Molecular and crystal structure of 1-amino-X-pyrazinium mesitylenesulfonates

Article abstract of DOI:10.1134/s1070428008020188

X-Ray diffraction analysis was performed of 1-amino-X-pyrazinium mesitylenesulfonates (X=H, 2-NH₂, 3-NHCOMe, 3-OMe, 3-Cl). In all events save 1,2-diaminopyrazinium cation the bond length of N-NH₂ was shorter than that of N-N bond but considerably longer than the length of the double bond N=N. In the 1,2-diaminopyrazinium cation the bond distance C ²-NH₂ was close to the length of a common double bond C=N indicating the iminium character of the cation. Quantum-chemical calculations [AM1, PM3, DFT/(PBE/3z), B3LYP/6-31G++(2d,p)] provided the geometry of cations similar to the experimental one. In the crystals under investigation motifs were observed of 0D, 1D, and 2D type mainly due to hydrogen bonds N-H???O and π-stacking interactions of the aromatic rings.

Full text of DOI:10.1134/s1070428008020188

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 2, pp. 292−301. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © R.V. Andreev, G.I. Borodkin, A.Yu. Vorob’ev, Yu.V. Gatilov, V.G. Shubin, 2008, published in Zhurnal Organicheskoi Khimii,
2008, Vol. 44, No. 2, pp. 296−304.
Molecular and Crystal Structure of 1-Amino-X-pyrazinium
Mesitylenesulfonates*
R. V. Andreeva, G. I. Borodkina,b, A. Yu. Vorob’eva,b,
Yu. V. Gatilova, and V. G. Shubina
aVorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, 630090 Russia; e-mail: gibor@nioch.nsc.ru
bNovosibirsk State University, Novosibirsk, Russia
Received June 5, 2007
Abstract—X-Ray diffraction analysis was performed of 1-amino-X-pyrazinium mesitylenesulfonates (X = H,
2-NH2, 3-NHCOMe, 3-OMe, 3-Cl). In all events save 1,2-diaminopyrazinium cation the bond length of N–NH2
was shorter than that of N–N. bond but considerably longer than the length of the double bond N=N. In the 1,2-
diaminopyrazinium cation the bond distance C2–NH2 was close to the length of a common double bond C=N
indicating the iminium character of the cation. Quantum-chemical calculations [AM1, PM3, DFT/(PBE/3z),
B3LYP/6-31G++(2d,p)] provided the geometry of cations similar to the experimental one. In the crystals under
...
investigation motifs were observed of 0D, 1D, and 2D type mainly due to hydrogen bonds N–H O and
π-stacking interactions of the aromatic rings.
DOI: 10.1134/S1070428008020188
N-Amine salts of azines are widely used as reagents
for arenes amination [2], preparation of imines [3],
versatile heterocyclic and biologically active compounds
[3–10]. Up till now the X-ray stadies of N-amine salts of
heteroaromatic compounds were limited to derivatives
of pyridine [11–14], isoquinoline [15], 1,10-phenanthro-
line [16], and azoles [17–20], but were lacking for
diazines.
N
N
X
Ià_Ie
X
N
N
N
MesSO3_
MesSO3_
MesSO3NH2
CH2Cl2
+
+
N+
X
The target of the present study was the investigation
by X-ray diffraction analysis of the molecular structure
of 1-amino-X-pyrazinium mesitylenesulfonates, the
estimation of effect of substituents in the pyrazinium
ring on the cation geometry, and also revealing the role
of hydrogen bonds and stacking interactions in the
formation of the crystalline structure of the salts.
NH2
IIIc, IIId, IIIe
NH2
IIà, IIb
X = H (a), NH2 (b), NHAc (c), MeO (d), Cl (e).
At X = H, Cl the cell contains two crystallographically
independent types of ions with slightly different
geometric parameters (Tables 1–6). The crystals of
mesitylenesulfonate IIa contain additionally water
molecules.
The amination of X-pyrazines Ia–Ie with O-mesityl-
sulfonylhydroxylamine occurred virtually regioselec-
tively with the formation of 1-amino-X-pyrazinium
mesitylenesulfonates IIa, IIb, IIIc–IIIe [1, 4], that made
it possible to obtain crystals of individual isomers fit for
X-ray diffraction study.
As seen from Tables 2–6 and Fig. 1 the skeleton of
cations of salts IIa, IIb, IIIc–IIIe is virtually planar and
atoms C and N according to the bond angles have the
hybridization close to sp2. The nitrogen of the amino
group insignificantly deviates from the plane of the
* For preliminary communication see [1].
292

MOLECULAR AND CRYSTAL STRUCTURE OF MESITYLENESULFONATES
293
Table 1. Data of X-ray diffraction analysis of 1-amino-X-pyrazinium mesitylenesulfonates IIa, IIb, IIIc–IIIe, parameters of
experiment and refinement
Table 2. Some bond lengths (Å), bond and dihedral angles (deg) of cation of salt IIa obtained by X-ray diffraction analysis and
quantum-chemical calculations
DFT
Parameter
X-ray study
1.380(3)
AΜ1
1.370
PΜ3
PBE/3z
1.382
1.360
1.360
1.391
1.339
1.339
1.360
119.9
119.9
118.5
123.2
119.9
116.6
123.2
118.5
112.0
111.6
111.6
0.0
B3LYP/ 6-31G++(2d,p)
1.382
N1–N7
1.376(3)
1.345(4)
1.338(4)
1.360(4)
1.326(5)
1.328(5)
1.372(5)
120.3(3)
119.8(3)
118.7(3)
123.8(3)
119.8(3)
115.6(3)
123.8(3)
118.3(3)
113(3)
1.437
1.379
1.378
1.402
1.352
1.352
1.402
119.9
119.9
119.2
120.9
119.7
119.9
120.9
119.2
112.8
110.8
110.8
173.1
–0.3
N1–C2
1.342(4)
1.342(4)
1.363(4)
1.332(4)
1.329(4)
1.361(4)
120.5(3)
119.6(3)
118.7(3)
123.4(3)
119.8(3)
115.8(3)
123.7(3)
118.6(3)
112(3)
1.383
1.383
1.417
1.346
1.346
1.417
120.9
121.0
119.6
123.2
117.7
116.6
123.2
119.6
110.8
111.0
111.0
172.0
0.0
1.355
1.355
1.391
1.335
1.335
1.391
119.7
119.7
118.5
123.2
119.9
116.7
123.2
118.5
111.8
111.5
N1–C6
C2–C3
C3–N4
N4–C5
C5–C6
C2N1N7
C6N1N7
N1C2C3
C2C3N4
C2N1C6
C3N4C5
N4C5C6
C5C6N1
H7N7H7'
N1N7H7
N1N7H7'
N7N1C2C3
N1C2C3N4
H7N7N1C2
H7'N7N1C2
110(3)
112(3)
108(3)
112(3)
111.5
175.0
–0.2
29.9
–174.9(3)
–0.5(5)
–178.5(3)
0.4(5)
–0.1
29.2
155.6
–28(2)
–28(2)
33.1
155.3
30.3
156.4
–153(2)
–152(2)
155.7
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ANDREEV et al.
294
Table 3. Some bond lengths (Å), bond and dihedral angles (deg) of cation of salt IIb obtained by X-ray diffraction analysis and
quantum-chemical calculations
DFT
Parameter
X-ray study
AΜ1
PΜ3
PBE/3z
1.420
B3LYP/ 6-31G++(2d,p)
N1–N7
N1–C2
1.418(4)
1.351(4)
1.368(4)
1.421(4)
1.306(4)
1.376
1.404
1.405
1.486
1.308
1.456
1.397
1.412
1.455
1.313
1.412
1.360
1.373
1.434
1.304
1.371
N1–C6
C2–C3
C3–N4
1.374
1.435
1.311
N4–C5
1.353(5)
1.340(5)
1.312(4)
116.2(3)
123.3(3)
116.4(3)
123.6(3)
120.5(3)
117.2(3)
122.9(3)
119.4(3)
120.7(3)
123.0(3)
118(4)
1.375
1.382
1.348
118.9
122.9
116.4
123.9
118.0
117.8
121.2
121.1
123.6
119.8
118.2
109.4
109.4
109.2
0.0
1.388
1.367
1.358
118.4
121.8
117.2
121.4
119.7
120.9
119.9
119.9
122.1
120.6
118.9
108.4
108.3
111.1
0.8
1.361
1.371
1.332
116.2
122.7
116.0
123.2
120.9
118.7
119.4
120.0
119.7
124.1
120.3
108.7
108.7
109.0
0.0
1.358
1.366
1.329
116.4
122.7
116.0
123.2
120.2
118.7
119.5
119.8
119.7
124.1
120.3
109.3
109.4
110.0
0.0
C5–C6
C2–NH2
C2N1N7
C6N1N7
N1C2C3
C2C3N4
C2N1C6
C3N4C5
N4C5C6
C5C6N1
N1C2NH2
C3C2NH2
H8N8H8'
H7N7H7'
N1N7Í7
N1N7Í7'
N7N1C2NH2
N7N1C2C3
110(4)
106(2)
107(2)
0.5(4)
–178.5(3)
180.0
180.0
–120.0
120.4
0.0
–179.5
–179.0
–119.4
121.3
–3.1
179.9
–179.9
–119.9
120.7
0.0
179.9
–179.9
–119.8
120.2
0.0
NH2C2N1C6 179.3(3)
H7N7N1C2
H7'N7N1C2
H8N8C2N1
–85(2)
157(3)
1(3)
Table 4. Some bond lengths (Å), bond and dihedral angles (deg) of cation of salt IIIc obtained by X-ray diffraction analysis and
quantum-chemical calculations
DFT
Parameter
X-ray study
ÀÌ1
ÐÌ3
PBE/3z
B3LYP/6-31G++(2d,p)
N1–N7
N1–C2
N1–C6
C2–C3
1.385(5)
1.340(5)
1.351(5)
1.403(6)
1.369(5)
1.333(5)
1.338(5)
1.374(6)
118.3(4)
120.3(4)
117.9(4)
123.0(4)
121.3(4)
1.372
1.376
1.377
1.444
1.384
1.385
1.331
1.420
120.7
120.0
120.2
120.2
118.8
1.431
1.368
1.372
1.417
1.391
1.379
1.339
1.410
119.5
119.7
118.9
120.7
120.4
1.385
1.351
1.361
1.412
1.372
1.334
1.332
1.391
119.2
119.0
117.8
121.9
121.6
1.387
1.343
1.352
1.409
1.372
1.341
1.327
1.389
119.8
119.0
118.0
121.5
121.8
C3–NH
C3–N4
N4–C5
C5–C6
C2N1N7
C6N1N7
N1C2C3
C2C3N4
C2N1C6
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MOLECULAR AND CRYSTAL STRUCTURE OF MESITYLENESULFONATES
295
Table 4. (Contd.)
DFT
Parameter
X-ray study
ÀÌ1
ÐÌ3
PBE/3z
B3LYP/6-31G++(2d,p)
C3N4C5
115.8(4)
124.6(4)
117.4(4)
121.8(4)
115.0(4)
120(4)
117.3
124.4
118.8
121.8
117.8
110.8
111.2
110.6
172.5
180.0
–20.5
119.0
121.7
119.2
123.0
116.1
112.9
111.2
110.9
173.6
179.6
–22.6
117.9
124.1
117.3
122.4
115.6
111.2
110.8
110.5
174.8
179.5
20.7
117.6
124.1
117.5
122.4
115.6
111.9
111.0
110.9
174.8
179.9
22.7
N4C5C6
C5C6N1
C2C3NH
NHC3N4
H7N7H7'
N1N7Í7
108(3)
N1N7Í7'
N7N1C2C3
NHC3N4C5
H7N7N1C2
106(2)
–178.5(4)
177.1(4)
–34(3)
Table 5. Some bond lengths (Å), bond and dihedral angles (deg) of cation of salt IIId obtained by X-ray diffraction analysis and
quantum-chemical calculations
DFT
Parameter
X-ray study
ÀÌ1
ÐÌ3
PBE/3z
1.386
1.346
B3LYP/6-31G++(2d,p)
N1–N7
N1–C2
1.354(3)
1.334(3)
1.370
1.373
1.432
1.373
1.412
1.373
N1–C6
1.363(3)
1.386(3)
1.331(3)
1.323(3)
1.350(3)
1.355(3)
119.4(2)
120.0(2)
117.9(2)
124.0(2)
120.6(2)
115.5(2)
124.0(2)
118.1(2)
115.3(2)
120.7(2)
124.0(2)
120(3)
1.383
1.438
1.356
1.365
1.339
1.418
120.6
120.5
119.2
122.8
118.3
116.0
124.0
119.5
113.5
123.6
122.8
111.0
111.2
110.9
172.3
180.0
–28.9
1.373
1.419
1.341
1.373
1.342
1.408
119.5
119.7
118.3
121.4
120.3
118.9
121.5
119.5
116.8
121.7
121.4
112.9
111.2
111.1
173.5
180.0
–28.8
1.366
1.415
1.322
1.338
1.338
1.387
119.9
118.9
118.1
122.4
121.0
117.1
123.7
117.7
115.6
122.0
122.4
111.6
111.1
110.8
174.8
–179.7
25.8
1.360
1.434
1.304
1.358
1.366
1.329
116.4
122.7
119.7
123.2
120.2
117.2
120.3
117.6
124.1
116.0
123.2
110.0
110.7
110.5
175.2
179.9
–179.9
C2–C3
C3–O
C3–N4
N4–C5
C5–C6
C2N1N7
C6N1N7
N1C2C3
C2C3N4
C2N1C6
C3N4C5
N4C5C6
C5C6N1
C2C3O
OC3N4
C2C3N4
H7N7H7'
N1N7Í7
N1N7Í7'
N7N1C2C3
OC3C2N1
H7N7N1C2
114(2)
113(2)
176.2(2)
–179.3(2)
36(2)
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ANDREEV et al.
296
Table 6. Some bond lengths (Å), bond and dihedral angles (deg) of cation of salt IIIe obtained by X-ray diffraction analysis and
quantum-chemical calculations
DFT
Parameter
X-ray study
1.338(6)
ÀÌ1
ÐÌ3
PBE/3z
B3LYP/6-31G++(2d,p)
N1–N7
1.345(6)
1.335(6)
1.343(6)
1.374(7)
1.720(5)
1.309(7)
1.337(6)
1.351(7)
119.9(4)
119.8(4)
117.2(5)
125.3(5)
120.3(4)
114.5(5)
124.2(5)
118.4(5)
117.3(4)
127(6)
1.370
1.381
1.381
1.426
1.684
1.359
1.341
1.419
120.6
121.0
119.9
122.4
118.0
116.6
123.7
119.4
117.4
110.9
111.0
111.2
172.2
179.0
–32.8
154.3
1.435
1.378
1.373
1.407
1.646
1.369
1.342
1.408
119.6
120.0
119.3
120.3
120.0
120.0
121.1
119.2
121.0
112.8
111.0
111.0
173.3
–179.0
30.0
1.381
1.356
1.363
1.401
1.718
1.329
1.339
1.390
119.8
119.6
117.9
123.3
120.5
116.9
123.3
118.1
117.7
112.3
111.5
111.7
175.0
180.0
–27.4
–153.8
1.383
1.348
1.353
1.399
1.715
1.323
1.332
1.388
119.4
119.6
117.9
122.9
120.6
117.5
122.8
118.2
118.7
111.3
111.0
111.3
175.1
180.0
30.5
N1–C2
1.354(6)
1.330(6)
1.352(7)
1.717(5)
1.318(7)
1.338(7)
1.351(7)
120.1(4)
120.3(4)
118.2(5)
124.9(5)
119.6(4)
114.2(5)
124.7(5)
118.4(5)
117.9(4)
121(5)
N1–C6
C2–C3
C3–Cl
C3–N4
N4–C5
C5–C6
C2N1N7
C6N1N7
N1C2C3
C2C3N4
C2N1C6
C3N4C5
N4C5C6
C5C6N1
C2C3Cl
H7N7H7’
N1N7Í7
N1N7Í7’
N7N1C2C3
ClC3C2N1
H7N7N1C2
H7'N7N1C2
115(3)
120(4)
117(4)
114(5)
179.0(3)
177.0(4)
20(4)
179.7(3)
176.9(4)
6(5)
170(4)
–171(5)
156.4
–155.2
pyrazine ring. The experimentally measured angles
C3N4C5 are significantly smaller than angles C2C3N4 and
N4C5C6 characteristically for the compounds with
a pyrazine ring [21–23]. In all cations the angles C2N1C6
are larger than angles C3N4C5 in conformity to the theory
of electron pairs repulsion [24].As show the bond angles
N1N7H7, N1N7H7', and H7N7H7' in cations of salts IIa,
IIb, IIIc, and IIId the amino group possesses a pyramidal
configuration, and in cation of salt IIIe its configuration
is close to planar. According to quantum-chemical cal-
culations in all cations the hybridization of the nitrogen
of amino group should be close to sp3 (Tables 2–6). In
all cases but in cation of salt IIb the bond length N1–
NH2 is less than ordinary bond Nplanar–N planar (1.401 Å)
or Nplanar–N pyramidal (1.420 Å) [25], but significantly
longer than the double bond N=N (1.25 Å) [26] indicating
weak involvement of the unshared electron pair of the
amino group nitrogen into the conjugation with the
pyrazine fragment. In cations of salts IIa, IIIc–IIIe the
bond distance N1–NH2 is considerably shorter that in
pyridine derivatives: N-amino-2,4,6-triphenylperidinium
cation (1.418 Å) [12], complex of 1-aminopyridinium
tetrafluoroborate with dibenzo-18-crown-6 (1.414 Å)
[14], 1-amino-1,10-phenanthrolinium cation (1.403 Å)
[16]. This is apparently caused by the acceptor effect of
the additional nitrogen in the ring of cations of salts IIa,
IIIc–IIIe.According to the resonance theory the increase
in the bond order between atom N1 and NH2 group should
increase the contribution into the resonance hybrid of
the saturated structures A–A'' and should result in
appearance of negative charge on atoms C2, C6, and N4;
therewith the high electronegativity of the nitrogen leads
to larger contribution of structure A'' compared to
analogous amino cations of the pyridine series. Taking
into consideration that the saturated structures A–A''
include two adjacent positively charged nitrogen atoms
their contribution into the resonance hybrid should not
be significant. The acceptor substituents should favor
the growth of this contribution and of the bond order N–
NH2. Actually, in the series of cations of salts IIa, IIId,
and IIIe a trend is observed to shortening of N1–NH2
bond that may be attributed to the growing conjugation
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 2 2008

MOLECULAR AND CRYSTAL STRUCTURE OF MESITYLENESULFONATES
297
Fig. 1. Structure of cations of salts IIa, IIb, IIIc–IIIe and of anion of salt IIa.
The structure of anions of salts IIa, IIb, IIIc–IIIe is
analogous (Fig 1) and similar to the structure of
ammonium mesitylenesulfonate [27].
between the NH2 group and atom N1 in keeping with the
increasing acceptor character of the substituent X.
N4
N
The data on geometry of cations obtained by X-ray
diffraction analysis are compared to results of quantum-
chemical calculations. Both semiempirical and ab initio
calculations give cations geometry close to experimental-
ly found, but as a rule the calculated bond lengths are
somewhat overestimated (Tables 2–6). The closest to the
experimental values of bond lengths were obtained by
method DFT [(PBE/3z) and B3LYP/6-31G++(2d,p)],
average deviation of bond distances CC, CN, CO, NN,
and CCl from the experimental values was 0.014 and
0.016 Å respectively. The calculations byAM1 and PM3
procedures give larger average deviations (0.033 and
0.038 Å respectively).
C5
C6
C3
C2
_
+
N1
+
N
N7
N+
H7'
H7
H
H
_
N
A
N
N
_
+
+
N
+
N
N
N
B
NH2
N+
N +
H
H
H
H
H
H
A'
A''
The analysis of the crystal structure of salts IIa, IIb,
IIIc–IIIe shows that the main building blocks governing
The presence of donor substituents in position 2
should decrease the contribution of structures A, A' and
decrease the order of this bond. Actually in the cation of
salt IIb the bond length N1–NH2 is close to the length of
an ordinary N–N bond, whereas the bond C2–NH2 is
shortened and close in the length to a common double
...
it are fragments N–H O leading to supermolecules (0D
architecture) or chains/bands (1D architecture) (cf. [28]).
Parameters of hydrogen bonds of salts IIa, IIb, IIIc–
IIIe are presented in Table 7. In the crystals of salts
IIId and IIIe the amino group plays the part of hydrogen
donor in the hydrogen bond forming as a result
supermolecules possessing a symmetry center (Fig. 2).
2
bond Csp =N (1.3 Å) [25]. This indicates a significant
contribution of iminium stricture B into the
corresponding resonance hybrid. The carbon-carbon
distances in the pyrazine ring of the cations of salts IIa,
IIb, IIIc–IIIe are close to the corresponding values in
pyrazine [21]; therewith introducing donor substituents
into positions 2 and 3 results in elongation of the bond
between atoms C2 and C3.
...
The form of the eight-membered ring ( OSO
... ...
N
)
2
of supermolecule IIId resembles a chair with equatorial
aromatic rings. Owing to π-stacking interactions in pairs
pyrazinium–pyrazinium (distances between the centers
and the planes are 3.48 and 3.31 Å respectively) and
...
interactions S-O π(pyrazinium) (cf. [29]) [O1-
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ANDREEV et al.
298
...
Table 7. Parameters of hydrogen bonds (D–H A) in crystals
of salts IIa, IIb, IIIc–IIIe
D–H⋅⋅⋅A
D–H⋅⋅⋅A,
D–H, Å H⋅⋅⋅O, Å
D⋅⋅⋅A, Å
IIa
deg
N7–H7⋅⋅⋅O2
0.99(4) 1.89(4)
0.79(3) 2.08(3)
0.95(4) 1.88(4)
171(3)
2.878(4)
2.843(3)
2.816(4)
2.805(4)
2.918(5)
2.740(5)
2.953(5)
N7–H7'⋅⋅⋅O2A
N7A–H7A⋅⋅⋅O1
164(3)
168(4)
N7A–H7'A⋅⋅⋅O1A 0.85(4) 1.96(4)
172(3)
O1W–H⋅⋅⋅O3
O1W–H⋅⋅⋅O3A
O1W–H⋅⋅⋅N4
IIb
-
-
-
-
-
-
-
-
-
N7–H7'⋅⋅⋅O2
N7–H7⋅⋅⋅O3
N8–H8'⋅⋅⋅O1
N8–H8...N4
IIIc
0.88(4) 2.19(4)
0.95(4) 2.05(4)
0.87(4) 1.95(4)
0.91(4) 2.21(4)
160(4)
159(3)
172(3)
147(4)
3.035(4)
2.958(4)
2.813(4)
3.018(4)
N7–H7⋅⋅⋅O3
N7–H7'⋅⋅⋅O2
N3–H3⋅⋅⋅O3
IIId
0.99(5) 2.02(5)
0.93(4) 2.01(4)
161(4)
167(4)
173
2.969(5)
2.923(5)
2.823(5)
0.86
1.97
N7–H7⋅⋅⋅O2
0.95(3) 1.91(3)
0.85(3) 2.01(3)
170(3)
177(3)
2.855(3)
2.859(3)
N7–H7'⋅⋅⋅O3
IIIe
N7–H7⋅⋅⋅O1
N7–H7'⋅⋅⋅O2
0.85(6) 2.01(6)
0.75(6) 2.08(6)
N7A–H7A⋅⋅⋅O2A 0.87(5) 1.99(5)
N7A–H7'A⋅⋅⋅O3A 0.87(6) 2.01(6)
167(5)
2.852(7)
Fig. 2. Fragments of packing of supermolecules in crystals of
salts IIId (a) and IIIe (e) (hydrogen atoms not shown). The
second crystallographically independent ions are marked with
A character in the numbers of atoms.
166(6)
158(4)
168(5)
2.813(7)
2.815(6)
2.870(6)
...
centroid(Cg), 3.317 Å, S–O1 Cg 100.2°] the super-
molecules form layers parallel to the ab plane (Fig. 2a).
Similar supermolecules having a symmetry center formed
in the crystal of IIIe salt (Fig. 2b), and therewith two of
them are crystallographically independent. Unlike
mesitylenesulfonate IIId the supermolecules are stacked
due to the π-stacking interaction between pyrazinium and
mesitylene rings of the contiguous supermolecules
resulting in layers formation parallel to the ac plane. The
distances between the centers and the planes are in the
range 3.48–3.62 and 3.45–3.51 Å respectively.
of bands along b axis (Fig. 3, b). Note the interactions
...
within the band C17A–H π(C9–C14) for the salt IIa with
... ...
parameters H Cg 2.74 Å, C–H Cg 164°, and also
...
...
shortened contacts C–H O: C5H5 O3 2.32,
...
...
C5AH5A O3A 2.32, C6H6 O1W 2.43 Å (cf. [31]). In the
crystal of salt IIIc also shortened contacts were observed:
...
inside the band C6H6 O4 (2.29 Å) and between the
...
bands C8H8A O1 (2.44 Å).
In the crystal of salt IIb form bands oriented along b
axis of another type, involving both amino groups
(Fig. 4). The amino group at the atom N1 is of sp3
hybridization and is turned from the plane of the
pyrazinium ring [torsion angle C2N1N7H7A –85(3) deg],
whereas the second amino group is planar and located in
the plane of the ring. This geometry of amino groups
The formation of molecular ensembles like
supermolecules of salts IIId and IIIe with a ring
...
... ...
(
OSO N )2 in the boat form is also observed in the
crystals of salts IIa and IIIc. However these ensembles
cannot be regarded as supermolecules [30] for in salt
IIa solvate water molecules combine them in wide bands
oriented along b axis (Fig. 3a), and in salt IIIc the uniting
role plays the aminoacetyl group leading to the formation
...
evidently originates from the hydrogen bonds N–H O.
...
Mark the interaction within the band S1–O1 π(pyrazin-
...
...
ium), O Cg (3.15 Å), S–O Cg [129.8(2) deg]. Owing
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 2 2008

MOLECULAR AND CRYSTAL STRUCTURE OF MESITYLENESULFONATES
299
...
to the hydrogen bonds N8–H8 N4 the bands are joined
into layers parallel to the ab plane.
Thus the substituent X in 1-amino-X-pyrazinium
mesitylenesulfonates significantly affects the cation
geometry, and the main building blocks governing the
...
crystal structure are the N–H O fragments leading to
the formation of supermolecules or chains/bands.
EXPERIMENTAL
X-Ray analysis was performed on diffractometers
Bruker P4 (MoKα-radiation) and Syntex P21 (CuKα-
radiation), graphite monochromators, θ/2θ-scanning and
ω-scanninga (salts IIa, IIId, IIIe and IIb, IIIc
respectively). Crystallographic data of the salts are
compiled in Table 1. The structures were solved using
SHELXS-97 software and refined by the least-squares
method in the anisotropic approximation applying the
program SHELXL-97 [32]. The hydrogens of amino
groups were refined in isotropic approximation, the other
hydrogen atoms, in isotropic approximation and using
rider model (salts IIb, IIId and IIIc, IIId respectively),
and also by a mixed procedure (for IIa). We failed to
localize the hydrogen atoms of water in salt IIa. The
atomic coordinates are deposited into the Cambridge
Structural Database (nos. CCDC 647105–647109).
The quantum-chemical calculations byAΜ1 and PΜ3
procedures were carried out using software package
ΜOPAC [33]. The calculations by DFT method in
approximations PBE [34] and B3LYP [35, 36] were
performed employing programs PRIRODA [37, 38]
{basis 3z, (11s6p2d)/[6s3p2d] for C and O, (5s1p)/[3s1p]
for H} and GAMESS [39]. The evaluation of the type of
the critical points on the potential energy surface was
performed by calculation of Hesse matrix [40].
Fig. 3. 1D motifs in crystals of salts IIa (a) and IIIc (b) (hy-
drogen atoms not shown save H17A in cation IIa). The second
crystallographically independent ions are marked withA char-
acter in the numbers of atoms.
We used in the study pyrazine (99+%), 2-amino-
pyrazine (98%), 2-chloropyrazine (98%), 2-methoxy-
pyrazine (98%) purchased from Lancaster. O-Mesityl-
sulfonylhydroxylamine (MesSO3NH2) and 2 acylamino-
pyrazine were prepared by procedures [4] and [41, 42]
respectively. Dichloromethane was purified by washing
with saturated solution of Na2CO3 followed by boiling
with activated carbon, drying, and distillation over
anhydrous CaCl2 [26].
General procedure of salts preparation. Asolution
of 2-X-pyrazine (~0.5 mmol) in 1 ml of dichloromethane
was cooled to 0°C and at vigorous stirring it was added
dropwise into a solution of MesSO3NH2 (~0.75 mmol)
in 1.5 ml of CH2Cl2 preliminary dried over Na2SO4 (in
Fig. 4. Fragment of 2D-motif in the crystal of IIb salt
(hydrogen atoms not shown save those of amino groups).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 2 2008

ANDREEV et al.
300
Inorg. Chem., 1990, vol. 29, p. 4016.
the case of mesitylenesulfonate IIId CHCl3 was used
for solvent and the salt was recrystallized from i-PrOH].
The mixture was stirred at 0°C for 30 min, then warmed
to room temperature and additionally stirred for 3 h. Into
the solution 10 ml of Et2O was added, the formed
precipitate was separated, washed with ether, and dried
in a vacuum. Yields of the salts IIa, IIb, IIIc–IIIe were
65, 75, 60, 82, and 40% respectively. Crystals of salts
IIa, IIIc, and IIIe for the X-ray diffraction study were
obtained by recrystallization from a mixture i-PrOH–
MeOH, 10:1. 1-Amino-pyrazinium mesitylenesulfonate
was precipitated by adding petroleum ether to the salt
solution in CH2Cl2 containing equimolar to the salt
amount of dibenzo-18-crown-6.
12. Filipenko, O.S., Aldoshin, S.M., Shilov, G.V., Makaro-
va, N.I., Kharlanov, V.A., and Knyazhanskii, M.I., Izv. Akad.
Nauk, Ser. Khim., 1995, p. 296.
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The study was carried out under a financial support
of the Russian Foundation for Basic Research (grants
nos. 06-03-32406 and 06-03-32229) and of Department
of Chemistry and Material Science of the Russian
Academy of Sciences (Program 5.1.9).
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