Products of interaction between Sulfur(IV) oxide and aqueous solutions of hexamethylendiamine and tert-Butylamine: The crystal structure of hexamethylenediammonium sulfate dihydrate

Article abstract of DOI:10.1134/S003602361212008X

The possibility of mild SO₂ oxidation in sulfur(IV) oxide-alkylamine-water-oxygen systems is demonstrated to yield onium sulfates.

Full text of DOI:10.1134/S003602361212008X

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2012, Vol. 57, No. 12, pp. 1559–1562. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © R.E. Khoma, A.A. Ennan, O.V. Shishkin, V.N. Baumer, V.O. Gel’mbol’dt, 2012, published in Zhurnal Neorganicheskoi Khimii, 2012, Vol. 57, No. 12,
pp. 1658–1661.
COORDINATION COMPOUNDS
Products of Interaction between Sulfur(IV) Oxide and Aqueous
Solutions of Hexamethylendiamine and tertꢀButylamine:
The Crystal Structure of Hexamethylenediammonium
Sulfate Dihydrate
R. E. Khomaa, b, A. A. Ennana, O. V. Shishkinc, V. N. Baumerc, and V. O. Gel’mbol’dta, d
a Physicochemical Institute of Environmental and Human Protection, Ministry of Education and Science of Ukraine,
National Academy of Sciences of Ukraine, Odessa, Ukraine
eꢀmail: rek@onu.edu.ua, r_khoma@farlep.net
b Mechnikov Odessa National University, Odessa, Ukraine
c Institute of Single Crystals, Kharkov, Ukraine
d Odessa National Medical University, Odessa, Ukraine
Received July 22, 2011
Abstract—The possibility of mild SO2 oxidation in sulfur(IV) oxide–alkylamine–water–oxygen systems is
demonstrated to yield onium sulfates.
DOI: 10.1134/S003602361212008X
The reaction between sulfur(IV) oxide and aliꢀ
phatic monoꢀ and diamines (L) in a gas phase and in
aprotic solvents was shown to yield complexes of comꢀ
EXPERIMENTAL
Synthesis of Hexamethyleneammonium Sulfate
Dihydrate (I)
position
n
SО2 L (n = 1, 2), whereas the same reaction
⋅
in water yields onium sulfates (LH)2SO3 and
(LH2)SO3 [1–3]. We found that bubbling sulfur(IV)
oxide into aqueous solutions of hexamethylenediꢀ
amine (HMDA) and tertꢀbutylamine (tertꢀBA), folꢀ
lowed by exposure of the products in air, yields onium
sulfates. Synthesis conditions and Xꢀray diffraction
A temperatureꢀcontrolled cell was filled with
HMDA solution (0.043 mol) in 10 mL of water; gasꢀ
eous SO2 was bubbled into the solution at
0°С for ~1 h
at a rate of 50 mL/min. The precipitateꢀcontaining
solution was kept in air at room temperature until
water was evaporated. The isolated white product (I)
data for compounds (MDAH2)SO4 · 2H2O (
tertꢀBAH)2SO4 (II) are reported here.
I) and
(10.35 g, yield 96.1% based on HMDA) was purified
by recrystallization from water.
(
O(13)
O(11)
O(3)
C(6)
S(1)
C(4)
C(3)
C(12)
C(10)
N(4)
C(2)
O(4)
O(2)
O(1)
N(2)
N(1)
C(5)
O(9)
C(1)
C(9)
C(8)
C(11)
O(5)
O(10)
N(3)
O(8)
O(6)
S(2)
C(7)
O(7)
O(12)
Crystal structure of compound
I
and thermal vibration ellipsoids (a 60% probability level).
1559

1560
KHOMA et al.
Table 1. Atomic coordinates (
104) for nonꢀhydrogen atoms
×
×
For C6H22N2O6S anal. calcd. (%): C, 28.79; N,
11.19; S, 12.81; H, 8.86.
and equivalent thermal corrections (Å2 103) in structure
I
Found (%): C, 28.91; N, 11.33; S, 12.92; H, 8.95.
Atom
S(1)
x
y
z
Ueq
Xꢀray diffraction analysis. For crystals of
C6H22.20N2O6.10 , monoclinic, FW = 252.12, space
group 2/ = 26.286(3) = 11.3980(8)
19.2641(19) = 117.177(13)
= 5134.5(8) Å3 at
= 105 K, = 16, F000 = 2192, crystal
= 1.305 g/cm3
0.3 0.1 mm, (Mo ) =
= 0.266 mm–1
, transmission coefficients Тmin
36, –10 15, –27
scans at 3.16 ≤ θ ≤ 30.0 , 14100 reflections measured,
І:
S
2290(1)
2893(1)
1572(1)
1507(1)
1917(1)
419(1)
2585(1)
2775(1)
3288(1)
2281(1)
1977(1)
289(1)
24(1)
35(1)
31(1)
36(1)
31(1)
27(1)
49(1)
42(1)
47(1)
60(1)
33(1)
65(1)
162(3)
50(1)
45(1)
27(1)
27(1)
26(1)
28(1)
28(1)
26(1)
27(1)
27(1)
26(1)
27(1)
28(1)
29(1)
29(1)
30(1)
28(1)
31(1)
С
c,
a
Å,
b
Å, c =
O(1)
O(2)
O(3)
O(4)
S(2)
O(5)
O(6)
O(7)
O(8)
O(9)
Å,
β
°, V
T
Z
ρ
,
2234(1)
size 0.4
×
×
μ
(λ
K
α
0.71073
Å)
/Тmax
=
2014(1)
0.901/0.974; –22
≤
h
≤
≤
k
≤
≤
l
≤
23,
ω
2018(1)
2502(1)
5536(1)
4326(1)
5735(1)
6396(1)
5536(1)
°
of which 7389 are independent reflections (Rint
0.023) and 5624 are observed reflections with Ihkl
=
>
–2406(1)
–2366(1)
–3010(1)
–2219(1)
–2088(1)
–3477(1)
2 (I); coverage degree of 98.8; fullꢀmatrix refinement
σ
615(1)
of 247 parameters with respect to F2 where the final
values for the observed reflections are RF = 0.0476,
–271(1)
887(1)
wR = 0.1398 (
pendent reflections),
0.699/0.658 e/Å3. Atomic coordinates, selected geoꢀ
metric parameters, and parameters for hydrogen
R
F = 0.0658, wR2 = 0.1587 for all indeꢀ
S
= 0.936, Δρmin/Δρmax=
⎯
–178(1)
3661(1) –1064(1)
4251(1) –1713(1)
3597(2) –3447(1)
bonding (HB) in the structure of
1, 2, and 3, respectively.
I are shown in Tables
O(10) –4638(1)
O(11) –4361(1)
The Xꢀray diffraction experiment was carried out
on an Oxford Diffraction diffractometer (Mo radiꢀ
K
α
ation, graphite monochromator, Sapphireꢀ3CDD
detector). Structures were solved and refined using the
SHELXꢀ97 program package [4]. Hydrogen atoms
were determined from difference synthesis and refined
using the rider model in methylene groups and in the
isotropic approximation in ammonium groups and
water molecules.
O(12)
O(13)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
5348(1)
1502(1)
6562(1)
3042(1)
1807(1)
–1800(1)
5941(1)
5604(1)
4971(1)
4610(1)
3992(1)
3647(1)
1209(1)
801(1)
5559(1)
–416(1)
2520(1)
3531(1)
4443(1)
3028(1)
2432(1)
2560(1)
2557(1)
2836(1)
3040(1)
3308(1)
4398(1)
4266(1)
4145(1)
3884(1)
3695(1)
3341(1)
4722(1)
750(1)
5357(1)
1822(1)
2764(1)
–233(1)
5090(1)
4211(1)
3966(1)
3102(1)
2894(1)
2031(1)
2621(1)
1757(1)
1611(1)
759(1)
Synthesis of tertꢀButylammonium Sulfate (II
)
A white crystallineproduct (II) was prepared
using the same sequence of operations for aqueous
solution with tertꢀBA (0.068 mol of amine in 35 mL
of Н2О) (isolated 8.32 g, yield 99.7% based on
tertꢀBA).
For C8H24N2O4S anal. calcd. (%): C, 39.32; N,
11.46; S, 13.12; H, 9.90.
Found (%): C, 40.21; N, 11.52; S, 12.93; H, 9.72.
Nitrogen, carbon, and hydrogen were determined
using a CHN elemental analyzer; sulfur was deterꢀ
mined using the Scheniger procedure [5, 6].
RESULTS AND DISCUSSION
189(1)
The figure shows the structure of the symmetrically
independent part of a unit cell of crystal I.
–226(1)
–828(1)
Hexamethylenediammonium cations have chainꢀ
like structure. Cationic chains in the structure are
stretched along the [101] direction. Sulfate ions and
647(1)
C(12) –1238(1)
–183(1)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 12 2012

PRODUCTS OF INTERACTION
Table 2. Bond lengths and bond angles in the structure of
1561
I
Bond
d
, Å
Bond
d
, Å
Bond
d, Å
S(1)–O(1)
S(1)–O(2)
S(1)–O(3)
S(1)–O(4)
S(2)–O(7)
S(2)–O(6)
S(2)–O(8)
S(2)–O(5)
1.4562(9)
1.4828(9)
1.4866(8)
1.4964(7)
1.4186(10)
1.4737(9)
1.4838(11)
1.4989(9)
N(1)–C(1)
N(2)–C(6)
N(3)–C(7)
N(4)–C(12)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
1.4738(13)
1.4747(14)
1.4690(14)
1.4796(15)
1.5173(13)
1.5101(14)
1.5262(13)
C(4)–C(5)
C(5)–C(6)
C(7)–C(8)
C(8)–C(9)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
1.5050(14)
1.5156(13)
1.5199(14)
1.5084(15)
1.5285(14)
1.5112(16)
1.5190(14)
Angle
ω
, deg
Angle
ω
, deg
O(1)S(1)O(2)
O(1)S(1)O(3)
O(2)S(1)O(3)
O(1)S(1)O(4)
O(2)S(1)O(4)
O(3)S(1)O(4)
O(7)S(2)O(6)
O(7)S(2)O(8)
O(6)S(2)O(8)
O(7)S(2)O(5)
O(6)S(2)O(5)
O(8)S(2)O(5)
109.64(5)
109.56(5)
110.96(5)
108.08(5)
108.34(5)
110.20(4)
110.25(6)
114.25(6)
105.87(6)
111.37(6)
107.10(6)
107.61(6)
N(1)C(1)C(2)
C(3)C(2)C(1)
C(2)C(3)C(4)
C(5)C(4)C(3)
C(4)C(5)C(6)
N(2)C(6)C(5)
N(3)C(7)C(8)
C(9)C(8)C(7)
C(8)C(9)C(10)
C(11)C(10)C(9)
C(10)C(11)C(12)
N(4)C(12)C(11)
111.84(9)
110.31(9)
112.74(9)
112.29(9)
110.78(9)
111.38(9)
111.63(9)
111.85(10)
113.19(10)
111.53(10)
112.49(10)
109.93(10)
water molecules bound to them via hydrogen bonds
are located near the plane = 0.25 in the cell unit.
According to the Xꢀray diffraction data, compound II
is tertꢀbutylammonium sulfate, which was structurally
characterized [6].
x
Cationic chains form a branched network of hydroꢀ
gen bonds predominantly with sulfate ions (Table 3).
Water molecules that are not bound to cations and
anions via the hydrogen bonds reside within voids
between the cationic chains (O(10), O(11), O(12)
atoms); the O(11) positions of water molecules are
only 20% filled.
Thus, the reactions in the systems under study can
be described by the following scheme:
2SO2 + 4RNH2 + 2H2O + O2
→
2(RNH3)2SO4,
where the redox conversion is apparently due to expoꢀ
sure of the reaction products to an unprotected atmoꢀ
sphere.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 12 2012

1562
KHOMA et al.
Table 3. Characteristics of D–H⋅⋅⋅A hydrogen bonds in structure
I
Distance, Å
DHA angle,
deg
D–H⋅⋅⋅A contact
Coordinates of atom A
D–H
H
⋅⋅⋅
A
D⋅⋅⋅A
O(9)–H(9C)⋅⋅⋅O(6)
O(9)–H(9D)⋅⋅⋅O(2)
O(10)–H(10D)⋅⋅⋅O(10)
O(10)–H(10C)⋅⋅⋅O(9)
O(11)–H(11C)⋅⋅⋅O(12)
O(11)–H(11D)⋅⋅⋅O(10)
O(12)–H(12C)⋅⋅⋅O(13)
O(12)–H(12D)⋅⋅⋅O(12)
O(13)–H(13A)⋅⋅⋅O(3)
O(13)–H(13B)⋅⋅⋅O(6)
O(13)–H(13B)⋅⋅⋅O(5)
N(1)–H(1C)⋅⋅⋅O(8)
N(1)–H(1D)⋅⋅⋅O(4)
N(1)–H(1E)⋅⋅⋅O(6)
N(1)–H(1E)⋅⋅⋅O(7)
N(2)–H(2C)⋅⋅⋅O(3)
N(2)–H(2D)⋅⋅⋅O(1)
N(2)–H(2D)⋅⋅⋅O(4)
N(2)–H(2E)⋅⋅⋅O(6)
N(2)–H(2E)⋅⋅⋅O(8)
N(3)–H(3C)⋅⋅⋅O(4)
N(3)–H(3C)⋅⋅⋅O(2)
N(3)–H(3D)⋅⋅⋅O(5)
N(3)–H(3E)⋅⋅⋅O(1)
N(4)–H(4C)⋅⋅⋅O(2)
N(4)–H(4D)⋅⋅⋅O(8)
N(4)–H(4D)⋅⋅⋅O(5)
N(4)–H(4E)⋅⋅⋅O(9)
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.92
0.96
0.96
0.90
0.89
0.89
0.92
0.92
0.92
0.92
0.87
0.88
0.95
0.95
0.95
0.93
1.92
1.90
1.92
1.95
2.30
2.03
1.94
1.95
1.94
2.32
2.34
1.90
1.89
1.87
2.62
1.91
2.25
2.43
2.32
2.34
1.96
2.55
1.93
1.95
1.95
2.15
2.19
2.06
2.7778(10)
2.7579(11)
2.7453(11)
2.8018(8)
176
176
160
171
118
174
161
175
168
149
150
171
165
172
114
175
157
129
138
155
177
118
168
173
150
143
150
167
x, y, z
x
x
– 1/2, –
y
+ 1/2,
z
– 1/2
–
x
– 1,
y
, –z
– 1/2
x
,
y,
z
2.8066(12)
2.8847(12)
2.7693(8)
–
x
, –
y
y
+ 1, –
, – – 1/2
z
–
x
– 1,
z
+ 1/2, –
y
+ 1/2,
z
+ 1/2
+ 1
2.8103(15)
2.7910(10)
3.0891(13)
3.1166(15)
2.7510(14)
2.7867(12)
2.8148(14)
3.1366(14)
2.8055(13)
3.0816(13)
3.0732(13)
3.0667(14)
3.1927(14)
2.8746(12)
3.0878(12)
2.7830(13)
2.8237(13)
2.8212(12)
2.9706(14)
3.0473(16)
2.9699(11)
–
x
+ 1, –
y
+ 1, –
z
x
,
y
y
y
,
z
x
+ 1/2,
+ 1/2,
– 1/2,
z
x
– 1/2, z
+ 1/2
+ 1/2
–x
+ 1/2,
y – 1/2, –z
x
+ 1/2, –
y
y
y
+ 1/2,
z
x
x
+ 1, –
+ 1, –
+ 1,
+ 1,
z
z
+ 1/2
+ 1/2
–
x
+ 1/2,
y
+ 1/2, –
z
+ 1/2
x
,
,
y
,
,
z
z
x
y
–
–
x
x
, –
y
y
+ 1, –
+ 1, –
z
z
, –
x
x
,
,
y
,
,
z
z
y
–
x
,
y
, –z
+ 1/2
–
x
+ 1/2,
y
+ 1/2, – + 1/2
+ 1/2, z – 1/2
z
x
– 1/2, –
y
x
x
,
,
y
,
,
z
z
y
–
x
– 1/2, –
y
+ 1/2, –
z
2. G. P. Sokhranenko, L. P. Berezina, V. A. Karpinꢀ
chik, and V. I. Nikitin, Zh. Neorg. Khim. 37, 2265
(1992).
3. S. V. Kurando, Candidate Dissertation in Chemistry
(Odessa, 1995).
Summarizing, let us note that the results described
above are the first structurally confirmed example of
mild oxidation of SO2 into onium sulfates in the sulꢀ
fur(IV) oxide–hexamethylenediamine
amine)–water–O2 systems.
(tertꢀbutylꢀ
4. G. M. Sheldrick, Acta Crystallogr., Sect A 64 (1), 112
(2008).
5. V. A. Klimova, The Basic Methods of Organic Analysis
REFERENCES
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(1984).
6. T. Guerfel, M. Briri, A. Jouini, J. Chem. Cryst. 30 (12),
799 (2000).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 12 2012