Crystal Structures and Density Functional Theory Calculations of <i>o</i>- and <i>p</i>-Nitroaniline Derivatives: Combined Effect of Hydrogen Bonding and Aromatic Interactions on Dimerization Energy

Helttunen, Kaisa; Lehtovaara, Lauri; Häkkinen, Hannu; Nissinen, Maija

doi:10.1021/cg4005714

Cited by 20 publications

(16 citation statements)

References 59 publications

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“…Thus, for ISSN 2052-5206 # 2015 International Union of Crystallography isolated medium-sized molecules it was demonstrated by Mitchell & Spackman (2000) that the promolecular Hirshfeld surface (HS; Hirshfeld, 1977) represents well the electron density isosurface. Recently it was demonstrated that the QTAIM and the Hirshfeld surface approaches can be complementary for the investigations of weak intermolecular interactions in crystal structures of organic and organometallic compounds (Chęciń ska et al, 2006(Chęciń ska et al, , 2007Howard et al, 2009;Hoser et al, 2010;Munshi et al, 2010;Mitra et al, 2013;Helttunen et al, 2013;Latosiń ska et al, 2014). Visualization and usability allowed the Hirshfeld surface-based approach to become a widespread method for the investigation of intermolecular bonding in molecular crystals, polymorphs or functional materials (Farrugia et al, 2008;Munshi, Skelton et al, 2008;Spackman & Jayatilaka, 2009; Bardelang et al, 2014;Lee et al, 2014).…”

Section: Introductionmentioning

confidence: 99%

Combined analysis of chemical bonding in a Cu^IIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches

Вологжанина

Kats

Penkova

et al. 2015

Acta Crystallogr Sect B

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Interaction of 1-(1H-pyrazol-5-yl)ethanone oxime (H2PzOx) with copper(II) chloride in the presence of pyridine afforded a binuclear discrete [Cu2(HPzOx)2Cl2py2] complex, which was characterized by Fourier transform-IR and electron paramagnetic resonance (EPR) spectra, magnetochemistry and high-resolution X-ray diffraction experiments. Multipole refinement of X-ray diffraction data and density-functional theory (DFT) calculations of an isolated molecule allowed charge and spin distributions to be obtained for this compound. Magnetochemistry data, EPR spectra and DFT calculations of an isolated molecule show antiferromagnetic coupling between copper(II) ions. The spin distribution suggests an exchange pathway via the bridging pyrazole ring in the equatorial plane of the CuN4Cl coordination polyhedron, thus providing support for the classical superexchange mechanism; the calculated value of the magnetic coupling constant -2J is equal to 220 cm(-1), which compares well with the experimental value of 203 ± 2 cm(-1). Chemical connectivity was derived by Bader's 'quantum theory of atoms in molecules' and compared with Voronoi tessellation and Hirshfeld surface representations of crystal space. All methodologies gave a similar qualitative and semi-quantitative description of intra- and intermolecular connectivity.

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Section: Introductionmentioning

confidence: 99%

Combined analysis of chemical bonding in a Cu^IIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches

Вологжанина

Kats

Penkova

et al. 2015

Acta Crystallogr Sect B

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“…In Table 5 and throughout the discussion, N o , N m , and N p refer to the amine N atoms that are ortho, meta, and para, respectively, to the nitro group. As has been noted previously, in hydrogen-bonded systems, geometry optimization often leads to structures that are substantially different from the crystallographic results because of the sometimes substantial intermolecular interactions in addition to hydrogen bonding that exist in the solid state (Hao, 2006), such asstacking (Helttunen et al, 2013). As Table 5 shows, the energy-minimized structures are consistant with the crystallographic results.…”

Section: Figurementioning

confidence: 73%

“…Hydrogen bonding plays an important role in areas ranging from drug design (Hao, 2006) to industrial uses such as explosives, pesticides and dyes (Helttunen et al, 2013). The presence of the two additional acceptor sites from the nitro group makes nitro-substituted aromatic amines of interest with respect to their formation of extended hydrogen-bonding networks.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen bonding in 4-nitrobenzene-1,2-diamine and two hydrohalide salts

Geiger

Parsons

2014

Acta Crystallogr C

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The structures of 4-nitrobenzene-1,2-diamine [C6H7N3O2, (I)], 2-amino-5-nitroanilinium chloride [C6H8N3O2(+)·Cl(-), (II)] and 2-amino-5-nitroanilinium bromide monohydrate [C6H8N3O2(+)·Br(-)·H2O, (III)] are reported and their hydrogen-bonded structures described. The amine group para to the nitro group in (I) adopts an approximately planar geometry, whereas the meta amine group is decidedly pyramidal. In the hydrogen halide salts (II) and (III), the amine group meta to the nitro group is protonated. Compound (I) displays a pleated-sheet hydrogen-bonded two-dimensional structure with R2(2)(14) and R4(4)(20) rings. The sheets are joined by additional hydrogen bonds, resulting in a three-dimensional extended structure. Hydrohalide salt (II) has two formula units in the asymmetric unit that are related by a pseudo-inversion center. The dominant hydrogen-bonding interactions involve the chloride ion and result in R4(2)(8) rings linked to form a ladder-chain structure. The chains are joined by N-H···Cl and N-H···O hydrogen bonds to form sheets parallel to (010). In hydrated hydrohalide salt (III), bromide ions are hydrogen bonded to amine and ammonium groups to form R4(2)(8) rings. The water behaves as a double donor/single acceptor and, along with the bromide anions, forms hydrogen bonds involving the nitro, amine, and ammonium groups. The result is sheets parallel to (001) composed of alternating R5(5)(15) and R6(4)(24) rings. Ammonium N-H···Br interactions join the sheets to form a three-dimensional extended structure. Energy-minimized structures obtained using DFT and MP2 calculations are consistent with the solid-state structures. Consistent with (II) and (III), calculations show that protonation of the amine group meta to the nitro group results in a structure that is about 1.5 kJ mol(-1) more stable than that obtained by protonation of the para-amine group. DFT calculations on single molecules and hydrogen-bonded pairs of molecules based on structural results obtained for (I) and for 3-nitrobenzene-1,2-diamine, (IV) [Betz & Gerber (2011). Acta Cryst. E67, o1359] were used to estimate the strength of the N-H···O(nitro) interactions for three observed motifs. The hydrogen-bonding interaction between the pairs of molecules examined was found to correspond to 20-30 kJ mol(-1).

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“…30 The nitro group also participates in electrostatic interaction between negatively charged oxygen atoms and positively charged nitrogen atoms. 31 As observed in many structures, 30 the nitro group acts as an acceptor for weak intermolecular interactions in MHE-4. In this structure, apart from invariant intramolecular N-H⋯O and O-H⋯O hydrogen bonds, intermolecular N-H⋯O and C-H⋯O interactions are also observed.…”

Section: Resultsmentioning

confidence: 99%

Invariant and variable intermolecular interactions in functionalized malonic acid half-esters: X-ray, Hirshfeld surface and PIXEL energy analyses

et al. 2015

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A series of functionalized malonic acid half-ester derivatives (parent compound MHE-1), with variations in functional groups at different positions on the aromatic ring, have been synthesized and crystal structures are determined at room temperature (296 K). The methyl Ĳ4-CH 3 , MHE-2) and chloro (4-Cl, MHE-3) derivatives are isomorphous with each other. The overall crystal packing of MHE-1-3 is similar. However, there are few differences observed between stacking of layers in these structures. Compounds with nitro Ĳ3-NO 2 , MHE-4) and ethyl ester Ĳ2-COOC 2 H 5 , MHE-5) substituents crystallize in different space groups and thus crystal packing is different when compared to MHE-1-3. In all the structures, intramolecular N-H⋯O and O-H⋯O hydrogen bonds generate a two fused SĲ6) ring motif. A detailed study is carried out to visualize intermolecular interactions observed in all five crystal structures (MHE-1-5) using Hirshfeld surface (HS) analysis with two dimensional fingerprint plots. The relative contribution of intermolecular H⋯H contacts in MHE-3 is substantially lower than that in MHE-1-2, though similar crystal packing arrangements of MHE-1-3 and MHE-2 and MHE-3 are isomorphous. From HS analysis it is clear that the observed H⋯H contact contribution (MHE-3) is a consequence of the presence of the chlorine substituent and growing contribution of Cl⋯H contacts. The relative contributions of other intermolecular contacts involving various atoms are comparable in MHE-1-3 structures. The intermolecular interaction energies are quantified using PIXEL for various molecular pairs extracted from respective crystal structures. Interestingly, there are some invariant and variable intermolecular contacts observed between different groups in all five structures.

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Crystal Structures and Density Functional Theory Calculations of o- and p-Nitroaniline Derivatives: Combined Effect of Hydrogen Bonding and Aromatic Interactions on Dimerization Energy

Abstract: This is a self-archived version of an original article. This version may differ from the original in pagination and typographic details.

Cited by 20 publications

References 59 publications

Combined analysis of chemical bonding in a Cu^IIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches

Combined analysis of chemical bonding in a Cu^IIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches

Hydrogen bonding in 4-nitrobenzene-1,2-diamine and two hydrohalide salts

Invariant and variable intermolecular interactions in functionalized malonic acid half-esters: X-ray, Hirshfeld surface and PIXEL energy analyses

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Crystal Structures and Density Functional Theory Calculations of o- and p-Nitroaniline Derivatives: Combined Effect of Hydrogen Bonding and Aromatic Interactions on Dimerization Energy

Abstract: This is a self-archived version of an original article. This version may differ from the original in pagination and typographic details.

Cited by 20 publications

References 59 publications

Combined analysis of chemical bonding in a CuIIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches

Combined analysis of chemical bonding in a CuIIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches

Hydrogen bonding in 4-nitrobenzene-1,2-diamine and two hydrohalide salts

Invariant and variable intermolecular interactions in functionalized malonic acid half-esters: X-ray, Hirshfeld surface and PIXEL energy analyses

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Product

Resources

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Combined analysis of chemical bonding in a Cu^IIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches

Combined analysis of chemical bonding in a Cu^IIdimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches