Triethanolammonium salicylate — Protic alkanolammonium ionic liquid

Article abstract of DOI:10.1016/j.molliq.2016.06.085

Triethanolammonium salicylate was synthesized, characterized by IR and NMR spectroscopy, elemrntal analysis, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The structure was established, and cation-anion interactions were investigated by X-ray diffraction analysis. It was found that exchange reaction occurs at triethanolammonium salts interaction with silver (I) nitrate, and the product structure was established by X-ray diffraction analysis. The influence of triethanolammonium salicylate solution on the growth properties of the fungus Rhizopus oryzae was studied.

Full text of DOI:10.1016/j.molliq.2016.06.085

Triethanolammonium salicylate – protic alkanolammonium ionic liquid
Y. Kondratenko, T. Kochina, V. Fundamensky, I. Ignatyev, T. Paniko-
rovskii, G. Nyanikova
PII:
DOI:
Reference:
S0167-7322(16)30242-2
doi: 10.1016/j.molliq.2016.06.085
MOLLIQ 5992
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
28 January 2016
7 June 2016
25 June 2016
Please cite this article as: Y. Kondratenko, T. Kochina, V. Fundamensky, I. Ignatyev, T.
Panikorovskii, G. Nyanikova, Triethanolammonium salicylate – protic alkanolammonium
ionic liquid, Journal of Molecular Liquids (2016), doi: 10.1016/j.molliq.2016.06.085
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ACCEPTED MANUSCRIPT
Triethanolammonium salicylate – protic alkanolammonium ionic liquid
1
*
1,2
1,3
2
Y. Kondratenko , T. Kochina , V. Fundamensky , I. Ignatyev , T.
4
3
Panikorovskii , G. Nyanikova
1
Grebenshchikov Institute of Silicate Chemistry RAS, nab. Makarova, 2, St. Petersburg, 199034
Russia
2
Department of radiochemistry, Institute of Chemistry, St. Petersburg State University, 7/9
University emb., St. Petersburg 199034, Russia.
3
St. Petersburg Stt. Inst. Technol., Moskovskii pr. 26, St. Petersburg, Russia
Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University,
4
University Emb., 7/9, 199034 St. Petersburg, Russia
*
Corresponding author. Tel.:+78123284802, e-mail: kondratencko.iulia@yandex.ru
Keywords: triethanolammonium salicylate; protatrane; ionic liquid; synthesis;
structure; antifungal activity.
Abstract
Triethanolammonium salicylate was synthesized, characterized by IR and NMR
spectroscopy. The structure was established, and cation-anion interactions were
investigated by X-ray diffraction analysis. It was found that exchange reaction
occurs at triehanolammonium salts interaction with silver (I) nitrate, and the
product structure was established by X-ray diffraction analysis. The influence of
triethanolammonium salicylate solution on the growth properties of the fungus
Rhizopus oryzae was studied.
1
. Introduction
Ionic liquids (ILs) are a class of relatively novel compounds comprising bulky,
organic cations and inorganic or organic anions. [1-3] Ionic liquids have attracted
much attention in various fields of science and technology (electrochemistry,
catalysis and organic synthesis, electrochemical sensors, and other areas) due to
their unique properties as suitable solvents for a broad scope of inorganic, organic
and polymeric materials. Their features such as high polarity, chemical and thermal
stability, as well as a wide interval of liquid state, [1-6] draw interest to them of the
large scope of chemist. Also, in recent years, ILs have attracted attention due to the
possibility of the design of a new compounds with unique properties, e.g.,
pharmacologically active ionic liquids by combining cations and anions with
desired properties [7-9].
Triethanolammonium salts of protic acids belong to the class of protic
alkanolammonium ionic liquids [10, 11], and due to their unique atrane structure
became known as protatranes [12, 13]. A number of studies have shown [14-18]

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that many protatranes have biological activity, which is mainly determined by the
atrane structure of the cation and the nature of an anion. The first compound of this
class was triethanolammonium salt of 2-methylphenyloxyacetic acid [2-
–
+
CH C H OCH COO] [NH(CH CH OH) ] (trecrezan), which is a drug of wide
3
6
4
2
2
2
3
spectrum of action (adaptogen, immunomodulator, etc.) [17, 18].
As determined by X-ray diffraction analysis [12, 19-27] protatrane cation
+
[
NH(CH CH OH) ] has a tricyclic structure with N→H bond, directed inward the
2
2
3
protatrane framework. Three oxygen atoms from hydroxyethyl groups
CH CH OH) of protatrane cation, which surround the hydrogen atom of NH
(
2
2
group, form three intramolecular trifurcate hydrogen bonds (endo-configuration,
figure 1).
Figure 1
Most of the known triethanolammonium salts have such atrane structure (figure 1).
+
These salts are formed by triethanolammonium cation [NH(CH CH OH) ] and
2
2
3
inorganic (X =Hal [23-25], NO [26], ClO [22], etc.) or organic (X = 2-
3
4
CH C H OCH COO [19], 4-ClC H SCH COO [20], HOOCCOO [27],
3
6
4
2
6
4
2
HOOCCH COO [27], C H (HCO)COO [28]) anions.
2
6
4
In the last work [28] the structure of triethanolammonium 2-formylbenzoate was
established by X-ray diffraction analysis. Triethanolammonium cation in this salt
has structure that differs significantly from other protatranes, since two
CH CH OH branches are directed along the NH group (endo-branches), but the
2
2
third branch (exo-branch) is pointed in a reverse direction. In this molecule the
existence of the exo-branch is conditioned by a hydrogen bond (1.79 Å) between
the hydroxyl group of protatrane cation and the oxygen atom of the 2-
formylbenzoate anion. Thus, the cation in this salt has an exo-endo conformation
(
figure 2).

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Figure 2
In this study we synthesized and characterized by IR and NMR spectroscopy a new
triethanolammnium salt of salicylic acid which belongs to the class of protic
alkanolammonium ILs. The structure of this compound was determined by single
crystal X-ray diffraction analysis.
The anion of this salt, as in the case of triethanolammonium 2-formylbenzoate, has
the substituent (OH-group) at the second carbon atom of aromatic ring. Therefore,
it is interesting to investigate the effect of this anion on the structure of protatrane
cation. The other aim of this study was to prepare a new silver-containing
compounds based on triethanolammonium salts, and to investigate the interaction
of triethanolammonium salicylate with silver (I) nitrate in polar medium (ethanol).
In addition we plan to investigate the influence of this triethanolammonium salt
solution on the growth properties of the fungus Rhizopus oryzae (culture Rhizopus
oryzae F-814), which belongs to the microorganism permitted for use in food
industry.

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2
. Experimental
IR spectra were recorded by the Nicolet 8700 (Thermo Scientific) FTIR
spectrometer. Pellets for studying IR spectra of compouds were produced by
pressing in KBr. Elemental analysis was performed on Elemental analyzer Euro
EA3028-NT for the simultaneous determination of C, H, N. NMR spectra in
DMSO-d6 2-5% solutions were registered on a Bruker Avance III spectrometer
1
13
[
400.13 ( Н), 100.613 MHz ( С)]. Chemical shifts presented below are relative to
1
13
residual signals of dimethyl sulfoxide (2.50 ppm for Н and 39.52 ppm for С)
29].
[
The single crystal X-ray diffraction experiment was performed on Agilent
Technologies Xcalibur Eos diffractometer at 100 K using monochromated MoKα
radiation. Experimental details are shown in Table 1. The structure has been solved
by the direct methods and refined by means of the SHELX program [30]
incorporated in the OLEX2 program package [31]. The carbon-bound H atoms
were placed in calculated positions and were included in the refinement in the
‘
riding’ model approximation, with U (H) set to 1.2U (C) and C–H 0.97 Å for
iso
eq
the CH groups, U (H) set to 1.5U (C) and C–H 0.96 Å for the CH groups and
2
iso
eq
3
U (H) set to 1.2U (C) and C–H 0.93 Å for the CH. All H atoms bonded to N and
iso
eq
O atoms were located in a difference Fourier map. Empirical absorption correction
was applied in CrysAlisPro [32] program complex using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. Supplementary
crystallographic data for this paper have been deposited at Cambridge
CrystallographicData Centre (CCDC 1448986) and can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif

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Table 1. Experimental details.
Crystal data
Triethanolammonium
salicylate
C H NO
Chemical formula
Mr
1
3
21
6
287.31
Crystal system, space group
Temperature (K)
a, b, c (Ǻ)
orthorhombic, Pca21
100
10.3205(7), 11,2445(8),
2
4,3654(17)
α, β, γ
V (Ǻ )
90, 90, 90
2827.6(3)
8
3
Z
Radiation type
Mo Kα
0.107
-
1
μ (mm )
Crystal size (mm)
Data collection
Diffractometer
0.18 × 0.17 × 0.15
Xcalibur, Eos
diffractometer
multi-scan
Absorption correction
T , T
0
.845, 1.000
min
max
No. of measured,
17583, 5776, 5246
independent and observed
[I>2σ(I)] reflections
Rint
0.025
θ - θ
min
3.21 - 27.50
max
Refinement
2
2
2
R[F > 2σ(F )], wR(F ), S
No. of reflections
No. of parameters
No. of restraints
0.032, 0.078, 1.05
5776
368
0
H-atom treatment
mixed
0.25, −0.22
-
3
Δρ , Δρ (e Ǻ )
max
min
2
.1. Synthesis
) Triethanolammonium salicylate was prepared by dropping the stoichiometric
1
amount of methanol solution of salicylic acid (7 mmol, 0.97 g.) to the methanol
solution of triethanolamine (7 mmol, 1.04 g.). The reaction mixture was stirred
during 1 h at 60-65 °C. After the completion of the reaction, methanol was
evaporated under the reduced pressure. The resulting product was yellowish

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viscous liquid. The yield of the reaction was 99 %. The crystals were grown from
the liquid phase at room temperature for a long period (over three months). The
final product was washed with diethyl ether and dried in vacuo. Elemental analysis
calculated for C H NO , %: С 54.35; H 7.37; N 4.88, found, %: С 53.32; H 7.18;
13
21
6
N 4.80. M.p. 62-64 °C.
1
+
НNMR spectrum (DMSO-d6, δ, ppm, J, Hz): 3.25 t (6H, 5.0, 5.0, HN -CH -CH -
2
2
+
+
OH), 3.77 t (6H, 5.0, 5.0, HN -CH -CH -OH), 4.5-9.4 m (5Н, HN -CH -CH -OH,
2
2
2
2
HO-С ), 6.64-6.72 m (2Н, С -Н), 7.21 t (1Н, 7.6, 7.6, С -Н), 7.71 d (1Н, 7.6,
Ar
Ar
Ar
С -Н)
Ar
1
3
+
+
СNMR spectrum (DMSO-d6, δ, ppm): 55.4 (HN -CH -CH -OH), 55.7 (HN -
2
2
CH -CH -OH), 116.0 (C -Н), 116.8 (C -Н), 119.2 (C ), 130.2 (C -Н), 132.2
2
2
Ar
Ar
Ar
Ar
-
(
C -Н), 162.1 (C ), 172.3 ( OOC- С )
Ar
Ar
Ar
2
) Silver salicylate was prepared by dropping the stoichiometric amount of ethanol
solution of silver nitrate (2 mmol, 0.34 g.) to the ethanol solution of
triethanolammonium salicylate (2 mmol, 0.57 g.) at stirring. The crystals of silver
salicylate were precipitated from solution almost immediately.
2
.3. Antifungal activity
The fungus Rhizopus oryzae F-814 was grown on glucose-peptone medium.
The solutions of triethanolammonium salt of salicylic acid with 0,01 %, 0,001 %
and 0,0001 % concentrations were introduced in the composition of the medium.
The cultivation was performed for three days at 28 °C. The amount of biomass was
determined by the gravimetric method. The amount of biomass in the control
sample was 3.7±0.1 g/L.
3
. Results and discussion
The interaction of triethanolamine (TEA) with salicylic acid leads to proton
transfer from the acid to a TEA molecule, and as result the triethanolammonium
cation and salicylate anion are formed. Structure of the resulting salt was
established, and cation-anion interactions were investigated by X-ray diffraction
analysis.

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3
.1. Structure and cation-anion interactions
The structure of triethanolammonium salicylate (figure 3) was determined
by single crystal X-ray diffraction (XRD) analysis. In contrast to
triethanolammonium 2-formylbenzoate [28] triethanolammonium cation
+
[
(OHCH CH ) NH] has endo-conformation: three oxygen atoms from
2
2 3
СH CH OH branches surround the hydrogen atom of the NH group, with the
2
2
formation of a trifurcated hydrogen bonds. The bond lengths and bond angles are
listed in table 2.
Table 2. Selected geometric parameters (Ǻ, °) for triethanolammonium
salicylate, the atom-numbering scheme are presented in the figure 3.
bond lengths (Ǻ)
N2-C15
N2-C21
N2-C35
N2-H2
C15-C28
C28-O1
C21-C30
C30-O9
C35-C29
C29-O4
C24-O6
C24-O11
C19-C24
C36-O13
bond angles ω (deg)
C35 N2 C15
1.510(2)
1.513(3)
1.510(2)
0.910(2)
1.513(2)
1.424(2)
1.508(2)
1.428(2)
1.508(2)
1.426(2)
1.264(2)
1.271(2)
1.502(3)
1.361(2)
111.45(15)
112.23(13)
111.77(14)
110.14(14)
111.01(14)
111.51(14)
107.00(14)
107.15(13)
107.66(13)
122.51(17)
120.15(15)
117.31(14)
120.62(16)
119.65(15)
C21 N2 C15
C35 N2 C21
C28 C15 N2
C30 C21 N2
C29 C35 N2
C15 C28 O1
C35 C29 O4
C21 C30 O9
O11 C24 O6
C19 C24 O6
C19 C24 O11
C19 C36 O13
C23 C36 O13

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Figure 3
Cation-anion interactions. It was found by XRD analysis that
+
-
triethanolammonium cation [(OHCH CH ) NH] are associated with COO - and
2
2 3
OH-groups of salicylate anion by intermolecular hydrogen bonds. One oxygen
atom of the anionic carboxyl group (O5) forms two intermolecular hydrogen bonds
(1.882 and 1.936 Å) with OH-groups of two cations. The second oxygen atom of
this carboxyl group (O10) forms the intramolecular bond with the proton of the OH
group of the salicylate anion (1.742 Å). The oxygen atom of this hydroxyl group of
salicylate anion acts not only as a proton donor, but also as a proton acceptor for
the weaker H-bonding (2.000 Å) with the OH-group of the triethanolammonium
cation (figure 4, table 3).

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Figure 4
The molecular packing. If we consider the structure along the a axis, we
can see that it is composed of three-layer corrugated walls lying in the ab plane and
linking together only by van der Waals bonds. Each of the walls consists of
+
duplicate columns of triethanolammonium [(OHCH CH ) NH] cations, oriented
2
2 3
along the a axis. In this connection the adjacent columns are constructed of
symmetrically unrelated cations, and the cations in adjacent columns are oriented
antiparallel, i.e. the hydrogen atoms at the nitrogen atom – N , and hence
am
hydroxyethyl CH CH OH branches turn in the opposite directions (Fig. 5 a).
2
2
Cations within the column do not directly interact with each other, but
connect with each other and with neighboring columns within the walls by
hydrogen bonds with anions of salicylic acid located on the periphery of the walls.
It should be noted that there is no anion, which would be directly connect two
cations located in the same column and arranged one under the other by hydrogen
bonds. Anions of salicylic acid, as well as cations are not connected directly with
each other, but link one cation from one column to another cation in the adjacent
column. Since no symmetry related cations have different coordinate along the a
axis, this leads to the formation of infinite walls perpendicular to the c-axis.
The walls are packed by “fish tail” type, which can be seen from a view
along the b axis (Fig. 5 b). The molecular packing and the nature of intermolecular
interactions in triethanolammonium salicylate are presented in figure 5 and table 3.

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Table 3. Hydrogen-bond lenghts for triethanolammonium salicylate (Ǻ, deg).
Atom-numbering scheme is shown in the figure 3.
D-H···A
O4-H4···O5a
O9-H9···O16b
O1-H1···O6
O13-H13···O11
O12-H12···O13c
O8-H8···O6a
O3-H3···O5
D-H
H···A
1.882(7)
2.000(8)
1.943(3)
1.729(11)
1.953(7)
1.888(8)
1.936(5)
D···A
D-H···A
174.31(1)
165.75(1)
175.51(2)
148.87(1)
171.83(5)
173.49(20)
167.10(2)
0.820(8)
0.820(6)
0.820(3)
0.819(2)
0.820(7)
0.820(9)
0.820(3)
2.699(2)
2.802(2)
2.761(2)
2.467(2)
2.767(2)
2.704(1)
2.741(2)
Symmetry code: a -1/2+x, -y, z; b -1/2+x, 1-y, z; c 1/2+x, -y, z

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Figure 5
IR spectroscopy
Triethanolammonium salicylate was investigated by IR spectroscopy. We
-
1
obtained the IR spectrum in the region of 4000-650 cm . The following
assignment of main bands is proposed.
-
1
The band at 3350 cm belongs to stretching vibrations of OH groups of
-
1
protatrane cation and the lower one at 3150 cm to NH stretching. These bands

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may be overlapped by ν(OH) of the COH group involved in the intramolecular
hydrogen bonding and CH stretchings of the phenyl ring. Methylene CH2
-
1
stretching modes of protatrane are responsible for bands in the 2930-2900 cm
spectral region. Similar frequencies have bands in triethanolammonium salts
formed by inorganic acids HHal (Hal = Cl, Br, J) [13]. Other vibrations of
-
1
triethanolammonium cation may be assigned to CH deformations (1490-1410 cm
2
-
1
-1
and 1250-1140 cm ). Bands in the 1090-917 cm region belong to CO, CN, and
CC vibrations of the TEA cage [13]. The 1640 cm and 1590 cm bands
-
1
-1
-
1
correspond to 1652 and 1582 cm bands in the IR spectrum of sodium salicylate
-
1
assigned to ν(C=O) and ν(CC) correspondingly [33]. The 1320 and 1290 cm
-
1
bands of triethanolammonium salicylate may correspond to 1317 cm (ν (C=O))
-
1
and 1299 cm (ν(CC)) bands of sodium salicylate [33]. In the same region may be
found deformation vibrations of the hydrogen bound COH group and phenyl ring
vibrations. Thus, the only vibrations which may characterize the carboxylic group
is the assymetric stretching at 1640 cm . It lies slightly lower than the
corresponding band in sodium salicylate (1652 cm ) but substantially higher than
-
1
-
1
-
1
-1
those of methyl (1682 cm ) and ethyl (1678 cm ) salicylate with asymmetric
carboxyl groups [34, 35].

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3
.2. Interaction with AgNO3
With the purpose of obtaining new silver-containing complexes, the interaction of
triethanolammonium salicylate with silver (I) salts was investigated in ethanol
media. According to [36, 37] the interaction of triethanolammonium salts of protic
acids with transition metals salts leads to the formation of water soluble complexes
with atrane structure (figure 6).
Figure 6
However, it was found experimentally that the interaction of triethanolammonium
salicylate with AgNO in the ethanol medium leads to the formation of insoluble
3
crystalline product. X-ray diffraction analysis found that the reaction product is
silver (I) salicylate of the dimeric structure (fig. 7). Similar reaction occurs with
triethanolammonium salt of benzoic acid. Thus, the exchange reaction is proceeded
at interaction of triethanolammonium salts with silver (I) nitrate, and insoluble
organic silver (I) salts are formed. Note that the direct interaction of silver (I) salts
with triethanolamine leads to the oxidation-reduction reaction in which silver ions
under the action of triethanolamine are reduced to metallic silver, and CH CH OH
2
2
groups of TEA are oxidized to aldehyde -CH CHO groups [38]. The structure of
2
silver (I) salicylate has already been established by X-ray diffraction previously
[
39], therefore the detailed description of its structure is omitted here.

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Figure 7
3
.3. The influence on growth properties of the fungus Rhizopus oryzae F-814
The fungus Rhizopus oryzae (R. oryzae) belongs to the class of Zygomycetes,
order of Mucorales, family of Mucoraceae. Different strains of R. oryzae are the
producers of lactic and fumaric acids, enzymes, amylase, glucoamylase, lipase,
protease, chitin deacetylase and biosorbents, which can find application in various
fields [40, 41]. It is known that salicylic acid is widely used in cosmetology and
medicine due to its antiseptic action. Based on the papers [14-18], it can be
expected that triethanolammonium salicylate would have a similar effect. We
investigated the effect of aqueous solutions of triethanolammonium salicylate on
the growth properties of the fungus Rhizopus oryzae F-814, the results are
presented in table 4.

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Table 4. The amount of biomass of the fungus R. oryzae, g/l in the presence of
solutions of triethanolammonium salicylate with 0.01%, 0.001% and 0.0001%
concentration
Concentration of solution of triethanolammonium
0
.0001 0.001
0.01
salicylate, %
The amount of biomass of the fungus R. oryzae, g/l 3.8±0.1 3.5±0.1 2.9±0.1
The amount of biomass in the control sample is 3.7±0.1 g/l.
From table 4 it is seen that with increasing the concentration of solution of
triethanolammonium salicylate, the amount of biomass of the fungus R. Oryzae is
reduced. Thus, solutions of triethanolammonium salicylate inhibit the growth of
this culture.
4
. Conclusion
Thus, the triethanolammonium salt of salicylic acid which belongs to the
class of protic alkanolammonium ionic liquids, was synthesized. The structure of
triethanolammonium salicylate was established by single crystal X-ray diffraction
analysis. It is shown that the cations have a protatrane structure with endo-
configuration (the presence three trifurcated hydrogen bonds). Cations are involved
in the formation of intermolecular hydrogen bonds with the oxygen of COO- and
the OH-groups of salicylate anion.
Interaction of triethanolammonium salicylate with AgNO leads to the
3
formation of a crystalline precipitate with dimeric structure С Н Аg О .
14
10
2
6
The influence of solutions of triethanolammonium salicylate on the growth
properties of the fungus Rhizopus oryzae F-814 was studied. It was found that the

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investigated ionic liquid inhibits the growth of this culture, the greatest effect is
observed when the concentration of the introduced salt is 0.01%.
Acknowledgements
Scientific researchers were performed at the «Centre for Optical and Laser
Materials Research», «Chemical Analysis and Materials Research Centre»,
«Centre for X-ray Diffraction Studies», «Magnetic Resonance Research Centre» of
Research park of St. Petersburg State University.
The work was supported by the Grant of St. Petersburg State University (№
1
2.38.218.2015).

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Figure Captions
Figure 1. Triethanolammonium salt of protic acid (X – anion of protic acid)
Figure 2. The structure of triethanolammonium 2-formylbenzoate [28]
Figure 3. The molecular species in triethanolammonium salicylate, with the atom-
numbering scheme. H atoms are not numbered
Figure 4. Cation-anion interactions in triethanolammonium salicylate
Figure 5.The molecular packing in triethanolammonium salicylate, viewed along
the a axis (a) and b axis (b). Dashed lines indicate the intermolecular hydrogen
bonding
Figure 6. The structure of metal-containing complexes with atrane structure (M =
Zn, Co, Ni, Mn, etc.; X = Hal, Y - the anion of carboxylic acid) [36, 37]
Figure 7. The structure of the silver (I) salicylate according to the XDA with the
the atom-numbering scheme. H atoms have been omitted

ACCEPTED MANUSCRIPT
Highlights

X-ray structure of triethanolammonium (TEA) salt of salicylic acid is
determined.


С Н Аg О dimer is formed by the reaction of TEA salicylate with AgNO .
Properties of fungus Rhizopusoryzae F-814 influenced by TEA salicylate are
14
10
2
6
3
studied.