2-(3,4-Dimethyl-5,5-dioxo-2H,4H-pyrazolo-[4,3-c][1,2]benzothia-zin-2-yl)acetic acid.

In the title mol-ecule, C(13)H(13)N(3)O(4)S, the heterocyclic thia-zine ring adopts a half-chair conformation in which the S and an adjacent C atom are displaced by 0.919 (3) and 0.300 (4) Å, respectively, on the same side of the mean plane formed by the remaining ring atoms. The mean planes of the benzene and pyrazole rings are inclined at a dihedral angle of 18.32 (12)° with respect to each other. The acetate group is oriented at 80.75 (8)° with respect to the pyrazole ring. The crystal structure is stabilized by O-H⋯N and C-H⋯O hydrogen bonds, resulting in fused eight- and seven-membered rings with R(2) (2)(8) and R(2) (2)(7) graph-set motifs, respectively.

Related literature

For the biological activity of benzothia­zine derivatives, see: Turck et al. (1996 ▶); Silverstein et al. (2000 ▶); Lombardino et al. (1973 ▶); Zinnes et al. (1973 ▶); Ahmad et al. (2010 ▶). For related structures, see: Siddiqui et al. (2008 ▶, 2009 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C13H13N3O4S

M = 307.32

Monoclinic,

a = 10.495 (4) Å

b = 8.415 (2) Å

c = 15.136 (6) Å

β = 91.034 (19)°

V = 1336.5 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 173 K

0.14 × 0.12 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T min = 0.964, T max = 0.974

5770 measured reflections

3048 independent reflections

2196 reflections with I > σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.110

S = 1.03

3048 reflections

193 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.35 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812023677/pk2415sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023677/pk2415Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812023677/pk2415Isup3.cml

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

C13H13N3O4S	F(000) = 640
Mr = 307.32	Dx = 1.527 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1947 reflections
a = 10.495 (4) Å	θ = 1.0–27.5°
b = 8.415 (2) Å	µ = 0.26 mm−1
c = 15.136 (6) Å	T = 173 K
β = 91.034 (19)°	Block, colorless
V = 1336.5 (8) Å3	0.14 × 0.12 × 0.10 mm
Z = 4

Nonius KappaCCD diffractometer	3048 independent reflections
Radiation source: fine-focus sealed tube	2196 reflections with I > σ(I)
Graphite monochromator	Rint = 0.033
ω and φ scans	θmax = 27.5°, θmin = 4.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −13→13
Tmin = 0.964, Tmax = 0.974	k = −10→10
5770 measured reflections	l = −19→19

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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F2) = 0.110	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.047P)2 + 0.650P] where P = (Fo2 + 2Fc2)/3
3048 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
S1	0.20345 (5)	0.30572 (6)	0.10421 (3)	0.03013 (16)
O1	0.07080 (15)	0.28041 (19)	0.08552 (10)	0.0419 (4)
O2	0.29133 (16)	0.17922 (17)	0.08858 (10)	0.0392 (4)
O3	0.65265 (14)	0.19936 (17)	0.27745 (10)	0.0328 (4)
O4	0.82589 (14)	0.30151 (18)	0.34514 (10)	0.0344 (4)
H4O	0.8579	0.2128	0.3330	0.052*
N1	0.21936 (16)	0.35819 (19)	0.20921 (10)	0.0258 (4)
N2	0.52959 (16)	0.54568 (18)	0.19902 (10)	0.0246 (4)
N3	0.52853 (15)	0.48638 (19)	0.28304 (10)	0.0234 (4)
C1	0.25731 (19)	0.4733 (2)	0.04545 (12)	0.0261 (4)
C2	0.1949 (2)	0.5191 (2)	−0.03202 (13)	0.0306 (5)
H2	0.1192	0.4665	−0.0512	0.037*
C3	0.2448 (2)	0.6428 (3)	−0.08089 (13)	0.0344 (5)
H3	0.2035	0.6747	−0.1344	0.041*
C4	0.3543 (2)	0.7200 (3)	−0.05234 (13)	0.0332 (5)
H4	0.3889	0.8027	−0.0873	0.040*
C5	0.4142 (2)	0.6782 (2)	0.02673 (13)	0.0284 (5)
H5	0.4883	0.7338	0.0464	0.034*
C6	0.36539 (19)	0.5540 (2)	0.07754 (12)	0.0250 (4)
C7	0.41474 (19)	0.5083 (2)	0.16483 (12)	0.0238 (4)
C8	0.34399 (18)	0.4208 (2)	0.22614 (12)	0.0225 (4)
C9	0.1114 (2)	0.4429 (3)	0.25009 (15)	0.0353 (5)
H9A	0.1249	0.4473	0.3143	0.042*
H9B	0.0318	0.3862	0.2366	0.042*
H9C	0.1061	0.5512	0.2264	0.042*
C10	0.41904 (18)	0.4087 (2)	0.30145 (12)	0.0228 (4)
C11	0.3945 (2)	0.3369 (2)	0.38914 (13)	0.0302 (5)
H11A	0.3108	0.2851	0.3879	0.036*
H11B	0.3958	0.4202	0.4344	0.036*
H11C	0.4605	0.2580	0.4030	0.036*
C12	0.64872 (19)	0.4694 (2)	0.33106 (13)	0.0262 (4)
H12A	0.6344	0.4829	0.3951	0.031*
H12B	0.7084	0.5533	0.3121	0.031*
C13	0.70744 (18)	0.3072 (2)	0.31454 (12)	0.0226 (4)

	U11	U22	U33	U12	U13	U23
S1	0.0322 (3)	0.0236 (3)	0.0343 (3)	−0.0031 (2)	−0.0082 (2)	0.0006 (2)
O1	0.0357 (9)	0.0422 (9)	0.0471 (9)	−0.0137 (7)	−0.0147 (7)	0.0061 (7)
O2	0.0499 (11)	0.0234 (8)	0.0441 (9)	0.0048 (7)	−0.0049 (7)	−0.0029 (6)
O3	0.0285 (8)	0.0275 (7)	0.0423 (8)	0.0018 (6)	−0.0052 (7)	−0.0026 (7)
O4	0.0251 (8)	0.0325 (8)	0.0454 (9)	0.0070 (6)	−0.0072 (7)	−0.0052 (7)
N1	0.0196 (9)	0.0262 (8)	0.0315 (9)	−0.0028 (7)	−0.0037 (7)	0.0022 (7)
N2	0.0240 (9)	0.0232 (8)	0.0268 (8)	0.0009 (7)	0.0010 (7)	0.0018 (7)
N3	0.0199 (9)	0.0239 (8)	0.0264 (8)	0.0003 (7)	−0.0019 (6)	0.0023 (7)
C1	0.0269 (12)	0.0238 (10)	0.0275 (10)	0.0046 (8)	0.0004 (8)	−0.0016 (8)
C2	0.0326 (13)	0.0298 (11)	0.0292 (10)	0.0041 (9)	−0.0047 (9)	−0.0052 (9)
C3	0.0406 (14)	0.0390 (12)	0.0234 (9)	0.0077 (10)	−0.0018 (9)	0.0026 (9)
C4	0.0337 (13)	0.0371 (12)	0.0291 (10)	0.0030 (10)	0.0057 (9)	0.0067 (9)
C5	0.0238 (11)	0.0310 (11)	0.0304 (10)	0.0012 (9)	0.0030 (8)	0.0019 (9)
C6	0.0226 (11)	0.0247 (10)	0.0277 (9)	0.0055 (8)	0.0010 (8)	−0.0005 (8)
C7	0.0215 (11)	0.0203 (9)	0.0296 (10)	0.0013 (8)	−0.0011 (8)	−0.0005 (8)
C8	0.0203 (10)	0.0195 (9)	0.0277 (9)	0.0005 (8)	0.0004 (8)	0.0009 (8)
C9	0.0210 (11)	0.0393 (12)	0.0456 (12)	−0.0035 (9)	0.0026 (9)	−0.0003 (10)
C10	0.0204 (10)	0.0198 (9)	0.0284 (9)	0.0013 (8)	0.0006 (8)	0.0006 (8)
C11	0.0279 (12)	0.0313 (11)	0.0313 (10)	−0.0019 (9)	−0.0008 (9)	0.0052 (9)
C12	0.0224 (11)	0.0262 (10)	0.0297 (10)	−0.0013 (8)	−0.0042 (8)	−0.0009 (8)
C13	0.0181 (10)	0.0266 (10)	0.0231 (9)	0.0000 (8)	0.0001 (7)	0.0033 (8)

S1—O2	1.4309 (16)	C3—H3	0.9500
S1—O1	1.4315 (17)	C4—C5	1.387 (3)
S1—N1	1.6550 (18)	C4—H4	0.9500
S1—C1	1.765 (2)	C5—C6	1.401 (3)
O3—C13	1.207 (2)	C5—H5	0.9500
O4—C13	1.320 (2)	C6—C7	1.462 (3)
O4—H4O	0.8400	C7—C8	1.407 (3)
N1—C8	1.429 (2)	C8—C10	1.378 (3)
N1—C9	1.483 (3)	C9—H9A	0.9800
N2—C7	1.341 (2)	C9—H9B	0.9800
N2—N3	1.366 (2)	C9—H9C	0.9800
N3—C10	1.355 (2)	C10—C11	1.485 (3)
N3—C12	1.452 (2)	C11—H11A	0.9800
C1—C2	1.388 (3)	C11—H11B	0.9800
C1—C6	1.401 (3)	C11—H11C	0.9800
C2—C3	1.385 (3)	C12—C13	1.520 (3)
C2—H2	0.9500	C12—H12A	0.9900
C3—C4	1.383 (3)	C12—H12B	0.9900
O2—S1—O1	118.95 (10)	C1—C6—C7	117.20 (18)
O2—S1—N1	107.64 (9)	N2—C7—C8	110.47 (17)
O1—S1—N1	108.08 (10)	N2—C7—C6	126.05 (17)
O2—S1—C1	107.32 (10)	C8—C7—C6	123.45 (18)
O1—S1—C1	109.78 (9)	C10—C8—C7	106.48 (17)
N1—S1—C1	104.07 (9)	C10—C8—N1	128.98 (17)
C13—O4—H4O	109.5	C7—C8—N1	124.53 (17)
C8—N1—C9	116.85 (16)	N1—C9—H9A	109.5
C8—N1—S1	110.29 (13)	N1—C9—H9B	109.5
C9—N1—S1	117.66 (13)	H9A—C9—H9B	109.5
C7—N2—N3	104.55 (15)	N1—C9—H9C	109.5
C10—N3—N2	112.87 (15)	H9A—C9—H9C	109.5
C10—N3—C12	125.58 (16)	H9B—C9—H9C	109.5
N2—N3—C12	118.72 (15)	N3—C10—C8	105.57 (16)
C2—C1—C6	121.69 (19)	N3—C10—C11	122.79 (17)
C2—C1—S1	119.80 (16)	C8—C10—C11	131.57 (18)
C6—C1—S1	118.48 (15)	C10—C11—H11A	109.5
C3—C2—C1	118.9 (2)	C10—C11—H11B	109.5
C3—C2—H2	120.6	H11A—C11—H11B	109.5
C1—C2—H2	120.6	C10—C11—H11C	109.5
C4—C3—C2	120.44 (19)	H11A—C11—H11C	109.5
C4—C3—H3	119.8	H11B—C11—H11C	109.5
C2—C3—H3	119.8	N3—C12—C13	110.94 (15)
C3—C4—C5	120.8 (2)	N3—C12—H12A	109.5
C3—C4—H4	119.6	C13—C12—H12A	109.5
C5—C4—H4	119.6	N3—C12—H12B	109.5
C4—C5—C6	119.9 (2)	C13—C12—H12B	109.5
C4—C5—H5	120.1	H12A—C12—H12B	108.0
C6—C5—H5	120.1	O3—C13—O4	125.03 (18)
C5—C6—C1	118.26 (18)	O3—C13—C12	124.07 (17)
C5—C6—C7	124.43 (18)	O4—C13—C12	110.90 (16)
O2—S1—N1—C8	64.00 (15)	N3—N2—C7—C6	176.09 (18)
O1—S1—N1—C8	−166.34 (12)	C5—C6—C7—N2	−18.7 (3)
C1—S1—N1—C8	−49.68 (15)	C1—C6—C7—N2	165.16 (18)
O2—S1—N1—C9	−158.49 (15)	C5—C6—C7—C8	159.33 (19)
O1—S1—N1—C9	−28.84 (17)	C1—C6—C7—C8	−16.8 (3)
C1—S1—N1—C9	87.83 (16)	N2—C7—C8—C10	1.5 (2)
C7—N2—N3—C10	2.1 (2)	C6—C7—C8—C10	−176.80 (17)
C7—N2—N3—C12	164.15 (16)	N2—C7—C8—N1	−177.84 (17)
O2—S1—C1—C2	105.04 (18)	C6—C7—C8—N1	3.8 (3)
O1—S1—C1—C2	−25.6 (2)	C9—N1—C8—C10	76.3 (3)
N1—S1—C1—C2	−141.05 (16)	S1—N1—C8—C10	−145.81 (18)
O2—S1—C1—C6	−73.08 (18)	C9—N1—C8—C7	−104.5 (2)
O1—S1—C1—C6	156.31 (16)	S1—N1—C8—C7	33.4 (2)
N1—S1—C1—C6	40.84 (18)	N2—N3—C10—C8	−1.2 (2)
C6—C1—C2—C3	3.3 (3)	C12—N3—C10—C8	−161.78 (17)
S1—C1—C2—C3	−174.78 (15)	N2—N3—C10—C11	−178.68 (17)
C1—C2—C3—C4	−0.6 (3)	C12—N3—C10—C11	20.8 (3)
C2—C3—C4—C5	−1.8 (3)	C7—C8—C10—N3	−0.2 (2)
C3—C4—C5—C6	1.5 (3)	N1—C8—C10—N3	179.14 (18)
C4—C5—C6—C1	1.1 (3)	C7—C8—C10—C11	177.0 (2)
C4—C5—C6—C7	−175.00 (19)	N1—C8—C10—C11	−3.7 (4)
C2—C1—C6—C5	−3.5 (3)	C10—N3—C12—C13	70.0 (2)
S1—C1—C6—C5	174.58 (15)	N2—N3—C12—C13	−89.5 (2)
C2—C1—C6—C7	172.87 (18)	N3—C12—C13—O3	−10.2 (3)
S1—C1—C6—C7	−9.0 (2)	N3—C12—C13—O4	168.99 (16)
N3—N2—C7—C8	−2.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···N2i	0.84	1.90	2.724 (2)	165
C9—H9A···O2ii	0.98	2.59	3.297 (3)	129
C5—H5···O4iii	0.95	2.59	3.476 (3)	155
C12—H12B···O3iii	0.99	2.35	3.303 (3)	160
C9—H9B···O1	0.98	2.49	2.867 (3)	102

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯N2i	0.84	1.90	2.724 (2)	165
C9—H9A⋯O2ii	0.98	2.59	3.297 (3)	129
C5—H5⋯O4iii	0.95	2.59	3.476 (3)	155
C12—H12B⋯O3iii	0.99	2.35	3.303 (3)	160

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