Spectroscopic Investigation, HOMO-LUMO and Mulliken analysis of 2-[2-(Butylamino-4-phenylaminothiazol)-5-oyl]benzothiazole by DFT study.
B. JiniKumari1, T. F. Abbs Fen Reji2*
1Research Scholar, Department of Chemistry and Research Centre, Nesamony Memorial Christian College, Marthandam-629165, Tamilnadu, India.
2Assistant Professor in Chemistry, Department of Chemistry and Research Centre, Nesamony Memorial Christian College, Marthandam-629165, Tamilnadu, India.
*Corresponding Author E-mail: ginirajesh11913@gmail.com
ABSTRACT:
The compound2-[2-(Butylamino-4-phenylaminothiazol)-5oyl] benzothiazolewas characterized by IR spectral data. The geometry of the molecule was investigated and optimized with the help of B3LYP/6-311G density functional theory (DFT) method using Gaussian 09’ software package. The calculated geometries such as bond lengths, bond angle, dihedral angle atomic charges and intensities of Vibrational bonds of the titled compound were investigated. The IR spectra are obtained and assigned by vibrational analysis and found to be reliable compared with the experimental results. The calculated Homo and LUMO energy gaps also confirm that charge transfer occurs within the molecule.
KEYWORDS:Gaussian, DFT, B3LYP, Mullikencharges, HOMO, LUMO.
INTRODUCTION:
Benzothiazole derivatives are fascinating chemical products used in the field of medicine as they have been found to possess a wide spectrum of biodynamic properties.1Benzothiazole analogs of dendrodoine derivatives have attracted a great deal of interest due to their biological and commercial importance.2 The study of benzothiazoles is, therefore, of practical and theoretical importance.3 A density functional theory of different benzothiazole derivatives have been calculated by using DFT/B3LYP method. Benzothiazole derivatives have long been therapeutically used for the treatment of various diseases. However, in recent years, 2-aminobenzothiazoles have emerged as an important pharmacophore in the development of antitumor agents. Benzothiazole is a privileged bicyclic ring system.
It contains a benzene ring fused to a thiazole ring. The small and simple benzothiazole nucleus is present in compounds involved in research aimed at evaluating new products that possess interesting biological activities like- antimicrobial, antitubercular, antitumour, antimalarial, anticonvulsant, anthelmintic, analgesic and anti-inflammatory activity.
Patil et al. reported the DFT study on dihydroxyphenyl benzothiazole by using B3LYP/6-31G (d)4. The main objective of this paper is to present, more accurate vibrational assignments, bond lengths, bond angles, atomic charges and HOMO-LUMO of 2-[2,4-bis(alkylamino)thiazol-5oyl]benzothiazole using DFT/B3LYP method. A systematic study on vibrational spectra and structure of 2-[2-(Butylamino-4-phenylaminothiazol)-5-oyl]benzothiazole.
Computational details:
The DFT computation of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl] benzothiazole has been performed using Gaussian’09 program package at the Becke-3Lee-Yang-Parr(B3LYP) level with standard 6-311G basis set. The optimized structural parameters are used in the vibrational frequency calculations at DFT level. At the optimized geometry of the title molecule no imaginary frequency modes are obtained, so there is a true minimum potential energy surface is found.
The assignments of the normal modes of vibration for the titled compound have been made by visual inspection of the individual mode using the Gauss view software5.The optimized structure of 2-[2-(Butylamino-4-phenylaminothiazol)-5-oyl]benzothiazole is given in figure 1.The optimized structural parameter calculated by B3LYP level with 6-311G basis set are given in Table 1.
Fig 1-Optimized structure of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl] benzothiazole
Table.1-Optimized geometrical parameters of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole at B3LYP with 6-311G level
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Parameters
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Bond lengths(Ĺ) |
Parameters |
Bond angles(◦) |
Parameters
|
Dihedral angle(◦) |
|
Calculated |
Calculated |
Calculated |
|||
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C1-C2 C1-C6 C1-N11 C2-C3 C2-S33 C3-C4 C3-H8 C4-C5 C4-H34 C5-C6 C5-H10 C6-H11 C7-C12 C7-S33 C12-O13 C12-C14 C14-C15 C14-S16 C15-N18 C15-N19 S16-C17 C17-N18 C17-N32 N19-H20 N19-C21 C21-C22 C21-C23 C22-C24 C22-H20 C23-C26 C23-H27 C24-C28 C24-H29 C26-C28 C26-H30 C28-H31 N32-H35 N32-C36 C36-H37 C36-H38 C36-C39 C39-H40 C39-H41 C39-C42 C42-H43 C42-H44 C45-H46 C45-H47 C45-H48
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1.4158 1.4016 1.3975 1.3947 1.8109 1.3945 1.0806 1.4083 1.0816 1.3898 1.0813 1.0801 1.2956 1.4793 1.8554 1.2665 1.4326 1.396 1.8585 1.3932 1.372 1.8296 1.3172 1.3485 1.0091 1.413 1.4027 1.4039 1.3947 1.0797 1.3942 1.0827 1.3981 1.0817 1.3972 1.0819 1.0812 1.0064 1.4712 1.0952 1.0893 1.5322 1.0942 1.0971 1.5384 1.095 1.0948 1.5356 1.0926
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C2-C1-C6 C2-C1-N11 C6-C1-N11 C1-C2-C3 C1-C2-S33 C3-C2-S33 C2-C3-C4 C2-C3-H8 C4-C3-H8 C3-C4-C5 C3-C4-H34 C5-C4-H34 C4-C5-C6 C4-C5-H9 C6-C5-H9 C1-C6-C5 C1-C6-H10 C5-C6-H10 N11-C7-C12 N11-C7-S33 C1-N11-C7 C7-C12-O13 C7-C12-C14 O13-C12-C14 C12-C14-C15 C12-C14-S16 C15-C14-S16 C14-C15-N18 C14C15-N19 C15-C16-N20 N18-C15-N19 C14-S16-C17 S16-C17-N18 S16-C17-N32 N18-C17-N32 C15-N18-C17 C15-N19-H20 C15-N19-C21 H20-N19-C21 N19-C21-C22 N19-C21-C23 C22-C21-C23 C21-C22-C24 C21-C22-H25 C24-C22-H25 C21-C23-C26 C21-C23-H27 C26-C23-H27 C22-C24-C28 C22-C24-H29 C28-C24-H29 C23-C26-C228 C23-C26-H30 C28-C26-H30 C24-C28-C26 C24-C28-H31 C26-C28-H31 C17-N32-H35 C17-N32-C36 H35-N332-C36 C2-S33-C7 N32-C36-H37 N32-C36-H38 N32-C36-C39 H37-C36-H38 H37-C36-C39 H38-C36-C39 C36-C39-H40 C36-C39-H41 C36-C39-C42 H40-C39-H41 H40-C39-C42 H41-C39-C42 C39-C42-C43 C39-C42-H44 C39-C42-C45 H43-C42-H44 H43-C42-C45 H44-C42-C45 C42-C45-H46 C42-C45-H47 C42-C45-H48 H46-C45-H47 H46-C45-H48 H47-C45-H48
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120.093 115.1965 124.7096 120.9802 110.344 128.6726 118.2985 121.0738 120.6275 121.1024 119.3143 119.5833 120.6216 119.5211 119.8573 118.9029 119.0731 122.024 127.9005 115.0886 116.8074 113.0213 117.2708 121.6109 120.9257 137.9546 113.0485 108.0485 116.2979 130.8737 112.7896 86.4782 114.9915 121.2594 123.7076 112.9138 111.8568 131.2734 115.7882 122.7441 117.8376 119.2895 119.8922 120.1678 119.8972 120.1678 119.9307 120.3804 119.3941 120.2213 120.8346 119.1106 120.0535 120.3656 119.4681 120.1632 119.2278 120.3694 120.4028 118.8779 122.9818 118.0159 86.3376 109.9129 107.45 110.9098 107.0582 110.3651 111.0299 109.0869 109.59 112.5434 106.7881 109.6931 108.9741 120.4658 109.3013 109.1342 112.9063 1063088 109.4977 111.1574 111.1719 111.1758 107.7198
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C6-C1-C2-C3 C6-C1-C2-S33 N11-C1-C2-C3 N11-C1-C2-S33 C2-C1-C6-C5 C2-C1-C6-H10 N11-C1-C6-C5 N11-C1-C6-H10 C2-C1-N11-C7 C6-C1-N11-C7 C1-C2-C3-C4 C1-C2-C3-H8 S33-C2-C3-C4 S33-C2-C3-H8 C1-C2-S33-C7 C3-C2-S33-C7 C2-C3-C4-C5 C2-C3-C4-H34 H8-C3-C4-C5 H8-C3-C4-H34 C3-C4-C5-C6 C3-C4-C5-H9 H34-C4-C5-C6 C4-C5-C6-C1 C4-C5-C6-H10 H9-C5-C6-C1 H9-C5-C6-H10 C12-C7-N11-C1 S33-C7-N11-C1 N11-C7-C12-O13 N11-C7-C12-C14 S33-C7-C12-O13 S33-C7-C12-C14 N11-C7-S33-C2 C12-C7-S33-C2 C7-C12-C14-C15 C7-C12-C14-S16 O13-C12-C14-C15 O13-C12-C14-S16 C12-C14-C15-N18 C12-C14-C15-N19 S16-C14-C15-N18 S16-C14-C15-N19 C2-C14-S16-C17 C15-C14-S16-C17 C14-C15-N18-C17 N19-C15-N18-C17 C14-C15-N19-H20 C14-C15-N19-C21 N18-C15-N19-H20 N18-C15-N19-C21 C14-S16-C17-N18 C14-S16-C17-N32 S16-C17-N18-C15 N32-C17-N18-C15 S16-C17-N32-H35 S16-C17-N32-C36 N18-C17-N32-H35 N18-C17-N32-C36 C15-N19-C21-C22 C15-N19-C21-C23 H20-N19-C21-C22 H20-N19-C21-C23 N19-C21-C22-C24 N19-C21-C22-H25 C23-C21-C22-C24 C23-C21-C22-H25 N19-C21-C23-C26 N19-C21-C23-H27 C22-C21-C23-C26 C22-C21-C23-H27 C21-C22-C24-C28 C21-C22-C24-H29 H25-C22-C24-C28 H25-C22-C24-H29 C21-C23-C26-C28 C21-C23-C26-H30 H27-C23-C26-C28 H27-C23-C26-H30 C22-C24-C28-C26 C22-C24-C28-H31 H29-C24-C28-C26 H29-C24-C28-H31 C23-C26-C28-C24 C23-C26-C28-H31 H30-C26-C28-C24 H30-C26-C28-H31 C17-N32-C36-H37 C17-N32-C36-C39 H35-N32-C36-H37 H35-N32-C36-H38 H35-N32-C36-C39 N32-C36-C39-H40 N32-C36-C39-H41 N32-C36-C39-C12 H37-C36-C39-H40 H37-C36-C39-H41 H37-C36-C39-C42 H38-C36-C39-H40 H38-C36-C39-H41 H38-C36-C39-C42 C36-C39-C42-H43 C36-C39-C42-H44 C36-C39-C42-C45 H40-C39-C42-H43 H40-C39-C42-H44 H40-C39-C42-C45 H41-C39-C42-C43 H41-C39-C42-H44 H41-C39-C42-C45 C39-C42-C45-H46 C39-C42-C45-H47 C39-C42-C45-H48 H43-C42-C45-H46 H43-C42-C45-H47 H43-C42-C45-H48 H44-C42-C45-H46 H44-C42-C45-H47 H44-C42-C45-H48 |
-0.3499 179.0499 179.8134 -0.7869 0.2514 -179.6848 -179.9283 -179.9283 0.1354 0.0317 -179.7965 0.2001 -179.978 -179.079 0.7429 0.9275 -179.7316 0.0389 179.9329 -179.738 0.1101 -0.1326 179.8422 179.9737 -0.0514 -0.0156 179.9187 -179.9904 -0.0561 175.3504 0.7466 -158.4195 16.5803 16.1047 -168.3955 -0.99 -176.2208 18.289 -155.3912 -166.8924 -19.4274 -166.1854 16.2746 7.6733 -169.8668 -169.0022 -6.5321 -4.3876 173.5951 -165.5769 27.0683 16.8151 -150.5397 4.6345 -177.624 -1.327 -179.0061 6.4241 -177.715 -176.0368 -0.1759 19.8626 -164.2981 -147.0962 28.743 176.425 -2.8178 0.6437 -178.5991 -176.0988 4.6487 -0.1111 -179.3636 0.5796 179.8269 178.665 -0.9285 -0.4964 -179.8526 178.7498 -0.6063 -0.0259 179.9263 179.5638 -0.484 0.5637 -179.3884 179.9154 -0.0368 -83.5476 32.6148 154.1339 92.347 -151.4906 -29.9715 -58.8495 57.7377 179.1638 179.0955 -64.3173 57.1088 60.5443 177.1315 -61.4421 -57.748 58.1294 -179.8562 -179.3908 -63.5134 58.501 64.0283 179.9057 -58.0799 -59.9316 60.0605 -179.9416 178.0591 -61.9488 58.0491 |
RESULTS AND DISCUSSION:
Molecular geometry:
The optimized structure of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole is given in figure 1.The optimized structural parameter calculated by B3LYP level with 6-311G basis set are given in Table1.The self-consistent field(SCF) energy of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole at B3LYP level with the basis set 6-311G is found to be -1902.8297 a.u; with dipole moment 5.8946 Debye.The bond lengths of C1-C2,C2-C3,C3-C4,C4-C5,C5-C6 and C6-C1 shows double bond character(aromatic bond). similarly,the bond lengths of C21-C22,C22-C24,C24-C28,C28-C26,C26-C23 and C23-C221 shows double bond characters (aromatic bond).The bond angle (C2-S33-C7) is very less (86.337◦) than the bond angle (N11-C7-C12)127.900◦ which is due to the fact that electro negativity of nitrogen is greater than sulphur.The dihedral angles shows that the molecule consists of two planes, indole ring lies in one plane but the thiazole and phenyl rings are lying in another plane.
Vibrational assignments:
In order to obtain the spectroscopic signature of the title compound,we performed a frequency calculation analysis6.Vibrational frequency were calculated by using B3LYP/6-311G,method. 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole molecules consists of 48 atom therefore it got 138 normal modes of vibrations.The scaling factor of 0.96 is used for getting theoretical vibrational frequency. Comparison of the frequencies calculated at DFT method using 6-311G basis set with experimental values reveal that the B3LYP method shows very good agreement with the literature observation.
The hetero aromatic molecule containing an N-H group and its stretching absorption occure in the7 region 3500-3220cm-1. Primary amine examined in dilute solution display two weak absorption bands one near 3500 cm-1 and the other near 3400 cm-1. These bands represent, respectively the asymmetric and symmetric N-H stretching modes.In the present work, the theoretical calculation indicate the scaled frequency values at 3484 and 3448cm-1 is assigned to N-H stretching vibration.Primary aromatic amines normally8 absorb at 1615-1580 cm-1.The N-H in-plane bending vibration computed by B3LYP/6-311G method good agreement with literature values. The presence of aromatic N-H out-of-plane bending vibration are appeared with in the region 767-673cm-1. In the present work, the theoretical calculation indicates, the scaled frequency values at 706 and 688cm-1 is assigned to N-H out-of-plane bending vibration.The aromatic structure shows the presence of C-H stretching vibrations in the region 3100-3000cm-1 which is the characteristic region for the ready identification of the C-H stretching vibrations.The C-H stretching vibration computed by B3LYP/6-311G method good agreement with literature observations. The C-H in-plane bending vibrations were observed in the9 region 1420-1000cm-1.These bands represents, the C-H in-plane–bending vibrations.In the present work, the theoretical calculation indicate the scaled frequency value at 1395 cm-1 is assigned to C-H in-plane-bending vibration. The presence of C-H out-of plane vibrations were observed10 in the region 999-750cm-1.In the present work, the C-H out-of-plane bending vibration computed by B3LYP/6-311G method good agreement with literature observation.Generally, the carbon-carbon stretching vibrations in aromatic compound from the band in the11 region 1650-1430cm-1.In the present study,the scaled frequency value at 1478cm-1 are assigned to carbon-carbon stretching vibration. The assignments of methyl group vibration make a significant contribution to the titled compound. The asymmetric C-H vibration for methyl group usually occurs in the region between 2975 cm-1 and 2920 cm-1. The theoretically computed values by B3LYP/6-311G method for C-H vibrations are found at 2964,2864cm-1. Thus the theoretically computed values for C-H vibrations nearly coincide with literature values.In the title compound the methyl in-plane bending modes occur in the range 1479-1411 cm-1. The C-H out-of plane bending vibrations occur at 888 cm-1 and 774 cm-1.The assignments are in agreement with the literature values.The carbonyl group is present in a large number of different classes of compounds,for which a strong band observed due to the C=O stretching vibration is in the region12 of 1850-1550 cm-1.The intensity of these bands can be increase due to conjugation or formation of hydrogen bonds.The lone pair of electrons on oxygen also determined the nature of the carbonyl group.In our present study the theoretically computed wave number for C=O stretching vibrations occur at 1571 cm-1.The in-plane and out-of plane C=O bending mode occur at 1522 cm and 849 cm-1.The identifications of C-N,C=N vibrations is a difficult task,since the mixing of several bands are possible in the region.Silver-stein et al. assigned C=N stretching absorption in the13 region 1382-1226 cm-1 for aromatic amines.The identification of wave number for C-N stretching in the side chains is rather difficult since there are problems in differentiatingwave number from others. The band at 1357 cm-1 corresponds C-N,C=N stretching vibrations.The C-S stretching vibration is expected in the region 710-685cm-1. While DFT calculations give the C-S stretching vibration at 637cm-1 is assigned to C-S stretching vibration.The carbonyl group is important and its characteristic frequency has been extensively used to study a wide range of compounds.
Fig 2 Calculated IR spectrum of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole
Table 2-Selected theoretical vibrational assignments along with their intensities of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole calculated at B3LYP/6-311G level
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Scaled frequency (cm-1) |
Intensity (km)Mol-1 |
Assignments |
|
3484 3448 3081 3078 3072 3068 3058 3053 3045 3044 3033 2967 2964 2957 2923 2901 2890 2881 2877 2866 1580 1574 1571 1545 1532 1523 1500 1490 1489 1486 1484 1480 1478 1475 1470 1458 1442 1432 1415 1395 1357 1346 1341 1330 1300 1299 1287 1284 1278 1268 1249 1245 1232 1204 1176 1167 1162 1159 1150 1109 1104 1084
1067 1034 1031 1016 1011 998 987 982 981 978 959 951 943 941 903 883 855 850 842 827 801 780 761 755 746 730 721 719 706 688 676 646 628 623 619 584 579 576 563 539 494 488 483 479 471 447 429 409 404 367 336 315 304 296 273 248 237 235 208 |
84.495 40.825 15.554 3.9744 29.611 31.9468 14.226 27.994 2.1032 1.1769 8.337 33.124 48.511 59.010 34.078 9.0670 42.336 52.858 24.991 18.530 31.088 2.2617 6.3170 286.13 9.6337 635.20 310.98 312.01 293.99 306.68 206.25 14.323 9.2974 21.145 9.7838 362.04 12.732 165.99 10.558 1.800 6.513 160.08 329.242 22.758 1.5570 71.396 22.059 12.021 12.012 7.3188 36.250 53.314 35.048 14.360 10.851 144.84 3.982 0.094 12.704 10.174 2.022 3.535
16.309 0.799 20.318 3.221 3.511 7.462 1.499 1.5263 0.8451 0.040 0.158 67.550 1.749 2.907 10.876 7.264 1.480 27.343 4.595 2.504 0.1608 2.2244 62.624 76.387 31.932 3.932 31.834 29.170 36.935 26.928 3.041 12.782 10.148 24.517 8.770 74.258 7.933 1.855 4.843 32.650 15.265 54.294 61.629 0.986 40.471 8.350 9.348 0.325 4.121 4.414 9.947 16.065 1.619 3.695 4.423 5.501 3.461 4.997 4.434 |
N32-H35 str(sym) N19-H20 str(sym) C6-H10,C5-H9,C4-H34,C3-H8 str(sym) C22-H25,C24-H29,C28,H31,C26-H30 str(sym) C3-H8,C4-H34,C5-H9,C6-H10str (asym) C22-H25,C26-H30,C28-H31,C24-H29,C23-H27str(asym) C3-H8,C4-H34,C5-H9,C6-H10str(asym) C22-H25,C23-H27,C26-H30,C28,H31,C24,H29str(asym) C3-H8,C4-H34,C5-H9,C6-H10str(asym) C22-H25,C23-H27,C26-H30,C28-H31,C24-C29str(asym) C23-H27,C26-H30,C28-H31,C24-H29str(asym) C36-H38-H37,C39-H41-H40,C42-H43-H44,C45-H47-H45,str(asym) C45-H46-H47-H48,C42-H43-H44str(asym) C45-H46-H47,C42-H43-H44,C45-H48,C36-H38-H37str(asym) C39-H41-H40,C36-H37-H38,C42-H43-H44,C45-H47-H46str(asym) C42-H43-H44,C39-H40-H41,C36-H37-H38str(asym) C45-H46-H47,C45-H48(sym)str C42-H43-H44,C45-H48,C36-H37-H38asym(str) C36-H37-H38,C39-H41-H40,C42-H43-H44asym(str) C39-H40-H41,C36-H37-H38,C42-H43-H44sym(str) C23-H27,C26-H30,C24-H29,C22-H25(ip bend)C-C(str),N18-C17(str) N19-H20,C-H(ip bend),C-C(str),C17-N18(str) N19-H20,C-H(ip bend),C-C(str),C-S(str),C-O(str) N32-H35,N19-H20,C-H(ip bend),N18-C17(str),C-C(str) C3-H8,C4-H34,C5-H9,C6-H10,C-S(ip bend),C-C(str) N32-H35,N19-H20,C36-H37,H38(ip bend),C-N(str) N32-H35,C-H(ip bend),C12-O139str),C-N(str) N19-H20,N32-H35,C-H(ip bend),C-O(str),C-N(str) C7-N11,C15-N19(str),C-S,C-O,C-H(ip bend) N19-H20,N32-H35,C-H(ip bend),C12-O13(str),C-N(str) N32-H35,C23-H27,C26-H30,C24-H29,C22-H25(ip bend)C-O(str),C-N(str),C-C(str) C45-H46-H47-H48(ipbend)N32-H35(ip bend) N32-H35,C-H(ip bend),C-C(str),C17-N18,C7-N11,C12-O13(str) C36-H37-H37-H38,C39-H40-H41,C42-H43-H44,C45-H46-H47-H48(ip bend) C39-H40-H41,C42-H43-H44,C45-H46-H47-H48(ip bend) C12-O13,C-C,C-N(str)C-S,C-H(ip bend) C5-H9,C4-H34,C3-H8,C6-H10(ip bend),C-O(str) C23-C27,C26-H30,C28-H31,C24-H29,C22-H25,N19-H20(ip bend) C6-H10,C5-H9,C4-H34,C3-H8,C2-S33(ip bend),C-N(str) C45-H46-H47-H48(ip bend) C36-H37-H38,C39-H40-H41,C42-H43-H44(ip bend),C-N(str) C36-H37-H38,C39-H40-H41,C42-H43-H44,C45-H47(ip bend),C-N,C-O(ip bend) C-N(str),C36-H37-H38,N32-H35(ip bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(ip bend),C12-O13(ip bend) C42-H43-H44,C39-H40-H41,C45-H47-H46-H48(ip bend) C7-N11,C12-O13(str),C-H(ip bend),C-N(ip bend) C42-H43-H44,C39-H40-H41,C45-H47-H46-H48(ip bend) C-C(str),C-O,C-N,C-S,C-H(ip bend) C42-H43-H44,C39-H40-H41,C45-H47-H46-H48(ip bend) C6-H10,C5-H9,C4-H34,C3-H8,C2-S33,C1-N11(ip bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25,C-N(ip bend) C42-H43-H44,C39-H40-H41,C45-H47-H46-H48,C-N(ip bend) C-H,C-N,C-O(ip bend) C23-H27,C26-H30,C28-H31,C22-H25,C24-H29(ip bend) C17-S16,C17-N18,C7-N11,(str),N-H,C-H(ip bend) C23-H27,C26-H30,C28-N31,C22-H25,C24-H29(ip bend) C6-H10,C5-H9,C4-H34,C3-H8,C2-S33(ip bend) C36-H37-H38,C39-H40-H41,C42-H43-H44,C45-H46-H47-H48(ip bend) C6-H10,C5-H9,C4-H34,C3-H8,C-N(ip bend),C12-O13,C2-S33(str) C6-H10,C5-H9,C4-H34,C3-HH8(ip bend),C-C,C-S(str) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25,C-N(ip bend),C-C,C-O(str) C6-H10,C5-H9,C4-H34,C3-H8,C36-H37-H38,C39-H40-H41,C42-C42-H43-H44 (ip bend) C14-S16,C2-S339str),C-N,C-H(ip bend) C36-H36-H37-N32-H35(ip bend),C36-N32(str) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(ip bend) C6-H10,C5-H9,C4-H34,C3-H8(ip bend),C-C(str) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(ip bend),C-C(str) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(ip bend),butyl group,C-N(ip bend) C-6-H10,C5-H9,C4-H34,C3-H8(ip bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(ip bend) C-N,C-C,C-S(str),C-H,C-N(ip bend) C5-H9,C6-H10,C4-H34,C3-H8(op bend) C36-H37-H38,C39-H40-H41,C42-H43-H44,C45-H46-H47-H48(op bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(op bend) C-H,N32-H35(op bend) C6-H10,C5-H9,C4-H34,C3-H8(op bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25,C-N(op bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(op bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(op bend) C36-H37-H38,C39-H40-H41,C42-H43-H44,C45-H46-H47-H48(op bend) C-H,C-N(op bend),C-S,C-0(str) C6-H10,C5-H9,C4-H34,C3-H8,C12-O13(op bend) C23-H27,C26-H30,C28-H31,C24-H24,C22-H25(op bend) C12-O13,C14-S16(str),C-H(op bend) C36-H37-H38,C39-H40-H41,C42-H43-H44,C45-H46-H47-H48(op bend) C12-O13,C-H(op bend),C-S(str) C6-H10,C5-H9,C4-H34,C3-H8,C12-O13(op bend) C-0,C-H,C-N(op bend),C-N,C-C(str) C23-H27,C26-H30,C28-H31,C24-H29,C22-H29(op bend) C6-H10,C5-H9,C4-H34,C3-H8,(op bend)C-S,C-C(str) N19-H20,N32-H35(op bend),C-H(op bend) N19-H20,N32-H35,C-H(op bend),C-S(str) C-N,C-H(op bend).C7-N11,C-C,C7-S33(str) C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(op bebend),C-N(str) C7-S33,C14-S16-C17(str),C12-O13,C-N,C-H(op bend) N19-H20,C17-S16,C-H,C-N(op bend),N18-C17(str) N18-C17(str),C-H,C-N(op bend) C-H(op bend),C-N,C-S(op bend)N18-C17(str) N19-H20,C14-S16(op bend) N19-H20,C23-H27,C26-H30,C28-H31,C24-H29,C22-H25(op bend) C-H,C-O,C-S,C-N(op bend) C-H,C-O,C-S,C-N(op bend) C2-S33,C-H(op bend) Ring vibration C17-S16(str) C6-H10,C5-H9,C4-H34,C3-H8,C2-S33(op bend) C23-H27,C26-H30,C28-H31,C24-H29,C22-H28(op bend) ring vibration ring vibration C-N,C-H,C-O,C-S(op bend) N19-H20,C12-O13,C14-S16(op bend) ring vibration ring vibration ring vibration ring vibration ring vibration ring vibration ring vibration phenyl ring vibration ring vibration ring vibration |
Abbreviations:sym-symmetric,asym-asymmetric,str-stretching,ip bend-in plane bending,op bend-out of plane bending.
Mulliken atomic charges:
Mulliken atomic charge calculation has an important role in the application of quantum chemical calculation to molecular system because of atomic charges effect dipole moment,molecular polarizability,electronic structure and more a lot of properties of molecular systems. The bonding capability of a molecule depends on the electronic charge on the chelating atoms.The atomic charge values have been obtained by mulliken population analysis.To validate the reliability of our results,the mulliken population analysis of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole has been calculated using B3LYP/6-311G basis set.The corresponding characteristics of the atomic charge populations of the constituent atoms are presented inTable 3. It was found that N (19) has more negative charge(-0.8435eV) and C(15) has more positive charge(0.6950eV).The mulliken atomic charge of all hydrogen and sulpur carries positive charge.
Table 3-Mulliken atomic charges
|
Atom |
Mulliken atomic charges |
Atom |
Mulliken atomic charges |
|
C C C C C C C H H H N C O C C S C N N H C C C C |
0.1775 -0.3727 -0.1250 -0.1564 -0.1560 -0.0186 -0.2115 0.17058 0.15625 0.16930 -0.3443 0.4422 -0.3915 -0.5504 0.6950 0.3376 0.1101 -0.4043 -0.8435 0.3405 0.3471 -0.1156 -0.1905 -0.1631 |
H C H C H H H N S H H C H H C H H C H H C H H H |
0.1998 -0.1615 0.1603 -0.1338 0.1551 0.1493 0.1522 -0.5233 0.4075 0.1526 0.3122 -0.2003 0.1885 0.2164 -0.3658 0.1924 0.1743 -0.3571 0.1788 0.1811 -0.5183 0.1789 0.1773 0.1806 |
HOMO-LUMO energy gaps:
The relative energy of the molecular orbitals have been calculated and a graphical representation of the highest occupied molecular orbital (HOMO) and the lowest un occupied molecular orbital (LUMO) of 2-[2,4-bis(alkylamino)thiazol-5oyl]benzothiazole are given in figure 3. LUMO is an electron acceptor that represents the ability to obtain an electron and HOMO represents the ability to donate an electron. The HOMO-LUMO energy gap of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazolehave been calculated at the B3LYP/6-311G level are shown in Table4.
Fig 3-HOMO-LUMO of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole
Table-4 HOMO-LUMO energy value calculated by B3LYP/6-311G level
|
Paremeters (a.u) |
B3LYP/6-311G |
|
HOMO LUMO HOMO-LUMO |
-0.2043 -0.0885 0.1158 |
CONCLUSION:
The structure of 2-[2-(Butylamino-4-phenylaminothiazol)-5oyl]benzothiazole was optimized by the DFT methods using the basis sets 6-311G.Using the optimized geometry,the vibrational frequencies,have been found to agree well with the literature reported values.The energy of highest occupied molecular orbital (HOMO) and lowest un occupied molecular orbital (LUMO) is also made.
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Received on 04.09.2017 Modified on 15.09.2017
Accepted on 22.10.2017 © AJRC All right reserved
Asian J. Research Chem. 2017; 10(6):819-826.
DOI:10.5958/0974-4150.2017.00137.7