Experimental and Theoretical Investigation of Structures, Stoichiometric Diversity, and Bench Stability of Cocrystals with a Volatile Halogen Bond Donor

We demonstrate the use of ball milling mechanochemistry for rapid, simple, and materials-efficient synthesis of the organic mineral paceite CaCu(OAc) 4 ·6H 2 O (where OAc – is the acetate ion), composed of coordination polymer chains containing alternating Ca 2+ and Cu 2+ ions, as well as its cadmium-based analogue CaCd(OAc) 4 ·6H 2 O. While the synthesis of paceite in aqueous solutions requires a high excess of the copper precursor, mechanochemistry permits the use of stoichiometric amounts of reagents, as well as the use of poorly soluble and readily accessible calcium carbonate or hydroxide reactants. As established by thermochemical measurements, enthalpies of formation of both synthetic paceite and its cadmium analogue relevant to the mechanochemical reactions are highly exothermic. Reactions can also be conducted using accelerated aging, a synthetic technique that mimics geological processes of mineral weathering. Accelerated aging reactivity involving copper(II) acetate monohydrate (hoganite) and calcium carbonate (calcite) provides a potential explanation of how complex organic minerals like paceite could form in a geological environment.

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“…A detailed description of the experimental setup and its use in monitoring cocrystal formation have been recently published. 30,42…”

Section: Resultsmentioning

confidence: 99%

Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue

Huskić

Novendra

et al. 2019

ACS Omega

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“…Where large quantities of halogen-bonded materials are desired (>100 mg), crystallization methods requiring solvent evaporation or solvent diffusion can be tedious to perform, often requiring many days or perhaps weeks to achieve the desired product in sufficient quantity. Mechanochemistry has been shown to be a favorable route for the halogen bond synthon, 54,59,60,61,62 offering a scalable and rapid method of preparing halogen-bonded cocrystals, 63,64 all without the need of large volumes of solvents. However, mechanochemistry by ball milling 65 has the inconvenience of yielding powdered products, requiring further manipulations in order to prepare a sample for SCXRD.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Cosublimation: A Rapid Route Toward Otherwise Inaccessible Halogen-Bonded Architectures

Szell

Gabriel

Caron‐Poulin

et al. 2018

Crystal Growth & Design

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Several synthetic techniques are available for the preparation of halogen-bonded adducts, including traditional solvent-evaporation methods and mechanochemistry. With the intention of reducing solvent usage and experimental times, we establish cosublimation as a synthetic technique for preparing halogen-bonded cocrystals, focusing on the C–I···N motif involving nitrogen-containing heterocycles. We selected four common halogen-bond donors (I2, 1,4-diiodobenzene, 1,4-diiodotetrafluorobenzene, 1,3,5-trifluoro-2,4,6-triiodobenzene) and four halogen-bond acceptors (2,3,5,6-tetramethylpyrazine, 1,4-diazabicyclo[2.2.2]octane, 2,2′-bipyridyl, 1-adamantanecarbonitrile), by virtue of their range in volatility, and explored all 16 combinations via the following methods: solvent evaporation, overnight cosublimation in a sealed glass tube using a two-zone furnace, and expedited cosublimation in a vacuum sublimation apparatus. We show that the raw crystals obtained from overnight cosublimation are of suitable quality for single-crystal X-ray diffraction, resulting in five new crystal structures, two of which are, currently, unobtainable through other methods. Of these new structures, the first halogen bond to the nitrile group of 1-adamantanecarbonitrile is reported, resulting in the formation of a supramolecular rotor in a spinning top configuration as evidenced by 13C and 15N solid-state NMR spectroscopy. Strikingly, the cosublimation approach overcomes an anticooperative halogen-bonding effect to produce fully saturated cocrystals of the tritopic halogen bond donor 1,3,5-trifluoro-2,4,6-triiodobenzene with 1,4-diazabicyclo[2.2.2]octane. Finally, we show that cosublimation can be used to rapidly prepare and purify bulk samples using a vacuum sublimation apparatus, enabling the scalable preparation of halogen-bonded cocrystals within 10 to 30 min using common laboratory equipment. The methods described here enable a broad exploration of the polymorphic landscape and may be extended to the facile preparation of other classes of cocrystals.

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“…The cocrystal ( tftib )( PPh 3 ) was obtained as a part of our program in exploring XB to unusual acceptors 21 . Slow evaporation of an equimolar solution of tftib and PPh 3 in acetonitrile gave colorless crystals that were characterized by single crystal X-ray diffraction at 103 K. Structure determination revealed that asymmetric unit consists of one molecule each of tftib and PPh 3 (Fig.…”

Section: Resultsmentioning

confidence: 99%

Halogen-bonded cocrystallization with phosphorus, arsenic and antimony acceptors

et al. 2019

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The formation of non-covalent directional interactions, such as hydrogen or halogen bonds, is a central concept of materials design, which hinges on using small compact atoms of the 2nd period, notably nitrogen and oxygen, as acceptors. Heavier atoms are much less prominent in that context, and mostly limited to sulfur. Here, we report the experimental observation and theoretical study of halogen bonds to phosphorus, arsenic and antimony in the solid state. Combining 1,3,5-trifluoro-2,4,6-triiodobenzene with triphenylphosphine, -arsine, and -stibine provides cocrystals based on I···P, I···As and I···Sb halogen bonds. The demonstration that increasingly metallic pnictogens form halogen bonds sufficiently strong to enable cocrystal formation is an advance in supramolecular chemistry which opens up opportunities in materials science, as shown by colossal thermal expansion of the cocrystal involving I···Sb halogen bonds.

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Experimental and Theoretical Investigation of Structures, Stoichiometric Diversity, and Bench Stability of Cocrystals with a Volatile Halogen Bond Donor

Cited by 24 publications

References 81 publications

Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue

Mechanochemical Synthesis, Accelerated Aging, and Thermodynamic Stability of the Organic Mineral Paceite and Its Cadmium Analogue

Cosublimation: A Rapid Route Toward Otherwise Inaccessible Halogen-Bonded Architectures

Halogen-bonded cocrystallization with phosphorus, arsenic and antimony acceptors

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