Vibrational Spectroscopy 81 (2015) 1–12

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

X-ray, tautomeric preference, vibrational spectra, and density

functional studies on benzoxazole and benzoxazoline derivatives
Ahmet Altuna,b,* , Serkan Dursunc, Naz M. Aghatabayd
a
Department of Physics, Fatih University, Büyükçekmece, Istanbul 34500, Turkey
b
Department of Genetics and Bioengineering, Fatih University, Büyükçekmece, Istanbul 34500, Turkey
c
Department of Physics, Qafqaz University, Xirdalan, Baku AZ0101, Azerbaijan
d
Department of Chemistry, Fatih University, Büyükçekmece, Istanbul 34500, Turkey

A R T I C L E I N F O A B S T R A C T

Article history: The solid-state X-ray diffraction, FT-IR, and FT-Raman measurements have been performed on bis
Received 18 January 2015 (benzoxazole-2-ylthio)methane. Molecular structures and normal vibrations of bis(benzoxazole-2-
Received in revised form 4 September 2015 ylthio)methane have been compared with those of its fragments in thiolic (2-mercaptobenzoxazole and
Accepted 5 September 2015
2-methylthiobenzoxazole) and thionic (benzoxazoline-2-thione and 3-methyl-benzoxazoline-2-thione)
Available online 8 September 2015
forms to elucidate substitutional effects. The observed IR and Raman bands of these molecules have been
assigned in the frameworks of calculated mode frequencies as well as the calculated IR and Raman
Keywords:
intensities at the B3LYP/6-311++G** level in gas phase. The assignments of all fundamental bands have
Bis(benzoxazole-2-ylthio)methane
Benzoxazole
been expressed in terms of internal coordinates and their percent potential energy distributions. The
Benzoxazoline thionic tautomers are significantly more stable than the thiolic tautomers (by more than 5 kcal/mol) with
X-ray structure a keto-enol transition state that lies more than 40 kcal/mol above the most stable thionic tautomers.
Infrared and Raman spectra Therefore, the thionic tautomers are the main species at room temperature. Despite the huge transition
Density functional theory (DFT) barrier, the thiolic tautomers can also exist according to the detailed vibrational spectral analyses.
Potential energy surface scans find that the thiolic tautomers have two stable conformations due to the
orientation of their SH and SCH3 moieties.
ã 2015 Elsevier B.V. All rights reserved.

1. Introduction widespread applications in industrial processes, their transition

metal complexes attract also considerable attention [19–22].
Benzoxazole and benzoxazoline are composed of benzene- In this study, we first synthesized bis(benzoxazole-2-ylthio)
fused deprotonated and protonated oxazole ring at the ring methane with the chemical formula of C15H10N2O2S2 and
nitrogen, respectively. They are found not only in several natural abbreviation of bis(BO-NS)Me (see Fig. 1), which emerges as a
products but also in pharmaceutical drugs such as priaxim [1,2]. useful ligand in coordination chemistry as it contains two units of
Since their thiol (mercapto, or sulfanyl) and thione derivates are nitrogen, oxygen, and sulfur atoms. We performed its solid-state X-
fungicidal and bacteriostatic reagents, they are efficient corrosion ray diffraction measurement to determine its crystal structure and
inhibitors for many metals and their alloys, and are used in recorded its solid-state FT-IR and FT-Raman spectra. Vibrational
recirculation of water systems and in regulating plant growth [3– selection rules of the crystalline phase were estimated through
10]. They find a great variety of applications in surface science factor group analysis. We then investigated thiolic (2-mercapto-
because they form adsorptive monolayers on metal and semicon- benzoxazole abbreviated as BO-NSH and 2-methylthiobenzoxa-
ductor substrates [11–14]. They are chelating agents with the zole abbreviated as BO-NSMe) and thionic (benzoxazoline-2-
presence of nitrogen, oxygen and sulfur in their contents. This thione abbreviated as BO-NHS and 3-methyl-benzoxazoline-2-
makes them effective collectors in flotation processes for separa- thione abbreviated as BO-NMeS) forms of the fragments of bis(BO-
tion of minerals [15,16] and for pre-concentration of transition NS)Me (see Fig. 1) to assess the substitutional effects on the
metal ions [17,18]. As being chelating agents and having structure and vibrational spectra. We calculated gas-phase
geometries and vibrational spectra of bis(BO-NS)Me, BO-NSH,
BO-NHS, BO-NSMe, and BO-NMeS with density functional theory
(DFT) using B3LYP hybrid functional, which has been already
* Corresponding author. Fax: +90 212 866 3402. proved to be very effective for vibrational studies of analogous
E-mail address: aaltun@fatih.edu.tr (A. Altun). compounds by using at least double-z Pople basis sets [23–31]. The

http://dx.doi.org/10.1016/j.vibspec.2015.09.001
0924-2031/ ã 2015 Elsevier B.V. All rights reserved.
2 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12

2. Experimental

2.1. Synthesis

All chemicals and solvents used for the synthesis of BO-NSMe/

BO-NMeS and bis(BO-NS)Me were reagent grade and processed as
purchased without further purification. For synthesizing BO-
NSMe/BO-NMeS, a solution of iodomethane (2.84 g, 20 mmol) in
EtOH (2 mL) was added dropwise to a solution of BO-NSH/BO-NHS
(3.02 g, 20 mmol) in EtOH (10 mL) and H2O (3 mL) containing KOH
(1.18 g, 21 mmol). The mixture was stirred at 75
C for over-night,
cooled to room temperature and poured into 80 mL of ice-cold
distilled water. The yellowish oily product was obtained, dissolved
in CH2CL2, dried in MgSO4 and filtered. The filtrate was evaporated
to dryness under vacuum obtaining a yellowish oily product
(2.50 g, 75%). Found (calculated) [C8H7NOS]: C, 58.21 (58.16); H,
4.30 (4.27); N, 8.43 (8.48); S, 19.32 (19.41). 1H NMR (CDCl3), dH in
ppm: 2.74 (s, 3H, CH3); 7.62–7.59 (m, 1H); 7.43–7.39 (s, 1H); 7.29–
7.19 (m, 2H). 13C{1H} NMR (DMSO-d6), dC in ppm: 162.58 (1C);
151.52 (1C); 140.99 (1C); 124.79(1C); 124.68 (1C); 118.53 (1C);
110.37 (1C); 35.45 (CH3).
Following the method described in literature [32,33], bis(BO-
NS)Me was prepared as follows: a solution of CH2Br2 (1.74 g,
10 mmol) in EtOH (2 mL, absolute) was added dropwise to a
refluxing solution of BO-NSH/BO-NHS (3.02 g, 20 mmol), EtOH
(4 mL) containing Na (0.46 g). The mixture was refluxed for two
hours, cooled to room temperature and poured into 100 mL of ice-
cold distilled water. The brownish product was purified using
soxhlet extraction technique by hexane, filling the thimble with
Fig. 1. The investigated compounds and the atom numbering scheme (see at Rot1 of celite and charcoal. Creamy white crystalline product was obtained
BO-NSMe). from solution and dried under vacuum (2.39 g, 76%, m.p. 129
C). 1H
NMR (DMSO-d6), dH in ppm: 5.32 (s, 2H, CH2); 7.65 (m, 2H); 7.37
computed vibrational frequencies, and IR/Raman intensities were (m, 2H). 13C{1H} (DMSO-d6), dC in ppm: 163.08 (1C); 152.01 (1C);
used to simulate the vibrational spectra and to identify normal 141.48 (1C); 125.29 (1C); 125.18 (1C); 119.02 (1C); 110.87 (1C);
modes in the experimental vibrational spectra. 35.95 (CH2).

Table 1
Crystal data and structure refinement of bis(BO-NS)Me located on a C2 axis with estimated standard deviations shown in parentheses for the last one
or two digits.

Empirical formula C15H10N2O2S2

Formula weight 314.37
Temperature 130(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Hall symbol C 2yc
Space group C2/c (C2h6); no. 15:b1
Point group 2/m (C2h)
Unit cell dimensions a = 21.2229(9) Å; b = 4.14370(10) Å; c = 18.0791(8) Å; a = 90
; b = 121.010(6)
; g = 90

Volume 1362.67(9) Å3
Z; ZB 4; 2
Density (calculated) 1.532 g/cm3
Absorption coefficient 0.395 mm–1
F(000) 648
Crystal size 0.5  0.1  0.1 mm3
Theta range for data collection 3.85
–30.51

Index ranges –30  h  30; –5  k  5; –24 l25
Reflections collected 11189
Independent reflections 2072 [Rint = 0.0229]
Completeness to theta = 30.51
99.8%
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 1 and 0.95296
Refinement method Full-matrix least-squares on F2
Data/restraints/parameters 2072/0/116
Goodness-of-fit on F2 1.059
Final R indices [I > 2s (I)] R1 = 0.0272; wR2 = 0.0751
R indices (all data) R1 = 0.0335; wR2 = 0.0767
Largest diff. peak and hole 0.367 and –0.224 eÅ3
 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12 3

difference Fourier map, and refined with isotropic thermal

parameters. The details of the structure refinement and crystal
data are given in Table 1.

3. Computational details

All quantum mechanical calculations were performed on

isolated (single) molecules by using Gaussian03 program package
and utilizing its fine numerical grid and tight SCF convergence
criteria [36]. Optimized gas-phase structures and force fields of the
compounds were obtained with B3LYP [37,38] hybrid density
functional by using triple-z quality split-valence 6-311++G** basis
set [39–41]. The 6-311++G** basis set extends the 6-31G basis with
five d-type polarization functions and one p-type diffuse function
on each atom other than hydrogen, a set of three p-type
polarization functions on each hydrogen atom, and one s-type
diffuse function on each atom. The B3LYP/6-311++G** level
calculations have already been shown to give converged geome-
tries and vibrational spectra on a large series of molecules [42].
Force fields of the compounds were calculated in the space of
Cartesian coordinates by analytic differentiation. They were then
transformed to internal coordinates for assigning normal modes in
terms of internal motions (stretching, n; out-of-plane deformation,
g ; in-plane deformation, b; torsion, t ) with their percent
contributions to the potential energy distribution (PED).
B3LYP obtains systematically overestimated vibrational fre-
quencies due to the neglect of the effects of crystal packing and
anharmonicity, and the incompleteness of basis set and dynamic
correlation. Therefore, the calculated frequencies are generally

Fig. 2. Relaxed PES scans connecting (a) Rot1 and Rot2 conformers of BO-NSH (b)
Rot1 of BO-NSH with BO-NHS.

2.2. Instrumentation

Analytical data were acquired with a Thermo Finnigan Flash EA

1112 analyzer. Melting point was obtained with an Electro-thermal
9100 melting-point apparatus. Routine 1H (400 MHz) and 13C
(100 MHz) spectra were recorded in CDCl3 or DMSO-d6 at ambient
temperature on a Bruker Ultrashield Plus 400 MHz instrument.
Chemical shifts (d) were given in units of parts per million (ppm)
relative to TMS. Analytical data, NMR and physical properties are
summarized for each experiment.
The FT-IR spectra of all the samples were recorded by inserting
them directly into the Nicolet 6700 FT-IR spectrometer with
attenuated total reflectance (ATR) method. FT-Raman spectra of all
the samples were recorded on a Bruker RFS 100/S spectrometer by
putting them directly in a Pyrex tube. The 1064 nm line of a near
infrared 1.5 W Nd:YAG air-cooled laser was used as excitation line.
A liquid nitrogen-cooled Ge detector was used. The output laser
power was arranged as 200 mW.
Single crystal X-ray diffraction data of bis(BO-NS)Me were
collected on a Bruker SMART-APEX CCD diffractometer at 130 K
using graphite monochromated MoKa radiation. The structure was
solved by direct methods using SHELX-97 [34] through WinGX
software [35] and refined by the full-matrix least-squares method
on all F2 data. Non-hydrogen atoms were refined with anisotropic
thermal parameters while all hydrogen atoms were located in a Fig. 3. Relaxed PES scans connecting (a) Rot1 and Rot2 conformers of BO-NSMe (b)
Rot1 of BO-NSMe with BO-NMeS.
4 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12

Table 2
Geometry parameters of the compounds in view.

Parameters Calculated Experimental

a
BO-NSH Rot1 BO-NSH Rot2 BO-NHS BO-NSMe Rot1 BO-NSMe Rot2 BO-NMeS bis(BO-NS)Me bis(BO-NS)Mea
Interatomic distance (Å)
S–C7 1.754 1.754 1.641 1.748 1.750 1.646 1.753 1.737
S-H/S-C8 1.348 1.348 1.826 1.829 1.828 1.804
N-H/N-C8 1.007 1.452
O–C2 1.380 1.381 1.378 1.379 1.381 1.374 1.380 1.388
O–C7 1.370 1.375 1.375 1.373 1.376 1.376 1.370 1.371
N–C1 1.400 1.399 1.390 1.399 1.396 1.393 1.399 1.410
N–C7 1.289 1.287 1.371 1.292 1.291 1.374 1.291 1.292
C1–C2 1.398 1.398 1.394 1.398 1.398 1.393 1.398 1.390
C1–C6 1.394 1.394 1.388 1.394 1.395 1.389 1.394 1.387
C2–C3 1.382 1.382 1.380 1.382 1.382 1.379 1.382 1.380
C3–C4 1.397 1.397 1.400 1.397 1.397 1.400 1.397 1.387
C4–C5 1.404 1.404 1.398 1.404 1.404 1.398 1.404 1.397
C5–C6 1.394 1.394 1.398 1.394 1.394 1.399 1.394 1.390
C–H (ring)b 1.083 1.083 1.083 1.083 1.084 1.083 1.083 0.974
C8–H (meth.)b 1.089 1.089 1.091 1.087 0.961

Bond angle (
)
C7–S–H (C8) 93.0 94.5 98.9 101.3 98.1 98.3
C7–N–H (C8) 121.4 125.0
C2–O–C7 103.6 103.5 108.7 103.7 103.6 108.6 103.7 103.1
C1–N–C7 103.9 104.1 110.9 104.0 104.2 109.7 104.1 103.6
N–C1–C2 108.8 108.8 104.8 108.8 108.8 105.7 108.7 108.7
N–C1–C6 131.4 131.4 134.1 131.4 131.5 133.3 131.5 131.1
C2–C1–C6 119.8 119.8 121.1 119.8 119.7 121.1 119.9 120.2
O–C2–C1 107.4 107.4 109.1 107.4 107.4 108.8 107.4 107.9
O–C2–C3 128.5 128.5 128.0 128.5 128.5 128.2 128.5 127.9
C1–C2–C3 124.1 124.1 122.9 124.1 124.1 123.0 124.1 124.3
C2–C3–C4 115.6 115.6 116.3 115.6 115.6 116.3 115.6 115.0
C3–C4–C5 121.5 121.5 121.3 121.5 121.5 121.3 121.5 121.9
C4–C5–C6 121.7 121.7 121.6 121.7 121.7 121.6 121.7 122.1
C1–C6–C5 117.3 117.3 116.8 117.3 117.3 116.8 117.3 116.6
S–C7–O 114.5 117.8 124.5 114.7 118.7 123.1 114.7 114.3
S–C7–N 129.1 125.9 129.0 129.2 125.3 129.7 129.1 128.9
O–C7–N 116.4 116.3 106.5 116.1 116.0 107.2 116.2 116.8
S–C8–Hb 108.7 109.0 107.3 107.1
H–C8–Hb 110.2 109.9 111.2 111.8

Torsional angle (
)
C1–N–C7–S 180.0 180.0 180.0 180.0 180.0 180.0 179.8 179.1
C8 (H)–N–C7–S 0.0 0.0
C2–O–C7–S 180.0 180.0 180.0 180.0 180.0 180.0 -179.7 179.4
N–C7–S–H (C8) 0.0 180.0 0.0 180.0 3.3 2.2
O–C7–S–H (C8) 180.0 0.0 180.0 0.0 -176.8 179.0
C7–S–C8–S 80.6 75.6
a
Due to symmetry, the parameters of one of the benzoxazole moieties are written.
b
Averaged values that belong to the same type of internal coordinates.

scaled for ease in relating the theoretical and experimental on BO-NHS as 0.955 for the frequencies above 2500 cm1, which
frequencies [43,44]. In this study, the scaling factors were derived correspond to XH stretchings (X = C, N, or S), and as 0.988 for the
remaining of the spectra. The standard deviation S and the mean
absolute deviation MAD of the computational estimates with these
two scaling factors (R2 = 0.999) from the experimental vibrational
frequencies of BO-NHS are only 12.4 and 8.4 cm1, respectively. The
smallness of these deviations and closeness of R2 to unity indicate
high correlation between the experimental and calculated
frequencies. The presently derived two scaling factors are already
very similar to the previously obtained factors at the same
computational level [26–29]. Therefore, we applied them to the
computed vibrational frequencies of all compounds considered in
this study. The scaled computational frequencies have then S and
MAD of 14.8 and 10.8 cm1 from the corresponding experimental
frequencies (R2 = 0.999), respectively. This ensures that the present
scaling factors are transferable to the computed vibrational
frequencies of related compounds.
IR and Raman spectra were simulated using the scaled
computational frequency (ni), computed IR intensity (IIR,i), and
Fig. 4. A view of the crystal packing of bis(BO-NS)Me.
 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12 5

Fig. 5. The experimental and simulated room temperature IR spectra of BO-NSH and BO-NHS.

relative Raman intensity (IRa,i) obtained from the computed Raman 4. Results and discussion
scattering activity (SRa,i) of each mode i by using the following
formula of the scattering theory [45–50]: 4.1. Structure determination

IRa;i ¼ f ðn0  ni Þ4 SRa;i BO-NSH and BO-NSMe both have two stable conformers
h i
ni 1  expðhckTni Þ (Rot1 and Rot2; Fig. 1) at room temperature arising from the
position of thiolic hydrogen and methyl group, respectively. The
where n0 is the excitation line of the laser used in Raman thiolic hydrogen or the methyl group is closer to the ring nitrogen
measurements in cm1 (1064 nm = 9398.5 cm1); h,c, and k are in Rot1 and to the ring oxygen in Rot2 of these molecules with Cs
Planck’s constant, speed of light, and Boltzmann’s constant; f is a symmetry (Fig. 1). The Rot1 conformers of BO-NSH and BO-NSMe
factor that is common for all peak intensities. In the following, we are 0.65 and 1.82 kcal/mol more stable than their Rot2 conformers
tabulate SRa,i rather than IRa,i to allow easy calculation of IRa,i for a with small rotational barriers, which are 3.64 and 4.61 kcal/mol
different laser, which can be used in future vibrational studies of with respect to Rot1, respectively (Figs. 2 and 3a). Zero-point
the present molecules. IR and Raman spectra were simulated by energies calculated using the scaled vibrational frequencies
using pure Lorentzian band shapes taking the full widths at the decrease the already small Rot1-Rot2 energy separation of BO-
half-height as 10 cm1. NSH and BO-NSMe by only 0.15 and 0.10 kcal/mol, respectively.
Therefore, if BO-NSH and BO-NSMe exist at room temperature,
they will be found as mixtures of their Rot1 and Rot2 conformers.

Fig. 6. The experimental and simulated room temperature Raman spectra of BO-NSH and BO-NHS.
6 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12

Fig. 7. The experimental and simulated room temperature IR spectra of BO-NSMe and BO-NMeS.

Fig. 8. The experimental and simulated room temperature Raman spectra of BO-NSMe and BO-NMeS.

To obtain energetic preference between thiolic and thionic analyses). NMR measurements recorded varying the temperature
forms of the molecules, the thiolic hydrogen and methyl group of from –90
C to +90
C suggest the presence of only thionic forms in
the Rot1 conformers were moved to the ring nitrogen progressively DMSO-d6 [23].
by an increment of 0.2 Å (Figs. 2 and 3b). Fixing only the N–H or N– The present computational energetic data about the conforma-
C8 distance, all other coordinates were optimized. These relaxed tional stabilities and keto-enol transition states of the benzoxazole
potential energy scans find that thionic forms are 8.33 and and benzoxazoline derivatives are quite similar to those obtained
5.51 kcal/mol more stable than the thiolic forms when the on the benzothiazole and benzothiazoline derivatives [51].
migrating atom/group is a hydrogen and methyl group, respec- Therefore, the relative energies are not much affected by the
tively. The corresponding keto-enol transition state lies more than presence of sulfur or oxygen in the ring system of the analogous
40 kcal/mol above the thionic forms, which is too huge for compounds.
accessing thiolic forms at room temperature. Therefore, according The key computational geometry parameters of the compounds
to the present calculations, the BO-NHS and BO-NMeS molecules together with the present X-ray data for bis(BO-NS)Me are listed in
with Cs symmetry are the main species at room temperature. BO- Table 2 by using the atom numbering scheme given on Rot1 of BO-
NSH and BO-NSMe are too minor if they exist (see vibrational NSMe in Fig. 1. As stated above, BO-NSH, BO-NHS, BO-NSMe, and
 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12 7

BO-NMeS have Cs symmetry while both calculations and X-ray data mode that includes vibrational frequency/intensity, symmetry
find C2 symmetry for bis(BO-NS)Me. As apparent from the view of species, and percent PED of each internal coordinate is as given in
crystal packing of bis(BO-NS)Me given in Fig. 4, bis(BO-NS)Me Tables 3–5. The normal modes of BO-NSH labeled with the
molecules interact to each other weakly in the solid state (see numbers 1–39 (Table 3) were correlated with the modes of BO-
Supporting Data for the detailed crystallographic data and the NHS (Table 3), BO-NSMe/BO-NMeS (Table 4), and bis(BO-NS)Me
factor group analysis described below in Section 4.2). Therefore, (Table 5) for ease in comparing the normal modes.
the solid-state and gas-phase structures of bis(BO-NS)Me must be The A0 and A00 symmetry types of the modes in the molecules
analogous. Consistently, MAD between the calculated and X-ray with Cs symmetry (i.e., BO-NSH, BO-NHS, BO-NSMe, and BO-
data for the bond lengths (excluding C H bonds, see below) and NMeS) refer to the in-plane and out-of-plane vibrations, respec-
bond angles is only 0.008 Å and 0.4
, respectively. tively. The A and B symmetry types of the vibrational modes for bis
Since the hydrogen atom has very small scattering for X-rays, (BO-NS)Me with C2 symmetry correspond to symmetric and
the C H bond lengths are generally obtained too short in X-ray antisymmetric (asym) modes, respectively. Both BO-NS moieties of
measurements (around 0.98 Å [52] as obtained in this X-ray study), bis(BO-NS)Me contribute to the normal modes either vibrating in-
which can be partially recovered by deuterium replacement. phase (symmetric, 44 A) or out-of-phase (asym, 43 B) with respect
However, neutron diffraction measurements find generally more to each other. The A and B types of the bis(BO-NS)Me normal
accurate C H bond lengths that are around 1.09 Å [52], similar to modes that are both IR and Raman active and involve with the
present computational results that vary between 1.08 and 1.09 Å. same BO-NS vibrations have almost the same frequencies, and are
The bond lengths obtained in the previous X-ray measurement given at the same row of Table 5.
for BO-NHS with bound bis(diiodine) [53] have a MAD of 0.04 Å The monoclinic phase of bis(BO-NS)Me crystallizes in the C2/c
from those in the computational structure of bare BO-NHS. This (C2h6) space group having primitive Bravais cell of 2/m (C2h) point
large difference in the bond lengths can be attributed to the group that include two symmetrically equivalent molecules
significant charge redistribution in BO-NHS upon bis(diiodine) (ZB = 2) connected by a center of symmetry (Table 1). This results
binding. in 23N = 186 normal modes. According to factor group analysis
When the substituent of the S atom (H or CH3) is transferred to [54,55] on the crystal data, the bis(BO-NS)Me crystal has three
the ring N, only the geometry parameters involving N C7 S acoustic modes (Au + 2Bu) and 183 optical modes that span 45Au
moiety of the present molecules change significantly: N C7 bond and 44Bu as IR-only active modes, and 46Ag and 46Bg as Raman-
C7 bond is shortened by 0.1 Å. Bond
is elongated by 0.1 Å while S only active modes. Therefore, the IR and Raman spectra of the bis
angles involving this moiety vary also by around 5
(Table 2). (BO-NS)Me crystal have not any common band. However, the
experimental IR and Raman bands of bis(BO-NS)Me have almost
4.2. Vibrational spectra the same frequencies (Table 5). This indicates that interactions
between bis(BO-NS)Me molecules are rather weak, which is
The experimental and simulated vibrational spectra (both IR already apparent from Table S5.
and Raman) of BO-NSH, BO-NHS, BO-NSMe, BO-NMeS, and bis(BO- Vibrational spectra of BO-NSH and BO-NHS were already
NS)Me are given in Figs. 5–9. The detailed analysis of each normal analyzed with DFT but with small basis sets [23,24], or with mode

Fig. 9. The experimental and simulated room temperature IR and Raman spectra of bis(BO-NS)Me.
8 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12

Table 3
Experimental and computed B3LYP/6-311++G** vibrational frequencies (in cm1) and normal mode descriptions of BO-NSH and BO-NHS.

No Experimental BO-NSH (Rot1) BO-NSH (Rot2) BO-NHS PED (%)a

IR Raman Calc. Scaled IIR SRa Calc. Scaled IIR SRa Calc. Scaled IIR SRa

3504 vw 3664 3499 84.72 105.43 A0 100 nNH

1 3068 vw 3071 vs 3206 3062 3.69 237.02 3206 3062 3.94 258.18 3211 3067 1.29 182.21 A0 100 nCH
2 3201 3057 7.23 80.37 3202 3058 6.85 58.59 3200 3056 6.90 167.76 A0 100 nCH
3 3038 vw 3187 3044 9.16 144.73 3187 3044 9.21 145.08 3191 3047 7.00 127.45 A0 100 nCH
4 3173 3030 2.71 62.18 3173 3030 2.67 61.75 3178 3035 1.15 54.42 A0 100 nCH
5 2686 2565 3.43 128.03 2685 2564 1.11 125.45 A0 100 nSH
6 1631 vw 1633 s 1654 1634 2.27 65.52 1653 1633 3.30 63.05 1662 1642 0.70 36.32 A0 54/53/53 nCC, 38/38/35 bCH,
h9 bNHi
7 1617 m 1618 s 1639 1619 7.92 12.72 1639 1619 10.08 14.96 1651 1631 30.51 41.64 A0 51/51/55 nCC, 39/39/28 bCH, 7/7/-
nCN, h15 bNHi
8 1558 w 1554 w 1548 1529 200.82 230.78 1557 1538 238.80 229.95 A0 44 nCN, 31 bCCC, 14 bCH, 10/9 bSH
1504 vs 1504 w 1520 1502 112.26 5.86 A0 42 bCH, 26 nCN+nCS, 21 bCCC,
11 bNH
9 1486 w, 1492 w 1504 1486 3.83 6.19 1504 1486 3.88 6.77 1502 1484 42.82 51.01 A0 54/56/54 bCH, 43/41/37 bCCC,
sh h7 bNHi
10 1474 s 1475 m 1477 1459 70.51 32.97 1477 1459 70.00 29.91 A0 63/64 bCH, 31 bCCC
1442 vs 1425 s, 1452 1435 593.39 41.19 A0 39 bCH, 21 nCN+nCS, 21 bCCC,
sh 20 bNH
11 1361 w 1365 m 1377 1360 3.51 18.99 1377 1360 3.62 18.03 A0 52bCCC, 36 bCH, 8 bNCO
1413 vs 1413 s 1393 1376 93.75 21.43 A0 51 bCCC, 34 bCH, 13 bNCO
12 1308 1292 3.08 13.60 1308 1292 3.75 17.02 A0 76 bCH, 20 bCCC
1298 vw 1313 1297 56.12 16.10 A0 69 bCH, 20 bCCC, 11 bNCO
13 1245 w 1256 1241 81.57 161.91 1257 1242 86.39 170.21 A0 52/50 bCH, 37/36 bCCC, 10/
10 bNCO
1233 w 1234 vs 1255 1240 109.40 122.49 A0 41 bCH, 23 bNH, 20 bCOC, 16 bCCC
14 1238 1223 49.39 12.27 1238 1223 24.33 7.71 A0 39 bCOC, 35 bCCC, 14 bCH, 12/
13 bSH
1275 m 1268 vs 1289 1274 42.69 73.86 A0 37 bCH, 27 bCCC, 23 bCNC, 11 bNH
15 1159 w 1158 m 1171 1157 0.66 11.81 1171 1157 0.58 10.83 1179 1165 0.08 8.00 A0 91/90/93 bCH
16 1129 vs 1133 m 1155 1141 120.28 17.85 1154 1140 95.20 24.35 1146 1132 103.57 5.40 A0 62/62/81 bCH, 18/20/- bCSH, 15/
15/- bCCC, h17 bNCOi
17 1091 s 1089 vw 1115 1102 36.40 1.30 1115 1102 36.13 0.63 1100 1087 85.30 0.96 A0 62/60/43 bCH, 23/23/33 bCCC, 9/
11/- bCSH, h20 bNCOi
18 1006 m 1011 vs 1024 1012 8.04 29.84 1024 1012 8.43 30.53 1029 1017 18.72 35.35 A0 48/49/48 bCH, 46/46/47 bCCC
19 976 vw 981 vw 980 968 0.00 0.24 981 969 0.01 0.07 974 962 0.00 0.05 A00 99 gCH
20 970 958 3.28 3.91 964 952 4.73 10.53 A0 47/53 bSH, 32/29 bNCO (sciss.), 21/
18 bCCC
929 vs 932 s 934 923 64.54 7.37 A0 70 bNCO (sciss.), 28 bCCC
21 945 934 2.90 0.02 945 934 2.95 0.01 932 921 2.78 0.04 A00 82 gCH, 17 gCCC
22 921 910 19.03 3.32 922 911 28.19 2.36 A0 42/43bSH, 33/26 bCCC, 25/
31 bNCO
1185 vw 1197 1183 86.78 1.56 A0 42 bNH, 20 bCCC, 19 bCOC, 18 bCH
23 888 877 19.70 9.76 893 882 14.93 4.81 A0 52/58 bCCC, 30/23 bSH, 18/
19 bNCO
884 w 885 w 894 883 2.83 2.79 A0 70 bCCC, 34 bNCO
24 854 w 853 w 859 849 0.10 0.09 859 849 0.15 0.08 850 840 0.04 0.06 A00 81 gCH, 18 gCCC
25 813 m 814 m 823 813 14.86 22.92 821 811 16.71 22.55 835 825 9.04 13.70 A0 79/78/69 bCCC, 21/22/18 nCS,
h13 bNHi
26 740 vs 758 749 83.68 0.57 758 749 86.34 0.52 750 741 86.11 0.49 A00 79/80/83 gCH, 17/17/14 gCCC
27 681 w 680 vw 738 729 3.23 0.09 730 721 0.99 0.09 720 711 0.27 0.07 A00 62/66/69 gCCC, 30/25/17 gCH,
h11 gNHi
28 646 vs 641 vw 681 673 0.11 0.12 678 670 0.11 0.20 655 647 4.01 2.60 A00 43/42/69 gNCO (wag.), 41/40/
22 gCH, 13/13/- gCCC
29 624 m 634 626 0.63 7.90 634 626 0.65 8.26 631 623 0.68 7.13 A0 98 bCCC
30 605 vs 606 m 604 597 0.75 1.31 604 597 0.73 1.27 627 619 13.65 14.27 A0 74/75/73 bCCC, 26/25/27 nSC
31 571 vw 583 576 0.01 0.15 582 575 0.19 0.15 572 565 1.56 0.03 A00 90/89/85 gCCC, 8/8/15 gNCO
32 474 468 1.97 0.41 474 468 1.60 0.09 487 481 2.14 0.98 A0 63/64/59 bCCC, 37/36/41 bCS(H)
33 432 427 4.83 0.09 433 428 3.75 0.08 A00 95/91 gCCC
300 296 0.03 3.17 A00 95 t(ring)
34 427 s 425 w 402 397 2.20 6.67 402 397 1.97 6.76 433 428 5.97 27.40 A0 100 breath.
35 323 vw 306 302 0.06 1.56 311 307 0.53 1.68 A00 100/85 t(ring), [15 gSH]
423 418 0.12 0.27 A00 86 t(ring), 11 gNH
36 267 vw 256 253 3.95 0.60 252 249 1.25 0.56 241 238 2.36 0.40 A00 54/71/67 gCCC, 28/8/- gSH, 18/21/
33 gNCO (twist.)
37 238 vw 235 232 16.88 0.53 A00 58 gSH, 36 g CCC
146 144 22.53 0.06 A00 60 gSH, 40 g CCC
479 m 493 487 77.59 0.35 A00 74 gNH, 19 gCCC
38 206 204 2.84 0.65 207 205 1.88 1.08 231 228 0.32 2.56 A0 77/77/92 b ring, 23/23/8 bCS
39 111 110 1.98 0.46 101 100 0.73 0.45 99 98 0.00 0.12 A00 82/60/88 t(ring), {18 gCS},
[40 gSH], h9 gCSi
a
The first, second, and third entries separated by “/” belong to Rot1 and Rot2 of BO-NSH, and BO-NHS, respectively. The contribution present only in the Rot1, Rot2, and BO-
NHS are given inside of {}, [], and h i, respectively.
 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12 9

Table 4
Experimental and computed B3LYP/6-311++G** vibrational frequencies (in cm1), IR intensities, Raman scattering activities, and normal mode descriptions of BO-NSMe and
BO-NMeS.

No Experimental BO-NSMe (Rot1) BO-NSMe (Rot2) BO-NMeS PED (%)a

IR Raman Calc. Scaled IIR SRa Calc. Scaled IIR SRa Calc. Scaled IIR SRa

1 3076 w 3077 m 3204 3060 4.81 248.01 3204 3060 4.81 273.10 3210 3066 1.83 205.29 A0 100 nCH
2 3059 m, 3199 3055 8.65 81.11 3200 3056 7.97 48.34 3201 3057 5.64 116.10 A0 100 nCH
sh
3 3029 w 3186 3043 9.32 147.49 3186 3043 9.61 149.62 3191 3047 8.33 144.15 A0 100 nCH
4 3009 w, 3012 w 3172 3029 2.59 60.92 3172 3029 3.00 64.28 3178 3035 1.45 54.31 A0 100 nCH
sh
3152 3010 2.82 88.68 3147 3005 3.03 90.62 3146 3004 0.43 22.31 A0 100 nCH3 (asym.)
3158 3016 2.25 45.96 3155 3013 3.40 47.39 3096 2957 16.21 80.13 A00 100 nCH3 (asym.)
2937 w 2934 s 3061 2923 15.87 188.50 3059 2921 15.18 186.39 3035 2898 36.81 163.11 A0 100 nCH3 (sym.)
6 1616 s 1652 1632 1.44 77.94 1651 1631 1.13 83.38 1664 1644 0.96 39.65 A0 53/53/54 nCC, 38/38/36 bCH
7 1600 w 1639 1619 6.21 11.25 1637 1617 8.45 10.07 1642 1622 17.37 47.68 A0 50/52/57 nCC, 38/40/31 bCH, 6/
6/- nCN, h8 bCH3i
8 1538 vw 1538 1520 227.71 288.54 1542 1523 283.27 290.71 A0 36/44 nCN, 26/9 bCH3, 24/
30 bCCC, 12/14 bCH
1496 vs 1503 vs 1508 1490 101.07 54.76 A0 47 bCCC, 27 bCH, 21 bCH3
9 1503 1485 3.12 6.80 1503 1485 4.01 7.19 1520 1502 22.92 4.89 A0 53/54/24 bCH, 39/39/19 bCCC,
h50 bCH3i
10 1449 vs 1455 s 1479 1461 81.25 31.45 1481 1463 7.68 4.31 1495 1477 45.90 23.19 A0 39/54/28 bCH, 39/15/56 bCH3, 19/
27/15 bCCC
1431 vw 1475 1457 8.60 17.74 1477 1459 103.23 43.02 1460 1442 62.71 2.56 A0 59/83/63 bCH3, 25/10/21 bCH,
13/-/9 bCCC
1457 1440 10.44 12.65 1462 1444 10.05 14.02 1495 1477 8.64 11.60 A00 100 gCH3
1325 m 1321 w 1364 1348 8.07 13.66 1368 1352 1.58 0.42 A0 93/80 bCH3, [10 bCCC, 7 bCH]
1402 1385 71.85 78.88 A0 31 bCH3, 29bCH, 24 bCCC, 16 nCN
11 1340 m 1377 1360 4.52 23.15 1378 1361 7.19 25.94 1364 1348 210.94 28.39 A0 51/36/29 bCCC, 37/27/30 bCH,
-/30/16 bCH3, 8/-/24 bCN
12 1283 w 1283 w 1307 1291 3.21 14.21 1308 1292 4.90 21.33 1306 1290 96.52 2.26 A0 75/75/68 bCH, 19/19/17 bCCC,
h9 bCH3i
13 1235 s 1239 vs 1257 1242 102.22 191.32 1259 1244 92.96 188.82 1252 1237 18.56 136.02 A0 51/51/39 bCH, 37/37/28 bCCC, 11/
10/23 nCO
14 1215 s 1219 m 1232 1217 37.53 9.85 1229 1214 14.51 12.38 A0 39/37 bCCC, 39/35 bCOC, 15/
14 bCH, [13 bCH3]
714 m 731 722 7.19 14.42 A0 43 bCCC, 34 nNCH3, 13 bNCO,
9 bCH
15 1147 w 1171 1157 1.17 14.55 1171 1157 0.98 11.98 1179 1165 2.65 7.23 A0 92/91/84 bCH, h10 bCCCi
16 1130 vs 1134 w 1149 1135 136.02 20.52 1146 1132 88.64 33.95 1137 1123 55.03 2.69 A0 64/64/53 bCH, 19/14/- bNCO,13/
12/12 bCCC, -/9/31 bCH3
17 1094 vs 1099 vw 1113 1100 53.26 1.02 1112 1099 50.96 0.78 1108 1095 38.05 9.88 A0 61/56/33 bCH, 23/22/28 bCCC, 13/
13/8 b NCO, -/8/26 bCH3
18 1004 vs 1024 1012 11.16 31.46 1024 1012 10.21 31.60 1028 1016 10.42 32.83 A0 45/48/45 bCH, 43/46/44 bCCC,
8/-/10 bCH3
1038 vs 1007 995 4.26 4.05 999 987 19.34 5.23 1063 1050 91.98 6.10 A0 79/89/40 bCH3 (rock), 8/-/
23 bCCC, 6/-/10 bCH, -/5/23 nCO
985 973 3.53 2.19 979 967 2.90 2.90 1152 1138 0.32 0.98 A00 97/90/96 gCH3
19 977 w 978 vw 976 964 0.00 0.20 977 965 0.42 0.09 974 962 0.01 0.05 A00 98/92/86 gCH, h14 bCCCi
20 922 m 925 w 943 932 10.77 6.50 941 930 2.93 0.02 A0 46/64 bNCO, 34/9 bCH3, 18/
26 bCCC
1181 w 1178 vw 1194 1180 160.63 5.15 A0 41 bCH3, 29 bCH, 14 bCNC,
12 bCCC
21 941 930 2.90 0.02 935 924 14.73 12.02 931 920 2.90 0.06 A00 82/81/82 gCH, 17 gCCC
23 884 vw 886 vw 899 888 2.82 4.71 900 889 2.48 5.07 893 882 5.37 4.15 A0 67/70/52 bCCC, 22/23/16 bNCO
(rock.), 10/7/31 bCH3
24 840 vw, 857 vw, 858 848 0.14 0.10 857 847 0.15 0.11 851 841 0.02 0.10 A00 80/81/77 gCH, 18 gCCC
br br
25 803 m 808 vs 824 814 14.55 27.60 822 812 15.58 26.75 851 841 11.32 9.11 A0 76/77/60 bCCC, 20/17 nCS. h23
bCH3i
26 739 vs 743 vw 757 748 81.62 0.65 757 748 83.06 0.62 751 742 85.83 0.64 A00 79/79/82 gCH, 16 gCCC
27 743 734 4.80 0.10 738 729 3.37 0.09 734 725 0.09 0.17 A00 59/62/54 gCCC, 33/30/36 gCH
693 w 702 694 3.32 10.40 699 691 1.30 10.81 A0 82/83 bSCH3, 16/15 bCCC
1357 vw 1391 1374 392.63 7.55 A0 46 nNCH3; 36 bCH; 16 nCN
28 654 w 684 676 0.05 0.32 682 674 0.02 0.03 653 645 0.39 1.85 A00 43/42/50 gNCO, 41/41/27 gCH,
13 gCCC
29 621 w 625 m 635 627 0.70 7.86 634 626 0.92 8.57 636 628 12.23 7.43 A0 94/97/77 bCCC; h15 bCH3, 7 nCSi
30 596 w 604 597 1.39 2.54 602 595 1.21 2.42 587 580 12.22 6.22 A0 69/70/65 bCCC, 20/20/- nSC, 10/
10/- bCH3, h33 bNCH3 i
31 577 w 582 575 0.05 0.16 582 575 0.02 0.11 576 569 0.03 0.07 A00 90/91/87 gCCC, 8 gNCO
32 493 vw 502 vw 510 504 0.46 1.65 504 498 0.44 1.51 A0 54/56 bCCC, 45/44 bCSCH3
557 w, 550 vw 541 535 4.45 1.91 A0 56 bCCC, 36 bCNCH3
br
33 423 w 434 429 4.95 0.07 433 428 4.98 0.05 430 425 3.64 0.30 A00 93/94/92 gCCC; 94 gCCC
34 405 400 4.65 3.08 403 398 4.21 3.79 433 428 7.40 25.72 A0 100 breath.
35 312 308 0.10 1.31 310 306 0.16 1.28 310 306 0.26 2.21 A00 91/90/87 t(ring)
38 280 277 4.11 5.81 286 283 4.31 3.38 A0 52/54 b ring, 47/46 bSCH3
10 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12

Table 4 (Continued)
No Experimental BO-NSMe (Rot1) BO-NSMe (Rot2) BO-NMeS PED (%)a

IR Raman Calc. Scaled IIR SRa Calc. Scaled IIR SRa Calc. Scaled IIR SRa

232 229 0.30 1.17 A0 94 b ring

36 254 251 0.33 0.62 249 246 0.32 0.55 273 270 0.00 0.54 A00 76/72/53 gCCC, 23/22/20 gNCO
(twist.), h27 g CH3 i
145 143 2.76 0.62 146 144 1.35 2.09 A0 52 bSCH3, 48 b ring
267 264 1.56 2.47 A0 69 bNCH3, 26 b ring
139 137 0.00 0.24 149 147 0.00 0.28 131 129 2.35 1.08 A00 69/80/45 gCH3, 28/18/54 t(ring)
39 102 101 0.37 0.62 100 99 1.09 0.70 102 101 0.23 0.01 A00 41/58/53 t(ring), 55/38/43 gCH3
64 63 3.47 0.40 26 26 1.26 0.35 70 69 0.02 0.69 A00 55/47/18 gCH3, 45/53/80 t(ring)
a
The first, second, and third entries separated by “/” belong to Rot1 and Rot2 of BO-NSMe, and BO-NMeS, respectively. The contribution present only in the Rot1, Rot2, and
BO-NMeS are given inside of {}, [], and h i, respectively.

Table 5
Experimental and computed B3LYP/6-311++G** vibrational frequencies (in cm1) and normal mode descriptions of bis(BO-NS)Me.

No Exp. Calculated Scaled IIR SRa Calculated Scaled IIR SRa PED (%)a

IR Raman

1 3094 vw 3079 m 3206 3062 1.73 372.94 A 3206 3062 8.19 129.42 B 100 nCH
2 3055 m 3201 3057 1.50 163.55 A 3201 3057 13.29 15.86 B 100 nCH
3 3029 w 3188 3045 2.25 304.87 A 3188 3045 17.22 60.13 B 100 nCH
3179 3036 9.72 30.22 B 100 nCH2 (asym.)
4 3004 w 3005 w 3173 3030 0.47 104.59 A 3173 3030 4.71 24.09 B 100 nCH
2946 m 3106 2966 0.18 114.48 A 100 nCH2 (sym.)
6 1618 s 1653 1633 0.17 189.04 A 1653 1633 1.71 47.26 B 55 nCC, 38/39 bCH
7 1595 m 1638 1618 0.45 24.52 A 1638 1618 7.59 4.19 B 51 nCC, 39 bCH
8 1503 vs 1509 vs 1538 1520 0.24 873.23 A 1536 1518 407.83 81.20 B 42/43 nCN, 28/30 bCCC, 14/15 bCH, 13/10 bCH2
(sciss.)
9 1504 1486 1.90 14.17 A 1504 1486 5.04 2.15 B 55/56 bCH, 40/41 bCCC
10 1451 vs 1458 w 1477 1459 4.38 130.60 A 1477 1459 167.38 19.97 B 62 bCH, 31 bCCC
1397 1380 16.56 119.77 A 92 bCH2 (sciss.)
11 1362 vw 1376 1359 0.51 42.22 A 1376 1359 8.30 13.96 B 52/51 bCCC, 38 bCH, 9/8 bNCO
12 1285 vw 1294 w 1308 1292 0.00 41.94 A 1308 1292 9.66 1.80 B 75 bCH, 20 bCCC
1272 1257 36.28 1.11 B 77 bCH2, 17 bCCC
13 1236 m 1236 s 1258 1243 16.28 527.16 A 1256 1241 251.72 48.41 B 51/46 bCH, 37/34 bCCC, 11/9 bNCO; [10 bCH2]
14 1224 w 1236 1221 12.07 15.87 A 33 bCCC, 25 bCH2, 24 bCOC, 13 bCH
14 1217 m 1232 1217 103.80 8.42 B 45 bCCC, 29 bCOC, 16 bCH
1205 s 1217 1202 2.65 8.37 A 63 bCH2, 28 bCCC
15 1181 w 1183 vw 1171 1157 0.07 36.15 A 1171 1157 1.69 5.61 B 92 bCH
16 1135 vs 1142 w 1153 1139 51.66 68.57 A 1149 1135 304.49 4.52 B 66/67 bCH, 18/16 bCOC, 12/10 bCCC
17 1094 vs 1103 vw 1115 1102 7.79 2.54 A 1113 1100 143.79 1.72 B 63/61 bCH, 23 bCCC, 12/13 bNCO
18 1004 w 1013 m 1024 1012 2.22 67.07 A 1024 1012 20.75 3.62 B 49/50 bCH, 43/48 bCCC
19 974 vw 976 964 0.01 0.11 A 976 964 0.00 0.19 B 99 gCH
20 932 s 933 w 950 939 4.37 14.36 A 952 941 7.69 0.60 B 51/55 bNCO, 36/37 bCCC, [10 bCH2 (rock.)]
21 942 931 3.56 0.08 A 942 931 2.01 0.08 B 82 gCH, 17 gCCC
23 889 m 889 vw 901 890 1.00 7.85 A 902 891 1.97 0.75 B 67/73 bCCC, 22/24 bNCO (rock.), [10 bCH2 (rock.)]
24 860 vw 862 vw 858 848 0.15 0.06 A 858 848 0.07 0.12 B 80 gCH, 18 gCCC
852 vw 835 825 38.97 5.37 B 61 bCH2 (rock.), 27 bCCC, 7 bNCO
25 815 m 823 813 2.14 61.26 A 821 811 16.02 4.47 B 78/66 bCCC, 20/16 nCS, [18 bCH2 (rock.)]
26 737 vs 737 vw 757 748 101.41 0.60 A 757 748 52.47 0.70 B 80 gCH, 15 gCCC
27 754 m 755 vw 744 735 8.90 0.16 A 745 736 6.63 0.05 B 59 gCCC, 34 gCH
732 vs, 702 694 105.49 2.50 B 73 gCSC, 20 gCCC
sh
28 675 vw 677 vw, 683 675 0.22 0.51 A 683 675 1.83 0.09 B 43/40 gNCO, 40/39 gCH, 13 gCCC
sh
661 w 661 w 653 645 2.54 11.73 A 57 bCSC, 36 bCCC
29 623 w 634 626 0.00 14.11 A 635 627 1.97 2.90 B 94/90 bCCC
30 594 w 605 598 0.14 6.24 A 601 594 2.59 1.04 B 72/71 bCCC, 21/20 nCS
31 570 vw 582 575 0.09 0.31 A 582 575 0.11 0.10 B 91 gCCC, 9/8 gNCO
32 511 vw 516 510 0.42 1.79 A 506 500 1.91 0.55 B 62/57 bCCC, 29/43 bCSC
33 433 428 6.49 0.14 A 433 428 2.88 0.02 B 95 gCCC
34 409 w 405 400 0.68 3.71 A 398 393 8.82 0.18 B 76/74 breath., 24/26 nSC
344 w 340 336 1.77 3.43 56 bSCS (sciss.), 44 bCCC
323 w 316 312 11.13 0.92 B 57 bSCS, 43 bCCC
35 314 sh 307 303 0.06 0.81 A 308 304 0.30 0.80 B 92/91 t(ring)
36 258 w 256 253 0.43 0.91 A 255 252 0.17 0.44 B 76/75 gCCC, 23 gNCO (twist.)
38 194 w 190 188 0.64 2.19 A 187 185 5.09 0.08 B 88/64 b ring, {12 bSCS (sciss.)}, [33 bCH2 (rock.)]
39 126 m 119 118 0.93 1.04 B 85 t(ring), 15 gSCS
39 101 s 106 105 1.60 2.18 A 88 t(ring), 12 gCS
84 s 72 71 0.11 0.88 A 100 gSCS
60 w 37 37 0.33 8.05 A 50 49 0.61 0.95 B 100 t(NCSC)
4 m 16 16 0.09 5.39 A 19 19 0.09 3.77 B 100 t(SCSC)
a
The first and second entries separated by “/” belong to the modes with the symmetry species of A and B, respectively.
 A. Altun et al. / Vibrational Spectroscopy 81 (2015) 1–12 11

assignments expressed only with the major internal coordinate 5. Conclusions

contribution [24]. Extending the size of the basis set to 6-311++G**
in this study improved the frequencies and assignments of several We have carried out B3LYP calculations on the structure and
modes, especially those involving X H vibrations (X = C, N, and S). vibrational spectra of thiolic (BO-NSH and BO-NSMe) and
The 6-311++G** basis set was already proven to give converged DFT thionic (BO-NHS and BO-NMeS) benzoxazole and benzoxazoline
frequencies and mode definitions compared its results with those derivatives together with the thiolic bis(BO-NS)Me by using the
of larger basis sets [28,42]. triple-zeta quality split-valance 6-311++G** basis set. Although
The experimental frequencies of some modes, such as, 6–8, 10, the thionic forms of the molecules are more stable than the
and 11, have large deviations (about 20 cm1) among the thiolic forms with huge transition states, the experimental
considered molecules, contrary to the similarity in their calculated vibrational spectra of these molecules are composed of the
frequencies. This should arise from the environmental effects overlap of the spectra of thionic and thiolic species. Therefore,
(packing difference in solid samples or being solid or liquid). thiolic forms should also exist at room temperature with minor
The calculated vibrational spectra for Rot1 and Rot2 of thiolic amounts. Thiolic forms are found in two stable conformations
species (BO-NSH and BO-NSMe) are indistinguishable from each (Rot1 and Rot2) arising from the orientation of their SH and
other (Figs. 5–8 and Tables 3 and 4). The calculated intensity SCH3 moieties. In this study, we have also determined solid-
patterns of the vibrational spectra of thionic species (BO-NHS and state X-ray structure of bis(BO-NS)Me. The X-ray and the
BO-NMeS) are too different from those of the thiolic species but computational B3LYP structures of bis(BO-NS)Me are found
similar to those of the experimental spectra (Figs. 5–8). Therefore, consistent to each other.
rough visual inspections on the vibrational spectra suggest the We assigned each normal mode in the experimental vibrational
presence of only thionic forms at room temperature, similar to the spectra of these molecules by using the present computational
result of previous NMR analyses [23]. This is because thiolic species results. All fundamental bands have been assigned in terms of
contain a smaller number of strong bands. However, detailed internal coordinates with their percent potential energy contri-
vibrational analyses (Tables 3 and 4) show that several bands of the butions. The effects of substitution at the nitrogen and sulfur atoms
thiolic species are actually present in the experimental vibrational have been analyzed.
spectra in addition to those of the thionic species. A few of such
bands can be exemplified with the modes 8, 10, 11, and 13 for BO-
Acknowledgment
NHS and BO-NSH (Figs. 5 and 6) and the modes 8, 14, and 20 for BO-
NMeS and BO-NSMe (Figs. 7 and 8). These modes are labeled with a
This work is supported by the Scientific Research Fund of Fatih
and b for the thionic and thiolic species on the vibrational spectra
University under the project numbers of P50011102_Y (1679) and
(Figs. 5–8), respectively. These labelings on Figs. 5–8 make clear
P50031301_G (3285).
that both thionic and thiolic species contribute to the vibrational
spectra at room temperature.
Appendix A. Supplementary data
The frequencies of CH3/2 stretchings for the present molecules
are found in the range 2900–3040 cm1 while the ring CH and NH
Supplementary data associated with this article can be found, in
stretchings are all found above 3000 cm1 (Tables 3–5), consistent
the online version, at http://dx.doi.org/10.1016/j.
with literature values of the corresponding vibration types
vibspec.2015.09.001.
[28,30,31,56–61]. The S C stretching cannot be assigned to a
unique mode as noted previously on analogous molecules [28,62].
References
It contributes to the modes 25 and 29 of BO-NMeS and modes 25,
30, and 34 of bis(BO-NS)Me in the range 390–815 cm1. [1] S. Haider, M.S. Alam, H. Hamid, S. Shafi, A. Dhulap, F. Hussain, P. Alam, S. Umar,
When the modes involve purely the vibrations of SH/NH and M.A.Q. Pasha, S. Bano, S. Nazreen, Y. Ali, C. Kharbanda, Eur. J. Med. Chem. 81
NCH3 moieties, their frequencies are significantly dependent on (2014) 204–217.
[2] R.D. Viirre, G. Evindar, R.A. Batey, J. Org. Chem. 73 (2008) 3452–3459.
the position of H and CH3 substituents (at S or N). For example, [3] B. Pergolese, M. Muniz-Miranda, A. Bigotto, J. Phys. Chem. B 110 (2006) 9241–
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