogen-bond donor are also presented. In solution, complex 13C and 19F multiplets are explained by considering the delicate interplay between various J couplings and subtle isotope shifts. In the solid state, the formation of (1)·Et3BuNBr is shown through significant 13C chemical shift changes relative to pure solid 1,3,5-tris(iodoethynyl)-2,4,6-trifluorobenzene.

Mechanochemistry and cocrystallization of 3-iodoethynylbenzoic acid with nitrogen-containing heterocycles: concurrent halogen and hydrogen bonding

Halogen bonding has been shown to be a versatile interaction for crystal engineering purposes, with characteristics that parallel those of hydrogen bonding. Here, we explore the potential of a new halogen bond donor, 3-iodoethynylbenzoic acid (1), which is functionalized with both halogen bond donor and hydrogen bond donor groups. We explore its crystal engineering potential by cocrystallizing it with a series of nitrogen-containing heterocycles, namely 2,3,5,6-tetramethylpyrazine, 1,4-diazabicyclo[2.2.2]octane, piperazine, and hexamethylenetetramine. In total, we report six new single-crystal X-ray diffraction structures, including those of 1 and five of its halogen-bonded cocrystals. The halogen-bonded cocrystals are further investigated using 13C magic-angle spinning solid-state NMR spectroscopy and the observed changes in chemical shifts are attributed to particular structural or crystallographic features. The 13C chemical shift of the ethynyl carbon bonded to the aromatic ring consistently decreased by several ppm upon halogen bond formation while that of the ethynyl carbon bonded to iodine increased. Furthermore, we show that these cocrystals are also readily prepared by mechanochemical ball milling, allowing for the rapid screening of cocrystal formation based on this halogen bond donor.

Halogen-bond driven self-assembly of triangular macrocycles

2-Iodoethynylpyridine and 2-iodoethynyl-1-methyl-imidazole self-assemble under halogen-bonding control into discrete macrocycles, viz. supramolecular triangles.

3-(1,2,2-Triiodoethenyl)benzoic acid

The title compound, C9H5I3O2, has a layered structure exhibiting O—H⋯O hydrogen bonds, as well as C—I⋯C and C—I⋯O halogen bonding. The C atoms of the ethenyl group are disordered over two sets of sites with refined occupancies of 0.545 (18) and 0.455 (18).

Comparing the Halogen Bond to the Hydrogen Bond by Solid-State NMR Spectroscopy: Anion Coordinated Dimers from 2- and 3-Iodoethynylpyridine Salts

Halogen bonding is an increasingly important tool in crystal engineering, and measuring its influence on the local chemical and electronic environment is necessary to fully understand this interaction. Here, we present a systematic crystallographic and solid-state NMR study of self-complementary halogen-bonded frameworks built from the halide salts (HCl, HBr, HI, HI3 ) of 2-iodoethynylpyridine and 3-iodoethynylpyridine. A series of single crystal X-ray structures reveals the formation of discrete charged dimers in the solid state, directed by simultaneous X- ⋅⋅⋅H-N+ hydrogen bonds and C-I⋅⋅⋅X- halogen bonds (X=Cl, Br, I). Each compound was studied using multinuclear solid-state magnetic resonance spectroscopy, observing 1 H to investigate the hydrogen bonds and 13 C, 35 Cl, and 79/81 Br to investigate the halogen bonds. A natural localized molecular orbital analysis was employed to help interpret the experimental results. 1 H SSNMR spectroscopy reveals a decrease in the chemical shift of the proton participating in the hydrogen bond as the halogen increases in size, whereas the 13 C SSNMR reveals an increased 13 C chemical shift of the C-I carbon for C-I⋅⋅⋅X- relative to C-I⋅⋅⋅N halogen bonds. Additionally, 35 Cl and 79/81 Br SSNMR, along with computational results, have allowed us to compare the C-I⋅⋅⋅X- halogen bond involving each halide in terms of NMR observables. Due to the isostructural nature of these compounds, they are ideal cases for experimentally assessing the impact of different halogen bond acceptors on the solid-state NMR response.