Nonbonding Lone Pair Research Articles

Stability, Chemical Bonding, and Electron Lone Pair Localization in AsN at High Pressure by Density Functional Theory Calculations.

The covalent bonding framework of crystalline single-bonded cubic AsN, recently synthesized under high pressure and high temperature conditions in a laser-heated diamond anvil cell, is here studied by means of density functional theory calculations and compared to single crystal X-ray diffraction data. The precise localization of the nonbonding electron lone pairs and the determination of their distances and orientations are related to the presence of characteristic structural motifs and space regions of the unit cell dominated by repulsive electronic interactions, with the relative orientation of the electron lone pairs playing a key role in minimizing the energy of the structure. We find that the vibrational modes associated with the expression of the lone pairs are strongly localized, an observation that may have implications for the thermal conductivity of the compound. The results indicate the thermodynamic stability of the experimentally observed structure of AsN above ∼17 GPa, provide a detailed insight into the nature of the chemical bonding network underlying the formation of this compound, and open new perspectives to the design and high pressure synthesis of new pnictogen-based advanced materials for potential applications of energetic and technological relevance.

A Possible Origin of Glasslike Thermal Conductivity in Phase‐Change Memory Crystals

Thermal processes play a crucial role in a variety of applications ranging from thermoelectrics, to thermal barrier coatings for turbines to memory devices, where materials with low thermal conductivity κ are essential for energy savings. By comparing two phase‐change materials, and , that have very similar thermal conductivities despite very different structures and bond strengths, it is argued that their phonon‐glass electron‐crystal properties stem from randomly oriented nonbonding lone–pair orbitals subtended at chalcogen atoms surrounding intrinsic vacancies.

Geminal bimetallic coordination of a carbone to main-group and transition metals.

The non-bonding carbone lone pair in geometrically-constrained antimony and bismuth carbodiphosphorane complexes readily complexed AuCl to afford rare examples of geminal bimetallic carbone coordination featuring a main-group metal.

Synthetic, structural and reactivity studies of a boryl-ethynyl Silylene.

The salt metathesis of a boryl-ethynyl lithium salt {[(HCDipN)2]B-CC-Li} with a monochlorosilylene [LSi(:)Cl; L = PhC(NtBu)2] produced an isolable boryl-ethynyl silylene {1; [(HCDipN)2]B-CC-Si(L)}. The Si(II) center in 1 possesses a nonbonding lone pair and forms a covalent bond with the ethynyl group. The characterization of 1 was carried out by multinuclear NMR spectroscopy, single-crystal X-ray structure analysis and DFT calculations. Additionally, a reactivity study of 1 was conducted towards oxygen-containing and aryl C-F substrates.

Dimetalloylene (M-E-M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E-X Bonds (X = N(SiMe3)2, OtBu) with an Iridium Hydride.

Reactions of the Ir(V) hydride [MeBDIDipp]IrH4 {BDI = (Dipp)NC(Me)CH(Me)CN(Dipp); Dipp = 2,6-iPr2C6H3} with E[N(SiMe3)2]2 (E = Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([MeBDIDipp]IrH)2(μ2-E)2 in good yields. Moreover, ([MeBDIDipp]IrH)2(μ2-Ge)2 was formed in situ from thermal decomposition of [MeBDIDipp]Ir(H)2Ge[N(SiMe3)2]2. These reactions are accompanied by liberation of HN(SiMe3)2 and H2 by the apparent cleavage of an E-N(SiMe3)2 bond by Ir-H. In a reversal of this process, ([MeBDIDipp]IrH)2(μ2-E)2 reacted with excess H2 to regenerate [MeBDIDipp]IrH4. Variations of the concentrations of reactants led to formation of the trimeric ([MeBDIDipp]IrH2)3(μ2-E)3. The further scope of this synthetic route was investigated with group 15 amides, and ([MeBDIDipp]IrH)2(μ2-Bi)2 was prepared via the reaction of [MeBDIDipp]IrH4 with Bi(NMe2)3 or Bi(O t Bu)3, to afford the first example of a 'naked' two-coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for formation of the products is proposed. Computational investigations of the Ir2E2 (E = Ge, Sn, Pb) compounds characterized them as open-shell singlets with confined nonbonding lone-pairs at the E centers. In contrast, Ir2Bi2 is characterized as having a closed-shell singlet ground state.

Fluorine-Modulated Electronic Structure and Atomic Bonding of the Titanium Surface.

The fluorine-adsorption-induced local bond relaxation and valence-energy-state evolution of the Ti(0001) surface were examined through density functional theory calculations. The predicted bond-band-barrier (3 B) correlation notation framework for the interaction of the fluorine adsorbate with Ti atoms formed a tetrahedral structure through the creation of four valence density-of-state features, namely bonding electron pairs, nonbonding lone pairs, holes, and antibonding dipoles. The bonding states resulted in the passivation of metal Ti surfaces, the formation of Tip dipoles and Ti+/p H-like bonds modulated the work function of the Ti(0001) surface, and the conversion of metallic Ti to semiconducting titanium fluoride by the holes. The findings of this study confirm the universal applicability of the 3 B correlation notation in the dynamics of fluorine chemisorption and the associated valence electrons involved in fluorination.

The role of lone-pair electrons on electrocatalytic activity of copper antimony sulfide nanostructures

Crystal engineering is an elegant approach to the synthesis and design of active electrocatalysts for the large-scale production of hydrogen. Better realization of the crystal structure of the electrocatalyst assists the development of active catalysts. Different properties such as thermal properties, optical properties etc., appear to be largely affected by the presence of nonbonding lone-pair in the crystal structure. In this work, we have studied the influence of nonbonding electron pairs residing in the crystal structure on the electrocatalytic activity of the electrocatalysts. Herein, we report the synthesis of the three distinct crystal phases of copper antimony sulfide nanostructures named chalcostibite (CuSbS2), skinnerite (Cu3SbS3), and famatinite (Cu3SbS4), and studied their electrocatalytic activity in neutral medium. Chalcostibite and skinnerite phase show much better activity towards electrocatalytic hydrogen evolution reaction than the famatinite phase. This is explained due to the presence of antimony (Sb) lone pair electron in the former two cases compared to the latter.

Molecular modeling of new thiazolyl-thiophene based compounds as antioxidant agents

The targeted N-(thiazol-2-yl)thiophene-2-carboxamide derivatives 4–9 were synthesized based on heterocyclization of the functionalized thiocarbamoyl precursors 1 and 2 with 2-chloroacetamido-thiazole (3). The synthesized compounds were studied using DFT/B3LYP level to explore their structural and electronic properties. The frontier molecular orbital, HOMO and LUMO, showed that HOMO was consisted mainly of heteroatoms non-bonding lone pairs of electrons and the π-orbitals of the phenyl and thiophene rings with minor contribution from the thiazole nucleus of the non-bonding lone pairs. Furthermore, the investigated compounds had low energy gap (ΔEH-L), 1.64–2.62 eV, with the derivatives 7 and 4 having lowest and highest gap, respectively. The synthesized compounds exhibited good NLO properties due to their lower charge transfer resistance. The antioxidant activity for the synthesized thiazolyl-thiophene hybrids showed rational antioxidant effectiveness over DPPH technique. The results showed that hybrids 5, 7 and 9 exhibited respectable antioxidant with IC50 values (32.26±0.07, 27.31±0.23 and 23.17±0.36), respectively. However, thiazolyl-thiophene hybrids 4, 6 and 8 were shown tolerable IC50 values (43.28±0.14, 35.36±0.11 and 37.52±0.04), respectively against both of BHT (Butylated hydroxytoluene) and Ascorbic acid as references. The molecular docking estimation was also used on the generated thiazolyl-thiophene hybrids (PDB Code- 3OXI). The hybrids 4, 6 and 8 demonstrated a high binding affinity for the 3OXI amino acids. The docking results were satisfactory, and they mirrored the findings of the antioxidant study.

Molecular modeling and docking of new 2-acetamidothiazole-based compounds as antioxidant agents

The highly versatile, 2-chloroacetamido-5-(4-chlorophenylazo)thiazole (2) was synthesized and used as a precursor for the production of five 2-(2-substitutedacetamido)thiazole compounds by its reaction with different types of nucleophiles such as piperidine, morpholine, 2-mercaptobenzothiazole, 4,6-dimethyl-2-mercaptonicotinonitrile and 6-amino-2-mercapto pyrimidin-4-ol. DFT/B3LYP calculations of the isolated derivatives showed that their HOMO consisted mainly of the non-bonding lone pairs of heteroatoms while LUMO were π*-orbitals of the 2-acetamido-5-(4-chlorophenylazo)thiazole moiety. Despite the close energy gap values (ΔEH-L) of the investigated compounds, the data showed that thiazole-pyrimidine derivative 8 has the highest energy gap while the thiazole-piperidine derivative 3a was the lowest. The DPPH antioxidant activity examination results, in comparison to BHT (Butylated hydroxytoluene) and Ascorbic acid as controls, showed that sulfide compounds 4, 6, and 8 had more respectable inhibitions (IC50 = 24.17–32.26 µg/mL). Moreover, the molecular docking studies of the synthesized derivatives using protein (PDB Code-2Y9X) indicated that the sulfide compounds 4, 6, and 8 had a superior binding score, −6.3934, −6.5735, and −7.2835 kcal/mol, respectively. The docking results were satisfactory, and they matched the antioxidant investigation's conclusions.

Single-Bonded Cubic AsN from High-Pressure and High-Temperature Chemical Reactivity of Arsenic and Nitrogen.

Chemical reactivity between As and N2, leading to the synthesis of crystalline arsenic nitride, is here reported under high pressure and high temperature conditions generated by laser heating in a diamond anvil cell. Single‐crystal synchrotron X‐ray diffraction at different pressures between 30 and 40 GPa provides evidence for the synthesis of a covalent compound of AsN stoichiometry, crystallizing in a cubic P213 space group, in which each of the two elements is single‐bonded to three atoms of the other and hosts an electron lone pair, in a tetrahedral anisotropic coordination. The identification of characteristic structural motifs highlights the key role played by the directional repulsive interactions between non‐bonding electron lone pairs in the formation of the AsN structure. Additional data indicate the existence of AsN at room temperature from 9.8 up to 50 GPa. Implications concern fundamental aspects of pnictogens chemistry and the synthesis of innovative advanced materials.

Tuning the Quantum Chemical Properties of Flavins via Modification at C8.

Flavins are central to countless enzymes but display different reactivities depending on their environments. This is understood to reflect modulation of the flavin electronic structure. To understand changes in orbital natures, energies, and correlation over the ring system, we begin by comparing seven flavin variants differing at C8, exploiting their different electronic spectra to validate quantum chemical calculations. Ground state calculations replicate a Hammett trend and reveal the significance of the flavin π-system. Comparison of higher-level theories establishes CC2 and ACD(2) as methods of choice for characterization of electronic transitions. Charge transfer character and electron correlation prove responsive to the identity of the substituent at C8. Indeed, bond length alternation analysis demonstrates extensive conjugation and delocalization from the C8 position throughout the ring system. Moreover, we succeed in replicating a particularly challenging UV/Vis spectrum by implementing hybrid QM/MM in explicit solvents. Our calculations reveal that the presence of nonbonding lone pairs correlates with the change in the UV/Vis spectrum observed when the 8-methyl is replaced by NH2, OH, or SH. Thus, our computations offer routes to understanding the spectra of flavins with different modifications. This is a first step toward understanding how the same is accomplished by different binding environments.

Tuning the Quantum Chemical Properties of Flavins via Modification at C8.

Flavins are central to countless enzymes but display different reactivities depending on their environments. This is understood to reflect modulation of the flavin electronic structure. To understand changes in orbital natures, energies, and correlation over the ring system, we begin by comparing seven flavin variants differing at C8, exploiting their different electronic spectra to validate quantum chemical calculations. Ground state calculations replicate a Hammett trend and reveal the significance of the flavin π-system. Comparison of higher-level theories establishes CC2 and ACD(2) as methods of choice for characterization of electronic transitions. Charge transfer character and electron correlation prove responsive to the identity of the substituent at C8. Indeed, bond length alternation analysis demonstrates extensive conjugation and delocalization from the C8 position throughout the ring system. Moreover, we succeed in replicating a particularly challenging UV/Vis spectrum by implementing hybrid QM/MM in explicit solvents. Our calculations reveal that the presence of nonbonding lone pairs correlates with the change in the UV/Vis spectrum observed when the 8-methyl is replaced by NH2, OH, or SH. Thus, our computations offer routes to understanding the spectra of flavins with different modifications. This is a first step toward understanding how the same is accomplished by different binding environments.

High-Pressure Phases of SnO and PbO: A Density Functional Theory Combined with an Evolutionary Algorithm Approach.

Tin monoxide, SnO, and its analog, lead monoxide, PbO, have the same tetragonal P4/nmm structure, shaped by nonbonding dispersion forces and lone pairs. The high-pressure phases of SnO and PbO have been explored in several experimental and theoretical studies, with conflicting results. In this study, the high-pressure structures of SnO and PbO are investigated using density functional theory calculations combined with an evolutionary algorithm to identify novel high-pressure phases. We propose that the monoclinic P21/m SnO and orthorhombic Pmmn PbO phases, which are metastable at 0 GPa, are a slight rearrangement of the tetragonal P4/nmm-layered structure. These orthorhombic (and their closely related monoclinic) phases become more favored than the tetragonal phase upon compression. In particular, the transition pressures to the orthorhombic γ-phase Pmn21 of SnO/PbO and the monoclinic phase P21/m of SnO are found to be consistent with experimental studies. Two new high-pressure SnO/PbO polymorphs are predicted: the orthorhombic Pbcm phase of SnO and the monoclinic C2/m of PbO. These phases are stabilized in our calculations when P > 65 GPa and P > 50 GPa, respectively. The weakening of the lone pair localization and elastic instability are the main drivers of pressure-induced phase transitions. Modulations of the SnO/PbO electronic structure due to structural transitions upon compression are also discussed.

Insights into the Factors Controlling the Origin of Activation Barriers in Group 13 Analogues of the Four-Membered N-Heterocyclic Carbenes.

The mechanisms of C–H bond insertion and alkene cycloaddition were investigated theoretically using five model systems: group 13 analogues of the four-membered nucleophilic N-heterocyclic carbenes (NHCs) (1E; E = group 13 element). The theoretical findings indicate that, except for 1B with H2C=CH2, these four-membered NHCs undergo insertion and [1 + 2] cycloaddition reactions with difficulty because their activation barriers are quite high (31 kcal/mol). The theoretically confirmed chemical inertness of the four-membered NHCs 1Ga and 1In might explain why they have been experimentally detected at room temperature. Additionally, our theoretical observations indicate that the reactivity of these four-membered NHCs featuring a central group 13 element follows the order 1B ≫ 1Al > 1Ga > 1In > 1Tl. The theoretical examination suggests that the smaller the atomic radius of the central group 13 element in the four-membered NHC analogue is, the larger the aromaticity of this carbenic molecule is, the higher the basicity of this carbenic molecule in nature is, the larger its nucleophilic attack on other oncoming molecules is, the smaller the barrier heights of its C–H bond insertion and [1 + 2] cycloaddition reactions will be, the higher its exothermicities for these products will be, and thus, the greater its reactivity will be. Moreover, the present theoretical findings reveal that the reactivity of 1B is governed by its highest occupied molecular orbital, a nonbonding sp2 lone pair orbital. In contrast, the reactivity of the four heavier 1E′ (E′ = Al, Ga, In, and Tl) molecules is mainly determined by their lowest unoccupied molecular orbital, a vacant p−π orbital. The conclusions gained from this study allow many predictions to be made.

Role of the solvent medium in the wet-chemical synthesis of CuSbS2, Cu3SbS3, and bismuth substituted Cu3SbS3

Co-thermal decompositions of equimolar concentrations of thiourea complexes ([Cu(tu)3]Cl and [Sb(tu)2]Cl3) in ethylene glycol and ethanolamine were attempted. Based on the results from powder X-ray diffraction, Raman spectroscopy, and energy dispersive spectral analysis of the products, Cu3SbS3 in cubic symmetry emerged from ethylene glycol. In contrast, orthorhombic CuSbS2 resulted from the ethanolamine medium. The generation of copper-rich and copper-poor sulfides was found to be the major reason behind the formation of these stoichiometries of the Cu-Sb-S system as verified by reacting the preformed Cu-S and Sb-S species in ethanolamine and ethylene glycol. Attempts to include bismuth (up to 50 mol%) for antimony were successful only in ethylene glycol medium. The inclusion of bismuth stabilized the orthorhombic form of Cu3SbS3, possibly due to the non-bonded lone pairs present on Bi3+ and Sb3+-ions. The inclusion of bismuth confirmed from the successful refinement of powder X-ray diffraction pattern by the Rietveld method, Raman spectroscopy, and energy dispersive spectroscopy analysis. CuSbS2, Cu3SbS3 (cubic) and Cu3Sb0.50Bi0.50S3 showed broad absorption extending up to visible region in their UV-visible spectra. The bandgap values of 1.31, 1.40 and 0.94 eV were estimated by Tauc plots for Cu3SbS3, CuSbS2, and Cu3Sb0.50Bi0.50S3, respectively. CuSbS2, Cu3SbS3 (cubic) and Cu3Sb0.50Bi0.50S3 showed broad absorption extending up to visible region in their UV-visible spectra. The bandgap values of 1.31, 1.40 and 0.94 eV were estimated by Tauc plots for Cu3SbS3, CuSbS2, and Cu3Sb0.50Bi0.50S3, respectively.

Boron nitride nanoclusters, nanoparticles and nanotubes as a drug carrier for isoniazid anti-tuberculosis drug, computational chemistry approaches

In this work, the ability of B12N12 fullerene-like nanoclusters as a drug carrier for isoniazid anti-tuberculosis drug has been studied by DFT methods. Binding energies in both gas and water phases are reported. The formed bonds between B12N12-FLN and Iso drug are studied and computed using QMAIM method. NPA is computed to obtain the total charges transferred in the B12N12-FLN-Iso drug complexes, NPA obtained values suggested that the cluster may oxidize the coordinated of Iso drug. The charge-transfer energy values are also computed and confirmed that the charges were transferred from the non-bonding lone-pair (n) of N and O atoms orbitals to the σ* orbitals of B and N atoms of B12N12-FLN. Also, the adsorption of Iso drug on BN nanoparticles surface (different sizes and shapes) and BN nanotubes was studied by Monte Carlo simulation. We found that increasing the BN size did not affect significantly on the adsorption energies of Iso drug for all various BN nanoparticles shapes. All adsorption energies obtained by MC calculations are negative values which revealed that the adsorption of the Iso drug molecule on BN surfaces is exothermic, spontaneous and energetically favourable. Also, the stability of B12N12-FLN-Iso drug complex in water explicitly was studied by MD simulations. MD simulation confirmed that iso-B12N12-FLN complexes are stable in the presence of water molecules. So, finally, we deduced that B12N12 fullerene-like nanoclusters can be acted as a drug carrier for isoniazid anti-tuberculosis drug. Communicated by Ramaswamy H. Sarma

Experimental and Theoretical Study of SbPO4 under Compression.

SbPO4 is a complex monoclinic layered material characterized by a strong activity of the nonbonding lone electron pair (LEP) of Sb. The strong cation LEP leads to the formation of layers piled up along the a axis and linked by weak Sb-O electrostatic interactions. In fact, Sb has 4-fold coordination with O similarly to what occurs with the P-O coordination, despite the large difference in ionic radii and electronegativity between both elements. Here we report a joint experimental and theoretical study of the structural and vibrational properties of SbPO4 at high pressure. We show that SbPO4 is not only one of the most compressible phosphates but also one of the most compressible compounds of the ABO4 family. Moreover, it has a considerable anisotropic compression behavior, with the largest compression occurring along a direction close to the a axis and governed by the compression of the LEP and the weak interlayer Sb-O bonds. The strong compression along the a axis leads to a subtle modification of the monoclinic crystal structure above 3 GPa, leading from a 2D to a 3D material. Moreover, the onset of a reversible pressure-induced phase transition is observed above 9 GPa, which is completed above 20 GPa. We propose that the high-pressure phase is a triclinic distortion of the original monoclinic phase. The understanding of the compression mechanism of SbPO4 can aid to improve the ion intercalation and catalytic properties of this layered compound.

Structural distortions of fullerene C60n (n = 0 to −6) by first principle density functional theory

The anions of C60 fullerene have geometrically multiple distortions. These geometric changes of C60 were directly related to the orbital changes called structural distortion effects. In this study, neutral C60 fullerene and its −1 to −6 anions were optimized by using DFT method. The geometric changes and the electronic properties were also investigated. Unrestricted calculations were applied to investigate the energy gap changes and density of states (DOS) spectrums as well. The electron localization function (ELF) along with the natural bond orbital (NBO) calculations were presented the considerable images from the changes of electron properties of C60 fullerene. The results show that in −5 and −6 anions lost π bonds and also can see creation of non-bonding lone pair in −6 anion. The calculations on the vibrational levels, structural changes such as changes in diameters and dipole moments of C60n (n = 0 to −6) were investigated as well. The most stable spin forms of the optimized C60 structures were chosen to observe structural distortions by using the DFT computational method. For some of the anions the wide changes of forms, energies of the valance orbitals and the energy states were investigated for the low and high spins. Also, the spin channel phenomenon was studied by using the results of DFT-B3LYP/6-31G∗ calculations. The NBO analysis was performed due to its beneficial information in the changes of fullerene electronic system properties for all the anion states in the selected computational level method. The changes of the calculated IR spectra patterns have discussed due to the charge changes of C60n (n = 0 to −6) and on the basis of the structural distortions role (John-Teller effect). A linear equation was obtained by using graph theory (GT) between the energy of HOMO and/or LUMO orbitals and load amount of anions. The DOS spectrums and HOMO and LUMO orbitals in the different discussed spin states show that all fullerene anions have different spin behavior and magnetic specifications, in which anions −2 and −3 anions of C60 act as the spin channels.

An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates

α-Tocopheryl succinate (α-TOS) is a very promising anticancer agent; however, the mechanism of its action and the role of the succinic moiety in biological activity still remains unclear. This paper, presents the first determination of the X-ray structure of α-TOS and 2,2,5,7,8-pentamethylchroman-6-yl succinate (PMCS). The X-ray data indicated high out of planarity deformation of the aryl ring in the chroman-6-ol system. α-TOS and PMCS differed in angle θ value (28.4° vs. 21.5°, respectively) and in their heterocyclic ring conformations: 2-endo-3-exo in PMCS, and 2-endo-3-exo and 2-exo-3-endo in α-TOS. Due to their strong intermolecular hydrogen bonds, both succinates form cyclically repeated dimeric structures in well assembled crystal supramolecular structures.A population analysis of α-tocopherol (α-TOC), 2,2,5,7,8-pentamethylchroman-6-ol (PMC) and their acyl derivatives was performed at B3LYP/6-31G(d,p)/CPCM level of theory using a natural bond orbital (NBO) analysis within the Gaussian 09 program package. For all compounds, relaxed scans were performed along torsion angle γ, and for low-energy conformers the Fukui functions were calculated: electron donor (ƒ−(r)), electron acceptor (ƒ+(r)), free radical (ƒo(r)) and dual descriptor (ƒ2(r)).In general, the differences observed between α-TOC and its acyl derivative structures result from the non-bonding lone pair of the phenolic oxygen and its interaction with aromatic system π electrons.

Stereochemistry and ab initio topology analyses of electron lone pair triplets and twins in interhalogen compounds and halogen suboxides

The paper reports a thorough investigation of little inspected two classes of group VIIA based crystals: interhalogen compounds ClF, ClF3, BrF3 and IF3 on one hand and halogen suboxides F2O, Cl2O and Br2O on the other hand, as well as rare gas fluorides (here exemplarily XeF4), all exhibiting peculiar stereochemistry of electron (non-bonding) lone pairs merging in forms of twins and triplets. Particularly with respect to the well known VSEPR (Valence Shell Electron Pair Repulsion) model we present original approach merging crystal chemistry and density functional theory (DFT) electron localization function (ELF) to provide accurate topologic analyses and precise metrics of electron lone pairs geometries. In this context we rewrite the chemical formulae above by adjoining E designing the lone pair (LP) and M* formulating the LP-bearing element: ClF{E3}, M*2OE2{E3}2 (M* = F, Cl, Br), M*F3E2 (M* = Cl, Br, I) and XeF4E2. Then in ClF{E3} and M*2OE2{E3}2 (M* = F, Cl, Br) family an original stereochemistry is developed with LP concentration in E triplets which generate electronic torus revolving around Cl and M* which in the neighborhood of largely electronegative F, exhibit cationic-like behavior. E around Cl in ClF and then around M* of the series under consideration exhibits an ellipsoidic shape with an equivalent sphere of influence radius (rE) increasing along with the atomic number Z, i.e. rE_F = 0.52 Å, rE_Cl = 0.65 Å and rE_Br = 0.70 Å. From selected sections in ELF data we obtained precise topology and metrics details of these tori. For M*2OE2{E3}2 family the E twins attached to O have also been localized, their size remaining constant with rE_O = 0.68 Å in all studied compounds. The lone pair twins in the series M*F3E2 (M* = Cl, Br, I; M* trivalent oxidation state) as well as in noble gas tetrafluoride XeF4E2 provide remarkable examples: rE evolution versus Z, rE_Cl = 0.77 Å (Z = 17), rE_Br = 0.85 Å (Z = Br) and rE_I = 0.90 Å (Z = 53), follow a linear expansion while in the xenon case with a close ZXe = 54 but with tetravalent oxidation state, Xe exhibits a radius rE_Xe = 0.95 Å, indicating the important influence of the charge magnitude on E volume. The interaction of cations with E centroïd: Ec -defined as the electronic volume attached to the lone pair- of neighboring molecules is plausible in explaining unusually short distances between cations. Even surrounded by E torus the cations obviously exert attractive influence through its vortex axis. Based on combined stereochemistry and ab initio topology analyses the paper endeavors showing the unavoidable necessity to accurately account for electron lone pairs: position of their centroïd, their shape, their size, and their deformation (knowing that the electron cloud which accompanies them exhibits a certain plasticity), in order to fully understand their remarkable influence on crystal networks.