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Structural and Theoretical Investigation of N’-[(E)-(4 Bromophenyl)(Phenyl)Methylidene]-4-Methylbenzenesulfonohydrazide Crystal Prepared by Slow Evaporation Method

V. Mohan1,2, P. Maadeswaran3, B. Babu4 and J. Chandrasekaran4

1Research and Development Center, Bharathiar University, Coimbatore - 641 046, Tamil Nadu, India.

2Department of Physics, K.S.Rangasamy College of Technology, Tiruchengode-637215, Tamil Nadu, India.

3Department of Energy Studies, Periyar University, Salem-636011, Tamil Nadu, India.

4Department of Physics, Sri Ramakrishna Mission Vidyalaya College of Arts and Science, Coimbatore - 641 020, Tamil Nadu, India.

Corresponding Author E-mail: maadesphysics@gmail.com

DOI : http://dx.doi.org/10.13005/ojc/330302

ABSTRACT:

The N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules were synthesized by condensation method. The synthesized N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide crystal geometric parameters were characterized by single crystal X-ray diffraction analysis. The crystal structure and optimized geometry parameter of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules were obtained by the B3LYP STO-3gG  level of basis set. The Mulliken charges, Highest Occupied Molecular Orbits (HOMO) and Lowest Unoccupied Molecular Orbits (LUMO) analyses have been done in order to calculate the energy gap, Ionization potential, Electron affinity; Global hardness, Chemical potential, global electrophilicity and Molecular electrostatic potential properties for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazid molecules were found out. The calculated HOMO and LUMO energies show that the charge transfer occurs in the N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazid molecules for B3LYP STO-3gG basis set.

KEYWORDS:

Crystal structure; X-ray diffraction; HOMO LUMO

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Mohan V, Maadeswaran P, Babu B, Chandrasekaran J. Structural and Theoretical Investigation of N’-[(E)-(4 Bromophenyl)(Phenyl)Methylidene]-4-Methylbenzenesulfonohydrazide Crystal Prepared by Slow Evaporation Method. Orient J Chem 2017;33(3).


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Mohan V, Maadeswaran P, Babu B, Chandrasekaran J. Structural and Theoretical Investigation of N’-[(E)-(4 Bromophenyl)(Phenyl)Methylidene]-4-Methylbenzenesulfonohydrazide Crystal Prepared by Slow Evaporation Method. Orient J Chem 2017;33(3). Available from: http://www.orientjchem.org/?p=33838


Introduction

Benzophenone can be used as a photo initiator in UV-curing applications [1] such as inks, imaging, and clear coatings in the printing industry. Benzophenone prevents ultraviolet (UV) light from damaging scents and colors in products such as perfumes and soaps. This can also be added to plastic packaging as a UV blocker to prevent photo-degradation of the packaging polymers or its contents. Its use allows manufacturers to package the product in clear glass or plastic (such as a PETE water bottle). Without it, opaque or dark packaging would be required. Its derivatives have been investigated extensively for their biological activities such as anti-fungal and anti-inflammatory [2-7].

In present study, Molecular geometry, Optimized parameters, Atomic charges, Mulliken charges,  HOMO (highest occupied molecular orbital) and LUMO (Lowest unoccupied molecular orbital) energies, Frontier orbital energy gap, Molecular electrostatic potential, properties are experimental and computed the performance of the computational methods for ab initio B3LYP STO-3gG basis set are compared.

Experimental

Synthesis

The 4-Bromoobenzophenone (1 mmol) and tosyl hydrazide (1mmol) were dissolved in ethanol (50 ml). The reaction mixture was heated under reflux for 3 hr and cooled gradually to room temperature [8]. The reaction mechanism is shown in Fig. 1. Crystals suitable for X-ray diffraction analysis were obtained by slow room temperature evaporation of the solution containing the compound. The as grown crystals of N-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide is depicted  in Fig. 2.

Figure 1: N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules synthesis reaction.

Figure 1: N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules synthesis reaction.



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Figure 2: As grown crystals of N’-[(E)-(4-Bromophenyl) (phenyl)methylidene]-4-methylbenzenesulfonohydrazide.

Figure 2: As grown crystals of N’-[(E)-(4-Bromophenyl) (phenyl)methylidene]-4-methylbenzenesulfonohydrazide.



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Computational Details

The quantum chemical calculation of N-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide has been performed using the B3LYP STO-3gG  level of basis set, using the Gaussian 09 Program. The optimized geometries corresponding to the minimum on the potential energy surface have been obtained by solving self-consistent field equation iteratively. The B3LYP STO-3gG level of basis set was used for HOMO-LUMO analysis, Electrostatic potential (MESP) properties were calculated by Gaussian 09 Program [9].

Characterization Techniques

Characterization: Single crystal X-ray intensity data of sucrose was collected at room temperature (T = 296 K) on a Bruker X8 KAPPA APEX-II CCD diffractometer equipped with graphite monochromated Mo Kα radiation. Initial unit cell parameters were obtained from SMART V5.05 software for CCD detector system; Bruker Analytical X-ray Systems, Madison, WI, 1998. Data integration, correction for Lorentz polarization effects and final cell refinement were performed by SAINTPLUS, V5.00 Software for the CCD detector system; Bruker Analytical X-Ray System, Inc.: Madison, WI, 1998. An empirical absorption correction based on the multiple measurements of equivalent reflections was applied using SADABS, Program for absorption correction using SMART CCD based on the method of Blessing. Structure was obtained by a combination of the direct methods and difference Fourier syntheses and refined by full-matrix least-squares on F2 using the SHELXTL.

Results and Discussion

Single Crystal X-Ray Diffraction

N-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide optimized geometric crystal structure is shown in the Fig. 3, belongs to the noncentrosymmetric monoclinic space group P21/c and the cell dimensions are a= 8.4480Å, b= 19.7198 Å, c= 12.9679 Å; α=γ =90˚ and  β=120.046; and V=1870.06 Å3. The packing diagram in N-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecule and crystal structure view along the (a) a-axis (b) b-axis, and (c) c-axis is presented in Fig. 4(a-c) and 5(a-c). The powder XRD pattern is shown in the Fig. 6.

Figure 3: Geometric structures of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide

Figure 3: Geometric structures of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide



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Figure 4: The molecule packing diagram in N’-[(E)-(4-Bromophenyl) (phenyl)methylidene]-4 methylbenzenesulfonohydrazide crystal and structure view along the (a) a-axis (b) b-axis (c) c-axis.

Figure 4: The molecule packing diagram in N’-[(E)-(4-Bromophenyl) (phenyl)methylidene]-4 methylbenzenesulfonohydrazide crystal and structure view along the (a) a-axis (b) b-axis (c) c-axis.



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Figure 5: The crystal packing diagram in N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide crystal and structure view along the (a) a-axis (b) b-axis (c) c-axis.

Figure 5: The crystal packing diagram in N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide crystal and structure view along the (a) a-axis (b) b-axis (c) c-axis.



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Figure 6: X-ray diffraction pattern of N’-[(E)-(4-Bromophenyl) (phenyl)methylidene]-4-methylbenzenesulfonohydrazide crystal.

Figure 6: X-ray diffraction pattern of N’-[(E)-(4-Bromophenyl) (phenyl)methylidene]-4-methylbenzenesulfonohydrazide crystal.



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In order to find the most optimized geometric parameters (bond length, bond angle and dihedral angles), the energy calculation are carried out for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide, using B3LYP STO-3gG  basis set  value is given in the Table (1-3). The hydrazones molecules are attracted considerable attention due to their biological activities and crystal structures of these compounds were reported [2-7].  Benzophenone and its derivatives have also been extensively investigated for their biological activities such as anti-fungal and anti-inflammatory. In present work, the title compound, C20H17BrN2O2S, was synthesized by Schiff base condensation reaction between 4-bromobenzophenone and tosyl hydrazine were used synthesized by N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules. The optimized geometric structure of molecule (Fig. 3) the bromo substituted with benzene ring (Br1-C3) forms bond length 1.8986 Å and 1.8973 Å for experimental and B3LYP STO-3gG  basis set  values respectively. The bromobenzophenone linked bridge tosyl hydrazine group (N1-N2) bond length is 1.4014 Å and 1.4519 Å experimental and theoretical values. The bond length of benzene ring carbon and hydrogen bond of  (C2-H2A), (C10-H10A), (C12-H12A), (C13-H13A) and (C20-H20C) values at 0.9499 Å, 0.9493 Å, 0.9509 Å, 0.9506 Å,  0.9497 Å & 0.9800 Å and 1.0977 Å, 1.0984 Å, 1.0984 Å, 1.0985 Å, 1.0985 Å & 1.1008 Å for experimental and theoretical values. Experimental values as compare to those theoretical values, more or less equal values are get.  The N’-[(E)-(4- Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules hydro-carbon of benzene ring are (H1A-C1-C2), (H1A-C1-C6), (C8-C9-H9A), (H9A-C9-C10), (C8-C13-H13A), (C12-C13-H13A) (H16A-C16-C17) (H18A-C18-C19) (C14-C19-H19A) and (C18-C19-H19A) bond angle values at 119.50°, 119.52°, 119.94°, 119.87°, 119.82°, 119.86°, 119.24°, 119.73°, 120.16° & 120.10° and 119.3254°, 119.6576°, 119.3914°, 119.9437°, 119.3903°, 119.9368°, 119.6115°, 119.5452°, 120.7595° & 120.8558° for experimental and B3LYP STO-3gG  basis set  values respectively. The bromine substituted benzene ring (Br1-C3-C4) 119.81° and 120.2469° for both values. The bond angle of crystal, molecules are linked through nitrogen and carbon (N1-C7-C6) values at 115.65° and 115.4307 ° for experimental and theoretical values. The molecules, bond angle between two benzene rings (C5-C6-C7) (C6-C7-C8) (C7-C8-C13) and (C11-C12-C13) values at 120.38°, 119.60°, 120.67°& 119.80° and 119.8369°, 119.3776°, 120.3213° & 120.1798 ° for experimental and B3LYP STO-3gG  basis set  values respectively. The dihedral angle between three benzene ring of N’-[(E)-(4- Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules in (C8-C9-C10-H10A), (C9-C10- C11-H11A), (H12A-C12-C13-C8), (C15-C14-C19-H19A), (H16A-C16-C17-C18), (C16-C17-C18-H18A) and (H18A-C18-C19-C14) values at 178.71°, -178.91°, 178.53°, 177.79°, 176.92°, -177.25° & 179.84° and  179.6285°, -179.7863°, 179.644°, 179.2793°, 179.5913°, -179.6164° & 179.9329° for experimental and B3LYP STO-3gG  basis set  values respectively.

Table 1: Optimized geometrical parameters for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules bond length(Å).

S. No Bond length Experimental B3LYP STO-3gG 

1

Br1-C3

1.8986

1.8973

2

S1-O1

1.4335

1.627

3

S1-O2

1.4390

1.6281

4

S1-N2

1.6575

2.0742

5

S1-C14

1.7589

1.9287

6

N1-N2

1.4014

1.4519

7

N1-C7

1.2929

1.3502

8

N2-H1N2

0.8127

1.087

9

C1-H1A

0.9499

1.0977

10

C1-C2

1.3908

1.4057

11

C1-C6

1.3984

1.4204

12

C2-H2A

0.9493

1.0984

13

C2-C3

1.3869

1.4163

14

C3-C4

1.3877

1.4188

15

C4-H4A

0.9500

1.0983

16

C4-C5

1.3877

1.4024

17

C5-H5A

0.9505

1.0985

18

C5-C6

1.4009

1.4228

19

C6-C7

1.4844

1.5079

20

C7-C8

1.4899

1.5225

21

C8-C9

1.3974

1.4198

22

C8-C13

1.3909

1.4205

23

C9-H9A

0.9498

1.0988

24

C9-C10

1.3925

1.4083

25

C10-H10A

0.9509

1.0984

26

C10-C11

1.3843

1.4087

27

C11-H11A

0.9502

1.0984

28

C11-C12

1.3864

1.4103

29

C12-H12A

0.9506

1.0985

30

C12-C13

1.3933

1.4066

31

C13-H13A

0.9497

1.0985

32

C14-C15

1.3900

1.4021

33

C14-C19

1.3887

1.4037

34

C15-H15A

0.9502

1.1019

35

C15-C16

1.3970

1.4088

36

C16-H16A

0.9503

1.0989

37

C16-C17

1.3963

1.417

38

C17-C18

1.3965

1.4175

39

C17-C20

1.5057

1.5387

40

C18-H18A

0.9502

1.0989

41

C18-C19

1.3882

1.4097

42

C19-H19A

0.9498

1.0999

43

C20-H20A

0.9806

1.1005

44

C20-H20B

0.9801

1.1042

45

C20-H20C

0.9800

1.1008

 

Table 2: Optimized geometrical parameters for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules bond angle(˚)

S. No

Bond angle Experimental B3LYP STO-3gG 

1

O1-S1-O2

119.55

122.0077

2

O1-S1-N2

107.91

105.7495

3

O1-S1-C14

107.62

111.4247

4

O2-S1-N2

104.08

111.3415

5

O2-S1-C14

111.01

107.7479

6

N2-S1-C14

105.77

95.3221

7

N2-N1-C7

117.06

116.4365

8

S1-N2-N1

111.23

104.0353

9

S1-N2-H1N2

111.79

102.2319

10

N1-N2-H1N2

117.59

107.2695

11

H1A-C1-C2

119.50

119.3254

12

H1A-C1-C6

119.52

119.6576

13

C2-C1-C6

120.98

121.0148

14

C1-C2-H2A

120.72

119.9058

15

C1-C2-C3

118.52

120.2135

16

H2A-C2-C3

120.75

119.88

17

Br1-C3-C2

118.19

120.3839

18

Br1-C3-C4

119.81

120.2469

19

C2-C3-C4

122.00

119.3691

20

C3-C4-H4A

120.60

119.8394

21

C3-C4-C5

118.81

120.0662

22

H4A-C4-C5

120.59

120.0943

23

C4-C5-H5A

119.66

120.5689

24

C4-C5-C6

120.76

121.1995

25

H5A-C5-C6

119.58

118.231

26

C1-C6-C5

118.90

118.1346

27

C1-C6-C7

120.72

122.0165

28

C5-C6-C7

120.38

119.8369

29

N1-C7-C6

115.65

115.4307

30

N1-C7-C8

124.75

125.1912

31

C6-C7-C8

119.60

119.3776

32

C7-C8-C9

119.94

121.1273

33

C7-C8-C13

120.67

120.3213

34

C9-C8-C13

119.36

118.5471

35

C8-C9-H9A

119.87

119.3914

36

C8-C9-C10

120.20

120.6594

37

H9A-C9-C10

119.94

119.9437

38

C9-C10-H10A

120.05

119.7477

39

C9-C10-C11

119.86

120.1663

40

H10A-C10-C11

120.08

120.086

41

C10-C11-H11A

119.77

120.1319

42

C10-C11-C12

120.42

119.7757

43

H11A-C11-C12

119.81

120.0925

44

C11-C12-H12A

120.07

120.0209

45

C11-C12-C13

119.80

120.1798

46

H12A-C12-C13

120.13

119.7992

47

C8-C13-C12

120.32

120.6705

48

C8-C13-H13A

119.82

119.3903

49

C12-C13-H13A

119.86

119.9368

50

S1-C14-C15

120.78

116.8293

51

S1-C14-C19

117.89

120.9216

52

C15-C14-C19

120.99

122.2344

53

C14-C15-H15A

120.72

119.2184

54

C14-C15-C16

118.49

118.8048

55

H15A-C15-C16

120.78

121.9758

56

C15-C16-H16A

119.26

119.7779

57

C15-C16-C17

121.50

120.6102

58

H16A-C16-C17

119.24

119.6115

59

C16-C17-C18

118.49

119.0239

60

C16-C17-C20

121.27

120.5254

61

C18-C17-C20

120.22

120.444

62

C17-C18-H18A

119.59

119.5142

63

C17-C18-C19

120.69

120.9404

64

H18A-C18-C19

119.73

119.5452

65

C14-C19-C18

119.74

118.3842

66

C14-C19-H19A

120.16

120.7595

67

C18-C19-H19A

120.10

120.8558

68

C17-C20-H20A

109.50

110.7846

69

C17-C20-H20B

109.52

110.3626

70

C17-C20-H20C

109.42

110.8128

71

H20A-C20-H20B

109.44

107.9849

72

H20A-C20-H20C

109.42

108.8753

73

H20B-C20-H20C

109.52

107.9249

 

Table 3: Optimized geometrical parameters for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules dihedral angle(˚).

S. No Dihedral angle Experimental B3LYP STO-3gG 

1

O1-S1-N2-N1

-70.31

175.4735

2

O1-S1-N2-H1N2

156.02

63.924

3

O2-S1-N2-N1

161.70

40.9306

4

O2-S1-N2-H1N2

28.03

-70.6188

5

C14-S1- N2-N1

44.64

-70.4822

6

C14-S1- N2-H1N2

-89.03

177.9683

7

O1-S1-C14-C15

-167.92

-142.9805

8

O1-S1-C14-C19

18.69

35.6574

9

O2-S1-C14-C15

-35.36

-6.6428

10

O2-S1-C14-C19

151.25

171.9951

11

N2-S1-C14-C15

76.93

107.7873

12

N2-S1-C14-C19

-96.46

-73.5748

13

C7-N1-N2-S1

-164.95

-137.9619

14

C7-N1-N2-H1N2

-34.23

-30.1186

15

N2-N1-C7-C6

173.73

-177.3678

16

N2-N1-C7-C8

-6.85

2.3895

17

H1A-C1-C2-H2A

0.38

0.4516

18

H1A-C1-C2-C3

-179.68

-179.2415

19

C6-C1-C2-H2A

-179.62

179.912

20

C6-C1-C2-C3

0.31

0.2188

21

H1A-C1-C6-C5

-178.81

178.9231

22

H1A-C1-C6-C7

1.98

0.1842

23

C2-C1-C6-C5

1.20

-0.5355

24

C2-C1-C6-C7

-178.01

-179.2744

25

C1-C2-C3-Br1

179.67

-179.9516

26

C1-C2-C3-C4

-1.09

0.1947

27

H2A-C2-C3-Br1

-0.40

0.3552

28

H2A-C2-C3-C4

178.85

-179.4986

29

Br1-C3-C4-H4A

-0.47

0.0194

30

Br1-C3-C4-C5

179.54

179.8679

31

C2-C3-C4-H4A

-179.70

179.8733

32

C2-C3-C4-C5

0.31

-0.2781

33

C3-C4-C5-H5A

-178.75

179.6607

34

C3-C4-C5-C6

1.26

-0.0499

35

H4-C4-C5-H5A

1.26

-0.4911

36

H4A-C4-C5-C6

-178.73

179.7983

37

C4-C5-C6-C1

-2.00

0.4515

38

C4-C5-C6-C7

177.21

179.2188

39

H5A-C5-C6-C1

178.01

-179.2656

40

H5A-C5-C6-C7

-2.78

-0.4983

41

C1-C6-C7-N1

157.08

164.5239

42

C1-C6-C7-C8

-22.38

-15.2485

43

C5-C6-C7-N1

-22.12

-14.194

44

C5-C6-C7-C8

158.43

166.0336

45

N1-C7-C8-C9

-58.22

-51.7809

46

N1-C7-C8-C13

123.45

127.4563

47

C6-C7-C8-C9

121.18

127.9675

48

C6-C7-C8-C13

-57.15

-52.7952

49

C7-C8-C9-H9A

1.75

-1.3717

50

C7-C8-C9-C10

-178.27

179.4752

51

C13-C8- C9-H9A

-179.90

179.3778

52

C13-C8- C9-C10

0.09

0.2248

53

C7-C8-C13-C12

179.65-

-179.1699

54

C7-C8-C13-H13A

-0.39

0.2613

55

C9-C8-C13-C12

1.31

0.0868

56

C9-C8-C13-H13A

-178.74

179.518

57

C8-C9-C10-H10A

178.71

179.6285

58

C8-C9-C10-C11

-1.30

-0.37

59

H9A-C9-C10-H10A

-1.31

0.4801

60

H9A-C9-C10-C11

178.69

-179.5184

61

C9-C10- C11-H11A

-178.91

-179.7863

62

C9-C10- C11-C12

1.11

0.2003

63

H10A-C10-C11-H11A

1.08

0.2151

64

H10A-C10-C11-C12

-178.89

-179.7982

65

C10-C11-C12-H12A

-179.75

-179.788

66

C10-C11-C12-C13

0.28

0.1101

67

H11A-C11-C12-H12A

0.27

0.1986

68

H11A-C11-C12-C13

-179.70

-179.9032

69

C11-C12-C13-C8

-1.50

-0.2544

70

C11-C12-C13-H13A

178.55

-179.6824

71

H12A-C12-C13-C8

178.53

179.644

72

H12A-C12-C13-H13A

-1.42

0.2159

73

S1-C14-C15-H15A

8.72

-0.528

74

S1-C14-C15-C16

-171.29

179.1197

75

C19-C14-C15-H15A

-178.10

-179.1466

76

C19-C14-C15-C16

1.89

0.5011

77

S1-C14-C19-C18

171.17

-179.033

78

S1-C14- C19-H19A

-8.83

0.7163

79

C15-C14-C19-C18

-2.21

-0.47

80

C15-C14-C19-H19A

177.79

179.2793

81

C14-C15-C16-H16A

-179.22

-179.9372

82

C14-C15-C16-C17

0.80

-0.1649

83

H15A-C15-C16-H16A

0.77

-0.2997

84

H15A-C15-C16-C17

-179.21

179.4726

85

C15-C16-C17-C18

-3.10

-0.1814

86

C15-C16-C17-C20

175.50

178.8862

87

H16A-C16-C17-C18

176.92

179.5913

88

H16A-C16-C17-C20

-4.48

-1.3411

89

C16-C17-C18-H18A

-177.25

-179.6164

90

C16-C17-C18-C19

2.78

0.2121

91

C20-C17-C18-H18A

4.14

1.3152

92

C20-C17-C18-C19

-175.84

-178.8563

93

C16-C17-C20-H20A

18.20

27.7399

94

C16-C17-C20-H20B

-101.81

-91.8077

95

C16-C17-C20-H20C

138.13

148.7013

96

C18-C17-C20-H20A

-163.22

-153.2058

97

C18-C17-C20-H20B

76.77

87.2466

98

C18-C17-C20-H20C

-43.29

-32.2444

99

C17-C18-C19-C14

-0.19

0.1045

100

C17-C18-C19-H19A

179.81

-179.6445

101

H18A-C18-C19-C14

179.84

179.9329

102

H18A-C18-C19-H19A

-0.16

0.1839

 

Mulliken Population Analysis

The atomic charges in molecules are fundamental to chemistry. For instance, atomic charge transfers in the chemical reaction [10, 11]. We have examined the Mulliken atomic charges in solution (Methanol) in Table 5. The Mulliken atomic charges calculated at the B3LYP STO-3gG. It is worthy to mention that C6, C7, and C17 atoms of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules exhibit positive charge, while C1, C2, C3, C4, C5, C8, C9, C10, C11, C12, C13, C14, C15, C16, C18, C19, and C20 atoms exhibits negative charges, Oxygen O1 and O2 has a maximum negative charges  -0.46224 and -0.47788 for this values B3LYP STO-3gG basis set. The maximum positive atomic charges (1.235288) are obtained for S1 which is sulfonate present in the functional group SO3-. The positive atomic charges are observed (0.027547) for bromine atoms. The magnitude of hydrogen atomic charges is hydrogen atomic charges are found to be only positive and negative charges obtain, this listed given in the Table 5 for this B3LYP STO-3gG basis sets for the N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules. The atomic charges plotted B3LYP STO-3gG basis set has been shown in Fig. 7. The nitrogen atoms presence of negative charges are N1 (-0.15703) and N2 (-0.45769) atoms. The above result shows that the natural atomic charges are more sensitive to the charges in the molecular structure the Mullikan’s net charges.

Figure 7: The charge distribution calculated by the Mulliken method for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesul fonohydrazide molecules.

Figure 7: The charge distribution calculated by the Mulliken method for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesul fonohydrazide molecules.

 



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Homo-Lumo Analysis

A deeper understand of chemical reactivity can be gained by this electronic absorption  corresponds to the  transition from the ground state to the first excited state and it is mainly described by one electron excitation from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) [12,13]. HOMO represents the ability to donate an electron and LUMO represent the ability to obtain an electron. The HOMO is delocalized over the Bromine substituted two benzene ring and bridge over the N-NH group. The LUMO is located on the Bromobenzophenone and tosylhydrazide group. Consequently, the HOMO-LUMO transition implies an electron density transfer from, the more aromatic part of the -conjucated system including the electron donor group to its more quinonid side and mainly to the electron with drawing end     The frontier molecular orbital’s of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide is shown in Fig. 8.  The energy value of HOMO is computed -0.11757 a.u. and LUMO is 0.01354 a.u. The energy gap is -0.10403 a.u. in for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules, respectively. Surface for the Frontier orbitals are drawn to understand the bonding scheme of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules. We examine the two important molecular orbital’s (MO) for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules: highest occupied MOs and lowest unoccupied and MOs which we denote HOMO and LUMO respectively.

Figure 8: The atomic orbital compositions of the frontier molecular orbital of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules.

Figure 8: The atomic orbital compositions of the frontier molecular orbital of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules.



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The calculated Self Consistent Field (SCF) energy of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide is –3958.29016076 a.u. at B3LYP STO-3gG  . The HOMO and LUMO energy gap explains the fact that eventual charge transfer interaction is taking place within the molecules.

Homo-Lumo Energy Gap and Related Molecular Properties

The HOMO, LUMO and HOMO-LUMO energy gap of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules in the B3LYP STO-3gG basis set has been calculated. The HOMO–LUMO energy gap reveals that the energy gap reflects the chemical activity of the molecule. Associated within the framework of SCF MO theory the ionization energy and electron affinity can be expressed through HOMO and LUMO orbital energies as I = -EHOMO and A= -ELUMO. The hardness corresponds to the gap between the HOMO and LUMO orbital energies. The larger the HOMO-LUMO energy gaps the harder the molecules [14]. The global hardness, η =1/2(ELUMO – EHOMO). The hardness has been associated with the stability of chemical system. The electron affinity can be used in combination with ionization energy to give electronic chemical potential, μ=1/2(EHOMO + ELUMO). The global electrophilicity index, ω = μ2/2η is also calculated and listed in Table 4.

Table 4: Comparison of HOMO, LUMO, energy gaps (e HOMO –LUMO), and related molecular properties of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules (a.u.).

Molecular properties

B3LYP STO-3gG

EHOMO

-0.11757

ELUMO

0.01354

∆EHOMO-LUMO gap (a.u.)

-0.10403

Ionisation Potential (I)

0.11757

Electron affinity(A)

-0.01354

Global Hardness (η )

-0.0646

Chemical potential (μ)

-0.0520

Global Electrophilicity (ω)

0.02089

 

Table 5: The charge distribution calculated by the Mulliken method for N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules.

Atoms Charges
Br1 0.02755
S1 1.23529
O1 -0.4622
O2 -0.4779
N1 -0.157
N2 -0.4577
H1N2 0.27162
C1 -0.1048
H1A 0.11081
C2 -0.1131
H2A 0.1125
C3 -0.0456
C4 -0.1141
H4A 0.11145
C5 -0.0986
H5A 0.11771
C6 0.0106
C7 0.07091
C8 -0.0065
C9 -0.1066
H9A 0.11488
C10 -0.1013
H10A 0.10916
C11 -0.1027
H11A 0.10733
C12 -0.1021
H12A 0.10731
C13 -0.1108
H13A 0.10722
C14 -0.1343
C15 -0.1123
H15A 0.10977
C16 -0.1076
H16A 0.10639
C17 0.03995
C18 -0.1083
H18A 0.10838
C19 -0.1024
H19A 0.1234
C20 -0.3411
H20A 0.11906
H20B 0.12395
H20C 0.12185

 

Molecular Electrostatic Potential (MEP)

The 3D plots of molecular electrostatic potential (MEP) of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecule is illustrated in Fig. 9. The MEP is a plot of electrostatic potential mapped onto the constant electron density surface. The MEP surface super-imposed on top of the total energy density. The MEP is a useful property to study reactivity given that an approaching electrophile will be attracted to negative region (where the electron distribution effect is dominant). In the majority of the MEPs, while the maximum negative region which preferred site of for electrophilic attack indication as red colour, the maximum positive region which preferred site for nucleophilic attack symptoms as blue colour. The importance of MEP lies in the fact that it simultaneous displays molecular size, shape as well as positive, negative and neutral electrostatic potential regions in terms of colour grading (Fig. 9) and is very useful in research of molecular  structure  with its physiochemical property relationship [15, 16]. The resulting surface simultaneously displays molecular size and shape and electrostatic potential value.

Figure 9: The Electrostatic potential of diagram in N’-[(E)-(4-Bromophenyl) (phenyl) methylidene] -4 methylbenzenesulfonohydrazide. Figure 9: The Electrostatic potential of diagram in N’-[(E)-(4-Bromophenyl) (phenyl) methylidene] -4 methylbenzenesulfonohydrazide.


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The different values of the electrostatic potential at the surface are represented by different colours. The potential increases in the order red < orange < yellow < green< blue. The colour code of these maps is the range between the HOMO – 1.437 a.u. (Deepest red) to 1.437 a.u. (Deepest blue) and LUMO is – 1.521 a.u. (Deepest red) to 1.521 a.u  in N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules. Whereas blue colour indicates the strongest attraction and red colour indicates the strongest repulsion. The regions of negative V(r) are usually associated with the lone pair of electro native atoms. The contour map of electrostatic potential of the N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecule has been constructed by the B3LYP STO-3gG basis set is shown in Fig. 10 also confirms the different negative (-4.700 a.u.) and positive (-4.700 a.u.) potential sites of the molecules  in accordance with the total electron density surface.

Figure 10: The total electron density surface mapped with electrostatic potential N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules. Figure 10: The total electron density surface mapped with electrostatic potential N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules. 

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Conclusion

In present investigation, N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide crystals were grown by slow evaporation method . The X-ray single crystal structural refinement indicated monoclinic structure and good crystalline quality. The of HOMO-LUMO analyses, energy value of HOMO was computed -0.11757 a.u. and LUMO was 0.01354 a.u. and HOMO-LUMO energy was -0.10403 a.u. The molecular electrostatic potential result reflected, the surface simultaneously displays molecular size and shape and electrostatic potential value. The total electron density surface mapped with electrostatic potential have different negative (-4.700 a.u.) and positive (-4.700 a.u.) potential sites. The Mulliken atomic charges calculated at the B3LYP STO-3gG. It was worthy to mention that C6, C7, and C17 atoms of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide molecules exhibit positive charge, while C1, C2, C3, C4, C5, C8, C9, C10, C11, C12, C13, C14, C15, C16, C18, C19, and C20 atoms exhibited negative charges, Oxygen O1 and O2 have been a maximum negative charges  -0.46224 and -0.47788 for those values B3LYP STO-3gG basis set. The theoretical molecular structures of N’-[(E)-(4-Bromophenyl)(phenyl)methylidene]-4-methylbenzenesulfonohydrazide were determined by the B3LYP STO-3gG. It is suggested this crystal will be used for nonlinear electro optic field.

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