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. 2023 Aug 2;13(33):23267-23284.
doi: 10.1039/d3ra03936f. eCollection 2023 Jul 26.

Supramolecular assemblies in the molecular complexes of 4-cyanophenylboronic acid with different N-donor ligands

Samina Easmin  1 , Venkateswara Rao Pedireddi  1
Affiliations

Supramolecular assemblies in the molecular complexes of 4-cyanophenylboronic acid with different N-donor ligands

Samina Easmin et al. RSC Adv. .

Abstract

Molecular complexes of 4-cyanophenylboronic acid (CB) with various N-donor compounds having different conformational features, for example, rigid (1,10-phenanthroline (110phen), 4,7-phenanthroline (47phen), 1,7-phenanthroline (17phen) and acridine (acr)) and linear (1,2-bis(4-pyridyl)ethane (bpyea), 1,2-bis(4-pyridyl)ethene (bpyee) and 4,4'-azopyridine (azopy)), have been reported. In all complexes, the -B(OH)2 moiety is found to be in a syn-anti confirmation, with the exception of structures containing 110phen, bpyee, and azopy, wherein, syn-syn conformation is observed. Further, CB molecules remain intact in all structures except in the complexes with some linear N-donor ligands, wherein -B(OH)2 transforms to monoester (-B(OH)(OCH3)) prior to the formation of corresponding molecular complexes. In such boronic monoester complexes, the conformation of -B(OH)(OCH3) is syn-anti with respect to the -OH and -OCH3 groups. Also, complexes mediated by azopy and bpyee exist in both hydrated and anhydrous forms. In these anhydrous structures, the recognition pattern is through homomeric (juxtaposed -CN and -B(OH)2) as well as heteromeric (between hetero N-atom and -B(OH)2) O-H⋯N hydrogen bonds, while only heteromeric O-H⋯N hydrogen bonds hold co-formers in all other structures. Depending upon the conformational features of both co-formers, molecules are packed in crystal lattices in the form of stacked layers, helical chains, and crossed ribbons. All structures are fully characterized by single-crystal X-ray diffraction and phase purity is established by powder X-ray diffraction. Additionally, correlation among structures is explained by calculating a similarity index and performing a Hirshfeld surface analysis to quantify the strength and effectiveness of different types of intermolecular bonds that stabilize these structures along with the presentation of energy frameworks, representing the strength of the interactions in the form gradient cylinders. Also, the morphology of each complex was computed by BFDH methodology to correlate with the actual crystal morphology and packing arrangement.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Chart 1
Chart 1
Fig. 1
Fig. 1. (a) Three-dimensional arrangement with voids, occupied by CH3OH molecules, in molecular complex, 1. (b) Basic recognition unit observed between complementary functional groups present in 1. (c) 1D helical chain and (d) left-handed and right-handed helical chains.
Fig. 2
Fig. 2. (a) Basic recognition unit observed in molecular complex, 2. (b) Criss-crossed network in the crystal lattice. (c) A double helix formed between CB and 47phen.
Fig. 3
Fig. 3. (a) A typical tetrameric unit in the crystal structure of 3. (b) Interaction between the tetramers in the crystal lattice. (c) Crossed tape networks in molecular complex, 3.
Fig. 4
Fig. 4. (a) Basic interaction in the form of a tetramer and between the adjacent tetramers in complex, 4. (b) Crinkle arrangement of CB molecules through C–H⋯N hydrogen bonds.
Fig. 5
Fig. 5. (a) Sheet arrangement of the molecules in the crystal lattice. (b) Basic recognition of CB with bpyea in hydrated complex 5. (c) Two-dimensional linear ribbon arrangement.
Fig. 6
Fig. 6. (a) Propagation of chain arrangement in the molecular complex, 6. (b) Crossed ribbon arrangement present in the crystal lattice.
Fig. 7
Fig. 7. (a) Three-dimensional stacked layer arrangement in the molecular complex, 6a. (b) The six-membered cyclic network formed in molecular recognition. (c) Interactions of the hexameric unit in the crystal lattice.
Fig. 8
Fig. 8. (a) Basic recognition of CB with bpyee in hydrated complex 7a. (b) Planar-sheet arrangement of the molecules in the crystal lattice. (c) Two-dimensional host–guest network.
Fig. 9
Fig. 9. (a) Molecular recognition observed in the monoester with azopy. (b) Stacked sheet arrangement found in the molecular complex 6b, separated by 3.4 Å. (c) Two-dimensional arrangement of the molecules in the crystal lattice, 6b.
Scheme 2
Scheme 2
Fig. 10
Fig. 10. XPac plot of interplanar angular deviation vs. angular deviation (°) for the pair of (a) 6/7, (b) 6b/7b and (c) 6a/PELMUR illustrating the degree of similarity (top right corner value indicates dissimilarity index).
Fig. 11
Fig. 11. Presentation of experimental shapes (top) and computed BFDH morphology (bottom) for each structure.
Fig. 12
Fig. 12. Hirshfeld surfaces and 2D fingerprint plots of 1–7, 6a, 6b, 7a and 7b.
Fig. 13
Fig. 13. The relative contribution of different types of intermolecular interactions in crystal lattices considering CB as a dominant surface 1–7, 6a, 6b, 7a and 7b.
Fig. 14
Fig. 14. Pictorial representation of the energy frameworks for some selected co-crystals.
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