Bulk polarity of 3,5,7-trinitro-1-azaadamantane mediated by asymmetric NO2(lone pair)...NO2(π-hole) supramolecular bonding

Molecular crystals exhibiting polar symmetry are important paradigms for developing new electrooptical materials. Though accessing bulk polarity still presents a significant challenge, in some cases it may be rationalized as being associated with the specific molecular shapes and symmetries and subtle features of supramolecular interactions. In the crystal structure of 3,5,7-trinitro-1-azaadamantane, C9H12N4O6, the polar symmetry of the molecular arrangement is a result of complementary prerequisites, namely the C 3v symmetry of the molecules is suited to the generation of polar stacks and the inherent asymmetry of the principal supramolecular bonding, as is provided by NO2(lone pair)...NO2(π-hole) interactions. These bonds arrange the molecules into a trigonal network. In spite of the apparent simplicity, the structure comprises three unique molecules (Z′ = 1 \over 3 + 1 \over 3 + 1 \over 3), two of which are donors and acceptors of three N...O interactions and the third being primarily important for weak C—H...O hydrogen bonding. These distinct structural roles agree with the results of Hirshfeld surface analysis. A set of weak C—H...O and C—H...N hydrogen bonds yields three kinds of stacks. The orientation of the stacks is identical and therefore the polarity of each molecule contributes additively to the net dipole moment of the crystal. This suggests a special potential of asymmetric NO2(lone pair)...NO2(π-hole) interactions for the supramolecular synthesis of acentric materials.

Download Full-text

Crystal structure of 2-oxo-2H-chromen-7-yl 4-fluorobenzoate

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s205698901800614x ◽

2018 ◽

Vol 74 (5) ◽

pp. 761-765 ◽

Cited By ~ 1

Author(s):

Akoun Abou ◽

Jules Yoda ◽

Abdoulaye Djandé ◽

Stéphane Coussan ◽

T. Jérémie Zoueu

Keyword(s):

Crystal Structure ◽

Benzene Ring ◽

Quantum Chemical ◽

Theoretical Data ◽

Acute Angle ◽

Hirshfeld Surface ◽

Supramolecular Interactions ◽

Stacking Interactions ◽

Compound C ◽

Good Agreement

In the title compound, C16H9FO4, (I), the benzene ring is oriented at an acute angle of 59.03 (15)° relative to the coumarin plane (r.m.s deviation = 0.009 Å). This conformation of (I) is stabilized by an intramolecular C—H...O hydrogen bond, which closes a five-membering ring. In the crystal, molecules of (I) form infinite zigzag chains along the b-axis direction, linked by C—H...O hydrogen bonds. Furthermore, the crystal structure is supported by π–π stacking interactions between neighbouring pyrone and benzene or coumarin rings [centroid–centroid distances in the range 3.5758 (18)–3.6115 (16) Å], as well as C=O...π interactions [O...centroid distances in the range 3.266 (3)–3.567 (3) Å]. The theoretical data for (I) obtained from quantum chemical calculations are in good agreement with the observed structure, although the calculated C—O—C—C torsion angle between the coumarin fragment and the benzene ring (73.7°) is somewhat larger than the experimental value [63.4 (4)°]. Hirshfeld surface analysis has been used to confirm and quantify the supramolecular interactions.

Download Full-text

Crystal structure and Hirshfeld surface analysis of (μ-2-{4-[(carboxylatomethyl)carbamoyl]benzamido}acetato-κ2 O:O′)bis[bis(1,10-phenanthroline-κ2 N,N′)copper(II)] dinitrate N,N′-(1,4-phenylenedicarbonyl)diglycine monosolvate octahydrate

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989019005164 ◽

2019 ◽

Vol 75 (5) ◽

pp. 667-674 ◽

Cited By ~ 6

Author(s):

Niels-Patrick Pook ◽

Arnold Adam ◽

Mimoza Gjikaj

Keyword(s):

Crystal Structure ◽

Surface Analysis ◽

Complex Cation ◽

Solvent Molecule ◽

Lone Pair ◽

Hirshfeld Surface ◽

Hirshfeld Surface Analysis ◽

Water Molecules ◽

Π Stacking ◽

Phenanthroline Ligands

The centrosymmetric binuclear complex cation of the title compound, [Cu2(C12H10N2O6)(C12H8N2)4](NO3)2·C12H12N2O6·8H2O, is composed of a CuII atom with a distorted trigonal–bipyramidal coordination environment defined by four N atoms from two bidentate 1,10-phenanthroline ligands and one oxygen atom from one-half of the monodentate N,N′-(1,4-phenylenedicarbonyl)diglycinate anion. The asymmetric unit is completed by one-half of the N,N′-(1,4-phenylenedicarbonyl)diglycine solvent molecule, which is located on a centre of inversion, by one nitrate counter-anion and four water molecules. In the crystal, the cationic complexes are linked via intermolecular π–π stacking and through lone-pair...π interactions involving the N,N′-(1,4-phenylenedicarbonyl)diglycinate anion and the phenanthroline ligands. The N,N′-(1,4-phenylenedicarbonyl)diglycine solvent molecule is involved in classical and non-classical hydrogen-bonding interactions, as well as π–π stacking interactions. The centroid-to-centroid distances between aromatic entities are in the range 3.5402 (5)–4.3673 (4) Å. The crystal structure is stabilized by further C—H...O contacts as well as by O—H...O and N—H...O hydrogen bonds between water molecules, the nitrate anions, the N,N′-(1,4-phenylenedicarbonyl)diglycinate ligands, N,N′-(1,4-phenylenedicarbonyl)diglycine solvent molecules and phenanthroline ligands, giving rise to a supramolecular framework. A Hirshfeld surface analysis was carried out to quantify these interactions.

Download Full-text

Undecacarbonyl[(4-methylsulfanylphenyl)diphenylphosphane]triruthenium(0): crystal structure and Hirshfeld surface analysis

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989018006989 ◽

2018 ◽

Vol 74 (6) ◽

pp. 791-795

Author(s):

Omar bin Shawkataly ◽

Hafiz Malik Hussien Abdelnasir ◽

Siti Syaida Sirat ◽

Mukesh M. Jotani ◽

Edward R. T. Tiekink

Keyword(s):

Crystal Structure ◽

Surface Analysis ◽

Metal Atom ◽

Hirshfeld Surface ◽

Hirshfeld Surface Analysis ◽

Cluster Compound ◽

Equatorial Position ◽

Carbonyl Ligands ◽

The Third ◽

Hirshfeld Surfaces

The title cluster compound, [Ru3(C19H17PS)(CO)11], comprises a triangle of Ru0 atoms, two of which are bonded to four carbonyl ligands. The third metal atom is bound to three carbonyl ligands and the phosphane-P atom of a dissymmetric phosphane ligand, PPh2(C6H4SMe-4); no Ru...S interactions are observed. The phosphane occupies an equatorial position and its proximity to an Ru—Ru edge results in the elongation of this bond with respect to the others [2.8933 (2) Å cf. 2.8575 (2) and 2.8594 (3) Å]. In the crystal, phenyl-C—H...O(carbonyl) and carbonyl-O...O(carbonyl) [2.817 (2) Å] interactions combine to form a supramolecular chain propagating along [111]; the chains pack without directional interactions between them. The carbonyl-O...O(carbonyl) and other weak contacts have an influence upon the Hirshfeld surfaces with O...H contacts making the greatest contribution, i.e. 37.4% cf. 15.8% for O...O and 15.6% for H...H contacts.

Download Full-text

1-Butyl-1-chloro-3-methyl-3H-2,1λ4-benzoxatellurole: crystal structure and Hirshfeld analysis

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989017003887 ◽

2017 ◽

Vol 73 (4) ◽

pp. 564-568

Author(s):

Julio Zukerman-Schpector ◽

Rodrigo Cunha ◽

Álvaro T. Omori ◽

Lucas Sousa Madureira ◽

Edward R. T. Tiekink

Keyword(s):

Crystal Structure ◽

Lone Pair ◽

Hirshfeld Surface ◽

The Other ◽

Asymmetric Unit ◽

Compound C ◽

Hirshfeld Analysis ◽

Independent Molecules ◽

Opposite Chirality ◽

Secondary Bonding

Two independent molecules comprise the asymmetric unit in the title benzoxatellurole compound, C12H17ClOTe. The molecules, with the same chirality at the methine C atom, are connected into a loosely associated dimer by Te...O interactions, leading to a {...Te—O}2core. The resultant C2ClO2donor set approximates a square pyramid with the lone pair of electrons projected to occupy a positiontransto then-butyl substituent. Interestingly, the TeIVatoms exhibit opposite chirality. The major difference between the independent molecules relates to the conformation of the five-membered chelate rings, which is an envelope with the O atom being the flap, in one molecule and is twisted about the O—C(methine) bond in the other. No directional intermolecular interactions are noted in the molecular packing beyond the aforementioned Te...O secondary bonding. The analysis of the Hirshfeld surface reveals the dominance of H...H contacts,i.e. contributing about 70% to the overall surface, and clearly differentiates the immediate crystalline environments of the two independent molecules in terms of both H...H and H...Cl/Cl...H contacts.

Download Full-text

Synthesis and redetermination of the crystal structure of salicylaldehyde N(4)-morpholinothiosemicarbazone

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989019011812 ◽

2019 ◽

Vol 75 (9) ◽

pp. 1389-1393 ◽

Cited By ~ 3

Author(s):

Dang Tran Buu ◽

Vu Duong Ba ◽

Minh Khoi Nguyen Hoang ◽

Trung Vu Quoc ◽

Linh Duong Khanh ◽

...

Keyword(s):

Molecular Structure ◽

Crystal Structure ◽

Hydrogen Bonding ◽

Hydrogen Bonds ◽

Surface Analysis ◽

Title Compound ◽

Phenyl Ring ◽

Hirshfeld Surface ◽

Hirshfeld Surface Analysis ◽

Supramolecular Interactions

The structure of the title compound (systematic name: N-{[(2-hydroxyphenyl)methylidene]amino}morpholine-4-carbothioamide), C12H15N3O2S, was previously determined (Koo et al., 1977) using multiple-film equi-inclination Weissenberg data, but has been redetermined with higher precision to explore its conformation and the hydrogen-bonding patterns and supramolecular interactions. The molecular structure shows intramolecular O—H...N and C—H...S interactions. The configuration of the C=N bond is E. The molecule is slightly twisted about the central N—N bond. The best planes through the phenyl ring and the morpholino ring make an angle of 43.44 (17)°. In the crystal, the molecules are connected into chains by N—H...O and C—H...O hydrogen bonds, which combine to generate sheets lying parallel to (002). The most prominent contribution to the surface contacts are H...H contacts (51.6%), as concluded from a Hirshfeld surface analysis.

Download Full-text

μ3-Chlorido-μ2-chlorido-(μ3-pyrrolidine-1-carbodithioato-κ4S:S,S′:S′)tris[(triethylphosphane-κP)copper(I)]: crystal structure and Hirshfeld surface analysis

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989017005382 ◽

2017 ◽

Vol 73 (5) ◽

pp. 720-725 ◽

Cited By ~ 2

Author(s):

Yi Jiun Tan ◽

Chien Ing Yeo ◽

Nathan R. Halcovitch ◽

Mukesh M. Jotani ◽

Edward R. T. Tiekink

Keyword(s):

Crystal Structure ◽

Hirshfeld Surface ◽

The Other ◽

Coordination Geometry ◽

Distorted Tetrahedron ◽

Terminal Position ◽

The Third ◽

The Core ◽

Dithiocarbamate Ligand ◽

Supramolecular Chains

The title trinuclear compound, [Cu3(C5H8NS2)Cl2(C6H15P)3], has the dithiocarbamate ligand symmetrically chelating one CuIatom and each of the S atoms bridging to another CuIatom. Both chloride ligands are bridging, one being μ3- and the other μ2-bridging. Each Et3P ligand occupies a terminal position. Two of the CuIatoms exist within Cl2PS donor sets and the third is based on a ClPS2donor set, with each coordination geometry based on a distorted tetrahedron. The constituents defining the core of the molecule,i.e.Cu3Cl2S2, occupy seven corners of a distorted cube. In the crystal, linear supramolecular chains along thecaxis are formedviaphosphane–methylene-C—H...Cl and pyrrolidine–methylene-C—H...π(chelate) interactions, and these chains pack without directional interactions between them. An analysis of the Hirshfeld surface points to the predominance of H atoms at the surface,i.e.contributing 86.6% to the surface, and also highlights the presence of C—H...π(chelate) interactions.

Download Full-text

Crystal structure, characterization, Hirshfeld surface analysis and DFT studies of two [propane 3-bromo-1-(triphenyl phosphonium)] cations containing bromide (I) and tribromide (II) anions: The anion (II) as a new brominating agent for unsaturated compounds

Journal of Molecular Structure ◽

10.1016/j.molstruc.2019.05.127 ◽

2019 ◽

Vol 1195 ◽

pp. 542-554 ◽

Cited By ~ 1

Author(s):

Seyed Reza Nokhbeh ◽

Mostafa Gholizadeh ◽

Alireza Salimi ◽

Hazel A. Sparkes

Keyword(s):

Crystal Structure ◽

Surface Analysis ◽

Hirshfeld Surface ◽

Structure Characterization ◽

Hirshfeld Surface Analysis ◽

Dft Studies ◽

Unsaturated Compounds ◽

Triphenyl Phosphonium ◽

Phosphonium Cations

Download Full-text

2,4-Diamino-6-phenyl-1,3,5-triazin-1-ium nitrate: intriguing crystal structure with high Z′/Z′′ and hydrogen bond numbers and Hirshfeld surface analysis of intermolecular interactions

CrystEngComm ◽

10.1039/d1ce00313e ◽

2021 ◽

Author(s):

Nicoleta Caimac ◽

Elena Melnic ◽

Diana Chisca ◽

Marina S. Fonari

Keyword(s):

Crystal Structure ◽

Hydrogen Bond ◽

Surface Analysis ◽

Intermolecular Interactions ◽

Title Compound ◽

Ionic Species ◽

Hirshfeld Surface ◽

Hirshfeld Surface Analysis ◽

Asymmetric Unit ◽

Space Group

The title compound crystallises in the triclinic centrosymmetric space group P1̄ with an intriguing high number of crystallographically unique binary salt-like adducts (Z′ = 8) and a total number of ionic species (Z′′ = 16) in the asymmetric unit.

Download Full-text