Crystal packing and theoretical analysis of halogen- and hydrogen-bonded hydrazones from pharmaceuticals. Evidence of type I and II halogen bonds in extended chains of dichloromethane

Abstract

The supramolecular assembly of halogenated and hydroxyl hydrazones derived from two well known pharmaceuticals, isoniazid (IsX, where X = I, Br, OH) and hydralazine (HyX, where X = I, Br, OH), was studied by X-ray crystallography and theoretical methods. Crystal packing of IsI and HyI shows weak IÁ Á ÁN and IÁ Á Á halogen bonds, whereas the hydrogen bonds are dominant in the brominated scaffolds IsBr and HyBr. Although the calculated IÁ Á ÁN interaction strength appears almost three times weaker than the O-HÁ Á ÁN contacts in the isoniazid-based hydrazones, the higher directionality of the halogen bonds induces a linear and planar architecture of self-complementary tectons, observed only with the help of a bridging water molecule in the case of IsOH. Finally, the X-ray structure of HyOH is characterized by an unexpected linear arrangement of clathrated dichloromethane molecules bound through type I and II halogen bonds. This rare phenomenon, observed in less than ten structures, was studied by coupled cluster-based energy decomposition.

Role of Halogen Substituents on Halogen Bonding in 4,5-DiBromohexahydro-3a,6-Epoxyisoindol-1(4H)-ones

“…In the crystal of 3a, the molecules are interacting through Br⋯Br type II [3,[44][45][46] of halogen bonding to form a 1D supramolecular chain along the b-axis [47], depicted in Figure 2. The Br(1)⋯Br(2) distance (3.638 Å) is shorter than twice the sum of the Bondiʹs van der Waals radii of the interacting atoms (Br + Br = 1.85 + 1.85 = 3.70 Å) [48], and the < C(4)−Br(1)⋯Br(2) angle is 169.68°.…”

“…X-ray structure of 3a-e.Although all 3a-e have at least two potential halogen bond donor centers (Br atoms in the isoindole moiety), there is no intermolecular halogen bonding in the compounds 3b and 3c. In the packing of 3a-e, the most noticeable intermolecular features are C−H• • • O, C−H• • • Br, and C-H• • • π hydrogen bonds, which can also cooperate with C−Br• • • Br, C−Br• • • π, and C−I• • • I types of halogen bonds.In the crystal of 3a, the molecules are interacting through Br• • • Br type II[3,[44][45][46] of halogen bonding to form a 1D supramolecular chain along the b-axis[47], depicted in Figure2. The Br(1)• • • Br(2) distance (3.638 Å) is shorter than twice the sum of the Bondi's van der Waals radii of the interacting atoms (Br + Br = 1.85 + 1.85 = 3.70 Å)[48], and the < C(4)−Br(1)• • • Br(2) angle is 169.68 • .…”

Synthesis, crystal growth, characterization and DFT investigation of a nonlinear optically active cuminaldehyde derivative hydrazone

“…Molecular electrostatic potential (MEP) and electrostatic potential (ESP) surface analyses on the IBIHM molecule were performed to elucidate and predict molecular reactive behavior (Berger et al, 2018). ESP can be computed using standard electronic structure theory packages or derived from experimental X-ray diffraction data providing a simple, easily accessible tool for understanding the electronic structure of a molecule.…”

“…These hydrazone derivatives can have different heteroatoms in their structure, which enable the use of hydrazones in coordination chemistry due to their physiological activities. These hydrazone derivatives have many pharmacological activities such as antiviral, analgesic, antiepileptic, antiinflammatory, antimicrobial, antioxidant, anticancer and anticholinesterase (Berger et al, 2018;El-Sabbagh & Rady, 2009;Sridhara et al, 2002;Angelova et al, 2017;Vasantha et al, 2015). Moreover, the hydrazone functional group is ubiquitous in various fields ranging from nonlinear optics (Abbotto et al, 2009), organic synthesis (Lazny & Nodzewska, 2010;Kobayashi et al, 2011), medicinal chemistry (Vicini et al, 2002;Loncle et al, 2004;Savini et al, 2004;Masunari & Tavares, 2007;Vicini et al, 2009), supramolecular chemistry (Lehn, 2012(Lehn, , 2013 and hole-transporting materials (Lygaitis et al, 2008).…”

Revisiting stacking interactions in tetrathiafulvalene and selected derivatives using tight-binding quantum chemical calculations and local coupled-cluster method

“…Thus, the DLPNO-CCSD(T) method could be used for 'real-world' supramolecular complexes. Indeed, the chemical applications of the DLPNO-CCSD(T) method have already emerged and studies have demonstrated the accuracy and efficiency of the approach (Sparta & Neese, 2014;Minenkov et al, 2015;Calbo et al, 2017;Berger et al, 2018;Zheng, Xie et al, 2020). On the other hand, however, the modelling of weakly bonded systems, such as molecular crystals, is always challenging (Corpinot & Bučar, 2019).…”