Synthesis, structural investigation and thermal stability of aqua magnesium(II) phthalocyanine adducts with 2-methoxyethylamine

Three new aqua magnesium phthalocyaninato complexes with 2-methoxyethylamine (MEA) in crystalline form have been obtained. The composition of the complexes depends on the crystallisation temperature. (MgPcH₂O)₂ · MEA (I) and (MgPcH₂O)₂ · 2MEA (II) were formed at about 170 °C and 80 °C, respectively, while room temperature (MgPcH₂O)₂ · 3MEA (III) was obtained. In all crystals the Mg atom is 4+1 coordinated, equatorially by four N-isoindole atoms of Pc ligand and axially by O atom of water molecule. The MgPc moiety is non-planar, the Mg(II) deviates by ∼0.5 Å from the N₄-isoindole plane towards the oxygen atom of water molecule. The MEA molecules in the crystals interact via hydrogen bonds with coordinated water molecules of MgPcH₂O. The arrangement of MgPcH₂O and 2-methoxyethylamine molecules is determined by O-H?N and O-H?O hydrogen bonds and by π-π interactions. The thermogravimetric analyses show characteristic steeps responsible for the loss of MEA molecules (at lower temperature) and water (at higher temperature) and finally all the complexes transform into β-MgPc. From among the complexes only complex II exhibits an intense near-IR absorption band in the solid-state, while spectra in MEA solution are identical for all the complexes.     

Theoretical characterization of SOME amides and esters DERIVATIVES of valproic acid

The equilibrium structures, the planarity of the C(=O)X linkage and the nature of the chemical bond in the Y−C(=O)−XR₁R₂ [where: Y= −CH−(CH₂−CH₂−CH₃)₂, X=N,O and R₁, R₂= H; alkyl and aryl groups and lone pair electrons (lp)] molecular fragment of derivates of Valproic acid (Vpa) with antiepileptic activity were studied systematically by means of B3LYP calculations and topological analysis of the electron localization function (ELF). The covariance parameter cov[Ω_i, Ω_j] reveals a dominating delocalization effect between the lone pair V(O₁), V(X) and the electron density of the H−C and H−X₁ bonds resulting from the existence of not only non-conventional intramolecular hydrogen bonding patterns as C−H...O/N but also a weak closed-shell stabilizing interaction type arising from a dihydrogen bonding as C−H...H−N, where H...H contacts at a significantly shorter distance than twice the hydrogen atom van der Waals radius. The analyzed data derived from ELF domains were found to be in agreement with the known features and properties of the hydrogen bonding interactions discussed in this work.     

Synthesis and crystal structure of a novel three-dimensional supramolecular network containing one-dimensional honeycomb-like channels

A novel supramolecular assembly containing honeycomb-like channels [Cu(mal)(bpy)] · 3H₂O (mal = malate, bpy = 2,2′-bipy) has been synthesized and characterized by elemental analyses, IR, EPR, TG, UV-Vis and single crystal X-ray diffraction. Compound 1 is constructed from spiral-shaped chains via O-H?O hydrogen bonds and π-π stacking interactions. To our knowledge, compound 1 represents the first supramolecular network constructed from the mixed malate and pyridine ligand.     

Intermolecular interactions between gold clusters and selected amino acids cysteine and glycine: a DFT study

The intermolecular interactions between Au_n (n = 3–4) clusters and selected amino acids cysteine and glycine have been investigated by means of density functional theory (DFT). Present calculations show that the complexes possessing Au-NH₂ anchoring bond are found to be energetically favored. The results of NBO and frontier molecular orbitals analysis indicate that for the complex with anchoring bonds, lone pair electrons of sulfur, oxygen, and nitrogen atoms are transferred to the antibonding orbitals of gold, while for the complex with the nonconventional hydrogen bonds (Au···H–O), the lone pair electrons of gold are transferred to the antibonding orbitals of O-H bonds during the interaction. Furthermore, the interaction energy calculations show that the complexes with Au-NH₂ anchoring bond have relatively high intermolecular interaction energy, which is consistent with previous computational studies.     

A ferromagnetically coupled tetranuclear pseudo-cubane copper(II) cluster: magnetic and ESR studies

A tetranuclear copper(II) complex [Cu₄(NSI)₄] · 2C₂H₅OH · 2H₂O (NSI=hydroxethylsalicydeneimine) has been synthesized and characterized by X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group P2(1), a=9.494(3) Å, b=18.687(5) Å, c=13.149(4) Å, β=110.162(5)°, Z=2, R₁=0.0482 and wR₂=0.0978. The crystal structure contains a tetranuclear pseudo-cubane core based on an approximately cubane array of alternating copper and oxygen atoms. Each copper atom resides in a distorted square planar coordination environment with one nitrogen and three oxygen atoms from two NSI ligands. The tetranuclear units are linked in the crystal by O-H?O hydrogen bonds and weak Cu?O co-ordination bonds into one-dimensional structure. Variable temperature (5-300 K) magnetic measurements indicate the existence of ferromagnetic interactions among copper atoms. The IR and ESR spectra have also been investigated.     

Effects of equatorial ligand bulk on the orientation of axial ligands in methyl organocobalt B12 models assessed by X-ray and NMR methods

We prepared two new analogues of ([CH₃Co((DO)(DOH)pn)L]⁺) [(DO)(DOH)pn = N²,N^2′-propane-1,3-diylbis(2,3-butanedione-2-imine-3-oxime)] B₁₂ models but with an O-BF₂-O unit replacing the O-H?O unit as follows: [CH₃Co((DO)(DOBF₂)pn)L]PF₆ with L = pyridine (py) and 1,5,6-trimethylbenzimidazole (Me₃Bzm). Our goal was to compare the properties of these new O-BF₂-O complexes with the well-established O-H?O analogues. The Co-CH₃¹H NMR shifts indicate that the BF₂ group makes the Co(III) less electron rich. The X-ray crystal structures determined for the new compounds were compared to the one known structure with L = imidazole (Im). With increasing size of L, in the series Im < py < Me₃Bzm, the plane of L orients so as to avoid the bulky BF₂ group. This orientation effect becomes apparent in the L ¹H NMR shifts, which are not sensitive to Co(III) electronic properties. Thus, in the O-BF₂-O versus the O-H?O analogue, the Me₃Bzm H4 signal shifts 0.41 ppm upfield from the anisotropic effect of the equatorial ligand double bonds. We advance the concept (applicable to a broad series of complexes) that steric interactions between L and the equatorial ligands are alleviated by a combination of Co-N_ax bond elongation and opening of the N_eq-Co-N_ax angles.     

Hydrogen bonding adducts of octamolybdate anions containing coordinately bound pyridiniumoxides

The reaction of [Mo₇O₂₄][NH₄]₆ with 3-hydroxypyridine (3-HOPy) and 4-hydroxypyridine (4-HOPy) in water resulted in the crystalline materials of [Mo₈O₂₆(3-OPyH)₂][3-HOPyH]₄ · 4H₂O (1) and [Mo₈O₂₆(4-OPyH)₂][4-HOPyH]₄ · 4H₂O (2), respectively. Crystal structures of the complexes 1 and 2 reveal that two of the OPyH moieties coordinately linked to two molybdate atoms of Mo₈O₂₆ clusters. The crystal structures of 1 and 2 are not iso-structural. However, in both cases the iso-structural Mo₈O₂₆(OPyH)₂ units join together via N-H?O hydrogen bonds to form linear ribbons which are further joined by H₂O molecules to form 2D-layers. The cavities or channels of these layers are occupied by the C-H?O, O-H?O and O-H?π aggregates of hydroxypyridinium cations.     

Density functional theory study on (LiNH<Subscript>2</Subscript>)<Subscript>n</Subscript> (<Emphasis Type="Italic">n</Emphasis> = 1–5) clusters

Geometrical structures and relative stabilities of (LiNH₂)_n (n = 1–5) clusters were studied using density functional theory (DFT) at the B3LYP/6-31G* and B3LYP/6-31++G* levels. The electronic structures, vibrational properties, N–H bond dissociation energies (BDE), thermodynamic properties, bond properties and ionization potentials were analyzed for the most stable isomers. The calculated results show that the Li–N and Li–Li bonds can be formed more easily than those of the Li–H or N–H bonds in the clusters, in which NH₂ is bound to the framework of Li atomic clusters with fused rings. The average binding energies for each LiNH₂ unit increase gradually from 142 kJ mol⁻¹ up to about 180 kJ mol⁻¹ with increasing n. Natural bond orbital (NBO) analysis suggests that the bonds between Li and NH₂ are of strong ionicity. Three-center–two-electron Li–N–Li bonding exists in the (LiNH₂)₂ dimer. The N–H BDE values indicate that the change in N–H BDE values from the monomer a1 to the singlet-state clusters is small. The N–H bonds in singlet state clusters are stable, while the N–H bonds in triplet clusters dissociate easily. A study of their thermodynamic properties suggests that monomer a1 forms clusters (b1, c1, d2 and e1) easily at low temperature, and clusters with fewer numbers of rings tend to transfer to ones with more rings at low temperature. E _g, E _HOMO and E _av decrease gradually, and become constant. Ring-like (LiNH₂)_3,4 clusters possess higher ionization energy (VIE) and E _g, but lower values of E _HOMO. Ring-like (LiNH₂)_3,4 clusters are more stable than other types. A comparison of structures and spectra between clusters and crystal showed that the NH₂ moiety in clusters has a structure and spectral features similar to those of the crystal.     

On the possible influence of different pathways of binding of amides with water on “Pyramidalization” of valence bonds of peptide group nitrogen

With the aim to study solvation effects in peptide structure organization, the behavior of the energy of different types of hydration in simple amines and amides has been analyzed. On the example of quantum-chemical DFT and PM3 calculations of amino derivatives of composition CH₃-(CH₂)₃)-NH₂, (CH3)₂-NH, CH₃-NH₂, NH₃, CH₂=CH-NH₂, H-CC-NH₂, O=C(CH)₃-N(CH₃)₂, O=C(CH₃)-NH(CH₃), O=C(CH₃)-NH₂, O=CH-N(CH₃)H, and O=CH-NH₂ it has been shown that: (1) in the given set of molecules, the proton acceptor N…H-O variant of hydrogen bonding of NH₂ group with a water molecule is dominating only for the simplest amines. Being primordially weaker, the proton donor N-H…OH variant of water H-bonding gradually increases in energy in the given set as the basicity of the compound decreases, and for the case of amides of carboxylic acids it becomes already a significant channel of the hydration; (2) the intermolecular N-H…O=C bonding of trans-N-methylacetamides, which models the peptide hydrogen bonds in proteins, induces “planarization” of its initially nonplanar O=C-NH fragments. However, the addition of water molecules to the complex through the proton acceptor N…H-O variant of binding of N atom not only restores but even strengthens the “pyramidalization” of valence bonds of peptide groups.     

Crystal Structure of 2′-Deoxycytidine Hemidihydrogenphosphate Reveals C+·C Base Pairs and Tight,Hydrogen-Bonded (H2PO4 −)∞ Columns (1)

Abstract

2′-Deoxycytidine hemidihydrogenphosphate has been crystallized in the hexagonal space group P6₂ with α=25.839(3), c = 12.529(1) Å. The structure has been solved using the Patterson search method. The asymmetric unit contains two protonated, base-paired 2′-deoxycytidine dimers and two H₂PO₄ ^? anions. The C⁺·C base pairs are composed of a protonated and a neutral species each and are triple H-bonded, the central N(3)…N(3) bonds being 2.850(7) and 2.884(5) Å. The conformations of the four nucleosides fall in the same category (sugar puckers 2·-endo, glycosidic links anti) but in one of them the glycosidic torsion angle is quite low with consequences in other geometrical parameters. The H₂PO₄ ^? anions are located on twofold axes and form two types of tight columns with P…P separations about 4.18 Å The neighboring units along a column are linked via two very short O…H…O hydrogen bonds (O…O about 2.49 Å) leading to effective equalization of the P-O bonds. The base pairs of the two dC⁺·dC cations are coplanar and form layers perpendicular to the phosphate columns repeating every c/3. Within the layers, the dimers form a network through 0(5′)…O(2) hydrogen bonds but their primary intermolecular interactions have the form of H-bond anchors [N(4)-H…O-P and 0(3′)-H…O-P] to the phosphate groups.     

A novel self-assembling of mixed tri- and dibutyltin macrocyclic complex with solvothermal synthesis method

The self-assembled reaction of 2-hydroxynicotinic acid, KOH and tri-n-butyltin chloride in CH₃OH and H₂O (V/V = 5:1) under solvothermal condition (150 °C) affords a novel mixed tri- and dibutyltin macrocyclic complex 1. Characterization of the complex 1 was achieved using elemental analysis, IR, NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy, TGA and X-ray crystallography diffraction analysis. X-ray data revealed that it is an unusual 16-membered macrocycle containing eight tin atoms, and they can be divided into four sorts by the distinct environments, the endocyclic tin atoms are best described as five- and six-coordinate and the exocyclic tin atoms as five-coordinate. Furthermore, a 2D corrugated sheet is formed by intermolecular C-H?Cl, O-H?N and O-H?O weak interactions.     

MP2, density functional theory, and molecular mechanical calculations of C-H···π and hydrogen bond interactions in a cellulose-binding module-cellulose model system

Exploring non-covalent interactions, such as C-H···π stacking and classical hydrogen bonding (H-bonding), between carbohydrates and carbohydrate-binding modules (CBMs) is an important task in glycobiology. The present study focuses on intermolecular interactions, such as C-H?π (sugar-aromatic stacking) and H-bonds, between methyl β-d-glucopyranoside and l-tyrosine—a proxy model system for a cellulose-CBM complex. This work has made use of various types of quantum mechanics (QM) and molecular mechanics (MM) methods to determine which is the most accurate and computationally efficient. The calculated interaction potential energies ranged between −24 and −38 kJ/mol. The larger interaction energy is due to H-bonding between the phenyl hydroxyl of tyrosine and the O4 of the sugar. Density functional theory (DFT) methods, such as BHandHLYP and B3LYP, exaggerate the H-bond. Although one of the MM methods (viz. MM+) considered in this study does maintain the C-H?π stacking configuration, it underestimates the interaction energy due to the loss of the H-bond. When the O-H bond vector is in the vicinity of O4 (O-H?O4 ≈ 2 Å, e.g., in the case of MP2/6-31G(d)), the torsional energy drops to a minimum. For this configuration, natural bond orbital (NBO) analysis also supports the presence of this H-bond which arises due to orbital interaction between one lone pair of the sugar O4 and the σ∗(O-H) orbital of the phenyl group of tyrosine. The stabilization energy due to orbital delocalization of the H-bonded system is ∼13 kJ/mol. This H-bond interaction plays an important role in controlling the CH/π interaction geometry. Therefore, the C-H?π dispersive interaction is the secondary force, which supports the stabilization of the complex. The meta-hybrid DFT method, M05-2X, with the 6-311++G(d,p) basis set agrees well with the MP2 results and is less computationally expensive. However, the M05-2X method is strongly basis set dependent in describing this CH/π interaction. Computed IR spectra with the MP2/6-31G(d) method show blue shifts for C1-H, C3-H, and C5-H stretching frequencies due to the C-H?π interaction. However, the M05-2X/6-311++G(d,p) method shows a small red shift for the C1-H stretching region and blue shifts for the C2-H and C3-H stretches. For the aromatic tyrosine C_δ1-C_ε1 and C_δ2-C_ε2 bonds in the complex, the calculated IR spectra show red shifts of 12 cm⁻¹ (MP2/6-31G(d)) and 5 cm⁻¹ (M05-2X/6-311++G(d,p)). This study also reports the upfield shifts of computed ¹H NMR chemical shifts due to the C-H?π interaction.     

Conformational analysis of an acyclic tetrapeptide: ab‐initio structure determination from X‐ray powder diffraction,Hirshfeld surface analysis and electronic structure

A terminally protected acyclic tetrapeptide has been synthesized, and the crystal structure of its hydrated form, Boc‐Tyr‐Aib‐Tyr‐Ile‐OMe·2H₂O ( 1 ), has been determined directly from powder X‐ray diffraction data. The backbone conformation of tetrapeptide ( 1 ) exhibiting two consecutive β‐turns is stabilized by two 4 → 1 intramolecular N―H · · · O hydrogen bonds. In the crystalline state, the tetrapeptide molecules are assembled through water‐mediated O―H · · · O hydrogen bonds to form two‐dimensional molecular sheets, which are further linked by intermolecular C―H · · · O hydrogen bonds into a three‐dimensional supramolecular framework. The molecular electrostatic potential (MEP) surface of ( 1 ) has been used to supplement the crystallographic observations. The nature of intermolecular interactions in ( 1 ) has been analyzed quantitatively through the Hirshfeld surface and two‐dimensional fingerprint plot. The DFT optimized molecular geometry of ( 1 ) agrees closely with that obtained from the X‐ray structure analysis. The present structure analysis of Boc‐Tyr‐Aib‐Tyr‐Ile‐OMe·2H₂O ( 1 ) represents a case where ab‐initio crystal structure of an acyclic tetrapeptide with considerable molecular flexibility has been accomplished from laboratory X‐ray powder diffraction data. Copyright © 2015 European Peptide Society and John Wiley & Sons, Ltd.     

Theoretical study of hydrogen bond interactions of fluvastatin with <Emphasis Type="BoldItalic">ι</Emphasis>-carrageenan and <Emphasis Type="Italic">λ</Emphasis>-carrageenan

The binding of the reductase inhibitor drug fluvastatin, hydroxy-3-methylglutaryl coenzyme A, with the hydrophilic ι- or λ-carrageenan polymers, serving as potential controllers of the drug’s release rate, have been studied at the density functional level of theory with the B3LYP exchange correlation functional. Three low energy conformers of fluvastatin have been calculated. The vibrational spectroscopic properties calculated for the most stable conformer were in satisfactory agreement with the experimental data. A series of hydrogen bonded complexes of the most stable conformer of fluvastatin anion with low molecular weight models of the polymers have been fully optimized. In almost all, intermolecular H-bonds are formed between the sulfate groups of ι- or λ-carrageenan and fluvastatin’s hydroxyls, resulting in a red shift of the fluvastatin’s O − H stretching vibrations. Cooperative intramolecular H-bonds within fluvastatin or ι-, λ-carrageenan are also present. The BSSE and ZPE corrected interaction energies were estimated in the range 281–318 kJ mol⁻¹ for ι-carrageenan - fluvastatin and 145–200 kJ mol⁻¹ for λ-carrageenan - fluvastatin complexes. The electron density (ρ _bcp) and Laplacian (∇² ρ _bcp) properties at critical points of the intermolecular hydrogen bonds, estimated by AIM (atoms in molecules) calculations, have a low and positive character (∇² ρ _bcp > 0), consistent with the electrostatic character of the hydrogen bonds. The structural and energetic data observed, as well as the extent of the red shift of the fluvastatin’s O − H stretching vibrations upon complex formation and the properties of electron density show a stronger binding of fluvastatin to ι- than to λ-carrageenan.     

Why are dimethyl sulfoxide and dimethyl sulfone such good solvents?

We have carried out B3PW91 and MP2-FC computational studies of dimethyl sulfoxide, (CH₃)₂SO, and dimethyl sulfone, (CH₃)₂SO₂. The objective was to establish quantitatively the basis for their high polarities and boiling points, and their strong solvent powers for a variety of solutes. Natural bond order analyses show that the sulfur–oxygen linkages are not double bonds, as widely believed, but rather are coordinate covalent single S⁺→O⁻ bonds. The calculated electrostatic potentials on the molecular surfaces reveal several strongly positive and negative sites (the former including σ-holes on the sulfurs) through which a variety of simultaneous intermolecular electrostatic interactions can occur. A series of examples is given. In terms of these features the striking properties of dimethyl sulfoxide and dimethyl sulfone, their large dipole moments and dielectric constants, their high boiling points and why they are such good solvents, can readily be understood. Figure Dimers of dimethyl sulfoxide (DMSO; left) and dimethyl sulfone (DMSO2; right) showing O S—O -hole bonding and C H—O hydrogen bonding. Sulfur atoms are yellow, oxygens are red, carbons are gray and hydrogens are white     

Abundance and arrangement of single,double and bifurcated hydrogen bonds in protein α-helices: Statistical analysis of PDB-select

Statistics are collected and analyzed for the possibility of hydrogen bonding in the secondary structures of globular proteins, based on geometric criteria. Double and bifurcated bonds are considered as pairs of admissible H-bonds with two proton donors or two proton acceptors, respectively. Most of such bonds belong to peptide groups in α-helices, with O _i …N _{i + 3} nearly as frequent as O _i …N _{i + 4}; in contrast, most of the 3/10-helical segments are too short to have any. Alternating double and bifurcated bonds in α-helices form an apparently cooperative network structure. A typical α-helical segment perhaps carries two stretches of the H-bond network broken in the middle. The constituent H-bonds are nonlinear: the hydrogen atom is off the straight line connecting the proton donor and proton acceptor atoms. This deflection is larger for H _{i + 3} vs. bond line O _i −N _{i + 3} than for H _{i + 4} vs. O _i −N _{i + 4}, and though the two kinds of bond have about the same length (exceeding those typical of low-molecular compounds), O _i …N _{i + 4} must be stronger than O _i …N _{i + 3}. Double/bifurcated bonds are also not coplanar, i.e., hydrogen atoms are beyond the N…O…N (or O…N…O) plane. The text was submitted by the authors in English.     

Double coned inverse sandwich complexes [M-(η4-C4H4)-M′] of Gr-IA and Gr-IIA Metals: theoretical study of electronic of structure and second hyperpolarizability

Molecular interaction between dioxane and methanol involves certain polar and nonpolar bonding to form a one to one complex. Interatomic distances between hydrogen and oxygen within 3 Å have been considered as hydrogen bonding. Optimizations of the structures of dioxane-methanol complexes were carried out considering any spatial orientation of a methanol molecule around a chair/boat/twisted-boat conformation of dioxane. From 45 different orientations of dioxane and water, 23 different structures with different local minima were obtained and the structural characteristics like interatomic distances, bond angles, dihedral angles, dipole moment of each complex were discussed. The most stable structure, i.e., with minimum heat of formation is found to have a chair form dioxane, one O-H…O, and two C-H…O hydrogen bonds. In general, the O-H…O hydrogen bonds have an average distance of 1.8 Å while C-H…O bonds have 2.6 Å. The binding energy of the dioxane-methanol complex is found to be a linear function of number of O-H…O and C-H…O bonds, and hydrogen bond length. Graphical Abstract

Sixteen orientations of methanol around dioxane converge to six local minima including the global minima with one H-O…H and two C-H…O hydrogen bonds.     

Hydrogen bond supramolecular self-assembly in nickel(II) dithiophosphates, Ni[S2P(OR)2]2, R = sec-Bu, iso-Bu, and their bis(pyrazole) adducts

The reaction between nickel(II) nitrate and potassium phosphorus-1,1-dithiolates (di-sec-butyl and di-iso-butyl) in methanol yields 2:1 complexes which were characterized by FT-IR and NMR spectroscopy. 2:1 pyrazole adducts of both compounds were also obtained.The X-ray diffraction analysis of the compounds reveals square planar, four-coordination geometry for the homoleptic compounds and a six-coordinated distorted octahedral geometry for the adducts. In Ni[S₂P(OBu^s)₂]₂ the molecules are associated through C-H?O hydrogen bonds (2.652 Å), and in Ni[S₂P(OBuⁱ)₂]₂ the molecules are associated through C-H?S hydrogen bonds (2.948 Å). The pyrazole adducts are associated through N-H?O bonds and N-H?S bonds from the pyrazole nitrogen atoms, to form supramolecular assemblies. Thus, Ni[S₂P(OBu^s)₂(Pz)₂]₂ (Pz = pyrazole) forms bi-dimensional layers through N-H?O and N-H?S bonds (2.502 and 2.965 Å, respectively), whereas Ni[S₂P(OBuⁱ)₂(Pz)₂]₂ forms linear chains with N-H?S bonds 2.728 Å. The dithiophosphato groups behave as isobidentate chelating ligands.     

A theoretical study on unusual intermolecular T-shaped X–H...π interactions between the singlet state HB=BH and HF, HCl, HCN or H2C2

The unusual T-shaped X–H...π hydrogen bonds are found between the B=B double bond of the singlet state HB=BH and the acid hydrogen of HF, HCl, HCN and H₂C₂ using MP2 and B3LYP methods at 6-311++G(2df,2p) and aug-cc-pVTZ levels. The binding energies follow the order of HB=BH...HF>HB=BH...HCl>HB=BH...HCN>HB=BH...H₂C₂. The hydrogen-bonded interactions in HB=BH...HX are found to be stronger than those in H₂C=CH₂...HX and OCB≡BCO...HX. The analyses of natural bond orbital (NBO) and the electron density shifts reveal that the nature of the T-shaped X–H...π hydrogen-bonded interaction is that much of the lost density from the π-orbital of B=B bond is shifted toward the hydrogen atom of the proton donor, leading to the electron density accumulation and the formation of the hydrogen bond. The atoms in molecules (AIM) theory have also been applied to characterize bond critical points and confirm that the B=B double bond can be a potential proton acceptor. The unusual T-shaped X–H...π hydrogen bonds are found between the B=B double bond of the singlet state HB=BH and the acid hydrogen of HF, HCl, HCN and H₂C₂     

Ni(II) coordination compounds based on mixed phthalate and aromatic amine ligands: synthesis, crystal structures and magnetic properties

Three new coordination compounds, [Ni(Pht)(Py)₂(H₂O)₃] (1), [Ni(Pht)(β- Pic)₂(H₂O)₃] · H₂O (2) and [Ni(Pht)(1-MeIm)₂(H₂O)₃] (3) (where Pht²⁻ = dianion of o-phthalic acid; Py = pyridine, β-Pic = 3-methylpyridine, 1-MeIm = 1-methylimidazole), have been synthesized and characterized by IR spectroscopy and thermogravimetric analysis. Crystallographic studies 1-3 reveal that each Ni(II) center has a distorted octahedral geometry being coordinated by two nitrogen atoms of aromatic amines, one oxygen atom from a carboxylate group of a phthalate ligand and three water molecules. Pht²⁻ anions act as monodentate ligands, while the remaining uncoordinated carboxylate oxygen atoms participate in the formation of hydrogen bonding. The uncoordinated oxygen atoms form hydrogen bonds with the coordinated water molecules from adjacent complexes creating a centrosymmetric dimer unit. Further, these dimer units are connected by O-H?O hydrogen bonds in double-chains. Depending on the nature of aromatic amines, the arrangement of these double-chains differs. The double-chains are held together only by van der Waals interactions in 1. In contrast, in 2 these chains form layers by π-π interactions between antiparallel molecules of β-Pic as well as by π-π interactions between β-Pic and Pht aromatic rings. In complex 3, the double-chains are knitted together via C-H?O hydrogen bonds between the methyl group of 1-MeIm and the coordinated carboxylate oxygen atom of Pht, as well as π-π contacts involving antiparallel 1-MeIm cycles. The thermal dependence of the magnetic susceptibilities for compounds 1 and 2 shows a weak antiferromagnetic interaction between the two Ni²⁺ ions of the hydrogen bonded dimers. For compound 3, a ferromagnetic interaction could be observed. Modeling the experimental data with MAGPACK resulted in: g = 2.22, |D| = 4.11 cm⁻¹ and J = −0.29 cm⁻¹ for compound 1, g = 2.215, |D| = 3.85 cm⁻¹ and J = −0.1 cm⁻¹ for compound 2 and g = 2.23, |D| = 4.6 cm⁻¹ and J = 0.22 cm⁻¹ for compound 3.