Synthesis, crystal structure, vibrational spectra, and thermochemical transformations of tris(hydroxymethyl)aminomethane

Article abstract of DOI:10.1134/S0036023614010069

A practically promising compound, tris(hydroxymethyl)aminomethane sulfate ((TRISH)₂SO₄, C₈H₂₄N ₂O₁₀S) was synthesized and studied by a set of experimental methods (elemental analysis, IR and Raman spectroscopy, mass spectrometry, thermogravimetry).

Full text of DOI:10.1134/S0036023614010069

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2014, Vol. 59, No. 1, pp. 1–6. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © R.E. Khoma, V.O. Gel’mbol’dt, O.V. Shishkin, V.N. Baumer, A.A. Ennan, 2014, published in Zhurnal Neorganicheskoi Khimii, 2014, Vol. 59, No. 1,
pp. 60–65.
PHYSICAL METHODS
OF INVESTIGATION
Synthesis, Crystal Structure, Vibrational Spectra,
and Thermochemical Transformations
of Tris(hydroxymethyl)aminomethane
R. E. Khomaa, b, V. O. Gel’mbol’dtc, O. V. Shishkind, e, V. N. Baumerd, e, and A. A. Ennana
a Physicochemical Institute for Human and Environmental Protection, Education Department,
National Academy of Sciences of Ukraine, Odessa State University, Odessa, Ukraine
b Mechnikov National University, ul. Petra Velikogo 2, Odessa, 270100 Ukraine
c Odessa National Medical University
d Institute of Single Crystals, National Academy of Sciences of Ukraine, pr. Lenina 60, Kharkiv, 310141 Ukraine
e Karazin Kharkiv National University, Kharkiv, Ukraine
Received April 2, 2013
Abstract—A practically promising compound, tris(hydroxymethyl)aminomethane sulfate ((TRISH)2SO4,
C8H24N2O10S) was synthesized and studied by a set of experimental methods (elemental analysis, IR and
Raman spectroscopy, mass spectrometry, thermogravimetry).
DOI: 10.1134/S0036023614010069
Tris(hydroxymethyl)aminomethane (HOCH2)3CNH2 were revealed from difference synthesis and refined by
(TRIS) is used as a ligand in the synthesis of coordinaꢀ
tion compounds and as a buffer component in bioꢀ
chemical research [1–3]. In addition, TRISꢀbased
compounds are of interest because they can be used as
electrooptical and nonꢀlinear optical materials [4, 5].
Salts of TRIS with a number of mineral and organic acids
were synthesized and characterized, for example,
hexafluorosilicate (TRISН)2SiF6 [6, 7] however, no
data on the structure or properties of the sulfate of proꢀ
tonated TRIS were reported. This communication
discusses the conditions of synthesis, structure, specꢀ
tral characteristics, and thermal transformations of the
the “riding” model. IR spectra were measured on a
Spectrum ВХ II FTꢀIR System instrument (Perkinꢀ
Elmer) (4000–350 cm–1 range; samples as KBr pelꢀ
lets); Raman spectra were recorded on a DFSꢀ24
spectrometer (excitation by a semiconductor laser at
532 nm; interferential monochromator); EI mass
spectra were run on an MXꢀ1321 mass spectrometer
(direct sample injection; ionizing electron voltage of
70 eV). The thermogravimetric experiments were perꢀ
formed on an ODꢀ102 PaulikꢀPaulikꢀErdey derivatoꢀ
graph (the samples were heated in air from 20 to
1000°C at a rate of 10 K/min; the sample weight was
sulfate (TRISН)2SО4
.
100 mg, a platinum crucible without a lid was used as
the sample holder; and calcined alumina was used as
the reference).
EXPERIMENTAL
Synthesis of tris(hydroxymethyl)aminomethane sulꢀ
fate (I). A solution of TRIS (0.05 mol) in 10 mL of
water was placed in a cell maintained in a thermostat,
and gaseous SO2 was bubbled through the solution at
Selected crystallographic data and structure refineꢀ
ment data for
system, space group
7.6213(7)
= 1509.9(2) Å3 at
= 1.497 g/cm3
F000 = 728; a spherical crystal of
diameter 0.3 mm; (Mo ) =
= 0.266 mm–1
0.71073 ; transmission coefficient = 0.925; –10
16, 17, –9 8; ꢀscan mode at ≤ θ ≤
; 3285 measured reflections; of these 1817 indeꢀ
pendent reflections (Rint = 0.039); and 458 observed
reflections with Ihkl > 2 ; coverage 91.7%; fullꢀ
matrix refinement of 135 parameters on F2; the final
ꢀfactors for the observed reflections: RF = 0.049,
wR2 = 0.166 ( F = 0.091, wR2 =0.191 for all indepenꢀ
dent reflections); 0.990; Δρmin Δρmax
0.33/0.41 e/Å3.
І
: C8H24N2O10S, FW = 340.35; trigonal
ꢀ3, = 15.1249(12)
= 293(2) K,
P
a
Å, c =
Z = 4,
Å,
V
T
0°С
at a 50 mL/min rate to reach pH < 1.0. The soluꢀ
tion with the precipitate was kept in air at room temꢀ
perature until water was evaporated. The isolated
white crystalline product (16.65 g, yield 97.9%) was
not additionally purified.
ρ
;
μ
(λ
K
α
Å
)
Т
≤
I
h
26
≤
⎯
17
≤
k
≤
≤
l
≤
ω
3°
°
The nitrogen, carbon, and hydrogen contents were
determined using a CHN elemental analyzer and sulꢀ
fur was quantified by the Schoeniger method [8].
Xꢀray diffraction analysis was performed on an Oxford
σ(I)
R
Diffraction diffractometer (Mo
K radiation, graphꢀ
α
R
ite monochromator, Sapphireꢀ3 CCD detector).
The structures were solved and refined using the
SHELXꢀ97 program package [9]. Hydrogen atoms
S
=
/
=
⎯
1

2
KHOMA et al.
O(5)
O(3A)
O(6)
O(4)
O(4A)
O(6A)
O(3)
S(2)
O(5A)
O(10A)
N(2)
O(2A)
O(9)
O(2D)
C(6A)
C(3)
O(8)
C(4)
O(1)
O(2B)
O(2C)
O(1A)
C(1)
C(5)
O(10B)
S(1)
N(1)
O(7)
C(6)
O(2)
C(2)
C(6B)
O(2E)
O(10)
Fig. 1. Atom numbering and thermal vibration ellipsoids in structure
I (probability level 50%). Symmetrically equivalent atoms
are designated by letters A to E. The bonds in the disordered components of sulfate ions are shown by dashed lines.
b
0
a
Fig. 2. Projection xy0 of structure I (hydrogen atoms are omitted). Hydrogen bonds are shown by dashed lines.
RESULTS AND DISCUSSION
The composition of compound was established
from elemental analysis data.
ions occur in special positions on threefold axes and in
symmetry centers and, hence, they are disordered. As
a result, the number of the compound formula units,
+
І
(
(
C3H
Z
) ( 2−), is unusual for a trigonal cell
12NO3 SO4
= 4). The location of sulfate ions (heavier scatterꢀ
2
For C6H22N2O6S anal. calcd. (%): C, 28.23; N.
8.23; S, 9.24; H, 7.11.
ing units) in special positions gives rise to a pseudopeꢀ
Found (%): C, 28.91; N, 8.45; S, 9.18; N, 7.25.
riod ' = /2, while the disorder of this ions leads to
a
a
noticeable increase in the diffuse background of scatꢀ
tered Xꢀradiation; as a result, the number of observed
The atom coordinates, selected geometric characꢀ
teristics, and hydrogen bond parameters of the strucꢀ
ture are summarized in Tables 1, 2, and 3, respectively.
reflections with
I
hkl > 2 (I) is relatively small irrespecꢀ
σ
tive of the exposure time.
The mutual location of the structural units is shown
in Fig. 1. The structure of
position of the independent part of the unit cell conꢀ
+
I is peculiar as a general
The packing of structural units in the lattice is
shown in Fig. 2. It can be seen that a threeꢀdimenꢀ
sional hydrogen bond network (see also Table 3) is
formed in the crystal only between the cations; the sulꢀ
tains only one cation, namely, the C3H basis
cation (N(1), C(1)–C(4), and O(7)–O(9) atoms and
12NO3
hydrogen atoms connected to them in Fig. 1), the secꢀ fate ions are not involved in these bonds, which is in
ond cation occurs on a threefold axis, and both sulfate line with the anion disorder in the structure.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 1 2014

SYNTHESIS, CRYSTAL STRUCTURE, VIBRATIONAL SPECTRA
3
Table 1. Atom coordinates (
×
104) and equivalent thermal factors (Å2 103) in structure
I
×
Atom
x
/
a
y
/b
z
/c
Ueq
S(1)
0
0
0
10000
5000
0
0
28(1)
28(1)
52(1)
52(1)
52(1)
52(1)
52(1)
52(1)
36(1)
38(1)
38(1)
37(1)
25(1)
26(1)
27(1)
35(1)
35(1)
36(1)
29(1)
34(1)
55
S(2)
O(1)
10000
10519(2)
5522(1)
5554(2)
3932(2)
4989(1)
9960(1)
8298(1)
6742(1)
8250(1)
8332(1)
6667
–1987(4)
603(2)
595(3)
602(3)
581(3)
–2003(3)
3362(1)
3360(1)
3361(1)
6641(1)
5034(1)
4977(2)
3074(2)
2442(2)
2429(2)
2435(2)
6930(3)
7559(2)
2674
O(2)
1059(1)
1059(2)
–516(1)
–550(1)
–3(1)
3257(1)
45(1)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
1698(1)
3293(1)
1663(1)
3333
O(10)
N(1)
N(2)
C(1)
1670(1)
2318(1)
567(1)
2112(1)
3333
8336(1)
9442(1)
7882(1)
7676(1)
6667
C(2)
C(3)
C(4)
C(5)
C(6)
2882(1)
3731
7320(1)
10125
8649
H(7)
H(8)
H(9)
H(10)
H(1A)
H(1B)
H(1C)
H(2)
H(2A)
H(2B)
H(3A)
H(3B)
H(4A)
H(4B)
H(6A)
H(6B)
–77
2695
57
1338
6269
2699
57
3633
8724
7313
56
1553
8824
5422
37
2263
8439
5429
37
1169
7730
5417
37
3748
7173
4649
40
2453
9445
1197
42
1941
9798
2613
42
569
8023
1187
42
209
7147
2583
42
1969
7537
1194
43
2847
8050
2585
43
2147
6942
7400
41
3019
7459
8802
41
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 1 2014

4
KHOMA et al.
Table 2. Bond lengths and angles in structure
I
Bond
d
, Å
Bond
d
, Å
Bond
d, Å
S(1)–O(1)
S(1)–O(2)
S(2)–O(3)
S(2)–O(5)
S(2)–O(4)
S(2)–O(6)
1.514(3)
1.4611(18)
1.4598(19)
1.468(2)
1.475(2)
1.527(2)
O(7)–C(2)
O(8)–C(3)
O(9)–C(4)
O(10)–C(6)
N(1)–C(1)
1.4171(15)
1.4204(16)
1.4152(15)
1.4077(15)
1.4934(16)
N(2)–C(5)
C(1)–C(4)
C(1)–C(3)
C(1)–C(2)
C(5)–C(6)
1.488(3)
1.5312(19)
1.5336(16)
1.5340(17)
1.5316(16)
Angle
ω
, deg
Angle
ω
, deg
O(2)#1S(1)O(2)
O(2)S(1)O(1)
O(3)S(2)O(5)
O(3)S(2)O(4)
O(5)S(2)O(4)
O(3)S(2)O(6)
O(5)S(2)O(6)
O(4)S(2)O(6)
N(1)C(1)C(4)
N(1)C(1)C(3)
110.59(7)
108.33(7)
111.49(11)
110.25(11)
111.20(11)
108.25(10)
107.00(10)
108.49(11)
108.66(11)
108.36(10)
C(4)C(1)C(3)
N(1)C(1)C(2)
C(4)C(1)C(2)
C(3)C(1)C(2)
O(7)C(2)C(1)
O(8)C(3)C(1)
O(9)C(4)C(1)
N(2)C(5)C(6)
C(6)#2C(5)C(6)
O(10)C(6)C(5)
109.79(10)
108.52(10)
111.19(11)
110.25(12)
111.40(11)
111.30(11)
111.89(11)
108.25(10)
110.67(9)
111.87(11)
Symmetric codes for equivalent atoms: #1 –y + 1, x – y + 2, z; #2 –y + 1, x – y + 1, z.
Table 3. Characteristics of hydrogen bonds D–H⋅⋅⋅A in structure
I
Distance, Å
D–H⋅⋅⋅A contact
DHA angle, deg
Coordinates of atom A
D–H
H⋅⋅⋅A
D⋅⋅⋅A
O(7)–H(7)⋅⋅⋅O(6)
O(7)–H(7)⋅⋅⋅O(4)
O(7)–H(7)⋅⋅⋅O(5)
O(8)–H(8)⋅⋅⋅O(2)
O(8)–H(8)⋅⋅⋅O(2)
O(9)–H(9)⋅⋅⋅O(6)
O(9)–H(9)⋅⋅⋅O(3)
O(9)–H(9)⋅⋅⋅O(5)
O(10)–H(10)⋅⋅⋅O(6)
O(10)–H(10)⋅⋅⋅O(3)
O(10)–H(10)⋅⋅⋅O(4)
N(1)–H(1A)⋅⋅⋅O(8)
N(1)–H(1B)⋅⋅⋅O(10)
N(1)–H(1C)⋅⋅⋅O(7)
N(2)–H(2)⋅⋅⋅O(9)
0.82
0.82
0.82
0.82
0.82
0.82
0.82
0.82
0.82
0.82
0.82
0.89
0.89
0.89
0.75
2.10
2.75
1.88
1.88
2.74
2.03
1.88
2.72
2.07
2.74
1.88
1.95
1.95
1.95
2.09
2.818(2)
3.378(2)
2.659(2)
2.647(2)
3.386(2)
146.4
135.0
159.3
155.2
136.5
153.1
153.9
136.5
150.8
136.4
156.4
161.0
161.6
161.3
162.6
x
x
–
–
y
y
+ 1,
+ 1,
x
x
+ 1, –
z
z
+ 1, –
–
x
+
y
, –
– 1, –
– 1, –
x + 1, z
–
x
+
y
x
y
+ 1,
, –
z
y
x
+
z
2.7895(19)
2.646(2)
–
x
x
, –y
+ 1, –
z
3.363(2)
–
+
, –y
+ 1, –
z
2.810(2)
–
x
y
, –x
+ 1,
+ 1,
z
+ 1
+ 1
3.384(2)
–
x
+
y
, –x
z
2.651(2)
x
x
–
–
y
y
+ 1,
+ 1,
x
x
+ 1, –
z
+ 1
+ 1
2.8103(13)
2.8100(14)
2.8028(13)
2.8159(12)
+ 1, –
z
y
– 1, –
x
+
y
x
, –z
+ 1
–
x
+
y
, –
+ 1,
z
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 1 2014

SYNTHESIS, CRYSTAL STRUCTURE, VIBRATIONAL SPECTRA
5
Table 4. Wave numbers (cm–1) of the IR and Raman abꢀ
MS of [MTRIS–CH2OH]+ (
= 72, = 24%; = 60,
18%; = 42, = 43%;
The results of analysis of the vibrational spectra of
TRIS and compound are presented in Table 4.
The following vibrations are active in the vibraꢀ
m
I
/
z
= 90,
= 53%;
= 30, = 40%.
I
= 100%);
sorption peaks in the spectra of TRIS and
I
m/
z
I
m
/
z
m
/z
= 44,
I =
m/z
I
m/z
I
TRIS
IR
(TRIS
IR
H
)2SO4 (I)
Assignment*
Raman
I
3400 s.br
3370 s
3330 sh
3300 s
2−
tional spectrum of the free
ion (Td symmetry):
SO4
ν2
F2, IR, Raman), 1105 cm–1
ν
ν
(OH), νas,s(NH2),
+
ν1
(A1
,
Raman), 983 cm–1
,
(
Е
,
, Raman), 450 cm–1
ν4 F2, IR, Raman),
,
3290 sh
3230 s.br
3000 s
2705 sh
2600 sh
2365 m
(
)
NH3
ν3
(
(
3200 m.br
611 cm–1 [10].
3096 m
2771 m
2670 m.br
2−
SO4
According to Xꢀray diffraction data, the
ions
+
ν
(
)
NH3
in the crystal structure of
I are distorted corresponding to
С1 local symmetry (according to the arrangement of sulꢀ
fate ions in the structure, the symmetry should be C3i),
1632 s
1648 w
δas,s(NH2),
+
1600 s
which changes the IR and Raman selection rules for
δas,s
(
),
NH3
1552 s
2−
SO4
the salt. In the region of
asymmetric stretching
1500 sh
1400 w
δ
(CNH)
bands, the Raman spectrum of I was found to exhibit
mediumꢀintensity lines (1129, 1036 cm–1) and an
intense line (1056 cm–1), which are attributable to
1340 m
1310 m
1295 m
1260 w
1343 w
δ
(COH), τ(CH2),
+
1306 m
splitting components of the triply degenerate ν3 (F2)
1295 m
1245 w
ρ
(
), ν(CC)
NH3
vibration. In the IR spectrum, these are matched by a
new mediumꢀintensity band at 1131 cm–1 and a strong
compound band at ~1036 cm–1, which comprises
+
1215 m
1175 m
1195 sh
1150 m
1206 m
1154 w
ω
(NH2),
(CH2)
ω
(
)
NH3
ω
apparently
ν
(СО) and (СN) vibrations.
ν
1090 m
1075 m
1131 m
1065 s
1129 m
1066 m
1056 s
SO24−
accompanied by appearance of a fully symmetric ν1
A1 I.
stretching band at 990 cm–1 in the IR spectrum of
Decrease in the symmetry of the
ion is
ν
(CO),
ν
(CN),
ν3(SO4)
(
)
1040 s
1036 s
1036 m
In the Raman spectrum, this vibration gives rise to the
1020 m
ν
(CC)
978 cm–1 band.
ν1(SO4)
990 m
944 s
978 m
The three components of the ν4 asymmetric bendꢀ
960 m
965 s
925 m
914 m
ing vibration of the 2− ion occur in the IR spectrum
+
SO4
ρ
(NH2),
ρ
(
),
NH3
915 w
890 m
805 m
915 m
870 m
of I as a fairly intense doublet with peaks at 618 and
ρ(CH2),
598 cm–1 and a clearly resolved shoulder at 578 cm–1.
These bands are easily interpreted upon comparison of
785 m
787 w
686 w
676 w
618 m
598 m
578 sh
526 w
514 w
490 w
765 s
696 m
the IR spectra of I and TRIS. In the Raman spectrum,
δ
(COH),
δ
(CCC),
these vibrations are responsible for two mediumꢀ
τ
(CO)
630 m
intensity lines at 607 and 580 cm–1.
607 m
580 m
The 526–423 cm–1 range of the IR spectrum of
which typically exhibits symmetric bending
I,
ν4(SO4)
SO24−
520 w
vibrations and the outꢀofꢀplane bending vibrations of the
cation, contains four lowꢀintensity bands (Table 4),
whereas in the Raman spectrum, only two weak bands
were detected at 456 and 411 cm–1. Hence, the IR
bands at 490 and 423 cm–1 can be assigned to the
δ
(NCC),
δ
(CCO),
470 w
445 w
456 w
411 w
ν2(SO4)
423 w
* Bending vibrations:
rocking vibration.
δ
is scissor;
ω
is wagging;
τ
is torsional, ρ is
split components of v2 (Е), while the bands at 526
and 514 cm–1 can be assigned to skeletal modes of the
cation, which are not usually manifested in the Raman
spectra.
Hꢀbond system. The 3290–2365 cm–1 range displays
+
Among the natural vibrations of the cation maniꢀ
broad structured stretching bands for the
+
ions
NH3
fested in the IR spectrum of
(ОH) with a peak at ~3400 cm–1, which shifts to
higher frequency on going from the spectrum of TRIS
to the spectrum of due to redistribution of the
I, note the broad band
involved in the Hꢀbonding. The δas,s
(
) modes occur
NH3
ν
as two relatively strong bands at 1632 and 1552 cm–1. In
I
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 1 2014

6
KHOMA et al.
+
REFERENCES
the Raman spectrum, vibrations of
ν(
) are
NH3
responsible for mediumꢀintensity bands at 3096 and
1. T. Nakamura, T. Nagasawa, F. Yu, et al., Appl. Environ.
Microbiol. 60, 4630 (1994).
2. F. Danel, M. Paetzel, N. C. J. Strynadka, and
M. G. P. Page, Biochemistry 40, 9412 (2001).
3. R. Kisilevsky, W. Szarek, and D. Weaver, US Patent
5972328, 26.10.1999.
+
2771 cm–1; the
δ
(
) modes having low activity in the
NH3
Raman spectra give rise to a weak band at 1648 cm–1.
According to thermogravimetry data, thermolysis
of compound
(endotherm at 130–155
I
is accompanied by melting of the salt
without mass loss) folꢀ
°С
4. J. Li. Tamarit, M. A. PerezꢀJubindo, and M. A. de la Fuenꢀ
lowed by elimination to the gas phase of 1 mole of
H2SO4 (products of its decomposition; endotherm at
te, J. Phys.: Condens. Matter
5. M. T. AverbuchꢀPouchot, C. R. Acad. Sci. Paris 318
191 (1994).
9, 5469 (1997).
,
225–260
TRIS destruction products (endotherm at Tmax
285°C). Attention is attracted by the obvious analogy
of the thermochemical behaviors of salts and
(TRISH)2SiF6 [6]: the hexafluorosilicate melts (endoꢀ
therm at 145–161 ) and decomposes to give off
1 mole of SiF4 and 2 moles of KF (endotherm at 200–
268 ) to the gas phase. The heats observed at higher
°С,
Δmexp = 27.5%,
Δ
mcalcd = 28.8%) [11] and
=
6. V. O. Gel’mbol’dt, L. A. Gavrilova, G. P. Sokhranenko,
and A. A. Ennan, Russ. J. Inorg. Chem. 48, 1431
(2003).
I
7. B. Kosturek, Z. Czapla, and A. Waskowska, Z. Naturꢀ
forsc. A 58, 121 (2003).
8. V. A. Klimova, Basic Organic Analysis Methods
°С
°С
(Khimiya, Moscow, 1975) [in Russian].
temperature are related to boiling and decomposition
of TRIS. This fact is in line with the similarity of acid
characteristics of sulfuric and hexafluorosilicic acids
and, as a consequence, almost equal thermal stabilities
of the corresponding onium salts.
In conclusion we would like no note that ethanolaꢀ
mines, which structurally resemble TRIS, react with
sulfur(IV) oxide under similar conditions to give
hydrogen sulfite (or sulfite) onium salts [12, 13]. Eviꢀ
dently, elucidation of the relationship between the
structure of the organic base L and the composition of
the onium product formed in the SO2–L–H2O system
and contacting with air oxygen (sulfite, hydrogen
sulfite or sulfate form) requires further research using
a broad range of bases of various structural classes.
9. G. M. Sheldrick, Acta Crystallogr. Sect. A 64, 112
(2008).
10. K. Nakamoto, K. Infrared and Raman Spectra of Inorꢀ
ganic and Coordination Compounds (Interscience, New
York, 1986; Mir, Moscow, 1991).
11. Handbook of Acid Productionh Engineer, Ed. by
K. M. Mamin (Khimiya, Moscow, 1971), p. 85 [in
Russian].
12. R. E. Khoma, V. O. Gel’mbol’dt, L. V. Koroeva, et al.,
Vopr. Khim. Khim. Tekhnol., No. 1, 133 (2012).
13. R. E. Khoma, A. A. Ennan, A. V. Mazepa, and
V. O. Gel’mbol’dt, Vopr. Khim. Khim. Tekhnol.,
No. 1, 136 (2013).
Translated by Z. Svitanko
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 1 2014