Journal of Molecular Structure 655 (2003) 479489 www.elsevier.

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Vibrational assignments and theoretical calculations of 1-phenyl-5mercaptotetrazole and 1-phenyl-5-mercaptotetrazolate

Barbara Pergolese*, Adriano Bigotto
Department of Chemical Sciences, University of Trieste, Via L.Giorgieri 1, Trieste 34127, Italy Received 11 March 2003; revised 21 May 2003; accepted 21 May 2003

Abstract The infrared and Raman spectra of 1-phenyl-5-mercaptotetrazole (PMT) and 1-phenyl-5-mercaptotetrazole sodium salt in the solid state and in solution have been measured. Detailed vibrational assignments of PMT and 1-phenyl-5mercaptotetrazolate (PMTA) have been performed. In order to give a rmer basis to the interpretation of the vibrational spectra, harmonic wavenumbers of PMT and PMTA have been calculated by means of MP2 and DFT/BPW91 calculations. The DFT calculations provide a satisfactory agreement between the calculated and observed wavenumbers without using scaling factors. Experimental evidence shows that PMT is present in the thione tautomer both in the solid state and in solution of polar solvents. q 2003 Elsevier B.V. All rights reserved.
Keywords: 1-Phenyl-5-mercaptotetrazole; 1-Phenyl-5-mercaptotetrazolate; Vibrational assignments; Density functional theory calculations; MP2 calculations

1. Introduction 1-Phenyl-5-mercaptotetrazole (PMT) has a widespread application both in the photographic and in the corrosion inhibition elds. As concerning to the photographic applications, PMT has an inhibiting effect on fog formation and on the development process [1,2]. The corrosion inhibition efciency of PMT on carbon steel and on copper and its alloys was extensively studied with spectroscopic, electrochemical and gravimetric techniques [3 5]. It was found that PMT formed in its thiolic ionized form, 1-phenyl* Corresponding author. Tel.: 39-40-5583950; fax: 39-405583903. E-mail address: pergoles@dsch.univ.trieste.it (B. Pergolese).

5-mercaptotetrazolate (PMTA), a stable surface complex on many metal surfaces [2,5,7]. Although vibrational spectroscopy was considered a powerful tool for investigating the bonding between PMT and metals, at best of our knowledge, no detailed vibrational assignment was proposed. Few infrared bands of solid PMT were discussed [1,5,8 11]. Some fundamentals observed in the IR and Raman spectra of solid PMT were also assigned on the basis of density functional theory (DFT) calculations of the thiol tautomer, even if, in the case of the mercaptoheterocyclic compounds, the thione tautomer is preferred in the solid state [12]. Although few fundamentals were discussed, there were many discrepancies in the interpretation of these bands. In particular, the assignment of the thioamide bands is a

0022-2860/03/$ - see front matter q 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0022-2860(03)00358-2

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B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489

very controversial point. Therefore, a detailed vibrational study of this compound was planned. Moreover, since PMT usually binds to metals in its ionized thiol form, PMTA, the nature of bonding to the metal can be described more accurately by means of the vibrational spectra of PMTA. Thus, it was thought worthy to extend our spectroscopic investigations of PMTA [7], by studying the infrared and Raman spectra in the solid state and the infrared spectra in aqueous solution. Theoretical calculations of the harmonic wavenumbers and related normal modes of vibration of PMT and PMTA were also performed, in order to give a rmer basis to the assignments of the vibrational spectra. Two theoretical methods (MP2 and DFT/BPW91) were compared for vibrational wavenumber prediction.

3. Computational details All the calculations were performed using the 98 package [13]. Geometries of PMT and PMTA were fully optimized at the second order Mller-Plesset perturbation theory and the density functional level with the Beckes 1988 exchange functional in combination with the Perdew-Wang 91 gradient-corrected correlation functional (BPW91). The 6-31G(d,p) basis set was used in the calculations of PMT and the 6-31 G(d,p) in those of PMTA. All the parameters were allowed to relax and all the calculations converged to an optimized geometry, which corresponds to a true energy minimum, as revealed by the lack of imaginary values in the wavenumber calculations. The atomic numbering of PMT and PMTA is indicated in Fig. 1. The calculated geometry parameters of PMT and PMTA are reported in Tables 1 and 2. The harmonic wavenumbers and the normal modes of vibration were calculated at the same level of approximation using the parameters corresponding to the structure obtained from the optimization step. Force constants in internal
GAUSSIAN

2. Experimental section 1-Phenyl-5-mercaptotetrazole (98%) and 1-phenyl-5-mercaptotetrazole sodium salt (PMTANa) (98%) were obtained from Aldrich. Deuterated PMT (PMT-d1 in the following) was obtained recrystallizing repeatedly PMT from methanol-d1. Infrared spectra were obtained in the range 4000 50 cm21 using a Perkin Elmer SYSTEM 2000 instrument. Polycrystalline samples were in the form of KBr pellets and Nujol mulls. Spectra of solutions were obtained by dissolving PMT in CDCl3 and CHCl3 and PMTANa in water and D2O. The IR spectra of the solutions of PMT and PMTANa were recorded between KBr and BaF2 windows, respectively. Raman spectra were obtained with a SPEX Ramalog instrument. An AT personal computer was used for data acquisition and monochromator control. Excitations were provided by 514.5 and 647.1 nm radiations from Spectra-Physics 165 argon and krypton ions lasers, respectively. The spectra of solutions were obtained by dissolving PMT in methanol and acetone and PMTANa in water. The samples were contained in capillary cells. The treatment of the spectral data was performed using the Perkin Elmer IRDM and the Galactic GRAMS386 software.

Fig. 1. Molecular structures: (a) PMT, (b) PMTA.

B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489 Table 1 Calculated bond lengths (A) and angles (deg) for 1-phenyl-5mercaptotetrazole Bond lengths MP2 N1 N2 N2 N3 N3 N4 N4 C5 N1 C5 C5 S6 H7 N4 N1 C8 C8 C9 C9 C10 C10 C11 C11 C12 C12 C13 C8 C13 H14 C9 H15 C10 H16 C11 H17 C12 H18 C13 1.366 1.304 1.348 1.372 1.385 1.650 1.010 1.422 1.397 1.393 1.397 1.396 1.394 1.396 1.081 1.082 1.082 1.082 1.079 DFT 1.375 1.270 1.352 1.371 1.385 1.663 1.009 1.428 1.399 1.393 1.396 1.395 1.394 1.397 1.084 1.086 1.086 1.085 1.082 N1 N2 N3 N2 N3 N4 N3 N4 C5 N4 C5 N1 C5 N1 N2 S6 C5 N4 H7 N4 N3 C8 N1 N2 C9 C8 N1 C10 C9 C8 C11 C10 C9 C12 C11 C10 C13 C12 C11 C12 C13 C8 C13 C8 C9 H14 C9 C10 H15 C10 C11 H16 C11 C12 H17 C12 C13 H18 C13 C8 Angles MP2 107.6 106.6 114.2 99.3 112.2 128.4 120.6 119.0 118.2 118.6 120.3 120.0 120.6 118.4 122.0 121.5 120.2 120.0 119.3 120.2 DFT 108.5 107.4 113.2 100.0 110.9 127.2 121.2 119.0 118.4 119.2 120.4 119.8 120.6 118.9 121.1 121.0 120.3 120.1 119.2 120.2

481

coordinates, which were calculated according to the procedure described elsewhere [14], were used for a standard zero-order GF-matrix treatment from which the vibrational wavenumbers and the Potential Energy Distribution (PED) were obtained. No scaling factors were applied to the force constants obtained from the DFT calculations, whereas two scaling factors were applied to the force constants obtained from the MP2 calculations: 0.85 to the C H stretching coordinates and 0.91 to the other internal coordinates for PMT, 0.87 to the C H stretching coordinates and 0.94 to the other internal coordinates for PMTA. The theoretical results are reported in Tables 3 and 4, together with the observed wavenumbers.

4. Results and discussion For PMT, both levels of theory predict the twisted conformation to be the most stable: the inter-ring torsion angle f calculated with the DFT and MP2 methods are 33.28 and 39.38, respectively. For PMTA, DFT calculation predicts the coplanar structure to be the most stable, whereas according to the MP2 method the twisted geometry is preferred: the predicted value of f is 35.58. The MP2 calculations of PMT and PMTA overestimate all the harmonic wavenumbers. On the contrary, the DFT calculations, without using scaling factors, provide a satisfactory agreement between the calculated and observed wavenumbers, except for N H and C H stretching fundamentals (Tables 3 and 4). Therefore, the interpretation of the vibrational spectra was carried out with the help of the DFT results. Most of the calculated normal modes involve either the tetrazole or the phenyl ring, thus, we can assume that the interaction between the two rings is weak, in agreement with the structural determination of the [Na(18-crown-6)(H2 O) 2] salt of PMTA [15]. Accordingly, the fundamentals of the phenyl ring should be very slightly affected by the deprotonation of PMT. Thus, it is very likely that the bands observed at approximately the same position in the spectra of both molecules can be assigned to phenyl modes. In the case of PMT the assignments were also performed taking into account the vibrational spectra of PMT-d1.

Table 2 Calculated bond lengths (A) and angles (deg) for 1-phenyl-5mercaptotetrazolate Bond lengths MP2 N2 N1 N3 N2 N4 N3 C5 N1 C5 N4 S6 C5 C7 N1 C8 C7 C9 C8 C10 C9 C11 C10 C12 C11 C12 C7 H13 C8 H14 C9 H15 C10 H16 C11 H17 C12 1.363 1.329 1.351 1.392 1.360 1.702 1.412 1.400 1.397 1.399 1.400 1.396 1.402 1.080 1.084 1.084 1.084 1.082 DFT 1.391 1.304 1.353 1.410 1.365 1.711 1.414 1.417 1.400 1.406 1.404 1.402 1.412 1.089 1.095 1.094 1.095 1.094 N1 N2 N3 N2 N3 N4 N3 N4 C5 N4 C5 N1 C5 N1 N2 S6 C5 N4 C7 N1 N2 C8 C7 N1 C9 C8 C7 C10 C9 C8 C11 C10 C9 C12 C11 C10 C7 C12 C11 C8 C7 C12 H13 C8 C9 H14 C9 C10 H15 C10 C11 H16 C11 C12 H17 C12 C7 Angles MP2 105.2 111.3 108.4 104.7 110.4 128.4 118.5 120.4 119.1 120.8 119.5 120.4 119.4 120.8 121.8 120.0 120.2 119.5 119.0 DFT 105.9 112.6 107.8 105.3 108.4 125.5 118.2 119.0 120.1 120.9 118.7 121.3 119.7 119.3 121.0 120.1 120.7 118.7 118.1

482

Table 3 Experimental spectral data, calculated wavenumbers and assignments for 1-phenyl-5-mercaptotetrazole

nobs: , Raman solid ~

3073 3066 (sh) 3050 3036 3020 1596 1494 1387 1361 1354 1275 1212 1170 1158 1093 1075 1051

nobs:; a Raman solution ~

3078 1599 1498 1374 1288 1208 1176 1162

nobs:; b IR solid ~
3065 3018 2956 2913 2900 2929 2803 2747 2725 2626 2593 2545 1594 1499 (sh) 1492 1456 1382 1361 1354 1329 1317 1298 1278 1210 1175 1156 1103 1093 1074 1051

nobs:; c IR solution ~
3416 3067 2924 2763 2548 1595 1499 1457 1364 1297 1277 1212 1047

ncalc , MP2 ~
3430 3054 3039 3030 3020 3010 1597 1594 1462 1489 1438 1413 1307 1365 1251 1228 1166 1155 1188 1077 1115 1027

ncalc , DFT ~
3598 3177 3169 3151 3140 3129 1608 1601 1478 1493 1448 1366 1348 1359 1312 1232 1170 1162 1180 1078 1096 1012

Assignment (PEDd) 100 r7,4 96 r18,13 91 r14,9, 7 r15,10 51 r16,11, 25 r17,12, 17 r15,10 48 r15,10, 47 r17,12 47 r16,11, 27 r15,10, 24 r17,12 n(N H S) n(N H S) n(N H S) n(N H S) n(N H S) n(N H S) n(N H S) n(N H S) n(N H S) n(N H S) 23 r9,10, 21 r12,13, 8 r8,13, 7 r10,11 20 r11,12, 18 r8,9, 16 r10,11,15 r8,13 12 r2,3, 8 r4,5, 6 r5,6, 13 a7,4,3, 11 a7,4,5 11 r1,8, 8 r8,9, 8 r8,13, 8 r10,11, 6 r11,12, 8 a15,10,9, 7 a18,13,12, 7 a14,9,10, 7 a17,12,13, 6 a15,10,11, 6 a17,12,11, 6 a18,13,8, 6 a14,9,8 10 r9,10, 9 r12,13, 7 r2,3, 9 a7,4,3, 8 a7,4,5, 8 a16,11,10, 8 a16,11,12, 6 a17,12,11 16 r2,3, 10 r8,9, 10 r9,10, 10 r8,13, 10 r11,12, 9 r10,11, 9 r12,13 43 r1,8, 20 r1,5 30 r2,3, 8 r8,13, 7 r9,10, 7 r8,9, 7 r11,12, 6 r10,11, 5 r4,5, 5 r12,13 13 a18,13,8, 13 a18,13,12, 11 a14,9,8, 9 a14,9,10, 8 a17,12,13, 7 a17,12,11, 5 a15,10,9, 5 a15,10,11 24 r5,6,15 r4,5, 7 r3,4, 16 a7,4,3, 14 a7,4,5 13 r4,5, 11 r1,5, 7 r1,8, 8 a14,9,10,7 a3,4,5, 7 a18,13,12, 6 a14,9,8 20 a16,11,10, 20 a16,11,12, 12 a15,10,11, 11 a15,10,9, 10 a17,12,11, 9 a17,12,13 12 r1,5, 8 r4,5, 7 r12,13, 6 r9,10, 9 a17,12,13, 7 a15,10,9, 7 a17,12,11, 6 a15,10,11, 5 a3,4,5 32 r3,4, 14 r1,2, 8 r12,13, 5 r9,10 17 r1,2, 12 r3,4, 9 r9,10,7 r12,13, 6 a18,13,12, 5 a14,9,10 17 r10,11, 13 r11,12, 12 r9,10, 9 r8,9, 8 r12,13, 5 r8,13

B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489

1037 1022 1004 990 832 752 694 682 665 616 571 509 458 (sh) 450 406 377 333 252 246 149 133 83 61 47 (sh) 30 (sh)
a b c d e f

1003 984 698 616 575 513 458 450 (sh) 409 370 328 246 (sh) 233

1014 1002 993 960 907 825 806 751 688 677 664 569 509 457f 450f 376f 328f 255f 149f 128f 69f

1030 (sh) 989 907 690 570 506e

1058 998 980 956 876 873 838 785 706 682 677 634 597 576 552 506 463 432 379 350 311 227 211 120 89 45

1038 1005 987 963 960 937 892 815

747 689 682 676 640 608 570 528 499 446 399 351 311 237 204 130 94 38

16 r11,12, 14 r10,11, 12 r8,9, 9 r8,13 22 r1,2, 18 r3,4, 22 a2,3,4, 15 a1,2,3, 6 a7,4,5 10 a9,10,11, 10 a12,13,8, 9 a8,9,10, 9 a11,12,13, 9 a13,8,9, 8 a10,11,12 27 g16,11, 11 g17,12, 9 g15,10, 13 t12,13, 10t9,10, 9 t11,12, 8 t10,11 14 r1,5, 11 r1,2, 7 r4,5, 16 g16,11, 5 g15,10, 6 t9,10 12 g15,10, 12 g17,12, 10 g14,9, 8 g18,13, 25 t9,10, 24 t12,13 26 g16,11, 16 g18,13, 16 g14,9, 16 t12,13, 13 t9,10 21 g18,13, 20 g14,9, 13 g15,10, 12 g17,12, 10 t8,13, 8 t8,9, 7 t10,11, 7 t11,12 g(NHS) 41 g16,11, 8 g14,9, 8 g18,13, 6 g17,12, 5 g15,10, 15 t9,10, 15 t12,13 16 r1,8, 18 a10,11,12, 8 a13,8,9, 5 a9,10,11 8 g15,10, 8 g17,12, 29 t2,3, 14 t3,4, 8 t9,10, 8 t12,13 12 g15,10, 12 g17,12, 16 t2,3, 11 t12,13, 10t3,4, 9 t9,10, 6 t8,13 61 g6,5, 11 t2,3 17 a11,12,13, 16 a9,10,11, 15 a8,9,10, 15 a12,13,8 37 r5,6, 7 r1,2, 11 a8,1,5, 5 g16,11 51 g7,4, 8 g6,5, 20 t2,3, 14 t3,4, 5 t4,5 10 r5,6, 22 g16,11, 17 t10,11, 17 t11,12 6 r1,5, 15 a4,5,6, 11 a1,8,9, 10 a1,5,6, 7a8,1,2, 5 a8,1,5 40 t12,13, 36 t9,10 20 r1,8, 17 a1,8,13, 9 a13,8,9, 6 a1,5,6 7 a1,8,9, 6 a4,5,6, 13 t8,13, 12 t8,9, 11 t4,5, 7 t10,11,7 t11,12 17 a1,5,6, 15 a4,5,6, 6 a1,8,9, 15 t4,5, 10t8,9, 9 t8,13 7 g7,4, 6 g6,5, 58 t4,5, 17 t1,5 Lattice vibration 11 a8,1,2, 10 a8,1,5, 8 a1,8,13, 8 a1,8,9, 25 t1,5, 10 t4,5, 9 t1,2 5 a8,1,5, 27 t1,5, 24 t8,13, 17 t8,9, 13 t1,2 Lattice vibration 79 t1,8 Lattice vibration

B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489

Raman spectrum in methanol solution. IR spectrum in KBr. IR spectrum in CDCl3 solution. PED obtained from DFT/BPW91 calculations; r stretching, a in-plane bending, g out-of-plane bending, t torsion; only contributions $5 are reported. IR spectrum in CHCl3 solution. IR spectrum in Nujol mull.

483

484

Table 4 Experimental spectral data, calculated wavenumbers and assignments for 1-phenyl-5-mercaptotetrazolate

nobs: , Raman solid ~

3078 3067 (sh) 3059 3048 (sh) 3025 1600 1504 1460 1401 1370 1314 1293 1280 1231 1215 1179 1160 1108 1076 1045 1022 1005 991(sh) 838 762 725

nobs:; a Raman solution ~

3078 1599 1501 1463 1384 1368(sh) 1314 1295(sh) 1283 1224 1176 1162 1103 1076 1018 1004 993(sh) 835 766 722

nobs:; b IR solid ~
3072 3058 1599 1502 1457 1393 1368 1316 1292 1278 1230 1178 1162 1110 1072 1044 1020 999 966 917 839 759

nobs:; a IR solution ~
1599d 1500 1460 1386 1365 1314 1295 1283 1222 1175 1161 1108 1074 1044 1018 999 969d 917d

ncalc , MP2 ~
3074 3066 3042 3028 3016 1614 1600 1505 1457 1435 1366 1291 1334 1191 1173 1155 1158 1123 1111 1074 1031 988 996 969 870 860 825 782 698 688

ncalc , DFT ~
3175 3122 3107 3099 3088 1601 1574 1485 1449 1363 1335 1275 1328 1251 1166 1145 1150 1100 1078 1030 1010 980 993 960 948 938 881 822 732 690

Assignment (PEDc) 98 r13,8 54 r10,15, 28 r11,16, 17 r9,14 52 r11,16, 42 r9,14 39 r10,15, 36 r9,14, 12 r11,16, 11 r12,17 86 r12,17, 7 r11,16 22 r8,9, 20 r11,12, 8 r7,12, 7 r9,10 22 r10,11,16 r9,10, 16 r7,8,14 r7,12 15 r1,7, 8 r7,8, 8 r9,10, 7 r7,12, 6 r10,11, 8 a8,9,14, 7 a7,12,17, 7 a11,12,17, 7 a10,9,14, 6 a12,11,16, 5 a10,11,16, 5 a9,8,13 16 r11,12, 15 r8,9,11 a11,10,15, 10 a9,10,15, 7 a10,11,16 14 r8,9, 14 r10,11,14 r7,12,13 r7,8, 11 r9,10, 9 r11,12 22 r1,7, 9 r4,5, 6 r2,3, 5 r11,12, 6 a11,12,17 21 r2,3, 12 r4,5,6 r1,7, 6 r7,12, 7 a7,12,17, 6 a11,12,17, 5 a13,8,7 27 r1,7, 12 r1,5, 9 a8,9,14, 8 a9,8,13, 7 a10,9,14, 5 a13,8,7 41 r2,3, 22 r4,5, 15 r5,6, 6 a5,1,2 6 r11,12, 12 a12,11, 16, 11 a10,11,16,11 a11,12,17, 10 a7,12,17, 10 a9,8,13, 9 a13,8,7, 8 a8,9,14, 7 a10,9,14 17 a11,10,15, 16 a9,10,15,11 a10,9,14, 9 a8,9,14, 8 a10,11,16, 8 a12,11,16 22 r3,4, 21 r1,5, 8 r4,5, 13 a3,4,5, 9 a4,5,6 43 r3,4, 12 r4,5, 5 r5,6, 15 a2,3,4, 6 a1,2,3 11 r8,9, 10 r11,12, 7 r10,11, 6 r1,2, 5 r9,10, 8 a9,8,13, 7 a9,10,15, 7 a11,12,17, 7 a11,10,15, 6 a7,12,17 22 r9,10, 15 r10,11, 9 r1,2, 6 r7,12, 6 a2,3,4 37 r1,2, 6 r7,8,16 a2,3,4,14 a1,2,3 11 a10,9,8, 10 a12,11,10, 10 a7,12,11, 10 a11,10,9, 9 a8,7,12, 9 a9,8,7 13 r7,8, 11 r7,12, 9 r11,12, 8 r9,10, 8 r8,9, 7 r10,11, 5 r4,5, 6 a5,1,2, 5 a4,5,1 22 g17,12, 15 g16,11, 48 t11,12,5 t12,7 30 r1,5, 23 r1,2, 12 r3,4, 9 r4,5, 5 a3,4,5 18 g14,9, 17 g13,8, 9 g15,10,42 t8,9,8 t9,10 39 g15,10, 12 g13,8,11 g17,12,6 g16,11, 13 t10,11,6 t9,10, 6 t8,9 21 g16,11, 19 g14,9, 17 g13,8, 6 g17,12,14 t9,10, 7 t7,8, 6 t10,11, 6 t12,7 52 g15,10, 17 t11,12, 16 t8,9 18 g6,5, 42 t2,3, 22 t3,4, 16 t4,5

B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489

700 615 570 502 467 443 411 395 366 342 333 245 222 116 88 72
a b c d e

699 615 571 506 457 412 331 240

698 687 568 498 393e 330e 248e 226e 183e 142e 121e 108e 90e 78e 63e

676 619 560 602 499 461 441 382 351 310 235 214 120 84 40

682 675 610 644 543 500 453 403 354 289 266 197 164 98 25

17 r1,7, 18 a11,10,9, 8 a8,7,12, 5 a10,9,8 21 g14,9, 19 g16,11,13 t8,9, 13 t11,12, 9 t10,11, 9 t7,8,8 t12,7,7 t9,10 18 a12,11,10, 17 a10,9,8, 16 a9,8,7, 15 a7,12,11, 5 a10,11,16 34 g6,5, 50 t2,3, 7 t1,2 45 r5,6, 7 r1,2,14 a7,1,5, 6 a7,1,2 36 g15,10, 5 g13,8, 22 t9,10, 21 t10,11 13 r5,6,7 r1,5,20 a4,5,6,13 a1,5,6,10 a7,1,2, 8 a7,1,5, 6 a1,7,8 38 t11,12, 36 t8,9 20 r1,7, 6 r1,2,6 r5,6,13 a1,7,12, 12 a8,7,12, 8 a7,1,2 11 g6,5, 32 t4,5, 18 t12,7,17 t7,8, 6 t10,11, 5 t9,10 6 r1,5, 28 a1,5,6, 20 a4,5,6, 20 a1,7,8, 15 a1,7,12 9 g6,5, 33 t4,5, 20 t1,5, 11 t7,8, 11 t12,7 Lattice vibration 32 a7,1,5, 24 a7,1,2, 15 a1,7,12, 14 a1,7,8 Lattice vibration Lattice vibration 39 t1,5, 16 t12,7, 15 t1,2, 11 t7,8 Lattice vibration 8 g17,12, 69 t1,7, 9 t11,12, 8 t12,7

B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489

Spectra in aqueous solution. IR spectrum in KBr. PED obtained from DFT/BPW91 calculations;r stretching, a in-plane bending, g out-of-plane bending, t torsion; only contributions $5 are reported. IR spectrum in D2O solution. IR spectrum in Nujol mull.

485

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B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489

4.1. Region 3500 2000 cm21 4.1.1. N H and S H stretching The IR spectra of PMT, both in the solid state and in solution, display bands attributable to the N H stretching mode (Fig. 2). In particular, the free N H stretching band at 3416 cm21 and a complex band centred at about 2900 cm21, related to the H bonded N H stretching, are observed in the IR spectra of CDCl3 solutions. Therefore, it can be evinced that in polar solvents PMT is present both in the free and H bonded thione forms. Since crystallographic data of PMT are not available, there is no experimental evidence about the type of hydrogen bonding undergone by PMT. However, it seems very likely that a strong intermolecular hydrogen bonding involves S and N(H), as found for other heterocyclic thiones [16,

17]. The infrared spectra of PMT in the solid state also display a broad and complex band centred at about 2900 cm21 characteristic of the H bonded N H stretching mode. This attribution is supported by the intensity decrease of this band upon deuteration and by the appearance of a new structured band centred at 2197 cm21, assigned to the N D stretching mode. Thus, it can be deduced that PMT is present in the thione form in the solid state. According to other authors [5,9,12] the weak peak present in the IR spectra of solid PMT at 2545 cm21 could be assigned to the S H stretching fundamental. They evinced from this observation that a certain amount of the thiol tautomer of PMT should be present in the solid state. However, the probability of observing a band assigned to the S H stretching mode in the infrared spectra in the solid state seems remote, because crystallographic studies of several nitrogen-containing heterocyclic thiones showed that the thione form tended to dominate in the solid state [11]. Moreover, it should be stressed that the S H stretching band is reported to occur with weak intensity in the IR spectra and with strong intensity in the Raman spectra in the 2600 2500 cm21 region [18]. Therefore, if the interpretation given by those authors was correct, a strong band should be observed in the Raman spectra in that range. However, in the 2600 2500 cm21 region, no bands can be observed in the Raman spectra of solid PMT. Regarding the behaviour of PMT in solutions, the Raman spectra of PMT in methanol also do not display any spectral feature attributable to the S H stretching mode in that range. Therefore, the IR peak at 2545 cm21 is very likely not matched with the S H stretching mode and it can be interpreted as a component of the structured H bonded N H stretching band. The origin of the components of the H bonded N H stretching band was thoroughly discussed by Flakus [19]. 4.1.2. C H stretching Raman spectra of PMT and PMTA are very similar in the 3100 3000 cm21 region. The Raman spectra of PMT in the solid state display ve bands at 3073, 3066 (sh), 3050, 3036, 3020 cm21 assigned to C H stretching modes (Fig. 3). In this region, the Raman spectra of PMT and PMTA in solution also display the same prole: one broad band centred at 3078 cm21, which is very likely the band envelope of the ve

Fig. 2. (a) IR spectrum of PMT in KBr. (b) IR spectrum of PMT in CDCl3 solution (solvent bands are marked with ).

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Fig. 3. (a) Raman spectrum of PMT in the solid state. (b) Raman spectrum of PMT in methanol solution (solvent bands are marked with ).

related to the calculated normal mode at 1478 cm21 which has a sizeable contribution from N H in-plane bending. This assignment is in agreement with the one proposed by other authors [5,8,10,11], who located the thioamide band I in the region 1485 1508 cm21. On the other hand, Bravo et al. [9] located it at 1593 cm21. From the comparison between the spectra of PMT and PMT-d1, it can be deduced that the IR band at 1210 cm21 is related to a fundamental with a noticeable contribution from N H in-plane bending (the so-called thioamide band II). The assignment of this mode is a controversial subject: in fact, our assignment is in agreement with the one proposed by Bravo et al. [9], whereas Ye et al. and Singh et al. [5,10] located this fundamental in the range 1300 1275 cm 21 and Raper [11] at 1358 cm21. The bands observed at 1596, 1494, 1275, 1170, 1158, 1004 cm21 and at 1600, 1504, 1280, 1179, 1160, 1005 cm21 in the Raman spectra of PMT and PMTA, respectively (Fig. 5), can be assigned to inplane phenyl ring modes. The attribution of these bands, whose positions are approximately the same in both compounds, is also supported by correlative arguments [20] and by the description of normal modes provided by PED. 4.3. Region 1000 50 cm21 As concerning to the benzene modes, taking also into account the assignments of the out-of-plane fundamentals for mono-substituted benzenes [20], the peaks present in the IR spectra of PMT in the solid state at 993, 960, 907, 825, 751 cm21 can be attributed to C H out-of-plane bending modes. According to the notation reported by Varsanyi the band at 993 cm21 could be related to the mode 5, the very weak peak at 960 cm21 to the mode 17a, the band at 907 cm21 to the mode 17b, the peak at 825 cm21 to the mode 10a and nally the band at 751 cm21 to the mode 11. It is of note that the peak at 825 cm21 in the IR spectra of PMT in the solid state is partially overlapped by a broad band centred at 806 cm21 attributable to the H bonded N H out-of-plane bending mode. This assignment is conrmed by the sizeable decrease of relative intensity of this band and the parallel appearance of a weak peak at 584 cm21 in the IR spectra of PMT-d1.

bands observed in the Raman spectra of the solid state. On the other hand, the IR spectra of the two compounds display discrepancies in this region due to the presence in the spectrum of PMT of the N H stretching band. In particular, an unambiguous choice of the C H stretching bands in the IR spectra of PMT both in the solid state and in solution is not possible due to the overlapping of the N H stretching band, whereas the IR spectra of PMTA in the solid display two C H stretching bands at 3072 and 3058 cm21. 4.2. Region 1600 1000 cm21 The IR spectra of PMT and PMTA display a strong band at about 1490 cm21 (Fig. 4). However, PMT spectrum also shows a shoulder at 1499 cm21, which is not present in the spectrum of PMTA. The IR spectrum of PMT-d1 does not display this shoulder and shows a new band at 1416 cm21. Thus, the shoulder located in the spectrum of PMT at 1499 cm21 can be assigned to a mode which involves to some extent the N H group. In particular, it is

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Fig. 4. Infrared spectra in KBr: (a) PMT; (b) PMTA.

According to literature [21], the vibrational assignment of the CyS stretching can be unambiguously performed only when the CyS group is bound to atoms other than nitrogen. The range in which this band is predicted to occur is very wide: 1570 850 cm21. Liu et al. [6] found the CyS stretching band in the IR spectra of PMT at 1407 cm21, and other authors [5,8] at 1050 cm21. However, in some cases this range can be wider, for example, upon comparison with

the spectra of the seleno-analogue, it was evinced that the CyS stretching band of imidazoline-2-thione fell at 507 cm21 [22]. Since the chemical environment of the CyS bond is rather similar in the mercaptotetrazole ring and in the imidazoline-2-thione ring, it is reasonable to expect the CyS stretching band to occur not far from the region in which this band is observed in the IR spectra of imidazoline-2-thione. Our DFT calculations predict the normal mode most

Fig. 5. Raman spectra in the solid state: (a) PMT, (b) PMTA.

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characterized as CyS stretching to occur at 570 cm21. Therefore, taking into account the results of calculations and the assignments of imidazoline-2-thione [22], the band located at 571 cm21 in the Raman spectra of PMT (Fig. 5) can be tentatively assigned to the CyS stretching fundamental. The assignment of the bands observed in the spectra of both compounds in the range 200 50 cm21 are to be considered tentative due to the presence of modes attributable of lattice vibrations.

5. Conclusions Detailed vibrational assignments of PMT and PMTA were performed. To this end the spectra of PMT-d1 were also recorded and theoretical calculations of both species were performed at MP2 and DFT levels of theory. A satisfactory agreement between calculated and experimental wavenumbers is provided by the DFT calculations with the BPW91 functional without using scaling factors, except for N H and C H stretching fundamentals, which are the most affected by anharmonicity. From the investigation of the vibrational spectra of PMT, it can be concluded that only the thione tautomer is present both in solid and in solution of polar solvents.

Acknowledgements This work was supported by a research grant of ` Ministero dellIstruzione, Universita e Ricerca of Italy. We would like to thank Professor Vinicio Galasso for his suggestions about the calculations.

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