Synthesis, crystal structure, spectroscopic analysis and computational study of (Z)-1-(2,4-dinitrophenyl)-2-((E)-3-(4-methoxyphenyl)-1-(thiophen-2-yl) allylidene) hydrazine by DFT and AIM approach

Article abstract of DOI:10.1016/j.molstruc.2015.02.029

Abstract The title compound was synthesized and characterized by IR, ¹H NMR, ¹³C NMR and single crystal X-ray diffraction studies. Quantum chemical calculations have been performed at DFT level of theory using B3LYP functional and 6-

Full text of DOI:10.1016/j.molstruc.2015.02.029

Accepted Manuscript
Synthesis, crystal structure, spectroscopic analysis and computational study of
(Z)-1-(2, 4-dinitrophenyl)-2-((E)-3-(4-methoxyphenyl)-1-(thiophen-2-yl) ally-
lidene) hydrazine by DFT and AIM approach
Ashok Kumar Singh, Ravindra Kumar Singh
PII:
S0022-2860(15)00114-3
DOI:
http://dx.doi.org/10.1016/j.molstruc.2015.02.029
MOLSTR 21327
Reference:
Journal of Molecular Structure
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Received Date:
Revised Date:
Accepted Date:
10 December 2014
5 February 2015
9 February 2015
Please cite this article as: A.K. Singh, R.K. Singh, Synthesis, crystal structure, spectroscopic analysis and
computational study of (Z)-1-(2, 4-dinitrophenyl)-2-((E)-3-(4-methoxyphenyl)-1-(thiophen-2-yl) allylidene)
hydrazine by DFT and AIM approach, Journal of Molecular Structure (2015), doi: http://dx.doi.org/10.1016/
j.molstruc.2015.02.029
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Synthesis, crystal structure, spectroscopic analysis and computational study of (Z)-1-(2,
4-dinitrophenyl)-2-((E)-3-(4-methoxyphenyl)-1-(thiophen-2-yl) allylidene) hydrazine by
DFT and AIM approach
Ashok Kumar Singh*, Ravindra Kumar Singh
Department of Chemistry, University of Lucknow, Lucknow 226 007, India
ABSTRACT
The title compound was synthesized and characterized by IR, 1H NMR, 13C NMR and single
crystal X-ray diffraction studies. Quantum chemical calculations have been performed at
DFT level of theory using B3LYP functional and 6-31G (d, p) as basis set. Potential
energy distribution (PED) for the normal modes of vibrations was done using Gar2ped
program. The time dependent density functional theory (TD-DFT) was used to find the
various electronic transitions within molecule in two different solvent of varying polarity.
Non linear optical (NLO) behavior of title compound was investigated in different solvents
by the computed value of first hyperpolarizability (β0). A combined theoretical and
1
experimental correlation of H and 13C NMR spectra are in good agreement. Stability of
molecules as a result of hyper-conjugative interactions and electron delocalization were
analyzed using NBO analysis. The HOMO and LUMO analysis is used to determine the
charge transfer within the molecule. Intramolecular interactions were analyzed by AIM
approach. The chemical reactivity descriptors were calculated to study the reactive sites
within molecule.
Keywords: Hydrazone; XRD; TD-DFT; Hyperpolarizability; NBO analysis; AIM approach
*Corresponding Authors: Cell: +91-9919663856
E-mail address: singhaks3@rediffmail.com (A.K. Singh)

Introduction
Hydrazones are an important class of compounds due to their various properties and
applications. Hydrazones having frame ―C=N―NH― constitute an important class of
compounds for [2 + 2] cycloadditions, 1, 3 dipolar cycloadditions and have been turned into a
valuable tool for the synthesis of azetidinones, pyrazoles, respectively [1, 2] and various other
N, O or S containing heterocyclic compounds such as oxadiazolines, thiazolidinones and
triazolines [3-7]. They constitute an important class of compounds for new drug
development. They are used as antimicrobial, anti-tubercular [8-11] and anti-diabetic agents
[12]. They have strong coordinating ability towards different metal ions [13, 14]. In addition,
aroyl hydrazones and their mode of chelation with transition metal ions present in the living
system have been of significant interest [15, 16]. The chemical stability of hydrazones and
their high melting point have recently made them attractive as prospective new material for
optoelectronic applications [17]. Phenyl hydrazones exhibit a series of good organic non-
linear optical (NLO) properties [18, 19].
Since most organic molecules forms molecular crystals in which the molecules are held
together by weak Van der Waals interactions, their macroscopic properties can roughly be
estimated from the microscopic properties of individual molecules. So, quantum chemical
calculations on a single molecule are useful tool not only in reproducing experimental results
but also in predicting properties of new materials. The discovery that conjugated organic
materials can exhibit large non-linear optical properties has triggered large scale theoretical
and experimental investigation in this area [20, 21]. The organic compounds showing high
hyperpolarizability are those containing an electron donating group or an electron
withdrawing group interacting through a system of conjugated double bonds.
In the present paper we report the synthesis, crystal and optimised structure along interactions
involved using quantum chemical calculations and AIM approach. Furthermore, quantum

chemical calculations are also performed to analyze the molecular structure, spectral analysis,
various intra-molecular interactions and chemical reactivity of the titled compound. AIM
approach has extensively been applied to classify and understand hydrogen bonding
interactions and ellipticity in the synthesized molecule. Local reactivity descriptors were
calculated to study the reactive site within the molecule.
Experimental
Material and methods
All experiments were carried out in under ambient atmosphere. All chemicals used were of
analytical grade. The solvent was purified and dried according to standard procedures (A.I.
Vogel, Practical Organic Chemistry). Thin layer chromatography (TLC) was performed on
Silica Gel ‘G’ (Merck, India) coated plates for monitoring the progress of reaction. The
chalcone (E)-3-(4-methoxy phenyl)-1-(thiophen-2-yl)prop-2-en-1-one was synthesized by
base catalyzed Claisen-Schmidt condensation reaction, by an earlier reported methods [22].
Melting points (oC) were determined in an open capillary by electro-thermal melting point
apparatus and were uncorrected. Elemental analysis (C, H, N, and S) was performed on
Varian Elementar – III analyzer. Infrared (IR) spectra were recorded in KBr pellets on Perkin
Elmer FTIR RX-1spectrometer from 4000-450 cm-1.1H nuclear magnetic resonance (NMR)
spectrum of synthesized compound was recorded in CDCl3 on Bruker DRX-300 MHz and
13C NMR Spectra was recorded on JOEL AL 300 FTNMR (75MHz) using (TMS) as internal
reference. Coupling constants J are expressed in Hertz (Hz). UV/Visible spectra were taken
on LABTRONICS LT2900 spectrophotometer equipped with a 1.0 cm quartz cell.
Synthesis
To a stirred and hot solution of (E)-3-(4-methoxyphenyl)-1-(thiophen-2-yl)prop-2-en-1-one
(5 mmol) added a hot (50-600C) acidic solution of 2,4-dinitrophenyl hydrazine, prepared by
careful addition of concentrated sulphuric acid (1.5 mL ) to suspension of 2,4-dinitrophenyl

hydrazine (1g, 5.05 mmol ) in methanol (15 mL).The hot mixture was stirred for 5-10 min.
and then refluxed for about 3h and then allowed to cool at room temperature. The precipitated
hydrazone was filtered and washed with 0.01M sulphuric acid, followed by cold ether. The
crude solid was purified by recrystallization from alcohol to give purified compound. The
compound was confirmed for its purity by melting point, elemental analysis and other
º
spectral studies. Scarlet red powder, Yield: 1.75g, 79%, Mp: 164-166 C, Anal. Calcd for
C20H16N4O5S (424.43) C, 56.60; H, 3.80; N, 13.20; S, 7.55. Found C, 56.76; H, 3.63; N,
13.08; S, 7.34%. Synthetic scheme for preparation of hydrazone compound is shown in Fig.1.
Fig. 1
X-ray crystallography
The crystal of X-ray quality for the compound was obtained by slow evaporation of
ethanol/diethyl ether solvent mixture at room temperature. X-ray crystallographic data was
recorded by mounting single reddish brown crystal of compound of size (0.300 x 0.220 x
0.200) mm3 on glass fibers. Cell determination and intensity data were collected at 298(2) K
on a Oxford diffraction XCALIBUR-S CCD area detector diffractometer system equipped
with graphite monochromated Mo Kα radiation λ = 0.71073 Å. The final unit cell
determination, scaling of data and correction for Lorentz and polarization effects were
performed. Symmetry related (multi-scan) absorption correction has been applied. Structure
solution by direct methods, followed by full matrix least square refinement technique on F2
using anisotropic displacement parameters, was performed using the WINGX v 2013.3 suite
[23] and SHELX-97 programs [24]. All non-hydrogen atoms were refined ansiotropically;
hydrogen atoms were located at calculated positions and refined using riding model. Figure
was prepared using ORTEP-3 [25]. Summary of crystallographic data is presented in Table 1.

Table 1
Computational details
The molecular geometry optimization and all quantum-chemical calculations have been
performed with Gaussian 09 program package [26] using DFT- B3LYP functional with
the 6-31G(d, p) basis set. The 1H NMR and 13C NMR chemical shifts were calculated by
employing Gauge Induced atomic orbital (GIAO)method [27]. A newly designed
functional, the long range Coulomb attenuating method (CAM-B3LYP) comprising of 81%
of B88 exchange at short-range and 65% of HF plus 35% of B88 at long-range [28], has been
applied and was reasonably capable of predicting the excitation energies and absorption
spectra of the D-π-A molecules having charge-transfer excitations [29-31].The energies and
intensities of the 30 lowest energy spin allowed electronic excitations were computed with
the help of TD-DFT using CAM-B3LYP method in vacuum and also in solvents using
polarized continuum model (PCM) [32]. The solvents parameters used were dichloromethane
and ethanol. Using the optimized coordinates of the compound, the first static
hyperpolarizability (β0) was calculated employing the finite field perturbation method in
vacuum as well as in the solvents having differing polarity using PCM model [32]. Stability
of molecules as a result of hyper-conjugative interactions and electron delocalization were
analyzed using natural bond orbital (NBO) analysis [33]. Potential energy distribution along
internal coordinates is calculated by Gar2ped software [34]. Internal coordinate system
recommended by Pulay et al. is used for the assignment of vibrational modes [35].
Presentation graphics including molecular geometries visualizations were done using Gauss
view 5.0 [36] program. The wave function obtained from the optimization was used to
calculate the topological parameters at the BCPs using the Bader’s theory of ‘Atoms in
Molecules, implemented in AIM 2000 software [37].

Results and discussion
Chemistry
According to the literature, hydrazones may exist as Z/E geometrical isomers about C=C
bond of ethylene bridge and about C=N bond of hydrazone moiety [38]. The synthesized
hydrazones is found to be in E-configuration with respect to -HC=CH-. This is confirmed by
presence of two, 1H doublet with coupling constant J in range of 16.0-16.5 Hz [39]. The
presence of distinct medium band at 974cm-1 is due to C-H out of plane bending of trans
disubstituted alkenes [40]. Due to possibility of different arrangement of substituent with
respect to –C=NH–, the existence of two isomers are possible. Such steric structural changes
are well reflected in NMR spectra as two set of resonance in low field region. In the 300MHz,
1H NMR (in CDCl3) spectra of compound paired peak for each proton of DNP ring and –HN-
N=, corresponding to (E) - and (Z) - forms of compounds with respect to C=N were clearly
observed. The intensities of paired peak differed from other, due to variable amount of E/Z
isomers, which are usually unequal. Two signals for N-H protons were found to be present at
δ11.67 and δ11.43 ppm. The relative integration for the two signals indicates that yield % of
(Z)- and (E)-isomers for compound is found to be 40.33% and 37.67%.The (Z)-isomer was
found to be somewhat more in comparison to (E)-isomer. This may be due to extra
stabilization of (Z) - isomer by intra-molecular N-H…O hydrogen bond.
Although the product hydrazone was found to be as (EE) - and (EZ)-isomeric mixture, but
the solid state crystal structure obtained is for predominating and more stable (EZ)-isomer.
So, all the quantum calculations, have been performed for isomer (Z)-1-(2, 4-dinitrophenyl)-
2-((E)-3-(4-methoxyphenyl)-1-(thiophen-2-yl) allylidene) hydrazine.

Crystal structure description
The ORTEP view of the title compound is shown in Fig. 2.The crystal structure of compound
shows that the molecule crystallises in triclinic system having space group P-1.The
asymmetric unit of compound was found to contain two molecules. The unit cell packing is
found to contain four molecules.The molecular structure is non-planar. The compound exists
in E-configuration with respect to their C8-C9 double bond with bond distance of 1.326Å.
The compound exists in Z-configuration with respect to their C=N double bond with bond
distance of 1.302Å.The two phenyl ring A and B are almost planar with dihederal angle of
2.04º-1.12º. The thiopene ring (Th) is somewhat perpendicular to ring A and B in order to
relieve the H…H steric strains. For unit I dihederal angle between DNP ring Ph2 and Th ring
is found to be 36.80˚ and between methoxy phenyl ring Ph1 and Th ring is 57.72˚ and for unit
II dihederal angle between ring Ph2 and Th ring is found to be 43.92˚ and between ring Ph1
and Th ring is 54.84˚.
Fig. 2
The analyses of X-ray crystal structure reveals the presence of several interactions. As seen
from the packing diagram of the unit cell, two asymmetric units interact with other units by
intermolecular H-bonds, as shown in Supplementary material (S Fig.1). Overall, interactions
results in supramolecular architecture of molecule expanding in cyclic dimeric manner,
producing three dimensional multilayered patterns. Hydrogen bonds geometry is shown in
Table 2.
Table 2
Thermodynamic properties
Thermodynamic quantities were calculated, applying vibrational frequency calculations for
all reactants and products at room temperature (298.15 K). The enthalpy (∆HReaction), Gibbs

free energy (∆GReaction) and entropy change of reaction (∆SReaction) were calculated and
arranged in Table 3. Reactants: 3-(4-methoxyphenyl)-1-(thiophen-2-yl) prop-2-en-1-one and
2, 4-dinitro phenyl hydrazine, products titled hydrazone and water (as byproduct) were
abbreviated as 1, 2, 3, and 4 respectively. For overall reaction, the enthalpy change
(∆HReaction), Gibbs free energy change (∆GReaction) and entropy change (∆SReaction) are
calculated to be 1.1923, 3.0120 kcal/ mol and 5.906 cal/mol K, respectively. The positive
values for ∆H and ∆G indicates that the reaction is endothermic and non-spontaneous at room
temperature. The reaction becomes spontaneous at elevated temperature and the temperature
gap will reduce in presence of catalyst (weak acid). Using thermodynamic relation,
equilibrium constant (Keq) for the title reaction is calculated as 6.183 x10-3 at room
temperature. Therefore, reaction is not favored in the forward direction at room temperature
and confirms the formation of product 3 at high temperature. Therefore refluxing condition is
required for the reaction.
Table 3
Optimized geometry
The optimized molecular structure of (Z)-1-(2, 4-dinitrophenyl)-2-((E)-3-(4-methoxyphenyl)-
1-(thiophen-2-yl) allylidene) hydrazine (3) was determined using Gaussian 09 program. The
geometrical parameters of crystal structure of synthesized compound are taken for
optimization of structure. Optimized molecular structure has C1 symmetry with energy of -
1764.854 au. Comparison between selected optimized geometrical parameters at B3LYP/6-
31G (d, p) with experimental X-ray crystallographic parameters is given in Table 4.
Optimized geometrical structure of compound is shown in Fig.3.
Table 4
Fig. 3

From the table, the elongation of C–C bond length of C4–C5 (1.4308 Å) and C4–C11 (1.4218
Å) than that of C5–C10 (1.3956 Å), C13–C14 (1.4056 Å) is because of the delocalization of
electron density of phenyl ring with the nitro groups. The aromatic ring of the title compound
is somewhat irregular and the spread of CC bond distance is 1.3825-1.4132 Å in Ph1 and
1.3810-1.4308 Å in Ph2, which is similar to the spread reported by Smith et al. [41]. Nitro
group is highly electronegative and tries to obtain additional electron density of the benzene
ring. It attempts to draw it from the neighboring atoms, which move closer together, in order
to share the remaining electrons more easily as a result, due to this the bond angle,
A(10,13,14) is found to be 121º, and A(4,5,10) is found to be 121.1º in the present
calculation, which is 120º for normal benzene. The C–H bond lengths in rings Ph1 and Ph2 of
the title compound lie respectively, between 1.083–1.085 Å and 1.081–1.082 Å. The
calculated bond length and bond angles of thiophene ring are in good agreement with the
experimental as well as with earlier reported value for such compounds.
Chambers et al. [42] reported the N–O bond lengths in the range 1.2201–1.2441 Å, C–N
length as 1.4544 Å. For the title compound, the C–N (NO2) bond lengths are 1.4528, 1.4591
Å and N-O bond lengths are in the range 1.2288–1.2466 Å, which are in agreement with the
reported values. The C–N–O angles are reported [43] in the range 117.4–118.7º, where as for
the title compound it is in range 117.4–118.7º.The bond angles of the NO2 group of the title
compound O17–N23–O29 = 122.8º, O29–N23–C5=118.7º, O17–N23–C5=118.5º and O16–
N20–O26 = 124.7º , O16–N20–C13 =117.4º, O26–N20–C13=117.9º are in agreement with
the values 123.5, 118.7, and 117.9º given by Saeed et al. [44].
The calculated C4–N3 bond distance of 1.3608 Å indicates that C–N bond shows partial
double bond character in this fragment. Also C–N bond length are found to be much shorter
than the average value for a single C–N bond (1.47Å), but significant longer than a C=N
double bond (1.22Å) [45], suggesting the presence of multiple bond character. The C=C bond

length is 1.3535Å and C–C bond lengths lie in the range 1.4843–1.4582Å which is in
agreement with reported literature[46]. Espinoza-Hicks et.al [47] has reported O–C aromatic and
O–CH3 bond length as 1.365Å and 1.428Å. In the present case, the respective bond lengths
are 1.3598 and 1.4213 Å.
When the X-ray structure of the title compound is compared with its optimized counterpart
conformational discrepancies are observed. Some discrepancies are observed in the
orientation of two phenyl rings and thiophene ring, which is defined by dihedral angle C21–
C9–C4–C12 = 2.02º (Ph1 and Ph2), C15–C9–C24–S1 = 57.72º (Ph1 and Th) and C5–C4–C24–
C25=36.8º (Ph2 and Th).These dihedral angles have been calculated at 2.02º,58.45º and
45.81º.When the geometry of hydrogen bond in the optimized is examined, the proton donor
group N3–H31 forms intra-molecular interaction with O17 atom, with bond length of 1.8574º
and a bond angle of 128.9º for calculated B3LYP. The N3―H31 involved in intra-molecular
H-bond are found to be 1.021Å (exp.0.884Å) and 1.021Å (exp.0.846Å) respectively. Major
discrepancy of about 5.5º in bond angle of N2―N3―H31 and 4.8º in bond angle of
C4―C3―H31 was observed. The discrepancies between the XRD results and the calculated
geometrical parameters are due to fact that the comparison made between experimental data,
obtained from solid state single crystal and calculated results are for isolated molecule in
gaseous state.
In spite of the differences, calculated geometric parameters represent a good approximation
and they are the basis for calculating other parameters, such as vibrational frequencies,
electronic absorption spectra, molecular electrostatic parameters and other optical and
spectroscopic properties.
IR spectra and vibrational assignments
The observed and calculated (scaled) vibrational wave numbers at B3LYP/6-31G (d, p) level
and their assignments using PED are given in Table 5. The calculated IR spectrum in the

region 4000–400 cm-1 is shown graphically in Fig. 4. The experimental IR spectrum is shown
in Supplementary material (S Fig. 2). The total number of atoms in compound is 46, which
give 132 (3n-6) vibrational modes. The calculated vibrational wave numbers are higher than
their experimental values for the majority of the normal modes. The calculated wave numbers
are scaled down using single scaling factor 0.9608 to discard of any harmonicity present in
real system [48]. The correlation graph is shown in Fig. 5. The value of correlation
coefficient found to be r = 0.999, showing good agreement with the calculated wave numbers
with experimental. The potential energy distribution (PED) and modes obtained from Gauss-
View program help in the assignment of the calculated harmonic vibrational wave numbers
and peaks of experimental FT-IR spectrum.
Table 5
Fig. 4
Fig. 5
C―N and N―H vibrations
In the IR spectrum of compound, two bands for C―N stretching vibration were observed,
one between aromatic carbon and nitrogen of sec. amine and other between aromatic ring
carbon and nitrogen of nitro group. Stretching vibration for C4―N3 was observed at 1489
cm-1, showing good agreement with the calculated wave number at 1492 cm-1. Stretching
vibration for C5―N23 and C13―N20 for two nitro groups was observed at 912 cm-1, shows
good agreement with the calculated wave number at 908 cm-1. The N―H stretching
vibrations generally give rise bands [49] at 3500-3300 cm-1. In the present study, the N-H
stretch of carbohydrazide part (―C=N―NH―) of molecule is observed at 3258 cm-1,
whereas it is calculated at 3311 cm-1.The N―H stretching frequency is red shifted by 53 cm-1
in the IR spectrum with a strong intensity from the computed frequency, which indicates the
weakening of the N―H bond due to the elongation of conventional hydrogen bond donor (N-

H bond) than the hydrogen bond free N―H group resulting in intra-molecular hydrogen
bond with the neighboring oxygen atom of nitro group [50]. Besides this N―H bending
vibration for secondary amine and N―H wagging vibration were observed at 1421 and 694
cm-1 showing good agreement with the calculated wave number at 1419 and 699 cm-1
respectively.
NO2 vibrations
The most characteristic bands in the spectra of nitro compounds are due to NO2 stretching
vibrations. The molecule under investigation possesses two nitro groups, and hence one
expects a symmetric and asymmetric vibration. In Aromatic nitro compounds symmetric and
asymmetric N=O stretching bands occur at slightly lower wave number than nitro-alkanes
due to conjugation with phenyl ring. Asymmetric stretching vibrations are always observed at
higher wave number than symmetric stretching vibrations. In nitro compounds NO2
stretching vibrations are located in the regions 1550–1300 cm-1[51]. Nitrobenzene derivatives
display νasNO2 in the region 1535 30 cm-1 and 3-nitropyridines at 1530 10 cm-1[52] and in
substituted nitrobenzene [53] νasNO2 appears strongly at 1345 30 cm-1 and in conjugated
nitro-alkenes [53] at 1345 15 cm-1. For the title compound, calculations give asymmetric
stretching vibrations of (N=O) at 1588 and 1556 cm-1, where as experimental was found to be
at 1588 cm-1. Symmetric stretching vibrations was observed at 1331 and 1309 cm-1, where as
calculated was found to be 1329 and 1309 cm-1 respectively. For nitrobenzene, δsc-NO2 is
reported [54] at 852 cm-1 and for 1, 3-dinitrobenzene at 904 and 834 cm-1. For the title
compound, this band was observed at 815 cm-1 and was calculated to be at 823 cm-1. In
aromatic compounds, the wagging mode ωNO2 is expected in the region 740 50 cm-1 with a
moderate to strong intensity [54]. The ωNO2 is reported at 701 and 728 cm-1 for 1, 2-
dinitrobenzene and at 710 and 772 cm-1 for 1, 4-dinitrobenzene [54]. For the title compound,
the band at 732 cm-1 in the IR spectrum is assigned as ωNO2 mode, which shows good

agreement with the calculated value at 732cm-1. The rocking mode ρNO2 is active in the
region 540 70 cm-1 in aromatic nitro compounds [54].This ρNO2 mode was calculated to be
at 507 cm-1. Varsanyi et al. [55] and Suryanarayana et al. [56] reported the ranges 70 20 and
65 10 cm-1 respectively, as the torsion mode of τNO2 for aromatic compounds. In the
present case, the deformation modes of NO2 are calculated to be present at 65 and 56 cm-1.
C=N and C=C vibrations
The observed C=N stretching vibration at 1511 cm-1 agrees well with the calculated wave
number which lies in region 1536–1516 cm-1. The C=C stretching vibration of olefinic bond
was observed at 1616 cm-1.The calculated wave number at 1618 cm-1 was assigned to the
stretching vibration mode of olefin present at C12―C7. In aromatic hydrocarbon, skeletal
vibrations involving carbon–carbon stretching within ring are absorbed mainly in region 1604
and 1409 cm-1. The wave number calculated at 1605 cm-1 and 1419 cm-1 was assigned to the
C=C stretches in benzene ring whereas experimentally it is observed at 1605 cm-1,1489 cm-1
and 1421 cm-1 respectively. The wave number calculated at 1516 cm-1 was assigned to the
C=C stretches in thiophene ring, shows good agreement with the calculated wave number at
1511cm-1.
C―H vibrations
According to internal coordinate system recommended by Pulay et al. [57], methyl (Me)
group associate with 5 types of vibrational frequencies namely: symmetric stretch,
asymmetric stretch, symmetric deformation, asymmetric deformation and rocking. The
observed stretching vibration of ether methyl (C―O―Me) at 3029, 2934 and 2901 cm-1 is in
agreement with the calculated wave number at 3032, 2965 and 2903 cm-1 respectively. An
asymmetric deformation of Me (C30) is observed at 1464 and 1447 cm-1 whereas the
calculated value found as merged peak at 1458 cm-1. Symmetric deformation of ―CH3 is
observed at 1428 cm-1, whereas the calculated is found to be at 1430 cm-1. The observed

methyl (C30) rocking at 1175 cm-1, agrees well with the calculated wave number at 1164 cm-
1. The aromatic and olefinic structure in this molecule shows the presence of C―H stretching
vibration in the region 3142–3050 cm-1, which is the characteristic region for the
identification of C―H stretching vibration [58]. The experimental spectra show only two
medium-weak band at 3102 and 3086 cm-1. Most prominent band of C―H out-of-plane
(“oop”) bending for aromatic rings, occurs in low frequency range between 968-689cm-1.The
C-H, out-of-plane bending vibrations for olefinic was observed at 974 cm-1 was assigned to
trans disubstituted alkene C(7)=C(12), shows good agreement with the calculated value at
966cm-1.
C―O and C―S vibrations
In the molecule methoxy group is present at C18 as CH3―O6―C18 ether linkage. The
presence of aryl alkyl ether displays stretching band at 1264 cm-1, shows good agreement
with the calculated value at 1261 cm-1. Symmetrical C―O stretching was observed at 1027
cm-1, where as calculated was found to be 1030 cm-1. The C―S stretching vibration for
C24―S1 and C28―S1 of thiophene ring was observed at 732 cm-1and 573 cm-1, was in
agreement with the theoretical value at 722 cm-1 and 573 cm-1.
1H and 13C NMR spectra
1
The H and 13C NMR chemical shifts of are calculated with GIAO approach using B3LYP
method and 6-31G (d, p) basis set [59]. Chemical shift of any atom (X) is calculated as
difference between isotropic magnetic shielding (IMS) of TMS and atom (X). It is defined by
an equation written as: δx = IMSTMS - IMSX.
1
The experimental and calculated values of H and 13C NMR chemical shifts of the title
1
13
compound are given in Table 6. The experimental H and C NMR spectra are shown in
Supplementary material (S Figs. 3 and 4). In order to compare the chemical shifts correlation,
graphics between the experimental and calculated 1H NMR chemical shifts are shown in Fig.

6. The correlation graph follow the linear equation (y= 0.940x + 0.423); where y is the
1
1
experimental H NMR chemical shift, x is the calculated H NMR chemical shift (in
ppm).The value of correlation coefficient (R2 = 0.993) shows that there is a good agreement
between experimental and calculated results. The correlation between the experimental and
the calculated 13C NMR chemical shifts of compound is given in Fig.7. The correlation graph
follow the linear equation (y = 0.837x + 17.32); where y is the experimental 13C NMR
chemical shift, x is the calculated 13C NMR chemical shift (in ppm).The graph shows good
correlation between the experimental and the calculated results with the coefficient of
regression R2 = 0.995.
Table 6
Fig. 6
Fig. 7
UV–Visible spectroscopy
To obtain the nature of electronic transitions, electronic excitation energies and oscillatory
strength, the UV–visible spectrum of compound has been studied by TD-DFT using CAM-
B3LYP method. The TD-DFT excitations were calculated both on the gas phase and in the
solvent using the IEF-PCM model (ethanol and dichloromethane). Experimental UV–Vis
spectrum of compound 3 in both solvents is shown in Fig. 8.The calculated electronic spectra
in gas phase and both the solvents are shown as Supplementary material (S Figs.5, 6 and 7).
As seen from the calculated spectra in solvent phase, two distinct absorption bands are found
in UV-region with λ max at 382 nm arising from H(110) → L(111) electronic transition and
λ max at 215 nm arising due to electronic transition from H-3(107) → L(111) molecular
orbitals. These bands are observed in experimental spectrum at 421 and 219 nm in DCM and
at 417 and 217 nm in solvent ethanol. The strong intensity band calculated at 382nm (f =

1.12-1.09) can be assigned to an intramolecular charge transfer (ITC) between donating and
acceptor fragments through charge transfer axis. By comparing the calculated spectra in two
solvents of different polarity, it is evident that calculated transitions do not exhibit
solvatochromic effects. The observed and calculated electronic transitions of high oscillatory
strength and their assignments, along with experimental wavelength in gas phase, ethanol and
DCM are presented in Table 7. However, in comparison to the gas phase spectrum, the bands
observed displays significant red shifting of 5 -18 nm in solvent dichloromethane and
ethanol. The experimental wavelength at 421 and 417 nm in DCM and ethanol shows
significant hyperchromic shift (red shift) in comparison to the calculated values at 382 nm.
The hyperchromic shift is occurring due to hydrogen bonding of the solvent effect. The
calculated electronic excitations give rise to the same pattern of bands, at energies and are in
good agreements with the experimental spectrum. The main difference between the
experimental and TD-DFT spectra arises from the relative intensities of the peaks observed at
215 nm in UV region. On the basis of calculated molecular orbital coefficients analysis and
molecular orbital plots for the title compound, the FMOs are mainly composed of p-atomic
orbital’s and so the nature of major electronic excitations are assigned to be π → π*.
Fig. 8
Table 7
Frontier molecular orbitals
The energy gap between the HOMO and LUMO is a critical parameter in determining
molecular electrical transport properties because it is a measure of electron conductivity [60].
Frontier molecular orbital’s HOMO and LUMO as well as other molecular orbitals involved
in electronic transitions, along their energy obtained from TD-DFT/CAM-B3LYP calculation
using PCM model for compound 3 in solvent dichloromethane are shown in Fig. 9. The

HOMOs are the orbital that could act as electron donor and the LUMOs are the orbital that
could act as electron acceptor [61]. As seen from MO’s plot, HOMO is mainly centered on
methoxy phenyl ring (which act as donor fragment) whereas LUMO is mainly located over
dinitro phenyl ring (which act as acceptor fragment). The HOMO–LUMO energy gap is an
important stability index and reflects the chemical stability of the molecule.
HOMO energy = -5.5783 eV
LUMO energy = -2.5578 eV
HOMO—LUMO energy gap = -3.0205 eV
Fig. 9
Molecular electrostatic potential (MEP)
The MEP is related to the electron density and is very useful descriptor in determining the
sites for electrophilic and nucleophilic reactions as well as hydrogen bonding interactions
[62, 63]. The electrostatic potential V(r) is also is also well suited for analyzing processes
based on the recognition of one molecule by another, as in drug-receptor and enzyme-
substrate interactions [64]. Being a real physical property, V(r) can be determined
experimentally by diffraction or by computational methods. Electrostatic potential correlates
with dipole moment, electronegativity, partial charges and site of chemical reactivity of the
molecule. It provides a visual method to understand the relative polarity of a molecule. The
negative electrostatic potential corresponds to an attraction of the proton by the concentrated
electron density in the molecule (colored in shades of red on the ESP surface), the positive
electrostatic potential corresponds to repulsion of the proton by atomic nuclei in regions
where low electron density exists and the nuclear charge is incompletely shielded (colored
shades of blue). The different values of electrostatic potential at the surface are represented
by different colors as red represents the region of most electronegative electrostatic potential,

blue represents region of most positive electrostatic potential and green represents region of
zero potential. Potential increases in the order red < orange < yellow < green < blue.
To predict reactive sites for electrophilic and nucleophilic attack for the investigated
molecule, the MEP at the B3LYP/6-31G (d, p) optimized geometry was calculated. The
electron density isosurface on to which the electrostatic potential surface has been mapped is
shown in Fig. 10.The negative (red and yellow) regions of MEP were related to electrophilic
reactivity and the positive (blue) regions to nucleophilic reactivity. From the MEP it is
evident that the negative charge covers the nitro group and oxygen atom of methoxy group
and the positive region is mainly over the methyl group. These sites give information about
region where the compound can have intermolecular interactions.
Fig. 10
NBO analysis
NBO analysis has an appealing aspect of highlighting the individual bonds and lone-pair
energy that play a vital role in the chemical processes [65, 66]. It is an important tool for
studying hybridization, covalence, hydrogen-bonding and Vander Waals interactions. In other
words natural bond orbital (NBO) provides supplementary structural information. The higher
value of E (2) (stabilization energy or energy of hyper conjugative interaction) points toward
the greater interaction between electron donors and electron acceptors (i.e. the more donating
tendency from electron donors to electron acceptors and the greater the extent of conjugation
in the system). For each donor NBO (i) and acceptor NBO (j), the strength of interaction (or
stabilization energy) E (2) associated with electron delocalization between donor and acceptor
is estimated by the second order energy lowering as [67]
ʚ̀ꢃꢄ ʛꢁ
ꢀꢀꢁꢂ ꢁ ꢂꢀꢃꢄ ꢁ ꢃꢃ
ʚꢄꢄ Ǝ ꢄꢃ ʛ

Where, qi is the population of donor orbital or donor orbital occupancy; εi, εj are orbital
energies (diagonal elements) of donor and acceptor NBO orbitals respectively; Fij is the off-
diagonal Fock or Kohn–Sham matrix element between i and j NBO orbitals.
Second-order perturbation theory analysis for selected donor (Lewis) and acceptor (non-
Lewis) orbital’s, of the Fock matrix in NBO basis calculated at B3LYP/6-31G (d,p) is
presented in Table 8 , which shows π-conjugation/resonance due to π-electron delocalization
in aromatic rings, primary and secondary hyper-conjugative interactions. The π-
conjugation/resonance due to π-electron delocalization is involved due to the π-π*
interactions whereas, the primary hyper conjugative interactions due to the various types of
orbital overlaps such as σ-π*, π-σ* n-σ* and secondary hyper conjugative interactions due to
the orbital overlap σ-σ*. Delocalization of electron density between occupied Lewis-type
(bonding or lone pair) NBO’s and unoccupied (antibonding) non-Lewis NBO’s corresponds
to a stabilizing donor-acceptor interactions.
The hyper-conjugative interactions of π (C9-C15) → π*(C21-C22)/π*(C18-C19), π (C18-
C19) → π*(C21-C22)/π*(C9-C15), π(C21-C22) → π*(C18-C19)/π*(C9-C15) are responsible
for conjugation of respective π bonds in methoxy phenyl (Ph1) ring and interaction of π (C9-
C15) → π*(C7-C12) with extended C(7)=C(12) bond. The electron density (ED) at the
conjugation of π bonds (1.63424-1.72423) of ring Ph1 and π* bonds (0.16263-0.39185) of
ring Ph1 indicates strong π delocalization within the ring and with conjugated olefinic bond
leading stabilization energy in range of 22.78-16.15 kcal/mol. The interactions π (C5-C10)
and π (C11-C14) of di-nitro phenyl (Ph2) ring with NO2 and -NH substituent’s of ring viz.
π(C5-C10) → π*(N3-C4)/π*(N23-O29) and π(C11-C14) → π*(N3-C4) stabilizes Ph2 ring by
energy in the region of 32.70-30.89 kcal/mol. The π → π* interactions viz. π (C24-C25)
→π*(C27-C28) and π (C27-C28) →π*(C24-C25) are responsible for delocalization of
respective π-electrons of thiophene ring, stabilizing the molecule in the region 16.13-14.74-

15.3 kcal/mol. The interactions of the conjugated system outside the rings viz. π (N2-C8) →
π*(C7-C12), π (C7-C12) → π*(C27-C28)/π*(C27-C28) and π*(N3-C4) → π*(N2-C8) are
also stabilizing the molecule up to 19.88-10.88 kcal/mol. The charge transfer interactions are
formed by the orbital overlap between bonding (π) and antibonding (π*) orbitals, which
results in intramolecular charge transfer (ICT) causing stabilization of the system. The
movement of π-electron cloud from donor to acceptor i.e. intramolecular charge transfer
(ICT) can make the molecule more polarized and the ICT must be responsible for the NLO
properties of molecule. Therefore, the titled compound may be used for non-linear optical
materials application in future.
The primary hyper conjugative interactions n→σ* responsible for weak intra-molecular
interactions between N3-H31…O17 (Intra-molecular H-bond) is from n1 (O17) → σ*(N3-
H31) and n2 (O17) → σ*(N3-H31) which increases ED (0.06208) that weakens the respective
bond leading to stabilization in range of 8.56-4.60 kcal/mol. The increased electron density at
the nitrogen atom (N3) leads to the elongation of respective bond length and a lowering of
corresponding stretching wave number. Other high energy interaction involving lone pair of
electron with antibonding π electrons are n2 (S1) →π*(C24-C25) and n2 (S1) →π*(C27-C28)
which increases ED (0.28211-0.32309) that weakens the respective bond leading to
stabilization within the range of 21.56-20.53 kcal/mol. The hyper conjugative interaction n2
(O6) →π*(C18-C19) indicates the delocalization of lone pair of electrons on oxygen atom of
–OCH3 group with antibonding π electrons of phenyl ring, which increases ED (0.39185) that
weakens the respective bond leading with stabilization energy of 32.21 kcal/mol. Various
secondary hyper-conjugative interactions (σ → σ*) are also associated with the molecule
which stabilizes the molecule maximum up to 5.13 kcal/mol. The hyper conjugative
interaction energy was deduced from the second-order perturbation approach. The NBO

analysis also describes the bonding in terms of natural hybrid orbital. The results are
tabulated in Supplementary material (S Table 1).
Table 8
Chemical Reactivity
Global reactivity descriptors
The chemical reactivity and site selectivity of the molecular systems have been determined
by the conceptual density functional theory [68]. Electronegativity (χ), chemical potential (µ),
global hardness (η), global softness (S) and electrophilicity index (ω) are global reactivity
descriptors, highly successful in predicting global reactivity trends. On the basis of
Koopman’s theorem [69], global reactivity descriptors are calculated using the energies of
frontier molecular orbital’s HOMO and LUMO.
According to Parr et al., electrophilicity index (ω) [70] is a global reactivity index similar to
the chemical hardness and chemical potential. This is positive and definite quantity. This new
reactivity index measures the stabilization in energy when the system acquires an additional
electronic charge (∆N) from the environment. The direction of the charge transfer is
completely determined by the electronic chemical potential of the molecule because an
electrophile is a chemical species capable of accepting electrons from the environments; its
energy must decrease upon accepting electronic charge. Therefore its electronic chemical
potential must be negative. The energies of frontier molecular orbitals (EHOMO, ELUMO),
energy band gap (EHOMO-ELUMO), electro negativity (χ), chemical potential (µ), global
hardness (η), global softness (S) and global electrophilicity index (ω) for 1, 2 and 3 are listed
in Table 9.
Table 9

When two molecules react, which one will act as an electrophile (nucleophile) will depend
upon higher (lower) value of electrophiicity index. The high value of electrophilicity index
shows that product (3) is stronger electrophile than reactants 1. Electrophilic charge transfer
(ECT) is defined as the difference between the ∆N max values of interacting molecules. If we
consider two molecules 1 and 2 approach to each other (i) if ECT > 0, charge flows from 2 to
1 (ii) if ECT < 0, charge flows from 1 to 2. ECT is calculated using equation ECT = (∆N
max)
(∆N max)2, where (∆N max)1 = (µ/η)1 and (∆N max)2 = (µ/η)2. ECT is
1
calculated as -0.3455 for reactant molecules 1 and 2, which strongly indicates that charge
flows from molecule 1 to 2. Therefore, 1 acts as very strong electron donor and 2 as electron
acceptor. The high value of chemical potential and low value of electrophilicity index (ω =
4.031 eV) for 1 favor its strong nucleophilic behavior. In the same way, the low value of
chemical potential and high value of electrophilicity index (ω=5.656 eV) for 2 favor its
electrophilic behavior.
Local reactivity descriptors
Fukui function is one of the widely used local density functional descriptors to model
chemical reactivity and selectivity. Local reactivity descriptors such as local softness (Sk),
Fukui function (fk) and local electrophilicity index (ωk) [71] have been used in DFT theory
for defining the reactive site within a particular molecule. Fukui function f(r)is considered as
one of the most fundamental indicator for defining the site selectivity in a given molecular
species and soft-soft type of interactions, the preferred reactive site in a molecule is the one
with maximum values of (fk, Sk, ωk) [72]. Using Hirshfeld atomic charges of neutral, cation
ͮ
&
ͯ
&
ͤ
and anion state of reactant (1), reactant (2) and product (3) Fukui functions (͚ , ͚ , ͚& ), local
ͮ
ͯ
ͤ
ͮ
ͯ
ͤ
softnesses (ͧ& , ͧ& , ͧ&) and local electrophilicity indices (!& , !& , !&) were calculated.
Fukui functions, local softnesses and local electrophilicity indices for selected atomic sites in
reactant (1), reactant (2) and product (3) using Hirshfeld atomic charges have been listed in

ͮ
&
Table 10. The maximum values of all the three local electrophilic reactivity descriptors (͚
ͮ
ͮ
, ͧ& ,!& ) at C-9 position of reactant (1) indicate that this site is prone to nucleophilic attack.
Using Hirshfeld atomic charges, the maximum values of local electrophilic reactivity
ͯ
&
ͯ
ͯ
descriptors (͚ , ͧ& ,!& ) at C-9 for reactant (1) and the maximum values of local nucleophilic
ͯ
&
ͯ
ͯ
reactivity descriptors (͚ , ͧ& , !& ) at N-18 for reactant (2) confirms the formation of
product molecule (3) i.e. Schiff base linkage (C8=N2) of hydrazone. The maximum values of
ͮ
&
ͮ
ͮ
local electrophilic reactivity descriptors (͚ , ͧ& , !& ) at carbon (C-8) for (3) indicate that
this site is more prone to nucleophilic attack and favor the formation of new heterocyclic
compounds by attack of nucleophilic part of the dipolar reagent on the C-8 site of C8=N2
bond.
Table 10
Non-linear optical property
Nonlinear optics deals with the interaction of applied electromagnetic fields in various
materials to generate new electromagnetic fields, altered in wave number, phase, or other
physical properties [73]. Organic molecules able to manipulate photonic signals efficiently
are of importance in technologies such as optical communication, optical computing, and
dynamic image processing [74]. DFT has been extensively used as an effective method to
investigate NLO properties of organic materials. In order to gain insight into NLO property
of title compound, the first static hyperpolarizability (β) were calculated by the finite field
perturbation method in vacuum as well as incorporating the solvent factors with increasing
polarity. First hyperpolarizability is a third rank tensor that can be described by a 3 × 3 × 3
matrix. The 27 components of the 3D-matrix can be reduced to 10 components due to the
Kleinman symmetry [75]. The components of β are defined as the coefficients in the Taylor
series expansion of the energy in the external electric field. When the external electric field is
weak and homogeneous this expansion becomes:

ͤ
ꢀ ꢁ ꢀ Ǝ μꢃ ̀ Ǝ 1/2 ̀ ̀ꢄ – 1/6ꢅꢃꢄ& ̀ ̀ ̀ ƍ 1/24ꢆꢃꢄ&'
ꢃ
ꢃꢄ
ꢃ
ꢃ ꢄ &
Where E0 is the energy of the unperturbed molecules, Fi the field at the origin and µi, α ij and
are the components of dipole moment, polarizability, and the first hyperpolarizability
β
ijk
respectively. Using the x, y and z components of β obtained from Gaussian 09 output, the
magnitude of the mean first hyperpolarizability tensor can be calculated.
The calculated first hyperpolarizability (β0) of the title compound in vaccum is 8.36 x10-
30esu, which is comparable with the reported values of related compounds [76].The β0 value
is about 10 times more than the β0 magnitude of standard p-nitro aniline (β0 = 0.83 × 10-30
esu) and 66.38 times than that of standard NLO material urea(0.13 × 10-30 esu). The β0 value
was found to increase slightly with polarity of solvent (Table 11). The calculated results show
much better first order non-linear optical (NLO) response. We conclude that the title
compound is an attractive object for future studies of nonlinear optical properties.
Table 11
Quantum theory of atoms in molecules (QTAIMs) analysis
Molecular graph of the compound 3, using AIM program at B3LYP/6-31G (d, p) level is
shown in Fig. 11. Geometrical as well as topological parameters are given in Supplementary
material (S Table 2).The various type of interactions visualized in molecular graph are
classified on the basis of geometrical, topological and energetic parameters (discussed as
Supplementary material). In this article, the Bader’s theory application is used to estimate
hydrogen bond energy (E). Espinosa [77] proposed proportionality between hydrogen bond
energy (E) and potential energy density (VBCP) at H—O contact: E = ½(VBCP). Weak
intramolecular hydrogen bond was found to be present between N2 … H34 and O17…H31.
According to AIM calculations, the total intramolecular H-bond energy was calculated as
−12.44 kcal/mol. The ellipticity (ε) at BCP is a sensitive index to monitor the π-character of

bond. The ε is related to λ1 and λ2, which correspond to the eigen values of Hessian
and defined by relationship: ε = (λ1/ λ2) − 1. The ellipticities (ε) of bond of aromatic rings at
BCP are in range of 0.176-0.310.The lower values of ellipticity (ε) confirm that that there is
delocalization of electron in aromatic rings. The ellipticity of chain C=C and N=N (in range
0.267-0.310), suggests that these bonds extends conjugation through delocalization of
aromatic ring electrons. The overall ellipticity value suggests that there is strong
delocalization in the molecule.
Fig 11
Statistical thermodynamics
On the basis of vibrational analysis and statistical thermodynamics, the standard
thermodynamics functions: heat capacity C0 , m entropy S0m and enthalpy H0 were obtained
P
m
at B3LYP/6-31G (d, p) and are listed in Table 12. It is found that the standard heat capacities,
entropies and enthalpy changes are increasing with temperatures ranging from 100 to 600 K
due to the fact the molecular vibrational intensities are increasing with temperatures. The
correlation equations between heat capacities, entropies, enthalpy changes and temperatures
were fitted by quadratic formula. Correlation graphs of thermodynamic functions vs.
temperature (T) are shown in Supplementary materials (S Figs. 8, 9 and 10). The
corresponding fitting equations between thermodynamic properties and temperature are as
follows:
ͤ
ꢁ
͂
ꢁ 211.7 ƍ 0.019͎ƍ 0.000͎ ꢁ, ʚ͌ ꢁ 0.999ʛ
(
ꢁ 15.78 ƍ 0.349͎Ǝ 0.000͎ ꢁʚ͌ ꢁ 0.999ʛ
ͤ
+,(
ꢁ
̽
ꢇ( ꢁ 74.09 ƍ 0.412͎Ǝ 0.000͎ ꢁʚ͌ ꢁ 0.999ʛ
ͤ
ꢁ
These equations above can be used to compute other thermodynamic functions and can
estimate the directions of chemical reactions according to the second law of thermodynamics

in thermo-chemical field [78].These equations will be helpful for the further studies of the
title compound.
Table 12
Conclusion
1
The structure of the titled compound was confirmed by IR, H NMR, 13C NMR and single
crystal X-ray diffraction. The geometrical parameters of the title compound are in agreement
1
with the XRD results. H and 13C NMR chemical shift were calculated with the help of
gauge-including atomic orbital (GIAO) approach showing good agreement with experimental
chemical shift. The vibrational wave numbers were examined theoretically and the normal
modes were assigned by potential energy distribution calculation. The UV–Visible spectrum
of compound studied by TD-DFT shows strong π → π* transitions. The calculated HOMO-
LUMO band gap shows the chemical reactivity and supports bioactivity of the molecule. A
computation of the first hyperpolarizability (β0) indicates that compound may be a good
candidate as a NLO material. Using NBO analysis the stability of the molecule arising from
hyper-conjugative interaction and charge delocalization through π-conjugated bridge has
been analyzed. Intra-molecular hydrogen interaction and ellipticity studied by AIM approach
showed weak hydrogen interactions and π-character of bond in aromatic ring. The calculated
maximum local electrophilic reactivity descriptors for C-8, indicates the favorable site for
nucleophilic attack at this position and favors the formation of new heterocyclic compounds.
Acknowledgement
The authors are thankful to the UGC major research project (F.No.39-701/2010-SR) and
SAIF- CDRI, Lucknow for providing spectral measurements facilities. We are thankful to our
department for providing center facility for computational research and chemistry department

of BHU, Varanasi for single crystal X-ray diffraction. Authors would also like to thank
Abhinav Kumar of our department for solving crystal structure.
Supplementary materials
CCDC 1018654 contains the supplementary crystallographic data for the title compound.
These data can be obtained free of charge at, http:www,ccdc.cam.ac.uk/conts/retrieving.html,
or from Cambridge Crystallographic data Center, 12 Union Road, Cambridge CB21EZ, UK;
fax (+44) 1223 336 033; or email:deposit@ccdc.cam.ac.uk. Supplementary data associated
with this article can be found, in the online version of this article.
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