ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2015, Vol. 60, No. 10, pp. 1199–1203. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © R.E. Khoma, V.O. Gel’mbol’dt, V.N. Baumer, A.N. Puzan, A.A. Ennan, 2015, published in Zhurnal Neorganicheskoi Khimii, 2015, Vol. 60, No. 10,
pp. 1315–1319.
COORDINATION
COMPOUNDS
Methylammonium Sulfate: Synthesis and Structure
R. E. Khomaa, b, V. O. Gel’mbol’dtc, V. N. Baumerd, e, A. N. Puzand, and A. A. Ennana
a Physicochemical Institute for Human and Environment Protection, Ministry of Education and Science of Ukraine, National
Academy of Sciences of Ukraine, ul. Preobrazhenskaya 3, Odessa, 65026 Ukraine
b Mechnikov National University, ul. Dvoryanskaya 2, Odessa, 65025 Ukraine
c Odessa National Medical University, per. Valikhovskogo 2, Odessa, 65026 Ukraine
d Institute for Single Crystals, National Academy of Sciences of Ukraine, pr. Lenina 60, Kharkiv, 61178 Ukraine
e Kharkiv National University, pl. Svobody 4, Kharkiv, 61077 Ukraine
eꢀmail: rek@onu.edu.ua
Received March 5, 2015
Abstract—The reaction between sulfur(IV) oxide and aqueous methylamine yields “onium” sulfate
(CH3NH3)2SO4, which was characterized by Xꢀray diffraction, IR spectroscopy, and mass spectrometry. The
structure of the sulfate is stabilized by a network of NH⋅⋅⋅O hydrogen bonds.
DOI: 10.1134/S0036023615100101
Methylamine (MA) is a reagent used in the syntheꢀ tra were recorded on a Perkin Elmer Spectrum BX II
FTꢀIR System spectrometer (range: 4000–650 cm–1;
samples in a BaF2 liquid cell); electronꢀimpact (EI)
mass spectra were taken on an MXꢀ1321 mass specꢀ
trometer (direct injection of a sample into the source;
energy of ionizing electrons, 70 eV).
sis of medicines, insecticides, fungicide, dyes, and
rocket fuels [1]. The methylammonium cation forms
salts with anions of various organic acids. Structurally
characterized methylammonium compounds are
chloride [2], dicitratoborate [3], bromide [4], trimoꢀ
lybdate hydrate [5], nitrate [6], perchlorate [7], and
hexafluorosilicate [8]. Methylammonium sulfate is a
commercial product (CAS 33689ꢀ83ꢀ7), though its
crystal structure has not been yet studied. Vilminot
et al. [9] only give crystallographic parameters for this
Xꢀray diffraction analysis was performed on an
Oxford Diffraction Xcalibur 3 diffractometer (MoK ,
α
graphite monochromator, Sapphireꢀ3 CCD detector).
The structure was solved and refined using the
SHELXꢀ97 software suite [11]. Hydrogen atoms were
found from a difference Fourier synthesis and refined
in the isotropic approximation with overall thermal
correction.
compound assigned to space group P21/c.
Here we describe the results of structural and specꢀ
troscopicl characterization of methylammonium sulꢀ
fate (CH3NH3)2SO4 isolated as a product of the reacꢀ
tion between sulfur(IV) oxide and aqueous MA in the
presence of air oxygen.
Selected crystallographic data and refinement
details for the structure of compound I are the followꢀ
ing: C2H12N2O4S, monoclinic, Mr = 160.20, space
group
13.5906(8)
P
21/
Å
c
,
,
a
β
Z
= 13.1442(7)
= 113.154(7)
= 8,
= 1.466 g/cm3
0.2 mm in size,
) = 0.71073 , transmittance coefficients
Å
°, V
,
b
= 8.8370(5)
= 1451.46(14) Å3 at
F000 = 688, crysꢀ
= 0.403 mm–1
Å, c =
EXPERIMENTAL
Synthesis of methylammonium sulfate (I). A temꢀ
peratureꢀcontrolled cell was poured with 40% aqueous
MA (20 mL), through which gaseous SO2 was passed
T
= 293(2) K,
ρ
,
μ
tal of 0.40
×
0.30
×
(
Тmin
λ
(Mo
K
Å)
α
at
The resulting yellow oilꢀlike product was allowed to
stand at < 15 in air until water evaporated. Sepaꢀ
rated colorless crystalline product (15.43 g; yield,
83.4%) is converted into an ionic liquid at temperature
above 20
0°С at a flow rate of 50 mL/min to adjust pH < 1.0.
/Т
max = 0.2953/0.9237;
≤
⎯
12
≤
h
≤
17, 11
≤
k ≤ 11,
–17
≤
l
17,
ω
ꢀscans at 2.94
°
≤ θ ≤ 27.50°, 6392 meaꢀ
T
°С
sured reflections, of which 3283 reflections are indeꢀ
pendent (Rint = 0.0248) and 2380 are observed with Ihkl
I
> 2
237 parameters on F 2: the final convergence values for
the observed reflections
F = 0.0394, wR2 = 0.1035
F = 0.582, wR2 = 0.1165 for all independent reflecꢀ
= 0.941, Δρmin Δρmax
–0.251/0.362 e/Å3.
σ(I); coverage, 98.6%; fullꢀmatrix refinement of
°С.
R
The nitrogen, carbon, and hydrogen were deterꢀ
mined on an elemental CHNꢀanalyzer, and the sulfur
(R
was estimated by the Schöniger method [10]. IR specꢀ tions),
S
/
=
1199