# Theoretical Studies of Structure, Spectroscopy, and Properties of a New Hydrazine Derivative

Authors: Hajar Sahebalzamani; Farshid Salimi; Elmira Dornapour
Journal: Journal of Chemistry
 (2013)

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## Abstract

We will report a combined experimental and theoretical study on molecular structure, vibrational spectra, and energies of (E)-1-(2,4-dinitrophenyl)-2-[(4-methylphenyl)methylidene]hydrazine (1). The molecular geometry and vibrational frequencies and energies in the ground state are calculated by using HF and DFT levels of theory with 6-311G basis sets. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The harmonic vibrational frequencies were calculated, and the scaled values have been compared with experimental FTIR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed bar-type spectrograms.


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## Body

## 1. Introduction

The properties of hydrazides and hydrazones are of interest due to their biological activities and their use as metal extracting agencies [1]. The hydrazones derivatives are used as fungicides and in the treatment of diseases such as tuberculosis, leprosy, and mental disorders. The complexes of various hydrazones are reported to act as inhibitors  of enzymes  [2]. Many substituted hydrazides are employed in the treatment of psychotic and psychoneurotic conditions. Carboxylic acid hydrazides are known to exhibit strong antibacterial activities which are enhanced by complexation with metal ions. Chemistry of Schiff bases has been intensively investigated in recent years, owing to their coordination properties and diverse applications. Schiff base hydrazones are widely used in analytical chemistry as a selective metal extracting agent as well as in spectroscopic determination of certain transition metals [3–6]. Schiff bases play an important role in inorganic chemistry as they easily form stable complexes with most transition metal ions in the periodic table. The development of the field of bioinorganic chemistry has increased the interest in Schiff base complexes, since it has been recognized that many of these complexes may serve as models for biologically important species [7–11]. Schiff base metal complexes have been widely studied because they have industrial, fungicide, antibacterial, anticancer, and herbicidal applications [12, 13].However, the detailed ab initio and DFT (LSDA) with 6-311G comparative studies on the complete FTIR spectra of compound (1) have not been reported so far. In this study, molecular geometry, optimized parameters, and vibrational frequencies are computed and the performance of the computational methods for the ab initio and DFT (LSDA) levels with the 6-311G basis sets is compared. The HOMO represents the ability to donate an electron, LUMO as an electron acceptor represents the ability to obtain an electron. The HOMO and LUMO energy calculated by the ab initio and DFT (LSDA) levels with the 6-311G basis sets.


## 2. Experimental

### 2.1. Computational Details

All calculations were performed using the Gaussian 03 program on a Windows-XP operating PC. The molecular structure of the title compound in the ground state is computed by performing the ab initio and DFT (LSDA) with the 6-311G basis sets.


## 2.1. Computational Details

All calculations were performed using the Gaussian 03 program on a Windows-XP operating PC. The molecular structure of the title compound in the ground state is computed by performing the ab initio and DFT (LSDA) with the 6-311G basis sets.


## 3. Results and Discussion

### 3.1. Molecular Geometry

The molecular structure of compound (1) belongs to C1 point group symmetry. The optimized molecular structure of title molecule is obtained from Gaussian 03W and Gaussview programs are shown in Figure1. The optimized structural parameters of compound  (1)  calculated by the ab initio and DFT (LSDA) levels with the 6-311G basis sets are listed in Table 1.Table 1
Optimized geometrical parameters for compound (1) at (HF/LSDA) methods by using 6-311G basis set.
Geometrical parameters
6-311G
HF
LSDA
Bond length (Å)
C1–C2
1.371
1.374
C2–C3
1.404
1.407
C3–C4
1.399
1.411
C4–C5
1.379
1.382
C5–C6
1.376
1.380
C6–C1
1.389
1.396
N13–C6
1.436
1.434
N13–O14
1.229
1.265
N13–O15
1.227
1.263
N10–C4
1.447
1.438
N10–O11
1.224
1.267
N10–O12
1.226
1.259
C3–N16
1.365
1.356
N16–N18
1.374
1.365
N18–C19
1.267
1.298
C19–C21
1.479
1.450
C21–C22
1.392
1.398
C21–C23
1.393
1.404
C22–C24
1.383
1.385
C26–C23
1.385
1.384
C28–C26
1.392
1.398
C24–C28
1.392
1.397
C28–N31
1.507
1.488
Bond angle (°)
C1–C2–C3
121.4
120.6
C2–C3–C4
117.2
118.2
C3–C4–C5
121.7
121.0
C4–C5–C6
119.1
118.8
C5–C6–C1
120.9
121.5
C1–C6–N13
119.6
119.2
C5–C6–N13
119.4
119.1
O14–N13–O15
123.5
124.2
C3–C4–N10
122.3
121.5
C5–C4–N10
115.7
116.9
C4–N10–O11
118.1
117.8
C4–N10–O12
117.7
117.7
11–N10–O12
124.0
124.1
C2–C3–N16
118.8
120.4
C4–C3–N16
123.8
121.3
C3–N16–N18
119.0
120.1
N16–N18–C19
120.7
118.0
N18–C19–C21
128.4
126.5
C19–C21–C22
119.5
121.1
C19–C21–C23
121.9
119.8
C21–C22–C24
120.7
120.4
C22–C24–C28
121.0
121.1
C24–C28–C26
118.0
118.2
C28–C26–C23
121.2
121.2
C26–C23–C21
120.5
120.1
C24–C28–C31
120.9
120.9
C26–C28–C31
120.9
120.8Figure 1
Molecular structure and atom numbering scheme adopted in this study for (1).


### 3.2. Vibrational Analysis

Vibrational spectroscopy was extensively used in organic chemistry for the identification of functional groups of organic compounds, the study of molecular conformations, reaction kinetics, and so forth. The observed and calculated data of the vibrational spectrum of compound (1) are given in Table2. The suggested reason was that the result obtained by the calculation was harmonic oscillation frequency, while the experimental value contained the anharmonic oscillation frequency. Assignment of compound systems could be proposed on the basis of frequency agreement between the computed harmonics and the observed fundamental modes. The calculated infrared spectra for different methods of compound (1) are presented in Figure 2. Correlation graphs between the scaled calculated and observed results for the assigned fundamentals in the region 4000–500 cm−1 are shown in Figure 3.Table 2
Observed and HF/DFT (LSDA) with 6-311G level calculated vibrational frequencies of compound (1).
Experimental
HF6-311G
Int. (IR)
LSDA6-311G
Int. (IR)
Vibrational assignments
3447
3814
66
3353
123
νNH
3311
3410
2
3150
8
νsCH
—
3361
8
3115
1
νasCH
3103
3356
3
3113
16
νsCH
—
3345
11
3100
6
νCH
—
3331
15
3080
1
νasCH
—
3242
23
3058
7
νasCH3
—
3161
39
2954
13
νsCH3
1615
1799
20
1642
113
νsC–C + βCH
1591
1873
9
1615
4
νsC–C + βCH + νsC–N
1511
1792
382
1608
38
νsC–N + βCH + βNH
1509
1741
7
1585
3
νC–C + βCH + βNH
1419
1681
54
1552
25
βCH
1366
1607
196
1493
34
βNH + νasNO2 + βCH
1331
1562
5
1450
76
νasNO2 + βCH
1257
1489
544
1305
690
βNH + νsNO2 + βCH
1092
1145
121
1066
61
νN–N + βCH+ βNH
1008
1136
1
1001
13
γCH
908
890
16
795
8
δNO2
831
873
7
759
8
γCN + γCH
740
811
23
713
8
ωNO2 + γCH
705
720
1
655
4
βC–C–C + βC–NO2+ ωNO2
508
571
30
487
34
γCH + γNHCalculated infrared spectra of compound (1).
(a)
(b)Scaled calculated vibrational frequencies in comparison to the experimental obtained data and correlation coefficients for compound (1).
(a)
(b)Comparing the observed and calculated frequencies shows that the results of our computations are in good agreement with the experiment.In the spectrum of ligand, the strong IR absorption at 3447 cm−1 is due to N–H frequency. The calculated stretching vibration modes of the N–H band for compound (1) with ab initio and DFT (LSDA) levels with the 6-311G basis sets are 3814 and 3353 cm−1 (unscaled), respectively. Obviously, LSDA functional gives results in closest agreement with the observed frequencies over the other methods surveyed. The experimental C=N bands were observed at 1591 cm−1 as sharp bands. The calculated stretching vibration mode of the C=N band for compound (1) with HF and LSDA methods at 6-311G basis set was somewhat shifted to the higher frequency appearing at 1792 and 1608 cm−1, respectively.The FT-IR spectrum showed absorption bands at 1092 cm−1 which were assigned to N–N and calculated theoretically by HF/LSDA at 1145 and 1066 cm−1 for compound (1).As can be seen from Figure3, experimental fundamentals have a good correlation with LSDA/6-311G.As a result, the fundamental vibrational are in good consistency with the experimental results and are found a good agreement above the predicated literature.


### 3.3. Orbital Analysis

The UV-Vis spectral analysis of compound (1) has been calculated by TD-HF/6-311G and TD-LSDA/6-311G methods along with measured UV-Vis data which are summarized in Table3. The UV-Vis spectrum of compound (1) is shown in Figure 4 as measured in acetonitrile solution. Both the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are the main orbitals that take part in chemical stability. The HOMO represents the ability to donate an electron, LUMO as an electron acceptor represents the ability to obtain an electron. The HOMO and LUMO energy calculated by the ab initio and DFT (LSDA) levels with the 6-311G basis set Figure 5. This electronic absorption corresponds to the transition from the ground to the first excited state and is mainly described by one electron excitation from the highest occupied molecular or orbital (LUMO). The HOMO is located over the group, and the HOMO→LUMO transition implies an electron density transfer to ring from chlorine and partially from ring.Table 3
Experimental and calculated absorption wavelength, energies, and oscillator strengths of compound (1) using the TD-HF/B3LYP/6-311G method.
Excitation energies
Wavelength cal. gas phase
Oscillator strength (f)
Expt.
HF/6-311G
LSDA/6-311G
HF/6-311G
LSDA/6-311G
HF/6-311G
LSDA/6-311G
4.345
2.350
285
527
0.0080
0.0224
367
4.425
2.582
280
480
0.0005
0.4102
—
4.755
2.863
260
432
0.0522
0.0003
259
4.847
2.901
255
427
0.0008
0.0025
—
4.956
3.081
250
402
0.8317
0.0002
—
5.529
3.119
224
397
0.0604
0.0058
220Figure 4
UV-Vis spectrum of (E)-1-(2,4-dinitrophenyl)-2-[(4-methylphenyl)methylidene]hydrazine.Figure 5
The atomic orbital compositions of the frontier molecular orbital for compound (1).The HOMO energy calculated by LSDA/6-311G method is higher than by HF method. The biggest LUMO energy value is 0.10537  a.u.  obtained using HF/6-311G. The biggest value of energy gap (ΔE) between HOMO and LUMO energies is −0.17595  a.u.  obtained at LSDA/6-311G whereas the smallest one is −0.47583  a.u.  obtained at HF/6-311G. The total energies are found to decrease with increase of basis set dimension.


## 3.1. Molecular Geometry

The molecular structure of compound (1) belongs to C1 point group symmetry. The optimized molecular structure of title molecule is obtained from Gaussian 03W and Gaussview programs are shown in Figure1. The optimized structural parameters of compound  (1)  calculated by the ab initio and DFT (LSDA) levels with the 6-311G basis sets are listed in Table 1.Table 1
Optimized geometrical parameters for compound (1) at (HF/LSDA) methods by using 6-311G basis set.
Geometrical parameters
6-311G
HF
LSDA
Bond length (Å)
C1–C2
1.371
1.374
C2–C3
1.404
1.407
C3–C4
1.399
1.411
C4–C5
1.379
1.382
C5–C6
1.376
1.380
C6–C1
1.389
1.396
N13–C6
1.436
1.434
N13–O14
1.229
1.265
N13–O15
1.227
1.263
N10–C4
1.447
1.438
N10–O11
1.224
1.267
N10–O12
1.226
1.259
C3–N16
1.365
1.356
N16–N18
1.374
1.365
N18–C19
1.267
1.298
C19–C21
1.479
1.450
C21–C22
1.392
1.398
C21–C23
1.393
1.404
C22–C24
1.383
1.385
C26–C23
1.385
1.384
C28–C26
1.392
1.398
C24–C28
1.392
1.397
C28–N31
1.507
1.488
Bond angle (°)
C1–C2–C3
121.4
120.6
C2–C3–C4
117.2
118.2
C3–C4–C5
121.7
121.0
C4–C5–C6
119.1
118.8
C5–C6–C1
120.9
121.5
C1–C6–N13
119.6
119.2
C5–C6–N13
119.4
119.1
O14–N13–O15
123.5
124.2
C3–C4–N10
122.3
121.5
C5–C4–N10
115.7
116.9
C4–N10–O11
118.1
117.8
C4–N10–O12
117.7
117.7
11–N10–O12
124.0
124.1
C2–C3–N16
118.8
120.4
C4–C3–N16
123.8
121.3
C3–N16–N18
119.0
120.1
N16–N18–C19
120.7
118.0
N18–C19–C21
128.4
126.5
C19–C21–C22
119.5
121.1
C19–C21–C23
121.9
119.8
C21–C22–C24
120.7
120.4
C22–C24–C28
121.0
121.1
C24–C28–C26
118.0
118.2
C28–C26–C23
121.2
121.2
C26–C23–C21
120.5
120.1
C24–C28–C31
120.9
120.9
C26–C28–C31
120.9
120.8Figure 1
Molecular structure and atom numbering scheme adopted in this study for (1).


## 3.2. Vibrational Analysis

Vibrational spectroscopy was extensively used in organic chemistry for the identification of functional groups of organic compounds, the study of molecular conformations, reaction kinetics, and so forth. The observed and calculated data of the vibrational spectrum of compound (1) are given in Table2. The suggested reason was that the result obtained by the calculation was harmonic oscillation frequency, while the experimental value contained the anharmonic oscillation frequency. Assignment of compound systems could be proposed on the basis of frequency agreement between the computed harmonics and the observed fundamental modes. The calculated infrared spectra for different methods of compound (1) are presented in Figure 2. Correlation graphs between the scaled calculated and observed results for the assigned fundamentals in the region 4000–500 cm−1 are shown in Figure 3.Table 2
Observed and HF/DFT (LSDA) with 6-311G level calculated vibrational frequencies of compound (1).
Experimental
HF6-311G
Int. (IR)
LSDA6-311G
Int. (IR)
Vibrational assignments
3447
3814
66
3353
123
νNH
3311
3410
2
3150
8
νsCH
—
3361
8
3115
1
νasCH
3103
3356
3
3113
16
νsCH
—
3345
11
3100
6
νCH
—
3331
15
3080
1
νasCH
—
3242
23
3058
7
νasCH3
—
3161
39
2954
13
νsCH3
1615
1799
20
1642
113
νsC–C + βCH
1591
1873
9
1615
4
νsC–C + βCH + νsC–N
1511
1792
382
1608
38
νsC–N + βCH + βNH
1509
1741
7
1585
3
νC–C + βCH + βNH
1419
1681
54
1552
25
βCH
1366
1607
196
1493
34
βNH + νasNO2 + βCH
1331
1562
5
1450
76
νasNO2 + βCH
1257
1489
544
1305
690
βNH + νsNO2 + βCH
1092
1145
121
1066
61
νN–N + βCH+ βNH
1008
1136
1
1001
13
γCH
908
890
16
795
8
δNO2
831
873
7
759
8
γCN + γCH
740
811
23
713
8
ωNO2 + γCH
705
720
1
655
4
βC–C–C + βC–NO2+ ωNO2
508
571
30
487
34
γCH + γNHCalculated infrared spectra of compound (1).
(a)
(b)Scaled calculated vibrational frequencies in comparison to the experimental obtained data and correlation coefficients for compound (1).
(a)
(b)Comparing the observed and calculated frequencies shows that the results of our computations are in good agreement with the experiment.In the spectrum of ligand, the strong IR absorption at 3447 cm−1 is due to N–H frequency. The calculated stretching vibration modes of the N–H band for compound (1) with ab initio and DFT (LSDA) levels with the 6-311G basis sets are 3814 and 3353 cm−1 (unscaled), respectively. Obviously, LSDA functional gives results in closest agreement with the observed frequencies over the other methods surveyed. The experimental C=N bands were observed at 1591 cm−1 as sharp bands. The calculated stretching vibration mode of the C=N band for compound (1) with HF and LSDA methods at 6-311G basis set was somewhat shifted to the higher frequency appearing at 1792 and 1608 cm−1, respectively.The FT-IR spectrum showed absorption bands at 1092 cm−1 which were assigned to N–N and calculated theoretically by HF/LSDA at 1145 and 1066 cm−1 for compound (1).As can be seen from Figure3, experimental fundamentals have a good correlation with LSDA/6-311G.As a result, the fundamental vibrational are in good consistency with the experimental results and are found a good agreement above the predicated literature.


## 3.3. Orbital Analysis

The UV-Vis spectral analysis of compound (1) has been calculated by TD-HF/6-311G and TD-LSDA/6-311G methods along with measured UV-Vis data which are summarized in Table3. The UV-Vis spectrum of compound (1) is shown in Figure 4 as measured in acetonitrile solution. Both the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are the main orbitals that take part in chemical stability. The HOMO represents the ability to donate an electron, LUMO as an electron acceptor represents the ability to obtain an electron. The HOMO and LUMO energy calculated by the ab initio and DFT (LSDA) levels with the 6-311G basis set Figure 5. This electronic absorption corresponds to the transition from the ground to the first excited state and is mainly described by one electron excitation from the highest occupied molecular or orbital (LUMO). The HOMO is located over the group, and the HOMO→LUMO transition implies an electron density transfer to ring from chlorine and partially from ring.Table 3
Experimental and calculated absorption wavelength, energies, and oscillator strengths of compound (1) using the TD-HF/B3LYP/6-311G method.
Excitation energies
Wavelength cal. gas phase
Oscillator strength (f)
Expt.
HF/6-311G
LSDA/6-311G
HF/6-311G
LSDA/6-311G
HF/6-311G
LSDA/6-311G
4.345
2.350
285
527
0.0080
0.0224
367
4.425
2.582
280
480
0.0005
0.4102
—
4.755
2.863
260
432
0.0522
0.0003
259
4.847
2.901
255
427
0.0008
0.0025
—
4.956
3.081
250
402
0.8317
0.0002
—
5.529
3.119
224
397
0.0604
0.0058
220Figure 4
UV-Vis spectrum of (E)-1-(2,4-dinitrophenyl)-2-[(4-methylphenyl)methylidene]hydrazine.Figure 5
The atomic orbital compositions of the frontier molecular orbital for compound (1).The HOMO energy calculated by LSDA/6-311G method is higher than by HF method. The biggest LUMO energy value is 0.10537  a.u.  obtained using HF/6-311G. The biggest value of energy gap (ΔE) between HOMO and LUMO energies is −0.17595  a.u.  obtained at LSDA/6-311G whereas the smallest one is −0.47583  a.u.  obtained at HF/6-311G. The total energies are found to decrease with increase of basis set dimension.



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*Source: 187974-2012-11-19.xml*