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

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.

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

M = 227.25

Monoclinic,

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

Mo Kα radiation

μ = 0.31 mm−1

T = 293 K

0.40 × 0.30 × 0.10 mm

Data collection

Kuma KM-4 four-circle diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.860, T max = 0.980

3688 measured reflections

2948 independent reflections

1085 reflections with I > 2σ(I)

R int = 0.064

2 standard reflections every 100 reflections intensity decay: 1.4%

Refinement

R[F 2 > 2σ(F 2)] = 0.069

wR(F 2) = 0.227

S = 1.02

2948 reflections

139 parameters

H-atom parameters constrained

Δρmax = 0.81 e Å−3

Δρmin = −0.72 e Å−3

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 ▶); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810047264/pv2349sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047264/pv2349Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C7H9N5O2S	F(000) = 944
Mr = 227.25	Dx = 1.500 Mg m−3
Monoclinic, C2/c	Melting point: 444 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 17.901 (1) Å	Cell parameters from 25 reflections
b = 8.1268 (7) Å	θ = 4.4–25.2°
c = 14.203 (3) Å	µ = 0.31 mm−1
β = 103.17 (1)°	T = 293 K
V = 2011.9 (5) Å3	Prism, colourless
Z = 8	0.40 × 0.30 × 0.10 mm

Kuma KM-4 four-circle diffractometer	1085 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
graphite	θmax = 30.1°, θmin = 2.3°
ω–2θ scans	h = −25→24
Absorption correction: ψ scan (North et al., 1968)	k = −1→11
Tmin = 0.860, Tmax = 0.980	l = −1→19
3688 measured reflections	2 standard reflections every 100 reflections
2948 independent reflections	intensity decay: 1.4%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.227	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
2948 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.81 e Å−3
0 restraints	Δρmin = −0.72 e Å−3

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, conventional 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 calculating 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.

	x	y	z	Uiso*/Ueq
S12	0.15935 (7)	0.15917 (15)	0.19815 (10)	0.0433 (4)
O13	0.1310 (2)	0.0271 (5)	0.1348 (3)	0.0748 (13)
O14	0.1737 (2)	0.1313 (5)	0.3001 (3)	0.0765 (13)
N1	0.0756 (2)	0.6040 (5)	0.1881 (3)	0.0412 (10)
N2	0.1192 (2)	0.4699 (5)	0.2062 (3)	0.0373 (9)
N4	0.02186 (19)	0.2860 (5)	0.1191 (3)	0.0361 (9)
N7	−0.0502 (2)	0.6833 (5)	0.0994 (3)	0.0388 (9)
N8	−0.1138 (2)	0.6061 (5)	0.0483 (3)	0.0435 (10)
C3	0.0915 (2)	0.3259 (5)	0.1696 (3)	0.0317 (9)
C5	−0.0227 (2)	0.4200 (5)	0.1003 (3)	0.0336 (10)
C6	0.0051 (2)	0.5751 (5)	0.1322 (3)	0.0332 (10)
C9	−0.0993 (2)	0.4447 (6)	0.0469 (3)	0.0377 (11)
C10	−0.0494 (3)	0.8619 (6)	0.1113 (4)	0.0586 (15)
H10A	−0.0770	0.8909	0.1594	0.088*
H10B	−0.0732	0.9128	0.0509	0.088*
H10C	0.0027	0.8995	0.1315	0.088*
C11	−0.1567 (3)	0.3236 (6)	−0.0021 (4)	0.0567 (14)
H11A	−0.2011	0.3804	−0.0381	0.085*
H11B	−0.1712	0.2539	0.0453	0.085*
H11C	−0.1350	0.2579	−0.0454	0.085*
C15	0.2416 (3)	0.2357 (8)	0.1689 (5)	0.0646 (17)
H15A	0.2807	0.1526	0.1803	0.097*
H15B	0.2593	0.3302	0.2083	0.097*
H15C	0.2303	0.2669	0.1020	0.097*

	U11	U22	U33	U12	U13	U23
S12	0.0358 (6)	0.0407 (7)	0.0504 (7)	0.0015 (6)	0.0035 (5)	0.0050 (6)
O13	0.058 (2)	0.044 (2)	0.108 (3)	0.0052 (19)	−0.011 (2)	−0.022 (2)
O14	0.075 (3)	0.096 (3)	0.057 (2)	0.030 (2)	0.012 (2)	0.036 (2)
N1	0.0313 (19)	0.047 (2)	0.042 (2)	−0.0005 (18)	0.0021 (16)	−0.0085 (19)
N2	0.0316 (18)	0.038 (2)	0.039 (2)	0.0034 (17)	0.0013 (15)	0.0006 (18)
N4	0.0315 (18)	0.040 (2)	0.035 (2)	−0.0049 (16)	0.0025 (16)	0.0024 (17)
N7	0.0339 (19)	0.040 (2)	0.040 (2)	0.0048 (18)	0.0033 (16)	−0.0033 (18)
N8	0.0247 (18)	0.063 (3)	0.041 (2)	0.0028 (18)	0.0028 (16)	0.000 (2)
C3	0.0264 (18)	0.036 (2)	0.031 (2)	−0.0035 (19)	0.0035 (16)	0.001 (2)
C5	0.0250 (19)	0.045 (3)	0.030 (2)	0.000 (2)	0.0058 (16)	0.003 (2)
C6	0.027 (2)	0.041 (3)	0.030 (2)	0.0020 (19)	0.0049 (16)	−0.006 (2)
C9	0.025 (2)	0.051 (3)	0.035 (3)	−0.004 (2)	0.0017 (18)	0.007 (2)
C10	0.057 (3)	0.052 (3)	0.061 (4)	0.014 (3)	0.000 (3)	−0.003 (3)
C11	0.036 (2)	0.065 (3)	0.062 (3)	−0.022 (3)	−0.005 (2)	0.006 (3)
C15	0.035 (3)	0.073 (4)	0.089 (4)	0.009 (3)	0.020 (3)	0.023 (3)

S12—O13	1.418 (4)	C5—C6	1.393 (6)
S12—O14	1.430 (4)	C5—C9	1.423 (6)
S12—C15	1.733 (5)	C9—C11	1.476 (6)
S12—C3	1.803 (4)	C10—H10A	0.9600
N1—N2	1.331 (5)	C10—H10B	0.9600
N1—C6	1.350 (5)	C10—H10C	0.9600
N2—C3	1.330 (5)	C11—H11A	0.9600
N4—C3	1.329 (5)	C11—H11B	0.9600
N4—C5	1.340 (5)	C11—H11C	0.9600
N7—C6	1.326 (5)	C15—H15A	0.9600
N7—N8	1.357 (5)	C15—H15B	0.9600
N7—C10	1.461 (6)	C15—H15C	0.9600
N8—C9	1.338 (6)
O13—S12—O14	118.6 (3)	N8—C9—C5	107.3 (4)
O13—S12—C15	108.7 (3)	N8—C9—C11	123.0 (4)
O14—S12—C15	109.4 (3)	C5—C9—C11	129.8 (4)
O13—S12—C3	107.5 (2)	N7—C10—H10A	109.5
O14—S12—C3	107.6 (2)	N7—C10—H10B	109.5
C15—S12—C3	104.0 (2)	H10A—C10—H10B	109.5
N2—N1—C6	113.5 (4)	N7—C10—H10C	109.5
N1—N2—C3	119.7 (3)	H10A—C10—H10C	109.5
C3—N4—C5	110.6 (4)	H10B—C10—H10C	109.5
C6—N7—N8	110.5 (4)	C9—C11—H11A	109.5
C6—N7—C10	129.1 (4)	C9—C11—H11B	109.5
N8—N7—C10	120.4 (4)	H11A—C11—H11B	109.5
C9—N8—N7	108.6 (3)	C9—C11—H11C	109.5
N4—C3—N2	130.3 (4)	H11A—C11—H11C	109.5
N4—C3—S12	116.0 (3)	H11B—C11—H11C	109.5
N2—C3—S12	113.6 (3)	S12—C15—H15A	109.5
N4—C5—C6	121.3 (4)	S12—C15—H15B	109.5
N4—C5—C9	132.7 (4)	H15A—C15—H15B	109.5
C6—C5—C9	106.0 (4)	S12—C15—H15C	109.5
N7—C6—N1	127.9 (4)	H15A—C15—H15C	109.5
N7—C6—C5	107.7 (4)	H15B—C15—H15C	109.5
N1—C6—C5	124.4 (4)
C6—N1—N2—C3	0.2 (6)	C10—N7—C6—N1	2.4 (8)
C6—N7—N8—C9	−0.8 (5)	N8—N7—C6—C5	1.0 (5)
C10—N7—N8—C9	179.0 (4)	C10—N7—C6—C5	−178.8 (5)
C5—N4—C3—N2	4.2 (6)	N2—N1—C6—N7	−177.7 (4)
C5—N4—C3—S12	−178.4 (3)	N2—N1—C6—C5	3.7 (6)
N1—N2—C3—N4	−4.5 (7)	N4—C5—C6—N7	177.2 (4)
N1—N2—C3—S12	178.1 (3)	C9—C5—C6—N7	−0.8 (5)
O13—S12—C3—N4	17.9 (4)	N4—C5—C6—N1	−3.9 (7)
O14—S12—C3—N4	−110.9 (4)	C9—C5—C6—N1	178.1 (4)
C15—S12—C3—N4	133.0 (4)	N7—N8—C9—C5	0.2 (5)
O13—S12—C3—N2	−164.3 (3)	N7—N8—C9—C11	179.5 (4)
O14—S12—C3—N2	66.9 (4)	N4—C5—C9—N8	−177.3 (4)
C15—S12—C3—N2	−49.2 (4)	C6—C5—C9—N8	0.3 (5)
C3—N4—C5—C6	0.0 (6)	N4—C5—C9—C11	3.5 (8)
C3—N4—C5—C9	177.3 (4)	C6—C5—C9—C11	−178.9 (5)
N8—N7—C6—N1	−177.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···O13i	0.96	2.51	3.442 (7)	163
C11—H11B···O14ii	0.96	2.42	3.341 (7)	161
C15—H15A···N2iii	0.96	2.59	3.466 (7)	152
Cg(pyrazole)—···.Cg(triazine)ii	.	.	3.778 (3)	.
Cg(pyrazole)—···.Cg(triazine)iv	.	.	3.416 (3)	.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10C⋯O13i	0.96	2.51	3.442 (7)	163
C11—H11B⋯O14ii	0.96	2.42	3.341 (7)	161
C15—H15A⋯N2iii	0.96	2.59	3.466 (7)	152

Symmetry codes: (i) ; (ii) ; (iii) .