Peculiarities of Br⋯Br bonding in crystal structures of polybromides and bromine solvates

Abstract

Analysis of supramolecular associates formed by Br⋯Br interactions in crystals of 204 polybromide and bromine-containing compounds has been carried out.

Strength of the [Z–I···Hal]− and [Z–Hal···I]− Halogen Bonds: Electron Density Properties and Halogen Bond Length as Estimators of Interaction Energy

“…However, in the condensed phase, molecules are usually bound with each other by a network of several non-covalent interactions, and an adequate fragmentation which affects only the bond of interest is often impossible. In such a situation, an approximation of E b through other parameters easily accessible from experiment becomes very important [ 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 ]. Among these parameters, bond distance [ 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 77 , 78 ], electron density properties [ 61 , 79 , 80 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 10...…”

“…However, in the condensed phase, molecules are usually bound with each other by a network of several non-covalent interactions, and an adequate fragmentation which affects only the bond of interest is often impossible. In such a situation, an approximation of E b through other parameters easily accessible from experiment becomes very important [51][52][53][54][55][56][57][58][59][60]. Among these parameters, bond distance [61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78], electron density properties [61,, and force constants [57,73,114,115] are the most common.…”

Atom-Efficient Halogen–Halogen Interactions Assist One-, Two-, and Three-Dimensional Molecular Zippers

“…Single-crystal X-ray diffraction analysis revealed intermolecular van der Waals (vdW) Br···Br interactions with interatomic distances of 3.65, 3.84, and 4.03 Å (Figure a,b,d). Though Bondi’s classification is widely employed in predicting noncovalent interactions, the existence of Br···Br interactions beyond the sum of van der Waals radii have been established recently. − Comprehensive analysis of the crystal structure substantiate the key roles played by Br···Br, Br···S, and π–π interactions in forming the 3D close packing of NTB 2 (Figure ). The crystal lattice of NTB 2 comprises of three different noncovalently interacting dimers (T1, T2, and stacked dimer (T3)), classified based on distinct interhalogen interactions.…”

Database Investigation of Halogen Bonding and Halogen···Halogen Interactions between Porphyrins: Emergence of Robust Supramolecular Motifs and Frameworks

“…The classification was based on geometrical criteria from different overviews of the field. 67,69 Contacts that were shorter than the sum of van der Waals radii of participating atoms but which could not readily fit into these geometrical parameters were classified simply as contacts. Seven structures contained more than one type of halogen atom, and the overall analysis included a total of 31 chlorinesubstituted porphyrin systems (Figure 2a), 73 brominated porphyrin systems (Figure 2b), and 47 entries containing iodine-bearing porphyrins (Figure 2c).…”

“…A broader, more general view of how the presence of halogen atoms could affect the molecular recognition and self-assembly of porphyrins in the solid state, however, might be accessible through considering the large collection of independently published crystal structures found in the CSD. Previously, surveys of CSD have been successfully used to gain insight into various aspects of molecular assembly in the solid state, ranging from understanding the geometries of select types of halogen or hydrogen bonds, − chalcogen bonds, and coordination polymers . Considering the richness of this continuously growing database, we have decided to conduct a survey of the CSD in order to gain a more general view of the role of halogens in directing the self-assembly of porphyrins in the solid state, across all three sites of functionalization, including Cl, Br, and I atoms, and with XB acceptor atoms other than nitrogen.…”