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

mercaptotetrazole 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-5-
mercaptotetrazolate (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 wide-
spread 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, electrochemi-
cal and gravimetric techniques [35]. It was found
that PMT formed in its thiolic ionized form, 1-phenyl-
5-mercaptotetrazolate (PMTA), a stable surface com-
plex 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 [1,5,811]. 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 mercapto-
heterocyclic 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
Journal of Molecular Structure 655 (2003) 479489
www.elsevier.com/locate/molstruc
*
Corresponding author. Tel.: 39-40-5583950; fax: 39-40-
5583903.
E-mail address: pergoles@dsch.univ.trieste.it (B. Pergolese).
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 investi-
gations 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 wave-
numbers 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 wave-
number prediction.
2. Experimental section
1-Phenyl-5-mercaptotetrazole (98%) and 1-phe-
nyl-5-mercaptotetrazole sodium salt (PMTANa)
(98%) were obtained from Aldrich. Deuterated PMT
(PMT-d
1
in the following) was obtained recrystalliz-
ing repeatedly PMT from methanol-d
1
. Infrared
spectra were obtained in the range 400050 cm
21
using a PerkinElmer SYSTEM 2000 instrument.
Polycrystalline samples were in the form of KBr
pellets and Nujol mulls. Spectra of solutions were
obtained by dissolving PMT in CDCl
3
and CHCl
3
and
PMTANa in water and D
2
O. The IR spectra of the
solutions of PMT and PMTANa were recorded
between KBr and BaF
2
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 PerkinElmer IRDM and the Galactic
GRAMS386 software.
3. Computational details
All the calculations were performed using the
GAUSSIAN 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
Fig. 1. Molecular structures: (a) PMT, (b) PMTA.
B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489 480
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 CH stretching coordinates
and 0.91 to the other internal coordinates for PMT,
0.87 to the CH 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 over-
estimate 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 CH 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)(H
2
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-d
1
.
Table 1
Calculated bond lengths (A

) and angles (deg) for 1-phenyl-5-

mercaptotetrazole
Bond lengths Angles
MP2 DFT MP2 DFT
N
1
N
2
1.366 1.375 N
1
N
2
N
3
107.6 108.5
N
2
N
3
1.304 1.270 N
2
N
3
N
4
106.6 107.4
N
3
N
4
1.348 1.352 N
3
N
4
C
5
114.2 113.2
N
4
C
5
1.372 1.371 N
4
C
5
N
1
99.3 100.0
N
1
C
5
1.385 1.385 C
5
N
1
N
2
112.2 110.9
C
5
S
6
1.650 1.663 S
6
C
5
N
4
128.4 127.2
H
7
N
4
1.010 1.009 H
7
N
4
N
3
120.6 121.2
N
1
C
8
1.422 1.428 C
8
N
1
N
2
119.0 119.0
C
8
C
9
1.397 1.399 C
9
C
8
N
1
118.2 118.4
C
9
C
10
1.393 1.393 C
10
C
9
C
8
118.6 119.2
C
10
C
11
1.397 1.396 C
11
C
10
C
9
120.3 120.4
C
11
C
12
1.396 1.395 C
12
C
11
C
10
120.0 119.8
C
12
C
13
1.394 1.394 C
13
C
12
C
11
120.6 120.6
C
8
C
13
1.396 1.397 C
12
C
13
C
8
118.4 118.9
H
14
C
9
1.081 1.084 C
13
C
8
C
9
122.0 121.1
H
15
C
10
1.082 1.086 H
14
C
9
C
10
121.5 121.0
H
16
C
11
1.082 1.086 H
15
C
10
C
11
120.2 120.3
H
17
C
12
1.082 1.085 H
16
C
11
C
12
120.0 120.1
H
18
C
13
1.079 1.082 H
17
C
12
C
13
119.3 119.2
H
18
C
13
C
8
120.2 120.2
Table 2
Calculated bond lengths (A

) and angles (deg) for 1-phenyl-5-

mercaptotetrazolate
Bond lengths Angles
MP2 DFT MP2 DFT
N
2
N
1
1.363 1.391 N
1
N
2
N
3
105.2 105.9
N
3
N
2
1.329 1.304 N
2
N
3
N
4
111.3 112.6
N
4
N
3
1.351 1.353 N
3
N
4
C
5
108.4 107.8
C
5
N
1
1.392 1.410 N
4
C
5
N
1
104.7 105.3
C
5
N
4
1.360 1.365 C
5
N
1
N
2
110.4 108.4
S
6
C
5
1.702 1.711 S
6
C
5
N
4
128.4 125.5
C
7
N
1
1.412 1.414 C
7
N
1
N
2
118.5 118.2
C
8
C
7
1.400 1.417 C
8
C
7
N
1
120.4 119.0
C
9
C
8
1.397 1.400 C
9
C
8
C
7
119.1 120.1
C
10
C
9
1.399 1.406 C
10
C
9
C
8
120.8 120.9
C
11
C
10
1.400 1.404 C
11
C
10
C
9
119.5 118.7
C
12
C
11
1.396 1.402 C
12
C
11
C
10
120.4 121.3
C
12
C
7
1.402 1.412 C
7
C
12
C
11
119.4 119.7
H
13
C
8
1.080 1.089 C
8
C
7
C
12
120.8 119.3
H
14
C
9
1.084 1.095 H
13
C
8
C
9
121.8 121.0
H
15
C
10
1.084 1.094 H
14
C
9
C
10
120.0 120.1
H
16
C
11
1.084 1.095 H
15
C
10
C
11
120.2 120.7
H
17
C
12
1.082 1.094 H
16
C
11
C
12
119.5 118.7
H
17
C
12
C
7
119.0 118.1
B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489 481
Table 3
Experimental spectral data, calculated wavenumbers and assignments for 1-phenyl-5-mercaptotetrazole
~ n
obs:
, Raman solid ~ n
obs:;
a
Raman solution ~ n
obs:;
b
IR solid ~ n
obs:;
c
IR solution ~ n
calc
, MP2 ~ n
calc
, DFT Assignment (PED
d
)
3416 3430 3598 100 r
7,4
3073 3078 3054 3177 96 r
18,13
3066 (sh) 3065 3067 3039 3169 91 r
14,9
, 7 r
15,10
3050 3030 3151 51 r
16,11
, 25 r
17,12
, 17 r
15,10
3036 3020 3140 48 r
15,10
, 47 r
17,12
3020 3018 3010 3129 47 r
16,11
, 27 r
15,10
, 24 r
17,12
2956 n(NH S)
2913 2924 n(NH S)
2900 n(NH S)
2929 n(NH S)
2803 n(NH S)
2747 2763 n(NH S)
2725 n(NH S)
2626 n(NH S)
2593 n(NH S)
2545 2548 n(NH S)
1596 1599 1594 1595 1597 1608 23 r
9,10
, 21 r
12,13
, 8 r
8,13
, 7 r
10,11
1594 1601 20 r
11,12
, 18 r
8,9
, 16 r
10,11
,15 r
8,13
1499 (sh) 1462 1478 12 r
2,3
, 8 r
4,5
, 6 r
5,6
, 13 a
7,4,3
, 11 a
7,4,5
1494 1498 1492 1499 1489 1493 11 r
1,8
, 8 r
8,9
, 8 r
8,13
, 8 r
10,11
, 6 r
11,12
, 8 a
15,10,9
, 7 a
18,13,12,
7 a
14,9,10
,
7 a
17,12,13
, 6 a
15,10,11
, 6 a
17,12,11
, 6 a
18,13,8
, 6 a
14,9,8
1456 1457 1438 1448 10 r
9,10
, 9 r
12,13
, 7 r
2,3
, 9 a
7,4,3
, 8 a
7,4,5
, 8 a
16,11,10
, 8 a
16,11,12
, 6
a
17,12,11
1387 1382 1413 1366 16 r
2,3
, 10 r
8,9
, 10 r
9,10
, 10 r
8,13
, 10 r
11,12
, 9 r
10,11
, 9 r
12,13
1361 1374 1361 1364 1307 1348 43 r
1,8
, 20 r
1,5
1354 1354 1365 1359 30 r
2,3
, 8 r
8,13
, 7 r
9,10
, 7 r
8,9
, 7 r
11,12
, 6 r
10,11
, 5 r
4,5
, 5 r
12,13
1329
1317
1298 1297
1275 1288 1278 1277 1251 1312 13 a
18,13,8
, 13 a
18,13,12
, 11 a
14,9,8
, 9 a
14,9,10
, 8 a
17,12,13
, 7 a
17,12,11
, 5
a
15,10,9
, 5 a
15,10,11
1212 1208 1210 1212 1228 1232 24 r
5,6
,15 r
4,5
, 7 r
3,4
, 16 a
7,4,3
, 14 a
7,4,5
1170 1176 1175 1166 1170 13 r
4,5
, 11 r
1,5
, 7 r
1,8
, 8 a
14,9,10
,7 a
3,4,5
, 7 a
18,13,12
, 6 a
14,9,8
1158 1162 1156 1155 1162 20 a
16,11,10
, 20 a
16,11,12
, 12 a
15,10,11
, 11 a
15,10,9
, 10 a
17,12,11
, 9
a
17,12,13
1188 1180 12 r
1,5
, 8 r
4,5
, 7 r
12,13
, 6 r
9,10
, 9 a
17,12,13
, 7 a
15,10,9
, 7 a
17,12,11
, 6
a
15,10,11
, 5 a
3,4,5
1103
1093 1093 1077 1078 32 r
3,4
, 14 r
1,2
, 8 r
12,13
, 5 r
9,10
1075 1074 1115 1096 17 r
1,2
, 12 r
3,4
, 9 r
9,10
,7 r
12,13
, 6 a
18,13,12
, 5 a
14,9,10
1051 1051 1047 1027 1012 17 r
10,11
, 13 r
11,12
, 12 r
9,10
, 9 r
8,9
, 8 r
12,13
, 5 r
8,13
B
.
P
e
r
g
o
l
e
s
e
,
A
.
B
i
g
o
t
t
o
/
J
o
u
r
n
a
l
o
f
M
o
l
e
c
u
l
a
r
S
t
r
u
c
t
u
r
e
6
5
5
(
2
0
0
3
)
4
7
9

4
8
9
4
8
2
1037 1030 (sh) 1058 1038 16 r
11,12
, 14 r
10,11
, 12 r
8,9
, 9 r
8,13
1022 1014 998 1005 22 r
1,2
, 18 r
3,4
, 22 a
2,3,4
, 15 a
1,2,3
, 6 a
7,4,5
1004 1003 1002 980 987 10 a
9,10,11
, 10 a
12,13,8
, 9 a
8,9,10
, 9 a
11,12,13
, 9 a
13,8,9
, 8 a
10,11,12
990 984 993 989 956 963 27 g
16,11
, 11 g
17,12
, 9 g
15,10
, 13 t
12,13
, 10t
9,10
, 9 t
11,12
, 8 t
10,11
876 960 14 r
1,5
, 11 r
1,2
, 7 r
4,5
, 16 g
16,11
, 5 g
15,10
, 6 t
9,10
960 873 937 12 g
15,10
, 12 g
17,12
, 10 g
14,9
, 8 g
18,13
, 25 t
9,10
, 24 t
12,13
907 907 838 892 26 g
16,11
, 16 g
18,13
, 16 g
14,9
, 16 t
12,13
, 13 t
9,10
832 825 785 815 21 g
18,13
, 20 g
14,9
, 13 g
15,10
, 12 g
17,12
, 10 t
8,13
, 8 t
8,9
, 7 t
10,11
, 7
t
11,12
806 g(NHS)
752 751 706 747 41 g
16,11
, 8 g
14,9
, 8 g
18,13
, 6 g
17,12
, 5 g
15,10
, 15 t
9,10
, 15 t
12,13
694 698 688 690 682 689 16 r
1,8
, 18 a
10,11,12
, 8 a
13,8,9
, 5 a
9,10,11
682 677 677 682 8 g
15,10
, 8 g
17,12
, 29 t
2,3
, 14 t
3,4
, 8 t
9,10
, 8 t
12,13
634 676 12 g
15,10
, 12 g
17,12
, 16 t
2,3
, 11 t
12,13
, 10t
3,4
, 9 t
9,10
, 6 t
8,13
665 664 597 640 61 g
6,5
, 11 t
2,3
616 616 576 608 17 a
11,12,13
, 16 a
9,10,11
, 15 a
8,9,10
, 15 a
12,13,8
571 575 569 570 552 570 37 r
5,6
, 7 r
1,2
, 11 a
8,1,5
, 5 g
16,11
506 528 51 g
7,4
, 8 g
6,5
, 20 t
2,3
, 14 t
3,4
, 5 t
4,5
509 513 509 506
e
463 499 10 r
5,6
, 22 g
16,11
, 17 t
10,11
, 17 t
11,12
458 (sh) 458 457
f

450 450 (sh) 450
f
432 446 6 r
1,5
, 15 a
4,5,6
, 11 a
1,8,9
, 10 a
1,5,6
, 7a
8,1,2
, 5 a
8,1,5
406 409 379 399 40 t
12,13
, 36 t
9,10
377 370 376
f
350 351 20 r
1,8
, 17 a
1,8,13
, 9 a
13,8,9
, 6 a
1,5,6
333 328 328
f
311 311 7 a
1,8,9
, 6 a
4,5,6
, 13 t
8,13
, 12 t
8,9
, 11 t
4,5
, 7 t
10,11
,7 t
11,12
252 246 (sh) 255
f
227 237 17 a
1,5,6
, 15 a
4,5,6
, 6 a
1,8,9
, 15 t
4,5
, 10t
8,9
, 9 t
8,13
246 233 211 204 7 g
7,4
, 6 g
6,5
, 58 t
4,5
, 17 t
1,5
149 149
f
Lattice vibration
133 128
f
120 130 11 a
8,1,2
, 10 a
8,1,5
, 8 a
1,8,13
, 8 a
1,8,9
, 25 t
1,5
, 10 t
4,5
, 9 t
1,2
83 89 94 5 a
8,1,5
, 27 t
1,5
, 24 t
8,13
, 17 t
8,9
, 13 t
1,2
61 69
f
Lattice vibration
47 (sh) 45 38 79 t
1,8
30 (sh) Lattice vibration
a
Raman spectrum in methanol solution.
b
IR spectrum in KBr.
c
IR spectrum in CDCl
3
solution.
d
PED obtained from DFT/BPW91 calculations; r stretching, a in-plane bending, g out-of-plane bending, t torsion; only contributions $5 are reported.
e
IR spectrum in CHCl
3
solution.
f
IR spectrum in Nujol mull.
B
.
P
e
r
g
o
l
e
s
e
,
A
.
B
i
g
o
t
t
o
/
J
o
u
r
n
a
l
o
f
M
o
l
e
c
u
l
a
r
S
t
r
u
c
t
u
r
e
6
5
5
(
2
0
0
3
)
4
7
9

4
8
9
4
8
3
Table 4
Experimental spectral data, calculated wavenumbers and assignments for 1-phenyl-5-mercaptotetrazolate
~ n
obs:
, Raman solid ~ n
obs:;
a
Raman solution ~ n
obs:;
b
IR solid ~ n
obs:;
a
IR solution ~ n
calc
, MP2 ~ n
calc
, DFT Assignment (PED
c
)
3078 3078 3074 3175 98 r
13,8
3067 (sh) 3072 3066 3122 54 r
10,15
, 28 r
11,16
, 17 r
9,14
3059 3058 3042 3107 52 r
11,16
, 42 r
9,14
3048 (sh) 3028 3099 39 r
10,15
, 36 r
9,14
, 12 r
11,16
, 11 r
12,17
3025 3016 3088 86 r
12,17
, 7 r
11,16
1614 1601 22 r
8,9
, 20 r
11,12
, 8 r
7,12
, 7 r
9,10
1600 1599 1599 1599
d
1600 1574 22 r
10,11
,16 r
9,10
, 16 r
7,8
,14 r
7,12
1504 1501 1502 1500 1505 1485 15 r
1,7
, 8 r
7,8
, 8 r
9,10
, 7 r
7,12
, 6 r
10,11
, 8 a
8,9,14
, 7 a
7,12,17
, 7 a
11,12,17
, 7
a
10,9,14
, 6 a
12,11,16,
5 a
10,11,16
, 5 a
9,8,13
1460 1463 1457 1460 1457 1449 16 r
11,12
, 15 r
8,9
,11 a
11,10,15
, 10 a
9,10,15
, 7 a
10,11,16
1401 1384 1393 1386 1435 1363 14 r
8,9
, 14 r
10,11
,14 r
7,12
,13 r
7,8
, 11 r
9,10
, 9 r
11,12
1370 1368(sh) 1368 1365 1366 1335 22 r
1,7
, 9 r
4,5
, 6 r
2,3
, 5 r
11,12
, 6 a
11,12,17
1314 1314 1316 1314 1291 1275 21 r
2,3
, 12 r
4,5
,6 r
1,7
, 6 r
7,12
, 7 a
7,12,17
, 6 a
11,12,17
, 5 a
13,8,7
1293 1295(sh) 1292 1295
1280 1283 1278 1283 1334 1328 27 r
1,7
, 12 r
1,5
, 9 a
8,9,14
, 8 a
9,8,13
, 7 a
10,9,14
, 5 a
13,8,7
1231 1224 1230 1222 1191 1251 41 r
2,3
, 22 r
4,5
, 15 r
5,6
, 6 a
5,1,2
1215
1179 1176 1178 1175 1173 1166 6 r
11,12
, 12 a
12,11, 16
, 11 a
10,11,16
,11 a
11,12,17
, 10 a
7,12,17
, 10 a
9,8,13
, 9
a
13,8,7
, 8 a
8,9,14
, 7 a
10,9,14
1160 1162 1162 1161 1155 1145 17 a
11,10,15
, 16 a
9,10,15
,11 a
10,9,14
, 9 a
8,9,14
, 8 a
10,11,16
, 8 a
12,11,16
1158 1150 22 r
3,4
, 21 r
1,5
, 8 r
4,5
, 13 a
3,4,5
, 9 a
4,5,6

1108 1103 1110 1108 1123 1100 43 r
3,4
, 12 r
4,5
, 5 r
5,6
, 15 a
2,3,4
, 6 a
1,2,3
1076 1076 1072 1074 1111 1078 11 r
8,9
, 10 r
11,12
, 7 r
10,11
, 6 r
1,2
, 5 r
9,10
, 8 a
9,8,13
, 7 a
9,10,15
, 7 a
11,12,17
,
7 a
11,10,15
, 6 a
7,12,17
1045 1044 1044 1074 1030 22 r
9,10
, 15 r
10,11
, 9 r
1,2
, 6 r
7,12
, 6 a
2,3,4
1022 1018 1020 1018 1031 1010 37 r
1,2
, 6 r
7,8
,16 a
2,3,4
,14 a
1,2,3
1005 1004 988 980 11 a
10,9,8
, 10 a
12,11,10
, 10 a
7,12,11
, 10 a
11,10,9
, 9 a
8,7,12
, 9 a
9,8,7
996 993 13 r
7,8
, 11 r
7,12
, 9 r
11,12
, 8 r
9,10
, 8 r
8,9
, 7 r
10,11
, 5 r
4,5
, 6 a
5,1,2
, 5 a
4,5,1
991(sh) 993(sh) 999 999 969 960 22 g
17,12
, 15 g
16,11
, 48 t
11,12
,5 t
12,7
870 948 30 r
1,5
, 23 r
1,2
, 12 r
3,4
, 9 r
4,5
, 5 a
3,4,5
966 969
d
860 938 18 g
14,9
, 17 g
13,8
, 9 g
15,10
,42 t
8,9
,8 t
9,10
917 917
d
825 881 39 g
15,10
, 12 g
13,8
,11 g
17,12
,6 g
16,11
, 13 t
10,11
,6 t
9,10
, 6 t
8,9
838 835 839 782 822 21 g
16,11
, 19 g
14,9
, 17 g
13,8
, 6 g
17,12
,14 t
9,10
, 7 t
7,8
, 6 t
10,11
, 6 t
12,7
762 766 759 698 732 52 g
15,10
, 17 t
11,12
, 16 t
8,9
725 722 688 690 18 g
6,5
, 42 t
2,3
, 22 t
3,4
, 16 t
4,5
B
.
P
e
r
g
o
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e
s
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,
A
.
B
i
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a
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M
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u
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a
r
S
t
r
u
c
t
u
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e
6
5
5
(
2
0
0
3
)
4
7
9

4
8
9
4
8
4
700 699 698 676 682 17 r
1,7
, 18 a
11,10,9
, 8 a
8,7,12
, 5 a
10,9,8
687 619 675 21 g
14,9
, 19 g
16,11
,13 t
8,9
, 13 t
11,12
, 9 t
10,11
, 9 t
7,8
,8 t
12,7
,7 t
9,10
615 615 560 610 18 a
12,11,10
, 17 a
10,9,8
, 16 a
9,8,7
, 15 a
7,12,11
, 5 a
10,11,16
602 644 34 g
6,5
, 50 t
2,3
, 7 t
1,2
570 571 568 499 543 45 r
5,6
, 7 r
1,2
,14 a
7,1,5
, 6 a
7,1,2
502 506 498 461 500 36 g
15,10
, 5 g
13,8
, 22 t
9,10
, 21 t
10,11
467 457 441 453 13 r
5,6
,7 r
1,5
,20 a
4,5,6
,13 a
1,5,6
,10 a
7,1,2
, 8 a
7,1,5
, 6 a
1,7,8
443
411 412 382 403 38 t
11,12
, 36 t
8,9
395 393
e

366 351 354 20 r
1,7
, 6 r
1,2
,6 r
5,6
,13 a
1,7,12
, 12 a
8,7,12
, 8 a
7,1,2
342
333 331 330
e
310 289 11 g
6,5
, 32 t
4,5
, 18 t
12,7
,17 t
7,8
, 6 t
10,11
, 5 t
9,10
245 240 248
e
235 266 6 r
1,5
, 28 a
1,5,6
, 20 a
4,5,6
, 20 a
1,7,8
, 15 a
1,7,12
222 226
e
214 197 9 g
6,5
, 33 t
4,5
, 20 t
1,5
, 11 t
7,8
, 11 t
12,7
183
e
Lattice vibration
142
e
120 164 32 a
7,1,5
, 24 a
7,1,2
, 15 a
1,7,12
, 14 a
1,7,8
116 121
e
Lattice vibration
108
e
Lattice vibration
88 90
e
84 98 39 t
1,5
, 16 t
12,7
, 15 t
1,2
, 11 t
7,8
72 78
e
Lattice vibration
63
e
40 25 8 g
17,12
, 69 t
1,7
, 9 t
11,12
, 8 t
12,7
a
Spectra in aqueous solution.
b
IR spectrum in KBr.
c
PED obtained from DFT/BPW91 calculations;r stretching, a in-plane bending, g out-of-plane bending, t torsion; only contributions $5 are reported.
d
IR spectrum in D
2
O solution.
e
IR spectrum in Nujol mull.
B
.
P
e
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g
o
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s
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,
A
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B
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6
5
5
(
2
0
0
3
)
4
7
9

4
8
9
4
8
5
4.1. Region 35002000 cm
21
4.1.1. NH and SH stretching
The IR spectra of PMT, both in the solid state and
in solution, display bands attributable to the NH
stretching mode (Fig. 2). In particular, the free NH
stretching band at 3416 cm
21
and a complex band
centred at about 2900 cm
21
, related to the H bonded
NH stretching, are observed in the IR spectra of
CDCl
3
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 under-
gone 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 cm
21
characteristic of the H bonded NH
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 cm
21
, assigned to the ND 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 cm
21
could be assigned
to the SH 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 SH stretching mode in the infrared
spectra in the solid state seems remote, because
crystallographic studies of several nitrogen-contain-
ing heterocyclic thiones showed that the thione form
tended to dominate in the solid state [11]. Moreover, it
should be stressed that the SH stretching band is
reported to occur with weak intensity in the IR spectra
and with strong intensity in the Raman spectra in the
26002500 cm
21
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 26002500 cm
21
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 SH stretching mode in that range.
Therefore, the IR peak at 2545 cm
21
is very likely not
matched with the SH stretching mode and it can be
interpreted as a component of the structured H bonded
NH stretching band. The origin of the components
of the H bonded NH stretching band was thoroughly
discussed by Flakus [19].
4.1.2. CH stretching
Raman spectra of PMT and PMTA are very similar
in the 31003000 cm
21
region. The Raman spectra of
PMT in the solid state display ve bands at 3073,
3066 (sh), 3050, 3036, 3020 cm
21
assigned to CH
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 cm
21
,
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
CDCl
3
solution (solvent bands are marked with ).
B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489 486
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 NH
stretching band. In particular, an unambiguous choice
of the CH 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 NH stretching band,
whereas the IR spectra of PMTA in the solid display
two CH stretching bands at 3072 and 3058 cm
21
.
4.2. Region 16001000 cm
21
The IR spectra of PMT and PMTA display a strong
band at about 1490 cm
21
(Fig. 4). However, PMT
spectrum also shows a shoulder at 1499 cm
21
, which
is not present in the spectrum of PMTA. The IR
spectrum of PMT-d
1
does not display this shoulder
and shows a new band at 1416 cm
21
. Thus, the
shoulder located in the spectrum of PMT at
1499 cm
21
can be assigned to a mode which involves
to some extent the NH group. In particular, it is
related to the calculated normal mode at 1478 cm
21
which has a sizeable contribution from NH 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 cm
21
. On the other hand, Bravo et al. [9]
located it at 1593 cm
21
. From the comparison
between the spectra of PMT and PMT-d
1
, it can be
deduced that the IR band at 1210 cm
21
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 13001275 cm
21
and Raper [11] at
1358 cm
21
.
The bands observed at 1596, 1494, 1275, 1170,
1158, 1004 cm
21
and at 1600, 1504, 1280, 1179,
1160, 1005 cm
21
in the Raman spectra of PMT and
PMTA, respectively (Fig. 5), can be assigned to in-
plane 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 100050 cm
21
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 cm
21
can be attributed
to CH out-of-plane bending modes. According to the
notation reported by Varsanyi the band at 993 cm
21
could be related to the mode 5, the very weak peak at
960 cm
21
to the mode 17a, the band at 907 cm
21
to
the mode 17b, the peak at 825 cm
21
to the mode 10a
and nally the band at 751 cm
21
to the mode 11. It is
of note that the peak at 825 cm
21
in the IR spectra of
PMT in the solid state is partially overlapped by a
broad band centred at 806 cm
21
attributable to the H
bonded NH 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 cm
21
in the IR
spectra of PMT-d
1
.
Fig. 3. (a) Raman spectrum of PMT in the solid state. (b) Raman
spectrum of PMT in methanol solution (solvent bands are marked
with ).
B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489 487
According to literature [21], the vibrational assign-
ment 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: 1570850 cm
21
. Liu
et al. [6] found the CyS stretching band in the IR
spectra of PMT at 1407 cm
21
, and other authors [5,8]
at 1050 cm
21
. 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 cm
21
[22]. Since the chemical environment
of the CyS bond is rather similar in the mercapto-
tetrazole 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. 4. Infrared spectra in KBr: (a) PMT; (b) PMTA.
Fig. 5. Raman spectra in the solid state: (a) PMT, (b) PMTA.
B. Pergolese, A. Bigotto / Journal of Molecular Structure 655 (2003) 479489 488
characterized as CyS stretching to occur at 570 cm
21
.
Therefore, taking into account the results of calcu-
lations and the assignments of imidazoline-2-thione
[22], the band located at 571 cm
21
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 20050 cm
21
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-d
1
were also recorded and theoretical calcu-
lations 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
NH and CH 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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[19] H.T. Flakus, Chem. Phys. 62 (1981) 103.
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