ONIUM SALTS OF SULFUR-CONTAINING OXYANIONS RESULTING
tion of PP octahydrate (0.05 mol of the amine in RESULTS AND DISCUSSION
737
10 mL of H O) resulted in 10.66 g of a white mixture
2
The mass spectrum of compound I displays frag-
of crystalline products IIIa, IIIb, and IIIc.
mentation typical for 1-n-alkylamines [11] resulting in
+
+
+
formation of [CH
2
=NH
2
] ion with peak of the maximal
MS: [M ] (m/z = 86, I = 34%); [M –H] (m/z =
L
L
intensity. Piperazine fragmentation products in the mass
spectrum of mixture of its onium salts IIIa, IIIb, and IIIc
agree well with the tabulated mass spectrum of PP [11].
Similar agreement is observed for MP.
+
8
5, I = 28%); m/z = 80, I = 28%; [SO ] (m/z = 64,
I = 24%); [CH CH NH=CH ] (m/z = 57, I = 30%);
2
+
2
2
2
+
+
[
(
1
CH =CHNH=CH ] (m/z = 56, I = 31%); [SO]
2 2
+
m/z = 48, I = 17%); [CH =NHCH ] (m/z = 44, I =
According to X-ray diffraction study, compound I
is ethylenediammonium sulfate structurally charac-
terized previously [2]. TMEDA produces a mixture of
2
3
+
00%); [CH =NH ] (m/z = 30, I = 31%).
2 2
Anal. calcd. (%): C, 24.90; H, 7.24; N, 14.51; S, onium sulfate IIa and dithionate dihydrate IIb. Struc-
1
7.75. Found (%): C, 24.98; H, 7.38; N, 14.43; S, ture IIa was also described in the literature [12] and is
1
7.67.
not discussed below. In structure IIb (Fig. 1), cation
and anion occupy the centers of symmetry while water
molecule is in a general position. Bond distances and
valence angles have common values for similar com-
pounds. Packing in crystal causes formation of 2D sys-
tem of hydrogen bonds (Table 2) producing layers in
Morpholinium sulfate monohydrate (IV). Similar
procedure for an aqueous solution of MP (0.10 mol of
the amine in 10 mL of H O) resulted in 12.62 g of
2
white crystalline product IV (yield 87.0% toward MP,
mp 20–22°C).
(
001) planes. Rietveld refinement for powder diffrac-
tion patterns of reaction product showed almost equal
content of compounds IIa and IIb in powder (IIa : IIb =
46 : 54).
+
+
MS: [M ] (m/z = 87, I = 66%); [M –H] (m/z =
L
L
+
8
6, I = 27%); [SO ] (m/z = 64, I = 27%); [M –
СH О] (m/z = 57, I = 100%); [M –СH О–H]
2
L
+
+
2
L
2
The reaction of SO with aqueous solution of PP
2
+
(
[
m/z = 56, I = 35%); [SO] (m/z = 48, I = 32%);
leads to formation of three compounds: sulfite mono-
hydrate IIIa, dithionate IIIb, and sulfate monohydrate
IIIc. The structure of compound IIIa (Fig 2) includes
both cations in the centers of symmetry. Bond dis-
tances and valence angles are common. The com-
pound forms a 3D system of hydrogen bonds in crystal
+
CH =NH ] (m/z = 30, I = 41%).
2
2
For C H N O S anal. calcd. (%): C, 33.10; H,
8
22
2
7
7
2
.64; N, 9.65; S, 38.57; M 290.34. Found (%): C,
9.76; H, 7.51; N, 9.53; S, 39.03.
(
Table 2). Both basis molecules in structure IIIb (Fig. 3)
Analysis for carbon, hydrogen, and nitrogen con-
are in general position. Dithionate ions in crystal are
located in (100) coordinate planes, cation layers are
located between them. A branched 3D system of
hydrogen bonds is formed in the structure (Table 2).
Structure IIIc includes two cations located in the cen-
ters of symmetry (Fig. 4). Crystal contains cation lay-
ers in (001) planes, while anions and water molecules
are located in cavities between the layers. The system
of hydrogen bonds in structure IIIc is three-dimen-
sional. To determine compound ratio in reaction
product, we calculated powder diffractogram of the
latter by the Rietveld method using found by us struc-
ture models IIIa, IIIb, and IIIc (Fig. 5). The found
composition is as follows (wt %): IIIa, 74.8; IIIb, 8.8;
IIIc, 16.4. Figure 5 shows that the reaction product
contains no other substances.
tent was carried out on a CHN analyzer, sulfur was
determined by the Schoniger technique [9]. X-ray dif-
fraction study of compounds II–IV was performed on
an Oxford Diffraction Xcalibur-3 diffractometer
(
MoK radiation, graphite monochromator, Sap-
α
phire-3 CCD detector). The structure was solved and
refined using SHELX-97 software package [10].
Hydrogen atoms were located from a difference-Fou-
rier map and refined using the Riding model for
methyl and methylene groups. Hydrogen atoms
involved in hydrogen bonding (HB) were refined in
isotropic approximation. X-ray powder diffraction
(
XRD) was accomplished on a Siemens D500 powder
diffractometer (Bragg–Bretano geometry, CuK radi-
α
ation, Ni filter). IR spectra were recorded on a Perkin-
Elmer Spectrum BX II FT-IR System spectropho-
The reaction of SO with aqueous solution of MP
–
1
2
tometer in 4000–350 cm region as KBr pellets, mass
spectra were obtained on a MX-1321 instrument
leads to only one compound, morpholinium (IV) sul-
fate monohydrate, whose structure is shown in Fig. 6.
Like in compound IIIc, the structure IV includes
anions and water molecules between cation layers pro-
ducing a 3D system of hydrogen bonds.
(
direct inlet into source, ionizing voltage 70 eV).
The main crystallographic data and refinement
results for structures IIa–IV are presented in Table 1.
Atom coordinates, structural factors and all refine-
The data of IR spectroscopy (Table 3) indicate that
ment results were deposited in the Cambridge Crystal- reaction product of PP contains sulfite ion, whereas
lographic Data Center (Table 1). Geometrical charac- other obtained products contain sulfate ions. The IR
teristics of hydrogen bonds observed in structures IIb– spectra of products obtained from TMEDA and PP
IV are given in Table 2.
exhibit also absorption bands of dithionate anions.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 62 No. 6 2017