High-<i>Z</i>′ structures of organic molecules: their diversity and organizing principles

Brock, Carolyn Pratt

doi:10.1107/s2052520616017297

Cited by 82 publications

(88 citation statements)

References 78 publications

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“…40 Figure 1: ORTEP of Clpp and CPK view of the N1-H1…N24 and C14-Cl14…C() contacts. [31][32][33][34][35][36][37][38][39] Clmp crystallises in the triclinic system (space group P , with Z=8), containing four independent molecules in the asymmetric unit (Z'=4) [73][74][75] (Figure 2). Trials in a subunit cell (with c-axis halved) in P2 1 /n gives a result with R = 0.11 having at least four non-H atoms with unusual displacement ellipsoids; this result was discarded.…”

Section: Crystal Structure Resultsmentioning

confidence: 99%

“…30 This may be a contributing factor in the isolation of the Clmp crystal structure with Z'=4. [73][74][75] Clop is isomorphous with the Brop crystal structure. 68 Molecules of Clop twist from nonplanar geometry (Figure 3) due to the influence of the ortho-Cl12 atom (Cl-syn) but the amido-pyridine group remains essentially planar due to the C26-H26…O1 intramolecular contact.…”

Section: Crystal Structure Resultsmentioning

confidence: 99%

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At the Interface of Isomorphous Behavior in a 3 × 3 Isomer Grid of Monochlorobenzamides: Analyses of the Interaction Landscapes via Contact Enrichment Studies

Gallagher

Farrell

Hehir

et al. 2019

Crystal Growth & Design

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The physicochemical properties of a 33 isomer grid of mono-chlorobenzamides (Clxx) are reported with comprehensive studies of their crystal structures and interaction environments (Clx = para-/meta-/ortho-chlorobenzoyl and x = para-/meta-/orthoaminopyridine substitutions). The nine compound Clxx series was synthesised from the three p-/m-/o-chlorobenzoyl chlorides and three p-/m-/o-aminopyridine isomers using standard synthetic procedures. Clxx exhibits some similarities to the related Fxx and Brxx congeners e.g. the isomorphous behaviour of Clpp (para-Chloro-N'-(parapyridyl)benzamide) with several close relatives, and there are five isomorphous pairs of Clxx and Brxx crystal structures. Notably Clmp and Clpm both crystallise with Z'=4 in space group P but show important differences. The overall lack of isomers crystallising with solvate molecules is noteworthy, except for Clmm(H 2 O). In all Clxx crystal structures, strong N-H…N hydrogen bonds form, however, Clpo also crystallises as the unexpected Clpo_O polymorph with N-H…O=C intermolecular hydrogen bonding. The Clxo triad (with orthopyridines) exhibits the expected cyclic N-H…N dimer formation with R 2 2 (8) hydrogen bonded rings. The H C atom type, forming weak C-H…Cl hydrogen bonds, is the only favoured interaction partner of chlorine in Clxx. Conformational analyses (gas phase) together with crystal contact enrichment studies place Clxx in context and at the interface of hydrogen and halogen bonding interactions, though strong hydrogen bonding dominates. In Clxx the interaction energies with nearest neighbours are shown to contribute to most of the lattice electrostatic energies. The melting temperatures T m show correlation with both molecular symmetry (Carnelley's rule) and total electrostatic energy of the weak interactions; in addition, these T m values can be well predicted from a linear fit combining both descriptors. In Clxx, N-H…N hydrogen bonds dominate, largely in the absence of solvates, and with five Clxx forming isomorphous pairs with Brxx analogues; Clpp being isomorphous with several close benzamide relatives. Analysis of T m reveals correlations involving both symmetry and electrostatic energies.

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Section: Crystal Structure Resultsmentioning

confidence: 99%

Section: Crystal Structure Resultsmentioning

confidence: 99%

At the Interface of Isomorphous Behavior in a 3 × 3 Isomer Grid of Monochlorobenzamides: Analyses of the Interaction Landscapes via Contact Enrichment Studies

Gallagher

Farrell

Hehir

et al. 2019

Crystal Growth & Design

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“…The crystal structures of 1 and 5 – 7 proved to be challenging due to a variety of disorder phenomena, especially 1 which crystallizes from numerous solvents, as well as by sublimation, in an unusual lattice with four molecules in the asymmetric unit ( Z′ = 4). There is a growing awareness of crystal structures with values of Z′ > 1,, the incidence of which has steadily been rising and achieved 16 % of all organic structures compiled in the Cambridge Crystallographic Database (CSD) in 2016. It is likely that this increasing incidence reflects improvements in crystallographic technology (hardware and software) since structures with more than one equivalent chemical entity in the asymmetric unit are usually more difficult to solve and to refine to publication quality.…”

Section: Introductionmentioning

confidence: 99%

Chemical and Electrochemical Oxidation of Tris(3,5‐di‐tert‐butylphenyl)phosphine – High Z′ Crystal Structures and Conformational Effects Associated with Bulky meta Substituents

et al. 2018

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Synthesis and single-crystal X-ray diffraction structures of (3,5-tBu 2 -C 6 H 3 ) 3 P, (3,5-tBu 2 -C 6 H 3 ) 3 PO·H 2 O, (3,5-tBu 2 -C 6 H 3 ) 3 PS and (3,5-tBu 2 -C 6 H 3 ) 3 PSe are reported. The structure of (3,5-tBu 2 -C 6 H 3 ) 3 P has Z′ = 4, with both M and P enantiomers of a helical conformation and a conformation with one flat ring in the same lattice. The pyramidality index, Σ{∠CPC}, is smaller for the helical compared to the flat conformers. All four have structures that are more pyramidal than the corresponding Ph 3 P(E) derivatives, which is attributed to stronger intramolecular dispersion forces. The oxide crystallizes with Z′ = 2 as a water-bridged dimer that is the most separated such dimer [a]

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“…82 There has also been growing interest in solid forms that do not conform to expected trends such as those with multiple molecules in the asymmetric unit (Z′ > 1). 83,84 Interestingly, while much work in crystal engineering has been concerned with the ability to design and control the ways in which molecules pack to give a crystal, work by Hosseini has also focussed on the macroscopic engineering of crystals themselves in a "crystal welding" approach involving the isomorphous deposition of closely related crystals of different metal complexes. 85 Figure 7.…”

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confidence: 99%

21st century developments in the understanding and control of molecular solids

Steed

2018

Chem. Commun.

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Journal Name COMMUNICATION This journal isThe first decades of the 21 st Century have seen very significant advances in the understanding, prediction and control of molecular solids. Advances in crystallization techniques, polymorphism, co-crystals, co-amorphous materials, crystal engineering and instrumentation have all contributed to what is now an extremely active field. There are huge fundamental implications as well as applications particularly in the pharmaceutical, agrochemicals and energetic materials sectors. This highlight article surveys some of the key recent developments.

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High-Z′ structures of organic molecules: their diversity and organizing principles

Cited by 82 publications

References 78 publications

At the Interface of Isomorphous Behavior in a 3 × 3 Isomer Grid of Monochlorobenzamides: Analyses of the Interaction Landscapes via Contact Enrichment Studies

At the Interface of Isomorphous Behavior in a 3 × 3 Isomer Grid of Monochlorobenzamides: Analyses of the Interaction Landscapes via Contact Enrichment Studies

Chemical and Electrochemical Oxidation of Tris(3,5‐di‐tert‐butylphenyl)phosphine – High Z′ Crystal Structures and Conformational Effects Associated with Bulky meta Substituents

21st century developments in the understanding and control of molecular solids

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