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Journal of Molecular Structure 654 (2003) 153–159 www.elsevier.

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Semi-empirical infrared spectra simulations of metal complexes of sulfanilamide
C. Topacli*, A. Topacli
Department of Physics Engineering, Faculty of Engineering, University of Hacettepe, Beytepe, 06532 Ankara, Turkey Received 20 December 2002; revised 1 March 2003; accepted 10 March 2003

Abstract The infrared spectra for Co and Cd complexes of sulfanilamide are studied by PM3 method. It has been found that the proposed structures for these compounds derived from IR spectra and X-ray powder diffraction patterns are consistent with the IR spectra simulated by PM3 method. The band assignments on the basis of the 3D dynamic image of the vibrations corresponding to significant modes have also given. Coordination effects on vibrational modes of anilino and sulfonamido groups of sulfanilamide are in close agreement with the observed results. q 2003 Elsevier Science B.V. All rights reserved.
Keywords: PM3 method; Sulfanilamide; Metal complexes; IR spectra

1. Introduction Sulfanilamide and its N-substituted derivatives have long been of considerable value in chemotherapy due to their antibacterial activity. The combined antibacterial activity of sulfanilamides and antimicrobial activity of heavy metals with a view to establish the relationship and importance of metal-drug interactions have been studied [1 –5]. Especially, the metal complexes of sulfa drugs have been found to be more bacteriostatic than the drugs themselves [6,7]. The synthesis and spectral characterization of some metal complexes of sulfanilamide had been investigated by several researchers [8 – 11]. We have reported only detailed spectral data on these compounds by using IR and X-ray powder diffraction techniques [11]. In that
* Corresponding author. Fax: þ 90-312-2992037. E-mail address: ctopacli@hacettepe.edu.tr (C. Topacli).

study, the comparison between the sulfanilamide wave numbers observed in the IR spectra of Co and Cd complexes and our measurements on crystalline sulfanilamide showed that sulfanilamide acted as a bidentate ligand, binding the metal ions through anilino and sulfonamide nitrogen’s. It had been also found that this result was consistent with the X-ray powder diffraction measurements and the low energy calculations. On the other hand, as far as we know no semi-empirical quantum mechanical simulations of IR spectra have been reported for the metal complexes of sulfanilamide. Recently, we have performed [12] some semi-empirical calculations on sulfonamides. In that study, the certain assignment of the most useful vibrational modes of sulfanilamide had been determined by using semi-empirical methods. In the present work, experimental vibrational data of the metal complexes of sulfanilamide are compared with those obtained using semi-empirical quantum

0022-2860/03/$ - see front matter q 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0022-2860(03)00201-1

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mechanical PM3 calculations. The assignment of the most useful vibrational modes of sulfanilamide are aided by the animation option of the HyperChem Demo Program [13] which gives a visual presentation of the shape of the vibrational modes.

2. Calculations Semi-empirical calculations were performed using HyperChem Release 6.03 Demo Program [13]. In the present study, only PM3 semi-empirical method is tested. In order to carry out semi-empirical IR spectra simulations the following means were used: full geometry optimization with the unrestricted Hartree – Fock basis, Polak Ribiere conjugate gradient algorithm, and convergence limit of 0.001 kcal mol21. All the calculations refer to isolated molecules in vacuum.

3. Result and discussion To the best of our knowledge, no semi-empirical quantum mechanical methods are used for simulating infrared spectra of the metal complexes of sulfanilamide. Recently, we have determined [12] the certain assignment of the most useful vibrational modes of sulfanilamide by using semi-empirical methods. In present study, we have carried out semi-empirical calculations using the PM3 method to determine the molecular conformations of the Co and Cd complexes of sulfanilamide. The initial geometries of sulfanilamide and its metal complexes for input to the semiempirical calculation were obtained by means of the MM þ molecular mechanic program for gas phase. In order to optimize the geometries of sulfanilamide and its metal complexes, the semi-empirical method PM3 are used. Selected bond lengths and angles from the geometry optimizations using PM3 semi-empirical calculations are displayed in Table 1. The optimized structures of metal complexes of sulfanilamide are illustrated in Fig. 1a and b. In this paper, IR spectra simulation studies aimed at determination of the molecular structure of complexes formed by sulfanilamide with transition metal ions (Co and Cd) are described. So far, a few experimental studies have been reported for sulfanilamide and its metal complexes. Narang and Gupta [8]

and Blasco et al. [9] had investigated some IR group frequencies of sulfanilamide to determine its possible transition metal binding sites. Recently, we have also reported the solid state IR spectra of sulfanilamide and its new Co and Cd complexes with the assignments of its some fundamental vibrations [11]. In present paper, as a continuation of our studies on the characterization of the metal complexes of sulfanilamide, the PM3 calculations are extended to simulate IR spectra of free and coordinated sulfanilamide by using the program package HyperChem Demo [13]. Table 2 gives the results of vibrational analysis where we gave not only the most important vibrational wave numbers but also the band assignments on the basis of the 3D dynamic image of the vibrations corresponding to each mode. In the present study, the observed [11] and calculated sulfanilamide vibrational wave numbers of Co and Cd complexes are compared with those of the free sulfanilamide. As seen from Table 2, comparing the calculated and observed wave numbers shows almost good conformity. The graphic presentation of the correlation between the experimental and calculated wave numbers is given in Fig. 2. In this study, comparison with the experimental data showed that the spectra simulated by PM3 method evidently matched good with the experimental wave numbers (correlation coefficient of about 0.98336 for Cd and 0.98155 for Co complexes) for the whole IR spectra range (Table 2). It is clear that the values of correlation coefficients are affected by the points corresponding to nðSO2 Þasym and nðSO2 Þsym vibrations of sulfanilamide: the experimental wave numbers obtained at 1311 and 1146 cm21 are strongly underestimated at 875 and 713 cm21 for Cd complex, respectively. The observed wave numbers at 1313 and 1145 cm21 for Co complex are also strongly underestimated at 876 and 703 cm21, respectively. If these vibrations are omitted, the PM3 calculations provide good linearity between the calculated and experimental wave numbers (correlation coefficient of 0.99469 for Cd complex and 0.99151 for Co complex). According to our earlier experimental study [11], NH2 vibrational modes of aniline ring and sulfonamido group were found to be much affected on complex formation. In that study, nðNH2 Þ asymmetric and symmetric vibrations (at 3474 and 3372 cm21, respectively,) of aniline in the IR of sulfanilamide had

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Table 1 Geometry parameters for the lowest-energy conformation of Co and Cd complexes of sulfanilamide obtained by molecular mechanics (MM). Atom labeling is according to the Fig. 1 ˚ Bond lengths (A) Parameter MM þ Bond angle (8) Parameter MM þ Torsion angles (8) Parameter MM þ

Co(Sulfanilamide)2 N(1)H(1) N(1)H(2) C(1)N(1) C(1)C(2) C(2)C(3) C(3)C(4) C(4)C(5) C(5)C(6) C(1)C(6) C(6)H(6) C(5)H(5) C(3)H(4) C(2)H(3) SC(4) SO(2) SO(1) N(2)S N(2)H(7) N(2)H(8) CoN(1)

1.042 1.041 1.432 1.341 1.341 1.346 1.345 1.342 1.341 1.103 1.102 1.104 1.102 1.742 1.438 1.438 1.628 1.021 1.022 1.863

H(1)N(1)H(2) H(2)N(1)C(1) H(1)N(1)C(1) N(1)C(1)C(2) N(1)C(1)C(6) C(2)C(1)C(6) C(1)C(6)H(6) C(5)C(6)H(6) C(5)C(6)C(1) C(6)C(5)H(5) C(4)C(5)H(5) C(6)C(5)C(4) C(3)C(4)C(5) C(5)C(4)S C(3)C(4)S C(4)C(3)C(2) C(4)C(3)H(4) C(2)C(3)H(4) C(3)C(2)H(3) C(1)C(2)H(3) C(1)C(2)C(3) C(4)SO(1) C(4)SO(2) N(2)SO(2) N(2)SO(1) O(2)SO(1) C(4)SN(2) SN(2)H(7) SN(2)H(8) H(7)N(2)H(8) CoN(1)H(1) CoN(1)H(2)

107 108 109 120 119 119 119 119 120 117 121 120 118 122 119 121 120 118 119 120 120 100 99 112 112 124 103 120 119 118 109 108

H(1)N(1)C(1)C(6) 27.54 H(2)N(1)C(1)C(2) 52.53 N(1)C(1)C(6)H(6) 21.50 N(1)C(1)C(2)H(3) 0.62 H(6)C(6)C(5)H(5) 20.03 H(5)C(5)C(4)S 21.53 SC(4)C(3)H(4) 1.28 H(4)C(3)C(2)H(3) 1.21 C(4)SN(2)H(8) 92.38 O(2)SN(2)H(7) 28.88 C(5)C(4)SN(2) 11.50 C(3)C(4)SO(1) 253.76 C(3)C(4)SO(2) 74.32 C(4)SN(2)H(7) 277.58 C(5)C(4)SO(2) 2104.53 C(5)C(4)SO(1) 127.36 C(5)C(4)C(3)H(4) 2179.80 C(4)C(5)C(6)H(6) 2179.59 C(3)C(4)C(5)H(5) 179.58 C(1)C(6)C(5)H(5) 179.69 C(2)C(1)C(6)H(6) 2178.77 CoN(1)H(1)C(1) 34.42 CoN(1)H(2)C(1) 123.53 C(1)C(2)C(3)H(4) 2178.55 C(6)C(1)C(2)H(3) 177.86 C(4)C(3)C(2)H(3) 2178.59 C(3)C(4)SN(2) 2169.62 C(2)C(3)C(4)S 2178.92 N(1)C(1)C(2)C(3) 2179.61 N(1)C(1)C(6)C(5) 178.77 C(1)C(6)C(5)C(4) 0.13 C(6)C(5)C(4)C(3) 20.87 C(5)C(4)C(3)C(2) 20.01 C(4)C(3)C(2)C(1) 1.64 C(3)C(2)C(1)C(6) 22.37 C(2)C(1)C(6)C(5) 1.49 C(6)C(5)C(4)S 178.00 O(1)SN(2)H(8) 214.90 O(1)SN(2)H(7) 175.12 O(2)SN(2)H(8) 2161.14 H(1)N(1)C(1)C(2) 169.67 H(2)N(1)C(1)C(6) 2124.68 C(4)SO(2)N(2) 109.01 C(4)SO(1)N(2) 2109.28 CoN(1)C(1)C(6) 114.34 CoN(1)C(1)C(2) 268.43 (continued on next page)

156 Table 1 (continued) ˚ Bond lengths (A) Parameter MM þ

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Bond angle (8) Parameter MM þ

Torsion angles (8) Parameter MM þ

Cd(Sulfanilamide)2 N(1)H(1) N(1)H(2) C(1)N(1) C(1)C(2) C(2)C(3) C(3)C(4) C(4)C(5) C(5)C(6) C(1)C(6) C(6)H(6) C(5)H(5) C(3)H(4) C(2)H(3) SC(4) SO(2) SO(1) N(2)S N(2)H(7) N(2)H(8) CdN(1)

1.041 1.041 1.430 1.340 1.341 1.346 1.346 1.342 1.340 1.103 1.102 1.104 1.103 1.742 1.438 1.439 1.628 1.021 1.022 2.177

H(1)N(1)H(2) H(2)N(1)C(1) H(1)N(1)C(1) N(1)C(1)C(2) N(1)C(1)C(6) C(2)C(1)C(6) C(1)C(6)H(6) C(5)C(6)H(6) C(5)C(6)C(1) C(6)C(5)H(5) C(4)C(5)H(5) C(6)C(5)C(4) C(3)C(4)C(5) C(5)C(4)S C(3)C(4)S C(4)C(3)C(2) C(4)C(3)H(4) C(2)C(3)H(4) C(3)C(2)H(3) C(1)C(2)H(3) C(1)C(2)C(3) C(4)SO(1) C(4)SO(2) N(2)SO(2) N(2)SO(1) O(2)SO(1) C(4)SN(2) SN(2)H(7) SN(2)H(8) H(7)N(2)H(8) CdN(1)H(1) CdN(1)H(2)

108 109 110 119 120 119 119 119 120 117 121 120 118 122 119 121 120 118 119 120 100 99 112 111 124 103 120 119 118 118 109 109

H(1)N(1)C(1)C(6) H(2)N(1)C(1)C(2) N(1)C(1)C(6)H(6) N(1)C(1)C(2)H(3) H(6)C(6)C(5)H(5) H(5)C(5)C(4)S SC(4)C(3)H(4) H(4)C(3)C(2)H(3) C(4)SN(2)H(8) O(2)SN(2)H(7) C(5)C(4)SN(2) C(3)C(4)SO(1) C(3)C(4)SO(2) C(4)SN(2)H(7) C(5)C(4)SO(2) C(5)C(4)SO(1) C(5)C(4)C(3)H(4) C(4)C(5)C(6)H(6) C(3)C(4)C(5)H(5) C(1)C(6)C(5)H(5) C(2)C(1)C(6)H(6) CdN(1)H(1)C(1) CdN(1)H(2)C(1) C(1)C(2)C(3)H(4) C(6)C(1)C(2)H(3) C(4)C(3)C(2)H(3) C(3)C(4)SN(2) C(2)C(3)C(4)S N(1)C(1)C(2)C(3) N(1)C(1)C(6)C(5) C(1)C(6)C(5)C(4) C(6)C(5)C(4)C(3) C(5)C(4)C(3)C(2) C(4)C(3)C(2)C(1) C(3)C(2)C(1)C(6) C(2)C(1)C(6)C(5) C(6)C(5)C(4)S O(1)SN(2)H(8) O(1)SN(2)H(7) O(2)SN(2)H(8) H(1)N(1)C(1)C(2) H(2)N(1)C(1)C(6) C(4)SO(2)N(2) C(4)SO(1)N(2) CdN(1)C(1)C(6) CdN(1)C(1)C(2)

26.98 53.31 20.85 0.26 0.13 20.42 0.32 0.56 92.04 28.91 11.64 253.43 74.62 277.74 2104.49 127.44 179.48 2179.55 2179.55 2179.95 179.68 2120.74 119.85 2179.34 179.72 2179.23 2169.23 2179.88 2179.83 2179.23 0.35 0.12 20.73 0.86 20.36 20.22 179.25 215.21 174.98 2161.28 172.47 2126.14 109.11 107.26 113.87 266.66

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Fig. 1. The optimized lowest-energy conformation of (a) Co complex (b) Cd complex of sulfanilamide with the atom labeling.

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Table 2 Calculated and observed (IR) wave numbers (in cm21) of normal vibrations of sulfanilamide and its metal complexes Assignment Sulfanilamide (obs.) Sulfanilamide (calc.) M(sulfanilamide)2 (M ¼ Co, Cd) Co (calc.) Co (obs.) 3454 3337 3369 3232 – – – 1632 1598 1501 1336 1313 1187 1145 1097 899 827 682 629 573 550 – – Cd (calc.) 2977 3101 2995 3078 3001 2992 2976 1646 1606 1513 1236 875 1161 713 1180 991 973 657 757 397 467 263 209 Cd (obs.) 3454 3358 3371 3242 – – – 1637 1600 1504 1341 1311 1186 1146 1098 900 828 680 – – 553 – –

na ðNH2 Þaniline na ðNH2 Þsulfanilamide ns ðNH2 Þaniline ns ðNH2 Þsulfanilamide nðCHÞ nðCHÞ nðCHÞ ds ðNH2 Þaniline nring nring dðCHÞ na ðSO2 Þ dðCHÞ ns ðSO2 Þ dðCHÞ þ dr ðNH2 Þaniline n(SN) þ p(CH) p(CS) þ p(CN) p(CS) þ p(CN) vðNH2 Þsulfanilamide ds ðSO2 Þ pring þ vðNH2 Þaniline þ vðSO2 Þ nðMNÞaniline nðMNÞsulfanilamide

3474 3350 3372 3261 3132 3112 3091 1627 1597 1505 1340 1317 1187 1144 1097 897 837 680 644 583 553

3237 3228 3157 3252 3004 2992 2985 1539 – 1519 1260 877 1164 709 1192 992 984 661 765 401 476

2936 2971 2963 3077 3012 2993 2984 1689 1606 1509 1235 876 1160 703 1190 999 974 653 750 395 460 282 226

n; stretching; d; in-plane bending; p, out of plane bending; v; wagging; r; rocking;. Subscript: a, asymmetric; s, symmetric, r, rocking, s, scissoring.

shifted upon coordination toward the lower wave numbers (at about 3454 and 3370 cm21) when compared with the free sulfanilamide molecule in the IR spectra of Co and Cd complexes. Similar shifts (about 30 cm21) had been observed nðNH2 Þ asymmetric and symmetric vibrations of sulfonamide group with regard to the ligand. Kangaraj and Rao [14] had observed analogous effects in the metal complexes of sulfamethoxazole. In the present study, the wave numbers of the NH2 stretching modes are also calculated at lower values than the corresponding ones in the free molecule (Table 2). In addition, NH2 scissoring mode of aniline ring had been observed at 1627 cm21 in the IR spectrum of sulfanilamide. This vibration had showed a small shift toward a higher wave number in the IR spectra of metal complexes. We observed analogous effects in the calculated wave numbers of NH2 scissoring modes of sulfanilamide. This band is calculated for Co and Cd complexes at 1689 and 1646 cm21, in comparison of corresponding

one (at 1590 cm21) of free sulfanilamide. These results suggested that the NH2 groups of aniline and sulfonamide are involved in the coordination with the metal ions. We had not observed any significant shifts in the fundamental vibrations of SO2 group in comparison to those of metal complexes. This result had showed that there was a little or weak interaction between sulfonyl oxygen and metal ions. As seen from Table 2, the asymmetric and symmetric stretching vibrations of free sulfanilamide are calculated at 877 and 709 cm21, respectively. These modes show no significant changes in metal complexes. Similar effects are found for calculated scissoring and wagging vibrations of SO2 group of free sulfanilamide. The calculated band at 992 cm21 are assigned to the nðSNÞ vibration of free sulfanilamide. This band was observed unshifted in the IR spectra of sulfanilamide [9,11]. According to this result, there was no interaction between sulfonamide nitrogen and metal ions. In this study, we did not calculate any significant

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could not be observed in the IR spectra of metal complexes. In present study, we are assigned these vibrational modes in the range of 200 – 300 cm21. As seen from Tables 1 and 2, the calculated M– N stretching wave numbers increase in the order Cd , Co while M –N bond lengths decrease in the complexes studied. In conclusion, IR spectra of sulfanilamide and its M(sulfanilamide)2 (where M ¼ Co, Cd) complexes indicated that metal atoms were bound to sulfanilamide molecules through both anilino and sulfonamide nitrogen’s. These experimental results are well confirmed by the theoretical spectra simulated by PM3 method. Due to the IR spectra simulated by PM3 method, the proposed molecular structures of metal complexes are consistent with those derived from the experimental study [11].

References
[1] M. Wruble, J. Am. Pharm. Assoc. 32 (1943) 80. [2] I. Mellan, U.S. Patent No. 2,507,537, Chem. Abstr. 44 (1950) 7030a. [3] S. Orosenzweig, W.M. Fuchs, U.S. Patent No. 2,536,095, Chem. Abstr. 45, 51861. [4] C.J. Linter, U.S. Patent No. 2,776970, Chem. Abstr. 51 (1957) 11388a. [5] C.L. Fox, Arch. Surg. 96 (1968) 184. [6] K.K. Panday, R. Kaushal, Indian J. Apply. Chem. 32 (1969) 96. [7] K.K. Chatturvedi, J.K. Gupta, Indian J. Chem. 13 (1975) 705. [8] K.K. Narang, J.K. Gupta, Indian J. Chem. 13 (1975) 705. [9] F. Blasco, L. Perello, J. Latorre, J. Borras, S. Garcia-Granda, J. Inorg. Biochem. 61 (1996) 143. [10] R.C. Maurya, P. Patel, Spectrosc. Lett. 32 (1999) 213. [11] A. Topacli, B. Kesimli, Spectrosc. Lett. 34 (4) (2001) 513. [12] C. Topacli, A. Topacli, Spectrosc. Lett. 35 (2) (2002) 207. [13] HyperChem Demo Release 6.03 for Windows, Hypercube, Inc., USA, 1999. [14] G. Kangaraj, G.N. Rao, Synth. React. Inorg. Met.-Org. Chem. 22 (5) (1992) 559. [15] A. Topacli, Spectrosc. Lett. 32 (1999) 729. [16] B. Kesimli, A. Topacli, J. Mol. Struct. 561 (2001) 55.

Fig. 2. Graphic correlation between the experimental and calculated wave numbers (in cm21) obtained by PM3 method for metal complexes of sulfanilamide (cc represents correlation coefficient).

shift in the SN stretching mode in comparison to one of the metal complexes. In this study, as seen from Table 2, the decrease in wave numbers of the most sensitive NH2 stretching modes with different metals in M(sulfanilamide)2 (M ¼ Cd and Co) complexes are also found to be in order of Cd , Co. The stabilities of metal complexes of sulfadimethoxine [15] and sulfamethoxazole complexes [16] were found in the similar order, which were in agreement with the increasing order of the second ionization potential of the metals. In the NH2 stretching, vibrations are calculated at lower values in the same order in comparison to those of the free sulfnilamide. Metal – N(ligand) stretching vibrations