A theoretical and experimental study on isonitrosoacetophenone nicotinoyl hydrazone: Crystal structure, spectroscopic properties, NBO, NPA and NLMO analyses and the investigation of interaction with some transition metals

Journal of Molecular Structure 1162 (2018) 125e139

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A theoretical and experimental study on isonitrosoacetophenone nicotinoyl hydrazone: Crystal structure, spectroscopic properties, NBO, NPA and NLMO analyses and the investigation of interaction with some transition metals
lu a, *, Hümeyra Batı b, Necmi Dege c Ays¸in Zülfikarog a

Department of Chemistry, Faculty of Arts & Sciences, Amasya University, 05000 Amasya, Turkey Department of Chemistry, Faculty of Arts & Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey c Department of Physics, Faculty of Arts & Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey b

a r t i c l e i n f o

a b s t r a c t

Article history: Received 9 December 2017 Received in revised form 18 February 2018 Accepted 20 February 2018 Available online 23 February 2018

A new hydrazone oxime compound, isonitrosoacetophenone nicotinoyl hydrazone (inapNH2), was synthesized and characterized by spectroscopic techniques (FT-IR, 1H-NMR and 13C-NMR) and singlecrystal X-ray diffraction. The molecular geometry, NMR chemical shift values and vibrational frequencies of the inapNH2 in the ground state have been calculated by using the Density Functional Method (DFT/B3LYP) with 6-31G(d) and 6-311þþG(d,p) basis sets. The computational results obtained were in agreement with the experimental results. The thermodynamic parameters of the inapNH2 were calculated at different temperatures, and the changes in thermodynamic properties were studied with increasing temperature. The molecular stability originating from charge transfer and hyperconjugative interactions in the title compound was analyzed using Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) analyzes. The Natural Population Analysis (NPA) charges obtained from NBO analysis were used in order to find out the possible coordination modes of the inapNH2 compound with metal ions. To predict the chemical reactivity of the molecule, the molecular electrostatic potential (MEP) surface map of inapNH2 was investigated and some of its global reactivity descriptors (chemical potential m, electronegativity c, hardness h and electrophilicity index u) were calculated using DFT. Furthermore, the strength of metaleligand interaction between chlorides of Co(II), Ni(II), Cu(II), Zn(II) and inapNH2, in both aqueous and ethanol phases, was elucidated by using the values of Charge Transfer (DN) and Energy Lowering (DE). The results indicated that the best interaction in both solvents is between CuCl2 and inapNH2. © 2018 Elsevier B.V. All rights reserved.

Keywords: Hydrazone oxime X-ray diffraction Density functional theory NBO NLMO Metaleligand interactions

1. Introduction Hydrazone and oxime derivatives occupy a special place among organic molecules because of their wide applications in analytical chemistry, medicine, bioorganic systems, electrochemistry, catalysis and industry [1e4]. Hydrazones possess antimicrobial, anticonvulsant, analgesic, anti inflammatory, antiplatelet, antipyretic, antitubercular and antitumoral properties [5e7]. Furthermore, they behave as nematicides, insecticides, herbicides, rodenticides and plant growth regulators. In industry, hydrazones have been widely

* Corresponding author.
lu). E-mail address: aysin.zulfi[email protected] (A. Zülfikarog https://doi.org/10.1016/j.molstruc.2018.02.079 0022-2860/© 2018 Elsevier B.V. All rights reserved.

studied as plasticizers and stabilizers for polymers, polymerization initiators, antioxidants, etc. In published literature, there is also information that these compounds are used as synthetic intermediates in various reactions [8]. In a similar way, oximes also have common areas of usage. These compounds exhibit a wide range of biological and pharmaceutical activities, such as fungicide [9,10] bactericide [9e11], analgesic, anti-inflammatory [12], antioxidant [9] and antitumor [4,13e15] properties. In industrial practices and engineering applications, oximes have been used as corrosion inhibitors for metal or metal alloys, as flotation collectors in mineral processing [16], and in the synthesis of materials with interesting properties such as single-molecule magnetism and single-chain magnetism [17]. Hydrazones and oximes bearing both nitrogen and oxygen

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donors that exhibit both hard and soft base characters are versatile ligands. Owing to their unique chemical reactivity, these compounds can form more stable complexes with metal ions. Therefore, hydrazones and oximes have been widely used in the detection, determination and extraction of metal ions in analytical chemistry for a long time [3,4,8,18e23]. In recent years, computational studies on hydrazones and oximes have been carried out to investigate their molecular properties, including chemical reactivity, charge distribution [24e41], their equilibrium structure, tautomerism and isomerism [27,29,41e45], their UVeVisible, FT-IR, Raman and NMR spectra [24e26,28,31e33,35,41,45e62] and their thermosalient effect [63]. However, to the best of our knowledge, the theoretical studies in published literature are very limited on hydrazone oxime [42,64e68]. Hydrazone oxime compounds include both hydrazone and oxime groups in their structure and are generally formed from condensation reactions of hydrazides with ketoximes [3,17,42,64e83]. In this work, a new hydrazone oxime compound, isonitrosoacetophenone nicotinoyl hydrazone (inapNH2), was synthesized and then characterized using FT-IR, 1H-NMR and 13CNMR, single-crystal X-ray diffraction technique as well as quantum chemical methods. Inspection of the molecular structure, vibrational and NMR spectra of inapNH2 were carried out using density functional theory (DFT/B3LYP) at 6-31G(d) and 6-311þþG(d,p) basis set levels. The bond parameters (bond lengths and angles) of the optimized molecular structures, the computed vibrational frequencies and the NMR chemical shift values are consistent with the experimental results. The thermodynamic properties (thermal energy, heat capacity, entropy, etc.) of inapNH2 were calculated at different temperatures in the gas phase. The delocalization effect from the lone pairs (donor) to the anti-bonding orbitals (acceptor) and the stabilization energies (E(2)) derived from the interactions between the donor and acceptor were investigated to predict molecular stability by means of Natural Bond Orbital (NBO) analysis. In order to shed light on the detailed information about the reactivity of inapNH2, the NPA atomic charges and MEP surface map were obtained and its chemical reactivity descriptors, e.g. chemical potential m, electronegativity c, hardness h, electrophilicity index u, were examined. Finally, the stabilities of metaleinapNH2 interaction were evaluated by energy lowering (DE) and charge Transfer (DN) values in both aqueous and ethyl alcohol phases. 2. Experimental methods 2.1. Material and spectroscopic measurements Nicotinic acid hydrazide, anhydrous ethanol and glacial acetic acid were obtained commercially and used without further purification. Isonitrosoacetophenone was synthesized according to procedures described in published literature [84]. 1H-NMR (400 MHz) and 13C-NMR (500 MHz) spectra of the title compound were recorded on Bruker spectrometers in DMSO-d6 using tetramethylsilane (TMS) as the internal standard. The infrared (IR) spectrum was performed on a MATTSON 1000 FT-IR spectrophotometer in the range of 4000 to 400 cm1 using the KBr pellet technique. 2.2. Synthesis of the title compound Nicotinic acid hydrazide (0.14 g, 1 mmol) and isonitrosoacetephenone (0.15 g, 1 mmol) were dissolved in hot anhydrous ethanol (20 ml). A few drops of glacial acetic acid were added to this solution. The reaction mixture was refluxed for 8 h. The white product formed was separated by filtration and washed with ethanol. The solid product was recrystallized from ethanol and acetone (1:1) to give crystals of the title compound. Scheme 1

shows the synthesis of inapNH2 (yield: 74%, melting point: 183  C). 2.3. X-ray diffraction analysis Single-crystal X-ray data were collected with a Stoe IPDS II [85] single-crystal diffractometer using monochromated MoKa radiation at 296 K. X-AREA [85] and X-RED [85] programs were used for cell refinement and data reduction, respectively. SHELXS-97 [86] and SHELXL-97 [86] programs were used to solve and refine the structure, respectively. ORTEP-3 for Windows [87] was used to prepare the figures. WinGX [88] and PLATON [89] software were used to prepare material for publication. The H atoms of the water molecule were located in a difference map and freely refined. H atoms attached to C, N and O atoms were positioned geometrically [CeH ¼ 0.930 Å, NeH ¼ 0.860 Å and OeH ¼ 0.820 Å] and treated as riding with Uiso(H) ¼ 1.2Ueq(C, N) and Uiso(H) ¼ 1.5Ueq(O). 3. Computational methods All theoretical calculations for the title compound were carried out with the Gaussian 09 quantum chemistry program [90] on a personal computer. Geometric optimization for inapNH2 in the ground state (in vacuo) was performed using molecular geometry taken from X-ray diffraction (XRD) experimental results without any constraints. Initial calculations were carried out using the Density Functional Theory (DFT) method with the restricted B3LYP [91e93] level of theory, using 6-31G(d) and 6-311þþG(d,p) basis sets, for all atoms. The harmonic vibrational frequencies were computed at the same theoretical levels for the molecule in the gas phase. The frequency values computed at these levels contain known systematic errors and, therefore, these values were scaled by 0.983 up to 1700 cm1 and by 0.958 for greater than 1700 cm1 at B3LYP/6311þþG(d,p) [94], while an identical scaling factor of 0.961 was applied for all B3LYP/6-31G(d) frequencies [95]. The vibrational frequency assignments were made using a GaussView molecular visualization program [96]. The vibrational frequency calculations, which gave positive frequency values, indicated that the optimized structures of inapNH2 at these levels were stable. The temperature dependent thermodynamic parameters (heat capacity ðC 0p;m Þ, entropy ðS 0m Þ and enthalpy ðH 0m Þ were calculated in the range from 200 K to 500 K from the vibrational frequency calculations of the title compound in the gas phase using the B3LYP/6-311þþG(d,p) level. The 1H and 13C-NMR chemical shifts for the optimized molecular geometry of the molecule were calculated at B3LYP/6-31G(d) and B3LYP/6-311þþG(d,p) levels by using GIAO (the Gauge-Independent Atomic Orbital) [97] approach in dimethyl sulfoxide (DMSO) solvent. The NMR chemical shifts were converted into the TMS scale by subtracting the calculated absolute chemical shielding of TMSewhose value was 32.16 ppm for the B3LYP/6-31G(d) level and 31.98 ppm for the B3LYP/6311þþG(d,p) level. In order to investigate the molecular stability and hyperconjugative interactions, Natural Bond Orbital (NBO) analysis [98] was carried out at B3LYP/6-311þþG(d,p) by means of the NBO 3.1 program as implemented in the Gaussian 09 W package. The atomic charge values were determined using the Natural Population Analysis (NPA) at B3LYP/6-311þþG(d,p) in the gas phase to predict donor atoms that may be coordinated to the metal ion. The reactive sites of the molecules were studied using molecular electrostatic potential (MEP), which was evaluated using the B3LYP/6-311þþG(d,p) method. Based on the frontier molecular orbitals, the various reactivity descriptors such as the energy gap (D(H-L)), the electronegativity (c), the chemical hardness (h), the chemical potential (m) and the electrophilicity index (u) were calculated in both aqueous and ethanol phases according to

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127

Scheme 1. The synthesis schematic for inapNH2.

following equations [97e101]:

DðH  LÞ ¼ ELUMO  EHOMO c ¼ ðEHOMO  ELUMO Þ=2 m ¼ c h ¼ ðELUMO  EHOMO Þ =2 u¼

m2 2h

To investigate the interactions of inapNH2 as a ligand with metal chlorides, the electronegativity, chemical hardness and chemical potential for CoCl2, NiCl2, CuCl2 and ZnCl2 were also calculated using the B3LYP/6-311þþG(d,p) method in the same solvents. Then the amount of Charge Transfer (DN) and Energy Lowering (DE) [98] which accompany the formation of metal complexes with inapNH2 (donor) and chlorides of Co(II), Ni(II), Cu(II), Zn(II) (acceptor) were computed using the same method.

DN ¼ ðcA  cB Þ=2ðhA þhB Þ DE ¼ ðcA  cB Þ2 =4ðhA þhB Þ

4. Results and discussion 4.1. Structural properties Isonitrosoacetophenone nicotinoyl hydrazone (inapNH2) crystallizes in the monoclinic, space group P21/c with Z ¼ 4 in the unit cell. Details of crystal parameters, data collection, structure solution and refinement are given in Table 1. The molecular structure and ORTEP [87] view of inapNH2, which contains pyridine and phenyl rings together with hydrazone and oxime groups, is shown Fig. 1. In the molecule, the dihedral angle between the benzene and pyridine ring is 7.48 (9) . As can be seen in Fig. 1, these rings are almost planar (r.m.s. deviation ¼ 0.0016 Å and 0.0037 Å). The optimized structural parameters of inapNH2 were calculated using the DFT/B3LYP method with 6-31G(d) and 6311þþG(d,p) basis sets. Some of the selected bond lengths and angles of the title compound are listed in Table 2 with the experimental data. The optimized molecular geometries of the title compound are shown in Fig. S1a and S1b (See Supplementary materials). The N2eN3 bond distance of 1.364 (17) Å is appreciably shorter than a typical NeN single bond, such as that found in free 2,4-dinitrophenylhydrazone at 1.405 (6) Å [102], n-nonanoic acid

hydrazide at 1.415 Å [103] and 1-benzoyl-2-(propan-2-ylidene) hydrazone at 1.3931 (13) Å [104]; this suggests the existence of a delocalized double bond [62,104,105]. This bond length has been found to be 1.3432 Å for B3LYP/6-31G(d) and 1.3423 Å for the B3LYP/6-311þþG(d,p). The title compound exists in keto form with the C9eO1 bond length of 1.209 (2) Å, typical of a carbon oxygen double bond [56,104,106], which was calculated at 1.2171 Å and 1.2116 Å for DFT using B3LYP/6-31G(d) and the B3LYP/6311þþG(d,p), respectively. The bond distances of the azomethine (C2eN2) and oxime groups (C1eN1) in the title compound were measured as 1.297 (2) Å and 1.269 (2) Å, respectively. These values, which are in good agreement with the data from similar hydrazone oxime compounds [42,46,65,66,107], show that these bonds are typical of a double bond localized between the C and N atoms. These bond distances were calculated to be 1.3022 Å and 1.2892 Å for the B3LYP/6-31G(d), and 1.2976 Å and 1.2836 Å using the B3LYP/6311þþG(d,p). The NeO distance of the free oxime is close to those commonly found in oxime derivatives [N1eO2 ¼ 1.377 (2) Å] [105,107,108] and were calculated to be 1.3954 Å and 1.3962 Å using B3LYP/6-31G(d) and B3LYP/6-311þþG(d,p), respectively. The dihedral angles of oxime and hydrazone groups are O2eN1¼C1eC2 ¼ 177.60 (17) and N3eN2¼C2eC3 ¼ 174.26 (15) . The values found in this study are in agreement with values in published literature, such as 177.6 (3) [66], 178.2 (15) [25], 179.69 (18) [65] and 173.92 (12) [28], 175.4 (3) [66] and 174.73 (12) [104]. These angles have been found to be 176.81 and 179.37 for the B3LYP/6-31G(d) level and 177.33 and 179.12 for the B3LYP/6-311þþG(d,p) level. As shown, both the oxime and hydrazone groups in the title compound are planar and have an E configuration [66,109,110]. The other selected parameters of the title compound are listed in Table 2. Furthermore, the crystal packing of isonitrosoacetophenone nicotinoyl hydrazone (inapNH2) forms an intra- and four intermolecular hydrogen bonds. These hydrogen bonds are shown in Table 3. The intra molecular NeH/N hydrogen bond is shown in Fig. 1. Also, the intermolecular OeH/O and OeH/N hydrogen bonds are shown in Fig. 2a and b. As can be seen in Fig. 1, the intramolecular NeH/N hydrogen bond forms with the N atom of the oxime group acting as an acceptor in the formation of an S(6) motif [42]. In inter-molecular hydrogen bondings, the O3 atom of a water molecule at (x, y, z) acts as a hydrogen-bond bifurcated donor, via atom H3A, to atoms O1 and N2 of the carbonyl and hydrazone groups at (1- x, -y, 1-z). Also, atom O3 at (x, y, z) acts as a hydrogenbond donor, via atom H3B, to atom N4 of the pyridine ring at (1 þ x, y, 1 þ z). As can be seen in Fig. 2a and b, the solvent water molecules form dimers by linking two molecules with different symmetry codes. These dimers proceed along the [101] direction. In addition to these hydrogen bonds, the O2 atom of the oxime group at (x, y, z) acts as a hydrogen-bond donor, via the H2 atom, to atom O3 at (1-x, ½þy,

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128 Table 1 Crystal data and experimental details for inapNH2. Chemical formula Molecular weight Temperature, K Wavelength, Å Crystal system Space group Unit cell parameters: a, b, c, Å; b, deg Volume, A3; Z Calculated density, g/cm3 Absorption coefficient, mm1 F(000) Crystal size, mm q range, deg h, k, l limits Measured/independent reflections Data completeness on q ¼ 26.5 , % Max. and min. transmission Reflections/restraints/parameters S factor on F2 R factor [I > 2s(I)] R factor (al data) Max. and min. residual electron density, e/A3

C14H12N4O2$H2O 286.29 296 0.71073 Monoclinic P21/c 11.8434(6), 13.3105(9), 9.2772(5), 110.187(4) 1372.63(14), 4 1.385 0.101 600 0.67  0.31  0.11 1.83e27.56 14  h  14, 12  k  16, 11  l  11 7889/2820 [Rint ¼ 0.031] 98.9 0.963 and 0.989 2820/0/198 1.01 R1 ¼ 0.0471, wR2 ¼ 0.097 R1 ¼ 0.0802, wR2 ¼ 0.108 0.144 and 0.195

½-z). All of these hydrogen bonds are effective in crystal packing. As seen in Table 2, the calculated geometrical parameters are generally in good agreement with the experimental structural parameters. There are minor differences between them. The reason for the differences is that the experimental results belong to the solid phase in which inter-molecular interactions occur, while the theoretical calculations are for the gas phase in which the molecules are isolated [111,112]. In order to compare the theoretical results with the experimental values, the root mean square error (RMSE) and maximum difference given in Table 2 are used. The maximum difference between experimental and calculated bond lengths is about 0.0635 Å for 6-31G(d) basis set and 0.0293 Å for 6311þþG(d,p). A global comparison was carried out by superimposing the molecular skeletons obtained from the theoretical calculations and the X-ray diffraction (Fig. 3), giving RMSE values of 0.340 Å and

0.147 Å for B3LYP/6-31G(d) and B3LYP/6-311þþG(d,p) levels, respectively. According to the magnitudes of RMSE, it can be concluded that the 6-311þþG(d,p) basis set correlates well for geometrical parameters when compared to the 6-31G(d) basis set.

4.2. NMR spectral analysis Nuclear Magnetic Resonance Spectroscopy (NMR) is the most powerful and versatile spectroscopic technique for understanding the relationship between the electronic properties and the molecular structure. The combined use of experimental measurements and theoretical calculations help us to accurately interpret and predict the structure of organic molecules and their complexes [26,113,114]. In this study, experimental 1H and 13C-NMR spectra of the title compound's powder were measured in DMSO-d6 (Figs. S2 and S3 Supplementary materials). GIAO 1H and 13C chemical shift values were calculated using the B3LYP method with the 631G(d) and 6311þþG(d,p) basis sets for the optimized geometry with respect to TMS in DMSO (dimethylsulfoxide) solvent. The experimental and calculated chemical shift values are given in Table 1S (See Supplementary materials). In the 1H-NMR spectra for the hydrazone oxime compound, the singlets observed at 13.06 ppm and 12.65 ppm are assigned to the characteristic oxime OH proton and NH proton, respectively. These chemical shifts, which are characteristic for oxime and hydrazone [3,74,77,79], were calculated to be 7.34 ppm (631G), 7.69 ppm (6311þþG(d,p)), and 11.62 ppm (631G) and 13.06 ppm (6311þþG(d,p)), respectively. While the NH proton signal shows good agreement with calculated values, the experimental shift of the oxime OH is significantly larger than calculated values. This may be explained by the inter-molecular hydrogen bonding neglected in the calculations [3]. The other values obtained for 1H-NMR chemical shifts of inapNH2 were (eCH]NeOH) at 9.08 ppm, PyH at 8.8e77.6 ppm and ArH at 7.77 to 7.6 ppm. These data are in agreement with those both previously reported for similar compounds and the calculated values given in Table 1S (See Supplementary materials) [3,113]. In the 13C-NMR spectra, the peak observed at 162.20 ppm is

Fig. 1. ORTEP drawing of the basic crystallographic unit of inapNH2, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and all H atoms are shown as small spheres of arbitrary radii.

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lu et al. / Journal of Molecular Structure 1162 (2018) 125e139 Table 2 Selected experimental and optimized geometric parameters of inapNH2. Parameter N1eC1 N1eO2 O1eC9 N2eC2 N2eN3 C9eN3 C9eC10 C3eC2 N4eC13 N4eC14 RMSEa Max. Differencea Bond angles ( ) C1eN1eO2 C2eN2eN3 O1eC9eN3 O1eC9eC10 N3eC9eC10 C9eN3eN2 N1eC1eC2 N2eC2eC1 N2eC2eC3 C1eC2eC3 RMSEa Max. Differencea Torsion angles ( ) C2eN2eN3eC9 O2eN1eC1eC2 N3eN2eC2eC3 O1eC9eN3eN2 C10eC9eN3eN2 C14eC10eC9eO1 C11eC12eC13eN4 C4eC3eC2eN2 N3eC9eC10eC11 N3eC9eC10eC14 C8eC3eC2eN2 C14eN4eC13eC12

Experimental

DFT/B3LYP/6-31G(d)

DFT/B3LYP/6-311 þþG(d,p)

1.269 (2) 1.377(2) 1.209 (2) 1.297(2) 1.364(17) 1.364(2) 1.499(2) 1.493(2) 1.327(3) 1.332(2)

1.2892 1.3954 1.2171 1.3022 1.3432 1.3945 1.4995 1.4890 1.3401 1.3955 0.0253 0.0635

1.2836 1.3962 1.2116 1.2976 1.3423 1.3933 1.5003 1.4891 1.3377 1.3327 0.0143 0.0293

113.65 117.31 123.11 122.46 114.42 119.42 121.59 126.62 115.30 117.84

111.14 119.98 123.49 122.62 113.89 119.63 121.99 127.08 115.53 117.31 1209 2,67

111.45 120.16 123.69 122.52 113.78 119.76 121.87 126.93 115.73 117.28 1204 2,85

173.61 176.81 179.37 5.28 175.47 22.28 0.52 151.16 24.77 156.97 27.61 0.115

173.22 177.33 179.12 5.81 174.96 26.61 0.25 149.93 29.56 152.64 28.73 0.065

(14) (15) (15) (15) (15) (15) (15) (14) (15) (14)

174.83 (17) 177.60 (17) 174.26 (15) 0.8 (3) 178.64 (15) 9.1 (3) 0.3 (4) 162.61 (18) 10.5 (3) 171.46 (18) 20.1 (3) 0.8 (4)

a RMSE and maximum differences between the bond lengths and angles computed using theoretical methods and those obtained from X-ray diffraction.

assigned to the carbonyl carbon C(9) in the molecule and was calculated to be 155.40 ppm (631G(d)) and 170.96 ppm (6311þþG(d,p)). This signal appeared downfield due to the conjugative effect of the NeNeCeO core of hydrazone [3,115]. The pyridine ring carbons (C13 and C14) attached to the N atom have bigger chemical shifts than other ring carbon atoms because the nitrogen atom has a greater electronegative property, which polarizes the electron distribution in its bond with adjacent carbon atoms [115,116]. The signals in the 136.02 to 127.44 ppm region belong to carbon atoms in a phenyl ring. As seen in Table 1S (See Supplementary materials), the theoretical 13C shift results for the title compound are generally closer to the experimental 13C shift data, which are in agreement with the data from other oximes and hydrazones [3,17,74,77,79,113,116].

4.3. IR spectral analysis The theoretical vibrational spectra were calculated at the B3LYP/ 6-31G(d) and B3LYP/6311þþG(d,p) levels in the gas phase, then scaled by 0.983 up to 1700 cm1 and 0.958 for greater than 1700 cm1 at B3LYP/6311þþG(d,p) [94], while an identical scaling factor of 0.961 was applied for all B3LYP/6-31G(d) frequencies [117]. The experimental and theoretical IR spectra are given in Figs. S4

129

Table 3 Hydrogen-bond geometry (Å,  ). DdH/A

DdH

H/A

D/A

N3eH3/N1 O2eH2/O3i O3eH3B/N4ii O3eH3A$$$O1iii O3eH3A$$$N2iii

0.86 0.82 0.82 (2) 0.81 (2) 0.81 (2)

1.92 1.93 2.04 (2) 2.45 (2) 2.53 (3)

2.593 2.667 2.859 3.056 3.301

DdH/A (2) (19) (2) (2) (2)

135 149 174 (3) 133 (2) 160 (3)

Symmetry codes: (i) x þ 1, y þ ½, z þ ½; (ii) x þ 1, y, z þ 1; (iii) x þ 1, y, z þ 1.

and S5 (See Supplementary materials). The vibrational band assignments were made using the Gaussian-View molecular visualization program [96]. The experimental frequencies and the corresponding computed results are summarized in Table 2S (See Supplementary materials). The experimental spectrum of the title compound showed a strong and broad band at 3352 cm1, which is attributed to the characteristic (OeH) oxime absorption. This band was calculated to be 3679 cm1 for the B3LYP/631G(d) level and 3663 cm1 for B3LYP/6311þþG(d,p) level. The band observed at 3135 cm1 indicates NeH stretching in the COeNHeN]CH azomethine group. This band was found to be 3302 cm1 and 3272 cm1 using B3LYP/ 631G(d) and B3LYP/6311þþG(d,p) levels, respectively. The differences between the experimental and theoretical values of these vibrations can be explained by the intra-molecular and intermolecular hydrogen bonding in the solid phase [118,119]. The hydrazone oxime compounds with (C]O), (C]N) and (NeO) groups as donor sites can coordinate to metal ions through the oxygen and nitrogen atoms [3,17,42,74,77,79]. The values of the vibration frequencies of these groups in the free hydrazone oxime compounds are very important because they give information about the coordination mode of the hydrazone oximes with the metal ions. In the experimental spectrum of our compound, y(C] O) stretching vibration produced a band at 1670 cm1, while the calculations for the B3LYP/631G(d) and B3LYP/6311þþG(d,p) levels reproduced this stretching vibration at 1723 cm1 and 1686 cm1, respectively. The oxime and azomethine C]N stretching vibrations give rise to a band at 1594 cm1 and 1543 cm1. The theoretically computed values of C¼Noxime and C¼Nazomethine stretching vibrations were found to be 1622 cm1 and 1535 cm1 for the B3LYP/ 631G(d) level and 1643 cm1 and 1549 cm1 for the B3LYP/ 6311þþG(d,p) level. The band observed at 1005 cm1 attributed to NeO stretching vibrations, which are characteristic for oximes, were calculated to be 997 cm1 for B3LYP/631G(d) level and 1008 cm1 for the B3LYP/6311þþG(d,p) level. As seen from Table 2S (See Supplementary materials), the B3LYP/631G(d) and B3LYP/6311þþG(d,p) levels used in this work produce results close to both each other and to experimental data. 4.4. Thermodynamic properties Several thermodynamic parameters (such as thermal energy, heat capacity, entropy, zero-point vibrational energies (ZPVE), rotational constants and rotational temperatures) were calculated using B3LYP with 6-31G(d) and 6-311þþG(d,p) basis sets at 298.150 K and 1 atm of pressure. Table 4 indicates the values of some thermodynamic parameters without experimental determinations. These calculated results are consistent with reported works [113,116], which are important to test the reliability of our results. Furthermore, based on the vibrational analysis and statistical thermodynamics, the standard thermodynamic functions of heat capacity ðC 0p;m Þ, entropy ðS 0m Þ and enthalpy ðH 0m Þ were obtained at the B3LYP/6-311þþG(d,p) level and listed in Table 5. It can be

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Fig. 2. a ORTEP drawing of the hydrogen bonds of inapNH2 with symmetry codes. 2b PLATON drawing of the hydrogen bonds of inapNH2 in the unit cell.

A. Zülfikarog
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131

Fig. 3. Atom-by-atom superimposition of the structures calculated (blue) by B3LYP/6-31G(d) and B3LYP/6-311þþG(d,p) over the X-ray structure (black) for inapNH2. Hydrogen atoms omitted for clarity. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

observed that these thermodynamic functions are increasing with temperature ranging from 200 to 500 K due to the fact that molecular vibrational intensities increase with temperature [116]. For inapNH2, the correlation equations between these thermodynamic properties and temperatures are as follows:

C 0p;m ¼ 7:6207 þ 0:2621T  1:0591  104 T 2 S 0m ¼ 71:7976 þ 0:3204T þ 9:5013  105 T 2 H 0m ¼ 0:9149 þ 0:0213T þ 9:4993  105 T 2




R2 ¼ 0:9998






R2 ¼ 0:9999




 R2 ¼ 0:9999

All the thermodynamic data can be used for further studies of the title compound and supply helpful information for the synthesis of some new oxime and hydrazone compounds. 4.5. NBO and NLMO analysis Nature Bond Orbital (NBO) analysis provides an efficient method for studying inter-molecular bonding and interaction among bonds and also provides a convenient basis for investigating charge transfer or conjugative interaction in molecular systems. Delocalization of electron density between occupied (bond or lone pairs) NBOs and formally unoccupied (antibond or Rydberg) NBOs correspond to a stabilizing donoreacceptor interaction [120e122]. This donoreacceptor interaction can be quantitatively described in terms of the NBO approach, which is expressed by means of the second-order perturbation interaction energy (E(2)). This energy represents the prediction of the off-diagonal NBO Fock matrix elements. It can be deduced from the second-order perturbation approach [123,124]:

Eð2Þ ¼ DEij ¼ qi

Fði; jÞ2 εj  εi

where qi is the ith donor orbital occupancy, εi, εj are diagonal elements (orbital energies) and F(i,j) is the off-diagonal NBO Fock matrix element. The larger the E(2) value, the more intensive is the interaction between electron donors and electron acceptors, i.e. the greater tendency for electron donors to donate to electron acceptors, and the greater the extent of conjugation of the whole system [121]. The Natural Bond Orbital (NBO) analysis has been performed on the title compound at the DFT/B3LYP/6-311þþG(d,p) level. A summary of electron donor orbitals, acceptor orbitals and the interaction stabilization energy that resulted from the secondorder perturbation theory analysis of the Fock matrix in the NBO

basis is presented in Table 6. For this table, the stabilization energies larger than 2 kcal/mol have been chosen. Intra-molecular interactions are formed by the orbital overlap between bonding (CeC), (CeO), (CeN), (CeH), (NeO), (NeN), (NeH) and (OeH), antibonding (CeC), (CeO), (CeN), (CeH), (NeO) and (NeN) orbitals, which results in intra-molecular charge transfer (ICT) causing system stabilization. These interactions are observed as an increase in electron density (ED) in antibonding orbitals that weaken the respective bonds [125]. The electron density of six single bonds of pyridine and phenyl rings (~1.977e) demonstrates delocalization within these rings leading to an average stabilization energy of 3.032 kcal/mol. Similarly, the ED at the conjugated p bonds (1.705e1.626e) and p* bonds (0.374e0.296e) of the pyridine and phenyl rings indicate strong p electron delocalization within rings. The hyperconjugative interactions of p (C3eC4) / p*(C7eC8)/p*(C5eC6), p (C7eC8) / p*(C3eC4)/p*(C5eC6), p (C5eC6) / p*(C3eC4)/ p*(C7eC8) are responsible for conjugation of the respective p bonds in the phenyl ring. These interactions result in an average stabilization energy of 19.95 kcal/mol. The interactions of the conjugate system in the pyridine ring: p (C10eC11) / p*(N4eC14)/ p*(C12eC13), p (N4eC14) / p*(C10eC11)/p*(C12eC13), p * (C12eC13) / p (C10eC11)/p*(N4eC14) also stabilized the pyridine ring up to 27.68 to 13.16 kcal/mol. In addition, LP(1) N4 in the pyridine ring is conjugated to the antibonding orbital of s*(C10eC14) and s*(C12eC13) contributing energy of 9.24 and 9.06 kcal/mol, respectively. The energies for interaction LP(1) N1 / s*(C1eH1) and LP(2) O2 / p* N1eC1 are 6.35 and 17.28 kcal/mol, respectively, indicate the intra-molecular hyperconjugative interactions between the oxime (eHC]NeOH) group. The energies for interaction s (N3eH3) / s*(O1eC9), LP(1) N2 / s*(N3eH3), LP(2) * * O1 / s (C9eN3) and LP(1) N3 / p (O1eC9) are 3.26, 9.11, 28.60 and 43.86 kcal/mol in the azomethine (eCOeNHeN]Ce) group. These interactions demonstrate the single-double bond arrangement that leads to keto-enol tautomerism. The intra-molecular hyperconjugative interactions of s (C1eH1) / s*(N2eC2) [ E(2) ¼ 4.51 kcal/mol], s (C1eC2) * (2) / s (N1eO2) [ E ¼ 4.91 kcal/mol], s (C7eC8) / s*(C3eC2) [ E(2) ¼ 3.24 kcal/mol], s (C4eC5) / s*(C2eC3) [ E(2) ¼ 3.36 kcal/ mol], s (C2eC3) / s*(N2eN3) [ E(2) ¼ 5.20 kcal/mol], s * (2) (N2eN3) / s (C2eC3) [ E ¼ 2.74 kcal/mol], p (N1eC1) / p*(N2eC2) [ E(2) ¼ 9.99 kcal/mol], p (N2eC2) / p*(N1eC1) [ E(2) ¼ 12.16 kcal/mol], p (C3eC4) / p*(N2eC2) [ E(2) ¼ 12.77 kcal/ mol] and p (N2eC2) / p*(C3eC4) [ E(2) ¼ 7.35 kcal/mol] indicate that strong hyperconjugative interactions of the s and p electrons among the oxime (eHC]NeOH) group, phenyl ring and azomethine (eCOeNHeN]Ce) group. However, the p (O1eC9) / p*(C10eC11) [ E(2) ¼ 3.65 kcal/mol] and p (C10eC11) / p*(O1eC9) [ E(2) ¼ 15.40 kcal/mol] bring about

132

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Table 4 The calculated thermodynamic parameters of inapNH2. Parameters

B3LYP/6-31G(d)

B3LYP/6-311 þþG(d,p)

Thermal energy, E (kcal/mol) Rotational Translational Vibrational Total

0.899 0.899 179.696 181.474

0.889 0.889 178.707 180.484

Heat capacity, Cv (cal/mol K) Rotational Translational Vibrational Total

2.981 2.981 70.206 76.168

2.981 2.981 70.206 76.168

Entropy, S (cal/mol K) Rotational Translational Vibrational Total

34.807 42.851 78.806 156.465

34.799 42.851 81.267 158.918

Rotational constants (GHZ) A B C

0.5812 0.1379 0.1153

0.58225 0.13783 0.11615

Rotational temperature (Kelvin) A B C

0.02789 0.00662 0.00554

0.02794 0.00661 0.00557

Thermal properties (Hartree/particle) Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibss Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Zero-point vibrational energy (kcal/mol)

0.268355 0.289197 0.290141 0.215800 986.226832 986.205990 986.205046 986.279388 168.39525

0.266488 0.287620 0.288564 0.213057 986.528003 986.506871 986.505926 986.581433 167.22343

stabilization between the azomethine (eCOeNHeN]Ce) group and pyridine ring. From the azomethine moiety, three important interactions also lead to the stability of the title molecule. These include the donation of lone pairs of LP(2) O1, LP(1) N2 and LP(1) N3 of the azomethine group to antibonding s*(C9eC10), s*(C1eC2) and s*(N2eC2) that correspond to the stabilization energies of 19.31, 12.10 and 34.39 kcal/mol. The intra-molecular NeH/N hydrogen bond in the NBO analysis result is caused by the interaction between the nitrogen lone pair LP(1) N1 and the antibonding orbital s*(N3eH3). Despite the fact that the energy contribution (9.11 kcal/mol) of the hyperconjugative interaction is weak, this E(2) value is chemically significant and can be used as a measure of the intra-molecular delocalization [117]. In addition, the p*(C10eC11) NBO conjugates with the respective bond of p*(O1eC9) resulting in an enormous stabilization energy of 131.73 kcal/mol. Similarly, the interactions of p*(N1eC1) / p*(N2eC2) [ E(2) ¼ 99.81 kcal/mol] and p*(N2eC2) / p*(C3eC4) [ E(2) ¼ 53.06 kcal/mol] are adding stability to the structure because of their higher E(2) values. Table 7 gives the occupancy and percentage of significant natural atomic hybrids of the Natural Bond Orbital (NBO) of the title compound calculated using the B3LYP/6-311þþG(d,p) method. The NBO hybrid analysis shows that all the CeN/NeH bond orbitals are polarized towards the nitrogen atom (ED, % ¼ 54.43 to 72.58 for N) and CeO/OeH/NeO bond orbitals towards the oxygen atom (ED,

Table 5 Thermodynamic properties of inapNH2 at different temperatures at the B3LYP/6311þþG(d,p). T(K)

H0m (kcal mol1)

ðC0p;m Þ (cal mol1 K1)

S0m (cal mol1 K1)

200.00 250.00 298.15 300.00 350.00 400.00 450.00 500.00

7.170 10.327 13.853 13.998 18.175 22.832 27.935 33.444

56.040 66.294 76.168 76.543 86.458 95.753 104.268 111.957

131.997 146.045 158.918 159.400 172.261 184.684 196.694 208.296

T: temperature; ðC0p;m Þ, heat capacity; ðS0m Þ entropy; (H0m Þ enthalpy.

% ¼ 58.33 to 73.69 for O). The hydrogen atoms have almost 0% p character in the OeH, NeH and CeH (eHC]NeOH) bonds. The first lone pair of N9 and second lone pairs of O2 and O3 have almost 100% p character. The natural localized molecular orbitals (NLMOs) show how bonding in a molecule is composed of orbitals localized around different atoms. The derivation of NLMOs from NBOs gives direct insight into the nature of the localized molecular orbital's “delocalization tails” [120,126]. Table 8 shows occupancy of significant NLMOs, the percentage of parent NBO and the atomic hybrid contributions of the title compound calculated at the B3LYP level using the 6-311þþG(d,p) basis set. As seen from Table 8, the most delocalized NLMO is p (C12eC13) for inapNH2. It has only about 80.5% contribution from the localized p (C12eC13) parent NBO, with the delocalized tail composed of contributions (~19.5) from hybrids of O1, C9, C10, C11, N4 and C14. Similarly, the NLMO of p(C7eC8) has a delocalized tail (~19) composed of hybrids of C3, C4, C5 and C6. The other most delocalized NLMOs in the title compound are p(C10eC11), p(C3eC4), p(N4eC14), p(C5eC6) and the NLMO due to the first lone pair of the nitrogen atom N3. They have nearly 15e19% delocalized tails. These larger amounts of delocalization indicate that the donor (C]C)/C]N bonds in the rings and the first lone pair of the nitrogen atom N9 are strongly delocalized into the neighboring regions. These interactions, which have rather larger E(2) values that can also be observed from the perturbation theory energy analysis are given in Table 6. 4.6. Atomic charges The calculation of atomic charges plays an important role in the application of quantum mechanical calculations to molecular systems because atomic charges affect dipole moment, molecular polarizability, electronic structure, acidityebasicity behavior and a lot more properties of molecular systems [127,128]. Natural Population Analysis (NPA) calculates atomic charges and orbital populations of molecular wave functions for general atomic orbital basis sets [129]. For the title molecule, the net charges are calculated by Natural Population Analysis (NPA). The calculated natural atomic charge values are obtained from the Natural Bond Orbital Analysis (NBO) [98] and are listed in Table 9. As can be seen in Table 9, the magnitudes of the carbon atomic charges change from 0.24228 to 0.6613. The carbonyl carbon atom (C9 ¼ 0.66113) is the most positive carbon atom due to the highly electronegative oxygen atom (O1 ¼ 0.56375) and nitrogen atom (N3 ¼ 0.44340) present in the adjacent position. In the phenyl and pyridine rings, because C atoms have a higher electronegativity than H atoms, seven C atoms bonded to H atoms have negative atomic charges. On the other hand, the C14 (0.10218) and C13 (0.06708) atoms in the pyridine ring have positive atomic charges. This is due to the attachment of the negatively charged nitrogen (N4) atom. Similarly, the carbon atoms (C1 ¼ 0.01338 and

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133

Table 6 Significant donoreacceptor interactions of inapNH2 and their second order perturbation energies. Type

Donor NBO (i)

ED (i)/e

Type

Acceptor NBO (j)

ED (i)/e

E(2) (kcal/mol)

E(j)-E(i) a.u.

F(i,j) a.u.

s p p s s s

N1eO2 N1eC1 O1eC9 O2eH2 N2 eN3 N2eC2

1.98782 1.94433 1.97805 1.99214 1.98652 1.98552

p

N2eC2

1.87699

s

C9eC10

1.97361

s s

C9eN3 C10eC11

1.98835 1.97484

p

C10eC11

1.64301

s s

C10eC14 C3eC14

1.97763 1.97335

p

C3eC4

1.64893

s

C3eC8

1.97154

s

C2eC3

1.96691

s s s

N3eH3 C1eH1 C1eC2

1.98434 1.97821 1.97148

s

C4eC5

1.97833

s

C7eC8

1.97915

p

C7eC8

1.65778

s

C11eC12

1.97899

p

N4eC14

1.70497

s

C5eC6

1.97965

p

C5eC6

1.66467

s

C6eC7

1.97990

s p

C12eC13 C12eC13

1.98522 1.62616

LP(1)

N1

1.93641

LP(1) LP(2)

O1 O1

1.98036 1.85756

O2 N2

1.89767 1.92114

LP(1)

N3

1.62488

LP(1)

N4

1.91792

LP(2)

O3

1.99034

C1eC2 N2eC2 C10eC11 N1eC1 C2eC3 C9eN3 C2eC3 N1eC1 C3eC4 N2eN3 C10eC11 C11eC12 N4eC14 N2eC2 C10eC14 C11eC12 O1eC9 N4eC14 C12eC13 C10eC11 C3eC8 C4eC5 N2eC2 C7eC8 C5eC6 C3eC4 C2eC3 C7eC8 N2eN3 N2eC2 C3eC8 C4eC5 C7eC8 O1eC9 N2eC2 N1eO2 C3eC8 C3eC4 C2eC3 C5eC6 C3eC8 C2eC3 C6eC7 C3eC4 C5eC6 C9eC10 C10eC11 C12eC13 C10eC11 C12eC13 C4eC5 C6eC7 C3eC4 C7eC8 C7eC8 C5eC6 C11eC12 C10eC11 N4eC14 N3eH3 C1eH1 C9eC10 C9eC10 C9eN3 N1eC11 C3eC2 N3eH3 C1eC2 O1eC9 N2eC2 C10eC14 C12eC13 C1eH1

0.03996 0.25907 0.34781 0.00999 0.03301 0.08914 0.03301 0.17435 0.37359 0.02107 0.02321 0.01603 0.01338 0.01709 0.03139 0.01603 0.26068 0.33356 0.29654 0.02321 0.02348 0.01554 0.25907 0.29705 0.33530 0.02373 0.03301 0.01495 0.02107 0.01709 0.02348 0.01554 0.01495 0.01407 0.01709 0.02679 0.02348 0.02373 0.03301 0.01634 0.02348 0.03301 0.01656 0.37359 0.33530 0.06809 0.02321 0.02599 0.34781 0.29654 0.01554 0.01656 0.37359 0.29705 0.01495 0.01634 0.01603 0.34781 0.33356 0.05963 0.02818 0.06809

LP(2) LP(1)

s* p* p* s* s* s* s* p* p* s* s* s* s* s* s* s* p* p* p* s* s* s* p* p* p* s* s* s* s* s* s* s* s* s* s* s* s* s* s* s* s* s* s* p* p* s* s* s* p* p* s* s* p* p* s* s* s* p* p* s* s* s* s* s* p* s* s* s* p* p* s* s* s*

3.39 9.99 3.65 2.85 2.74 2.29 2.04 12.16 7.35 3.76 2.13 2.00 2.78 2.39 3.56 2.87 15.40 26.40 16.65 3.71 3.85 2.98 12.77 18.71 20.31 3.94 2.12 2.81 5.20 2.55 2.03 2.18 2.02 3.26 4.51 4.91 2.08 3.38 3.36 2.76 3.18 3.24 2.72 21.31 21.27 3.56 3.17 2.35 13.16 27.68 2.80 2.61 20.40 18.69 2.70 2.65 2.54 23.95 15.77 11.53 6.35 2.23 19.31 28.60 17.28 2.26 9.11 12.10 43.86 34.39 9.24 9.06 2.71

1.29 0.36 0.40 1.34 1.33 1.31 1.35 0.32 0.36 1.07 1.22 1.23 1.21 1.40 1.27 1.28 0.30 0.28 0.29 1.27 1.27 1.27 0.26 0.29 0.28 1.25 1.14 1.28 1.05 1.23 1.22 1.23 1.24 1.29 1.12 0.90 1.25 1.27 1.15 1.28 1.27 1.15 1.27 0.28 0.28 1.13 1.28 1.28 0.32 0.32 1.28 1.28 0.28 0.29 1.29 1.27 1.29 0.28 0.27 0.85 0.88 1.10 0.66 0.66 0.33 0.83 0.77 0.82 0.30 0.28 0.89 0.90 0.94

0.059 0.057 0.037 0.055 0.054 0.050 0.047 0.057 0.049 0.057 0.045 0.044 0.052 0.052 0.060 0.054 0.062 0.077 0.063 0.061 0.062 0.055 0.053 0.067 0.068 0.063 0.044 0.054 0.066 0.050 0.045 0.046 0.045 0.058 0.064 0.059 0.046 0.058 0.056 0.053 0.057 0.055 0.053 0.068 0.069 0.057 0.057 0.049 0.058 0.084 0.053 0.052 0.069 0.066 0.053 0.052 0.051 0.074 0.059 0.089 0.067 0.045 0.103 0.124 0.069 0.039 0.075 0.090 0.106 0.091 0.082 0.082 0.045

0.08914 0.17435 0.03301 0.05963 0.03996 0.26068 0.25907 0.03139 0.02599 0.02818

(continued on next page)

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134 Table 6 (continued ) Type

Donor NBO (i)

ED (i)/e

Type

Acceptor NBO (j)

ED (i)/e

E(2) (kcal/mol)

E(j)-E(i) a.u.

F(i,j) a.u.

p* p* p*

N1eC1 N2eC2 C10eC11

0.17736 0.24961 0.34781

p* p* p*

N2eC2 C3eC4 O1eC9

0.25907 0.37359 0.26068

99.81 53.06 131.73

0.02 0.02 0.01

0.075 0.056 0.066

C2 ¼ 0.14347) of the oxime and azomethine groups also have positive charges. All hydrogen atoms are positively charged. The hydrogen atoms (H2 ¼ 0.46901 and H3 ¼ 0.40834) attached to the oxime oxygen (O3) and amide nitrogen (N9) bear more positive charge compared to others. Four nitrogen atoms of the title molecule exhibit negative charges, but the N3 atom joined in the formation of the intra-molecular hydrogen bond and the N4 atom in the pyridine ring have a higher negative charge value than the

other nitrogen atoms. However, the maximum negative atomic charges are around the oxygen atoms (O1 ¼ 0.56378 and O2 ¼ 0.53511) of the carbonyl and oxime groups. On the whole, considering the atomic charge distributions and the steric effect, the O2, O3, N1, N5 and N9 atoms in which the negative charge is delocalized can serve as coordinating sites for metal ions and thus the title compound can act as a multidentate ligand through the nitrogen and oxygen atoms.

Table 7 Selected Lewis orbitals (occupied bond or lone pair) of inapNH2 with their valence hybrids performed at B3LYP/6-311þþG(d,p): Lpeloan pair, ED(e)eelectron density and (ED, %)epercentage electron density. Bond

Type

ED(e)

Atom

ED, %

%s

%p

%d

NBO Hybrid Orbital

N1eO2

s

1.98782

N1eC1

s

1.99181

p

1.94433

s

1.99302

p

1.97805

O2eH2

s

1.99214

N2eN3

s

1.98652

N2eC2

s

1.98552

p

1.87699

C9eC10

s

1.97361

C9eN3

s

1.98835

C10eC14

s

1.97763

C3eC4

s

1.97335

p

1.64893

C3eC8

s

1.97154

C3eC2

s

1.96691

N3eH3

s

1.98434

C1eH1

s

1.97821

C1eC2

s

1.97148

N4eC14

s

1.98662

p

1.70497

N4eC13

s

1.98661

LP(1)N1 LP(1)O1 LP(2)O1 LP(1)O2 LP(2)O2 LP(1)N2 LP(1)N3 LP(1)N4

e e e e e e e e

1.93641 1.98036 1.85756 1.99201 1.89767 1.92114 1.62488 1.91792

N1 O2 N1 C1 N1 C1 O1 C9 O1 C9 O2 H2 N2 N3 N2 C2 N2 C2 C9 C10 C9 N3 C10 C14 C3 C4 C3 C4 C3 C8 C3 C2 N3 H3 C1 H1 C1 C2 N4 C14 N4 C14 N4 C13 N1 O1 O1 O2 O2 N2 N3 N4

41.67 58.33 59.40 40.60 58.37 41.63 64.29 35.71 68.36 31.64 73.69 26.31 47.11 52.89 59.07 40.93 54.43 45.57 48.05 51.95 37.07 62.93 52.05 47.95 51.01 48.99 50.37 49.63 51.39 48.61 49.79 50.21 72.58 27.42 62.26 37.74 49.69 50.31 59.11 40.89 60.09 39.91 59.14 40.86 e e e e e e e e

16.54 21.12 42.37 32.37 0.01 0.03 40.34 32.79 0.52 0.49 21.46 99.84 25.12 30.56 41.86 31.91 0.00 0.01 36.41 30.52 30.13 36.72 33.94 37.93 34.56 35.52 0.02 0.02 34.51 34.97 30.89 33.74 32.39 99.91 33.02 99.94 34.84 34.26 35.83 32.10 0.00 0.00 35.40 31.82 41.50 59.17 0.01 57.50 0.00 33.08 0.36 28.87

83.22 78.77 57.54 67.53 99.84 99.77 59.54 67.05 99.36 99.11 78.45 0.16 74.75 69.37 58.05 68.00 99.84 99.86 63.55 69.44 69.76 63.24 66.02 62.03 65.40 64.45 99.95 99.94 65.46 64.99 69.07 66.23 67.56 0.09 66.93 0.06 65.13 65.71 64.08 67.81 99.85 99.85 64.51 68.08 58.46 40.81 99.92 42.48 99.95 66.85 99.64 71.05

0.24 0.11 0.09 0.10 0.14 0.20 0.12 0.15 0.12 0.41 0.09 e 0.13 0.07 0.08 0.09 0.16 0.13 0.04 0.05 0.11 0.04 0.04 0.04 0.04 0.04 0.03 0.04 0.04 0.04 0.04 0.03 0.04 e 0.05 e 0.04 0.04 0.09 0.10 0.15 0.15 0.09 0.10 0.03 0.02 0.08 0.02 0.05 0.07 0.01 0.08

sp5.03 sp3.73 sp1.36 sp2.09 p p sp1.48 sp2.04 p p sp3.66 s sp2.98 sp2.27 sp1.39 sp2.13 p p sp1.75 sp2.28 sp2.32 sp1.72 sp1.94 sp1.64 sp1.89 sp1.81 p p sp1.90 sp1.86 sp2.24 sp1.96 sp2.09 s sp2.03 s sp1.87 sp1.92 sp1.79 sp2.11 p p sp1.82 sp2.14 sp1.41 sp0.69 p sp0.74 p sp2.02 p sp2.46

O1eC9

A. Zülfikarog
lu et al. / Journal of Molecular Structure 1162 (2018) 125e139 Table 8 The occupacy of significant NLMOs, percentage from parent NBO and atomic hybrid contributions of inapNH2. Bond

Occupany Percentage from parent NBO Hybrid contributions

p(C10eC11) 2.00000

81.2067

p(C3eC4)

2.00000

82.3483

p(C7eC8)

2.00000

80.9905

p(N4eC14)

2.00000

84.6481

p(C5eC6)

2.00000

82.4490

p(C12eC13) 2.00000

80.5351

LP(1)N3

2.00000

80.6170

Atom

%

O1 C9 C10 N3 C11 N4 C14 C12 C13 N2 C9 C3 C4 C8 C2 C5 C6 C7 C3 C4 C8 C5 C6 C7 C10 C11 N4 C14 C12 C13 N2 C8 C4 C8 C2 C5 C6 C7 O1 C9 C10 C11 N4 C14 C12 C13 N1 O1 N2 C9 C10 C3 N3 C1 C2

0.744 1.500 46.456 0.206 34.860 2.034 8.070 3.071 2.891 0.825 0.100 41.584 40.766 6.087 1.049 6.069 1.808 1.366 4.550 4.865 39.666 4.574 4.847 41.326 2.712 2.965 52.871 31.826 1.992 7.557 0.212 3.643 4.257 2.054 0.276 39.704 42.790 6.910 0.141 0.287 2.466 9.417 2.987 4.016 45.570 35.026 0.499 3.114 4.280 6.600 0.129 0.244 80.631 0.658 3.257

4.7. Molecular electrostatic potential The molecular electrostatic potential (MEP), created in the space around a molecule by its nuclei and electrons, is very helpful in interpreting and predicting the reactive behavior of a wide variety of chemical systems in both electrophilic and nucleophilic reactions, which are the study of biological recognition processes, including drugereceptor, enzymeesubstrate interactions and hydrogen bonding interactions [130,131]. ! The electrostatic potential, V( r ) at any point r is given by the following equation:

135

  !0 ! Z r d r0 r X Z ! A  Vð r Þ ¼ !   !   R A  r/  r0  r/ A   where ZA is the charge on nucleus A, located at RA, and p(r) is the electronic density function of the molecule obtained from its ! computed wave function. V( r ) is a real physical property that can be determined experimentally as well as computationally [130,132]. To investigate the reactive sites of the title compound, the molecular electrostatic potentials were evaluated using the B3LYP/6311þþG(d,p) method. The different values of the electrostatic potential at the surface are defined by different colors. Potential increases in the order red < orange < yellow < green < light blue < blue. Fig. 4 shows the electrostatic potential contour map where the negative (red and yellow) regions of MEP are related to electrophilic attacks and the positive (blue) regions are related to nucleophilic reactivity. As can be seen in Fig. 4, the negative regions in the studied molecule are mainly localized over the O1, N4, N2, N3, O2 and N1 atoms with values around 0.063 a.u., 0.045 a.u., 0.038 a.u., 0.035 a.u., 0.028 a.u. and 0.002 a.u., respectively. Thus, it can be predicted that the most preferred region for electrophilic attack is around the oxygen atom (O1) of the carbonyl group. By contrast, a maximum value of 0.069 a.u. is found on the oxime hydrogen (H2) atom in the positive regions of V(r) indicating that this site is probably involved in nucleophilic processes. The MEP is also used to identify sites for intra- and intermolecular interactions [133]. When an intra-molecular interaction occurs, the electrostatic potential of the negative atom becomes less negative and the positive region of the other atom becomes less positive [133,134]. For the MEP surface in the studied molecule, the weak negative region associated with the N1 atom, and also the weak positive region at the nearby H3 atom, are indicative of intra-molecular (N1/H3eN3) hydrogen bonding [134,135]. 4.8. Frontier molecular orbital energies and chemical reactivity The Density Functional Theory (DFT) is one of the important tools to define and justify chemical concepts that give information about the reactivity of molecules [136e138]. For the title compound, the chemical reactivity descriptors were obtained by the DFT method employing the B3LYP/6-311þþ(d,p) level. Table 10 shows the values of the calculated frontier orbital energies (EHOMO, ELUMO), total energies (Etotal), energy gap (D(H-L)) and global reactivity descriptors (electronegativity (c) chemical potential (m), chemical hardness (h) and electrophilicity index (u)) for inapNH2 in aqueous and ethyl alcohol phases. The frontier orbitals, such as HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital), are very important quantum chemical parameters because they determine the way molecules interacts with each other. The HOMO orbital can act as an electron donor, while the LUMO orbital can act as an electron acceptor. The molecules with a high energy HOMO orbital tend to donate electrons to lower energy unoccupied orbitals of an acceptor such as a metal ion [16,137]. The HOMOeLUMO gap and total energy are important stability indexes. A low total energy and large band gap indicate high stability and low chemical reactivity. In other words, a smaller band gap and higher total energy indicate less stability and higher reactivity of a molecule, and the easier the electron transition will be [16]. In addition to this, the lower the value of chemical potential (m), chemical hardness (h)

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136

Table 9 Calculated atomic chargesa by Natural Population Analysis (NPA). Atom N1 O1 O2 H2 N2 C9 C10 C3 N3 H3 C1 H1 C4 H4 C8 H8 C2 C11 a

B3LYP/6-311þþG(d,p) (NPA) natural charges

Atom

0.18445 0.56375 0.53511 0.46901 0.20032 0.66113 0.17247 0.07011 0.44340 0.40834 0.01338 0.23232 0.20612 0.21334 0.16648 0.23014 0.14347 0.15634

H11 N4 C5 H5 C6 H6 7C H7 C14 H14 C12 H12 C13 H13 O3 H3A H 3B

B3LYP/6-311þþG(d,p) (NPA) natural charges 0.21152 0.44564 0.21109 0.20805 0.19931 0.20633 0.19674 0.20803 0.10218 0.20957 0.24228 0.21373 0.06708 0.18926 0.92718 0.46988 0.46401

Atomic charge unit (a.u.).

Table 10 The calculated quantum chemical parameters of inapNH2. Quantum chemical parameter

Water (Ɛ ¼ 78.39)

Ethanol (Ɛ ¼ 24.55)

EHOMO (a.u) ELUMO (a.u) Etotal (a.u) D(H-L) (a.u) (HOMO-LUMO) c (a.u) m (a.u) h (a.u) u (a.u)

0.2408 0.0969 986.8176 0.14390 0.16888 0.16888 0.07195 0.198196

0.2406 0.0967 986.8164 0.14388 0.16865 0.16865 0.07194 0.197684

Table 11 Interaction of donor (inapNH2) with CoCl2, NiCl2, CuCl2 and ZnCl2. Acceptor

hA

Aqueous phase 0.08946 CoCl2 NiCl2 0.07999 CuCl2 0.09041 ZnCl2 0.06269 Ethanol phase 0.08817 CoCl2 NiCl2 0.09022 CuCl2 0.06246 ZnCl2 0.12439

hD

cA

cD

DN

DE

0.07195 0.07195 0.07195 0.07195

0.17678 0.17866 0.22475 0.17996

0.16888 0.16888 0.16888 0.16888

0.7074 0.8196 5.6458 0.7957

0.0027 0.0038 0.1497 0.0042

0.07194 0.07194 0.07194 0.07194

0.19222 0.17781 0.22443 0.17871

0.16865 0.16865 0.16865 0.16865

2.0026 0.7686 5.6465 0.6968

0.0236 0.0035 0.1575 0.0035

and global electrophilicity index (u), the better the donor properties will be [16,138]. The energy gap, EHOMO, total energy, chemical potential (m), chemical hardness (h) and global electrophilicity index (u) values given in Table 10 for inapNH2 in both the aqueous and ethanol phases show that the title compound has slightly stronger electron-donating ability in the ethanol phase.

D: donor (inapNH2) A: acceptor (metal(II) chlorides).

4.9. Metal (acceptor)eLigand (donor) interaction

5. Conclusions

The metaleligand bond strength between the interaction of acceptor and donor has recently been evaluated with the help of quantum chemical parameters, such as the energy lowering DE and charge transfer DN values [136,138]. The values of DE and DN for the interaction of donor (inapNH2 ligand) and acceptor (CoCl2, NiCl2, CuCl2 and ZnCl2) are evaluated and listed in Table 11. The metal bond strength between the interaction of acceptor (metal (II) chloride) and donor (inapNH2 ligand) increases as the charge transfer (DN) increases and the energy lowering (DE) decreases. The bond strength of inapNH2 with metal chlorides based on the values DN and DE follow the sequence CuCl2 > NiCl2 z ZnCl2 z CoCl2 in the aqueous phase and CuCl2 > CoCl2 > NiCl2 z ZnCl2 in the ethanol phase. The values of DN and DE indicate that the most stable complex formation in both is between

In this study, a new hydrazone oxime compound was synthesized and characterized by X-ray crystallography, IR, 1H-NMR and 13 C-NMR spectral techniques. In addition to the experimental studies, most of the properties of the molecular structure were calculated using B3LYP/6-31G(d) and B3LYP/6-311þþG(d,p) methods. The X-ray structure is slightly different from its optimized molecular structures because the crystal structure in the solid phase is stabilized by the inter-molecular OeH/O and OeH/N hydrogen bonds that supply the leading contribution to stability. However, the theoretical calculations were conducted in the gas phase. The B3LYP/6-311þþG(d,p) method can reproduce the title compound better than the B3LYP/6-31G(d) method. In order to study vibrational, NMR and thermodynamic properties of inapNH2, the theoretical calculations were successfully performed by using DFT with the B3LYP/6-31G(d) and B3LYP/6-311þþG(d,p) levels. The spectroscopic results obtained are in good agreement with the experimental values. The correlations between the thermodynamic properties (heat capacity, entropy, enthalpy) and temperatures show that thermodynamic parameters increase with increasing temperature. The intra- and inter-molecular contacts and the stability of the title compound have been interpreted using NBO and NLMO analysis with B3LYP/6-311þþG(d,p). NBO/NPA atomic charges were determined to predict the possible electron donating centers on the inapNH2 that can likely interact with metal ions. The results indicated that the inapNH2 may coordinate with carbonyl, oxime group oxygen and with azomethine, oxime and amide nitrogen atoms as a multidentate ligand to the metal ions. By using HOMO and LUMO energy values for the molecule in the aqueous and ethanol phases, quantum chemical parameters have been calculated at the B3LYP/6-311þþG(d,p) level. The results show that the reactivity of the compound is slightly higher in the ethanol phase than in the water phase. Finally, the metal bond strength between the interaction of metal(II) chlorides (acceptor) and inapNH2 (donor) were investigated with the quantum chemical

Fig. 4. Molecular Electrostatic Potential map calculated with the B3LYP/6311þþG(d,p) level.

inapNH2 and CuCl2.

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parameters of energy lowering DE and charge transfer DN in both solvents. The values of the DE and DN parameters for interaction between the inapNH2 and CoCl2, NiCl2, CuCl2 and ZnCl2 indicate that the inapNH2 can form complexes with these metal(II) chlorides, and the most stable complex formation is between inapNH2 and the Cu(II) ion. Based on these results, it can be said that inapNH2 can be used as a chelating ligand in the detection, determination and extraction of metal ions, especially Cu (II) ions, in both aqueous and ethanol phases. Acknowledgements € r for his help The authors thank Professor Dr. Orhan Büyükgüngo with the data collection and acknowledge the Ondokuz Mayıs University Research Projects Unit for financial support of project F446 and the Amasya University Research Projects Unit for financial support of project FMB-BAP-018.

[16]

[17]

[18]

[19]

[20] [21]

[22]

Appendix A. Supplementary data

[23]

Supplementary data associated with this article can be found in the online version, at https://doi.org/10.1016/j.molstruc.2018.02. 079. These data include MOL files and InChiKeys of the most important compounds described in this article.

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