1,3-Dimethyl-5-methyl-sulfonyl-1H-pyrazolo-[4,3-e][1,2,4]triazine.

Abstract

In the title compound, C(7)H(9)N(5)O(2)S, the pyrazolo-[4,3-e][1,2,4]triazine fused-ring system is essentially planar [maximum deviation = 0.0420 (3) Å]. In the crystal, mol-ecules related by twofold axes are linked into a mol-ecular net via inter-molecular C-H⋯O and C-H⋯N hydrogen bonds. π-π inter-actions are observed between the triazine and pyrazole rings of mol-ecules related by the the twofold axis and inversion symmetry with centroid-centroid distances of 3.778 (3) and 3.416 (3) Å, respectively.

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1,3-Dimethyl-5-methylsulfonyl-1H-
pyrazolo[4,3-e][1,2,4]triazine
Mariusz Mojzych, Zbigniew Karczmarzyk* and Waldemar
Wysocki
Department of Chemistry, University of Podlasie, ul. 3 Maja 54, 08-110 Siedlce,
Poland
Correspondence e-mail: kar@uph.edu.pl
Received 28 October 2010; accepted 15 November 2010
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.006 A ˚;
R factor = 0.069; wR factor = 0.227; data-to-parameter ratio = 21.2.
In the title compound, C7H9N5O2S, the pyrazolo[4,3-e][1,2,4]-
triazine fused-ring system is essentially planar [maximum
deviation = 0.0420 (3) A˚]. In the crystal, molecules related by
twofold axes are linked into amolecular net via intermolecular
C—H???O and C—H???N hydrogen bonds. ?–? interactions
are observed between the triazine and pyrazole rings of
molecules related by the the twofold axis and inversion
symmetry with centroid–centroid distances of 3.778 (3) and
3.416 (3) A˚, respectively.
Related literature
For background to sulfones, see: Ingall (1984). For our work
on the development of convenient synthetic approaches for
the construction of biologically active heterocycles, see:
Karczmarzyk et al. (2007). For related structures, see: Hirata et
al. (1996); Rykowski et al. (2000); Cherng-Chyi et al. (1994).
Experimental
Crystal data
C7H9N5O2S
Mr= 227.25
Monoclinic, C2=c
a = 17.901 (1) A˚
b = 8.1268 (7) A˚
c = 14.203 (3) A˚
? = 103.17 (1)?
V = 2011.9 (5) A˚3
Z = 8
Mo K? radiation
? = 0.31 mm?1
T = 293 K
0.40 ? 0.30 ? 0.10 mm
Data collection
Kuma KM-4 four-circle
diffractometer
Absorption correction: scan
(North et al., 1968)
Tmin= 0.860, Tmax= 0.980
3688 measured reflections
2948 independent reflections
1085 reflections with I > 2?(I)
Rint= 0.064
2 standard reflections every 100
reflections
intensity decay: 1.4%
Refinement
R[F2> 2?(F2)] = 0.069
wR(F2) = 0.227
S = 1.02
2948 reflections
139 parameters
H-atom parameters constrained
??max= 0.81 e A˚?3
??min= ?0.72 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
C10—H10C???O13i
C11—H11B???O14ii
C15—H15A???N2iii
Symmetry codes: (i) x;y þ 1;z; (ii) ?x;y;?z þ1
D—HH???AD???AD—H???A
0.96
0.96
0.96
2.51
2.42
2.59
3.442 (7)
3.341 (7)
3.466 (7)
163
161
152
2; (iii) ?x þ1
2;y ?1
2;?z þ1
2.
Data collection: KM4B8 (Gałdecki et al., 1996); cell refinement:
KM4B8; data reduction: DATAPROC (Gałdecki et al., 1995);
program(s) used to solve structure: SHELXS97 (Sheldrick, 2008);
program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); soft-
ware used to prepare material for publication: SHELXL97 and
WinGX (Farrugia, 1999).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: PV2349).
References
Cherng-Chyi, T., Dau-Chang, W., Long-Chih, H., Ming-Chu, C. & Yu, W.
(1994). J. Chem. Soc. Perkin Trans. 1, pp. 2253–2257.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Gałdecki, Z., Kowalski, A., Kucharczyk, D. & Uszyn ´ski, L. (1996). KM4B8.
Kuma Diffraction, Wrocław, Poland.
Gałdecki, Z., Kowalski, A. & Uszyn ´ski, L. (1995). DATAPROC. Kuma
Diffraction, Wrocław, Poland.
Hirata, K., Nakagami, H., Takashina, J., Mahmud, T., Kobayashi, M., In, Y.,
Ishida, T. & Miyamoto, K. (1996). Heterocycles, 43, 1513–1519.
Ingall, A. H. (1984). Comprehensive Heterocyclic Chemistry, edited by A. R.
Katritzky & C. W. Rees, Vol. 3, pp. 939–942. New York: Pergamon Press.
Karczmarzyk, Z., Mojzych, M. & Rykowski, A. (2007). J. Mol. Struct. 829, 22–
28.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–
359.
Rykowski, A., Mojzych, M. & Karczmarzyk, Z. (2000). Heterocycles, 53, 2175–
2181.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
organic compounds
o3226
Mojzych et al.
doi:10.1107/S1600536810047264
Acta Cryst. (2010). E66, o3226
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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Acta Cryst. (2010). E66, o3226 [ doi:10.1107/S1600536810047264 ]
1,3-Dimethyl-5-methylsulfonyl-1H-pyrazolo[4,3-e][1,2,4]triazine
M. Mojzych, Z. Karczmarzyk and W. Wysocki
Comment
Sulfones have proven to be valuable synthons for the synthesis of a wide variety of biologically active heterocyclic systems
(Ingall, 1984). As an extension of our efforts directed towards the development of convenient synthetic approaches for
the construction of biologically active heterocycles (Karczmarzyk et al., 2007), we report herein the crystal and molecular
structure of the title compound.
The geometry (bond lengths, angles and planarity) of the title molecule (I) is very similar to those observed in closely re-
lated structures (Hirata et al., 1996; Rykowski et al., 2000). In the title molecule, a substitution by methylsulfonyl group in the
1,2,4-triazine ring results in a significant deformation of the endocyclic angles N2—C3—N4 of 130.3 (4)° and C3—N4—C5
of 110.6 (4)°. This effect is caused probably by the strong electron-withdrawing property of SO2CH3 substituent and has
been reported in similar structures (Cherng-Chyi et al., 1994).
In the crystal structure, the molecules related by 2-fold axes are linked into molecular net via intermolecular C—H···O and
C—H···N hydrogen bonds (Fig. 2 and Tab. 1). In addition, the π-electron systems of the pyrazolo[4,3-e][1,2,4]triazine fused
rings belonging to inversion- (one side) and 2-fold axis- (other side) related molecules overlap each other, with centroid-to-
centroid separation of 3.416 (3) Å between the pyrazole ring at (x, y, z) and triazine ring at (-x, 1 - y, -z), and 3.778 (3) Å
between pyrazole ring at (x, y, z) and triazine ring at (-x, y, 1/2 - z). The π···π distances are 3.2375 (18) and 3.2719 (18)
Å, respectively.
Experimental
To a solution of 2,3-dimethyl-5-methylsulfanyl-1H-pyrazolo[4,3-e][1,2,4]triazine (1 mmol) in benzene (20 ml), water (30
ml), potassium manganate (VII) (3 mmol), catalitic amounts of tetrabuthylammonium bromide (0.2 mmol) and acetic acid
(1.5 ml) were added. The reaction mixture was stirred at room temperature for 1 h. A saturated solution of Na2S2O5 in water
was then added to the mixture until the purple colour disappeared. The organic layer was separated and the aqueos phase was
extracted with benzene (3x10 ml). The combined organic extracts were dried over anhydrous MgSO4 and concentrated in
vacuo. The residue was purified by column chromatography on silica gel (eluent: chloroform) to afford the title compound
as a yellow solid. Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of an ethanol solution.
Refinement
The H atoms were positioned geometrically and treated as riding on their C atoms, with C—H distances of 0.96 Å and were
included in the refinement with Uiso(H) = 1.5Ueq(C).

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Figures
Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement el-
lipsoids for non-H atoms.
Fig. 2. A view of the molecular packing in (I). Dashed lines indicate C—H···X (X = O, N) in-
termolecular interactions.
1,3-Dimethyl-5-methylsulfonyl-1H-pyrazolo[4,3-e][1,2,4]triazine
Crystal data
C7H9N5O2S
F(000) = 944
Dx = 1.500 Mg m−3
Melting point: 444 K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 25 reflections
θ = 4.4–25.2°
µ = 0.31 mm−1
T = 293 K
Mr = 227.25
Monoclinic, C2/c
Hall symbol: -C 2yc
a = 17.901 (1) Å
b = 8.1268 (7) Å
c = 14.203 (3) Å
β = 103.17 (1)°
V = 2011.9 (5) Å3
Z = 8
Prism, colourless
0.40 × 0.30 × 0.10 mm
Data collection
Kuma KM-4 four-circle
diffractometer
Radiation source: fine-focus sealed tube
graphite
ω–2θ scans
Absorption correction: ψ scan
(North et al., 1968)
Tmin = 0.860, Tmax = 0.980
3688 measured reflections
2948 independent reflections
1085 reflections with I > 2σ(I)
Rint = 0.064
θmax = 30.1°, θmin = 2.3°
h = −25→24
k = −1→11
l = −1→19
2 standard reflections every 100 reflections
intensity decay: 1.4%

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Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
sites
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.069
wR(F2) = 0.227
H-atom parameters constrained
S = 1.02
w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.81 e Å−3
Δρmin = −0.72 e Å−3
2948 reflections
139 parameters
0 restraints
Special details
Experimental. Yield: 95% and m.p. 444 K. 1H NMR (CDCl3) δ: 2.77 (s, 3H), 3.57 (s, 3H), 4.39 (s, 3H); IR (KBr,ν, cm-1): 2920, 1330,
1120; MS (m/z, %): 227 (8) [M+], 199 (32), 120 (21), 95 (51), 79 (94), 67 (28), 52 (100). Analysis calculated for C7H9N5O2S: C 37.00,
H 3.99, N 30.82%; found: C 37.01, H 3.85, N 30.76%.
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The
cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds
in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used
for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculat-
ing R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice
as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
0.15935 (7)
0.1310 (2)
0.1737 (2)
0.0756 (2)
0.1192 (2)
0.02186 (19)
−0.0502 (2)
−0.1138 (2)
0.0915 (2)
−0.0227 (2)
0.0051 (2)
−0.0993 (2)
−0.0494 (3)
−0.0770
y
0.15917 (15)
0.0271 (5)
0.1313 (5)
0.6040 (5)
0.4699 (5)
0.2860 (5)
0.6833 (5)
0.6061 (5)
0.3259 (5)
0.4200 (5)
0.5751 (5)
0.4447 (6)
0.8619 (6)
0.8909
z
0.19815 (10)
0.1348 (3)
0.3001 (3)
0.1881 (3)
0.2062 (3)
0.1191 (3)
0.0994 (3)
0.0483 (3)
0.1696 (3)
0.1003 (3)
0.1322 (3)
0.0469 (3)
0.1113 (4)
0.1594
Uiso*/Ueq
0.0433 (4)
0.0748 (13)
0.0765 (13)
0.0412 (10)
0.0373 (9)
0.0361 (9)
0.0388 (9)
0.0435 (10)
0.0317 (9)
0.0336 (10)
0.0332 (10)
0.0377 (11)
0.0586 (15)
0.088*
S12
O13
O14
N1
N2
N4
N7
N8
C3
C5
C6
C9
C10
H10A

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H10B
H10C
C11
H11A
H11B
H11C
C15
H15A
H15B
H15C
−0.0732
0.0027
−0.1567 (3)
−0.2011
−0.1712
−0.1350
0.2416 (3)
0.2807
0.2593
0.2303
0.9128
0.8995
0.3236 (6)
0.3804
0.2539
0.2579
0.2357 (8)
0.1526
0.3302
0.2669
0.0509
0.1315
−0.0021 (4)
−0.0381
0.0453
−0.0454
0.1689 (5)
0.1803
0.2083
0.1020
0.088*
0.088*
0.0567 (14)
0.085*
0.085*
0.085*
0.0646 (17)
0.097*
0.097*
0.097*
Atomic displacement parameters (Å2)
U11
0.0358 (6)
0.058 (2)
0.075 (3)
0.0313 (19)
0.0316 (18)
0.0315 (18)
0.0339 (19)
0.0247 (18)
0.0264 (18)
0.0250 (19)
0.027 (2)
0.025 (2)
0.057 (3)
0.036 (2)
0.035 (3)
U22
0.0407 (7)
0.044 (2)
0.096 (3)
0.047 (2)
0.038 (2)
0.040 (2)
0.040 (2)
0.063 (3)
0.036 (2)
0.045 (3)
0.041 (3)
0.051 (3)
0.052 (3)
0.065 (3)
0.073 (4)
U33
0.0504 (7)
0.108 (3)
0.057 (2)
0.042 (2)
0.039 (2)
0.035 (2)
0.040 (2)
0.041 (2)
0.031 (2)
0.030 (2)
0.030 (2)
0.035 (3)
0.061 (4)
0.062 (3)
0.089 (4)
U12
0.0015 (6)
0.0052 (19)
0.030 (2)
−0.0005 (18)
0.0034 (17)
−0.0049 (16)
0.0048 (18)
0.0028 (18)
−0.0035 (19)
0.000 (2)
0.0020 (19)
−0.004 (2)
0.014 (3)
−0.022 (3)
0.009 (3)
U13
0.0035 (5)
−0.011 (2)
0.012 (2)
0.0021 (16)
0.0013 (15)
0.0025 (16)
0.0033 (16)
0.0028 (16)
0.0035 (16)
0.0058 (16)
0.0049 (16)
0.0017 (18)
0.000 (3)
−0.005 (2)
0.020 (3)
U23
0.0050 (6)
−0.022 (2)
0.036 (2)
−0.0085 (19)
0.0006 (18)
0.0024 (17)
−0.0033 (18)
0.000 (2)
0.001 (2)
0.003 (2)
−0.006 (2)
0.007 (2)
−0.003 (3)
0.006 (3)
0.023 (3)
S12
O13
O14
N1
N2
N4
N7
N8
C3
C5
C6
C9
C10
C11
C15
Geometric parameters (Å, °)
S12—O13
S12—O14
S12—C15
S12—C3
N1—N2
N1—C6
N2—C3
N4—C3
N4—C5
N7—C6
N7—N8
N7—C10
N8—C9
1.418 (4)
1.430 (4)
1.733 (5)
1.803 (4)
1.331 (5)
1.350 (5)
1.330 (5)
1.329 (5)
1.340 (5)
1.326 (5)
1.357 (5)
1.461 (6)
1.338 (6)
C5—C6
C5—C9
C9—C11
C10—H10A
C10—H10B
C10—H10C
C11—H11A
C11—H11B
C11—H11C
C15—H15A
C15—H15B
C15—H15C
1.393 (6)
1.423 (6)
1.476 (6)
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
O13—S12—O14
O13—S12—C15
O14—S12—C15
118.6 (3)
108.7 (3)
109.4 (3)
N8—C9—C5
N8—C9—C11
C5—C9—C11
107.3 (4)
123.0 (4)
129.8 (4)

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O13—S12—C3
O14—S12—C3
C15—S12—C3
N2—N1—C6
N1—N2—C3
C3—N4—C5
C6—N7—N8
C6—N7—C10
N8—N7—C10
C9—N8—N7
N4—C3—N2
N4—C3—S12
N2—C3—S12
N4—C5—C6
N4—C5—C9
C6—C5—C9
N7—C6—N1
N7—C6—C5
N1—C6—C5
107.5 (2)
107.6 (2)
104.0 (2)
113.5 (4)
119.7 (3)
110.6 (4)
110.5 (4)
129.1 (4)
120.4 (4)
108.6 (3)
130.3 (4)
116.0 (3)
113.6 (3)
121.3 (4)
132.7 (4)
106.0 (4)
127.9 (4)
107.7 (4)
124.4 (4)
N7—C10—H10A
N7—C10—H10B
H10A—C10—H10B
N7—C10—H10C
H10A—C10—H10C
H10B—C10—H10C
C9—C11—H11A
C9—C11—H11B
H11A—C11—H11B
C9—C11—H11C
H11A—C11—H11C
H11B—C11—H11C
S12—C15—H15A
S12—C15—H15B
H15A—C15—H15B
S12—C15—H15C
H15A—C15—H15C
H15B—C15—H15C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C6—N1—N2—C3
C6—N7—N8—C9
C10—N7—N8—C9
C5—N4—C3—N2
C5—N4—C3—S12
N1—N2—C3—N4
N1—N2—C3—S12
O13—S12—C3—N4
O14—S12—C3—N4
C15—S12—C3—N4
O13—S12—C3—N2
O14—S12—C3—N2
C15—S12—C3—N2
C3—N4—C5—C6
C3—N4—C5—C9
N8—N7—C6—N1
0.2 (6)
−0.8 (5)
179.0 (4)
4.2 (6)
−178.4 (3)
−4.5 (7)
178.1 (3)
17.9 (4)
−110.9 (4)
133.0 (4)
−164.3 (3)
66.9 (4)
−49.2 (4)
0.0 (6)
177.3 (4)
−177.9 (4)
C10—N7—C6—N1
N8—N7—C6—C5
C10—N7—C6—C5
N2—N1—C6—N7
N2—N1—C6—C5
N4—C5—C6—N7
C9—C5—C6—N7
N4—C5—C6—N1
C9—C5—C6—N1
N7—N8—C9—C5
N7—N8—C9—C11
N4—C5—C9—N8
C6—C5—C9—N8
N4—C5—C9—C11
C6—C5—C9—C11
2.4 (8)
1.0 (5)
−178.8 (5)
−177.7 (4)
3.7 (6)
177.2 (4)
−0.8 (5)
−3.9 (7)
178.1 (4)
0.2 (5)
179.5 (4)
−177.3 (4)
0.3 (5)
3.5 (8)
−178.9 (5)
Hydrogen-bond geometry (Å, °)
D—H···A
C10—H10C···O13i
C11—H11B···O14ii
C15—H15A···N2iii
Cg(pyrazole)—···.Cg(triazine)ii
Cg(pyrazole)—···.Cg(triazine)iv
Symmetry codes: (i) x, y+1, z; (ii) −x, y, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) x+1/2, y+3/2, z.
D—HH···AD···AD—H···A
0.96 2.513.442 (7) 163
0.962.423.341 (7)161
0.962.59 3.466 (7) 152
.. 3.778 (3).
.. 3.416 (3).

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Fig. 1

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Fig. 2