Ethyl 2-(3,4-dimethyl-5,5-dioxo-1H,4H-benzo[e]pyrazolo-[4,3-c][1,2]thia-zin-1-yl)acetate.

In the title mol-ecule, C(15)H(17)N(3)O(4)S, the heterocyclic thia-zine ring adopts a twist-boat conformation, which differs from that in related compounds, with adjacent S and C atoms displaced by 0.981 (4) and 0.413 (5) Å, respectively, on the same side of the mean plane formed by the remaining ring atoms. The mean plane of the benzene ring makes a dihedral angle of 23.43 (14)° with the mean plane of the pyrazole ring. In the crystal, mol-ecules are connected by weak C-H⋯O hydrogen bonds to form a three-dimensional network. The H atoms of the methyl group attached to the pyrazole ring were refined over six sites with equal occupancies.

Related literature

For background literature and crystal structures of related pyrazolo­benzothia­zine derivatives, see: Aslam et al. (2012 ▶); Ahmad et al. (2012 ▶). For the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C15H17N3O4S

M = 335.38

Monoclinic,

a = 8.3027 (2) Å

b = 8.5915 (3) Å

c = 22.3476 (7) Å

β = 90.674 (2)°

V = 1594.00 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 173 K

0.20 × 0.18 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T min = 0.956, T max = 0.965

15091 measured reflections

3576 independent reflections

2820 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.127

S = 1.10

3576 reflections

210 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.45 e Å−3

Data collection: COLLECT (Nonius, 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/S1600536812039797/lh5533sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039797/lh5533Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812039797/lh5533Isup3.cml

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

C15H17N3O4S	F(000) = 704
Mr = 335.38	Dx = 1.398 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3460 reflections
a = 8.3027 (2) Å	θ = 1.0–27.5°
b = 8.5915 (3) Å	µ = 0.23 mm−1
c = 22.3476 (7) Å	T = 173 K
β = 90.674 (2)°	Block, colourless
V = 1594.00 (8) Å3	0.20 × 0.18 × 0.16 mm
Z = 4

Nonius KappaCCD diffractometer	3576 independent reflections
Radiation source: fine-focus sealed tube	2820 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω and φ scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −10→10
Tmin = 0.956, Tmax = 0.965	k = −11→11
15091 measured reflections	l = −28→28

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0235P)2 + 2.7353P] where P = (Fo2 + 2Fc2)/3
3576 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.45 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	Occ. (<1)
S1	0.60768 (7)	0.28409 (8)	0.67513 (3)	0.02293 (16)
O1	0.6208 (2)	0.4498 (2)	0.67696 (8)	0.0301 (4)
O2	0.7203 (2)	0.1922 (2)	0.70884 (8)	0.0295 (4)
O3	0.1309 (3)	−0.4262 (3)	0.64119 (9)	0.0435 (6)
O4	0.1716 (3)	−0.2669 (3)	0.56356 (10)	0.0537 (7)
N1	0.6194 (2)	0.2279 (3)	0.60491 (9)	0.0233 (5)
N2	0.4504 (3)	−0.1506 (3)	0.61898 (9)	0.0251 (5)
N3	0.5677 (3)	−0.1867 (3)	0.57904 (10)	0.0296 (5)
C1	0.4117 (3)	0.2290 (3)	0.69663 (11)	0.0231 (5)
C2	0.3265 (3)	0.3239 (3)	0.73520 (12)	0.0289 (6)
H2	0.3708	0.4194	0.7490	0.035*
C3	0.1753 (3)	0.2761 (4)	0.75310 (13)	0.0365 (7)
H3	0.1166	0.3378	0.7806	0.044*
C4	0.1088 (3)	0.1396 (4)	0.73138 (13)	0.0352 (7)
H4	0.0046	0.1088	0.7438	0.042*
C5	0.1925 (3)	0.0476 (3)	0.69173 (12)	0.0300 (6)
H5	0.1438	−0.0440	0.6760	0.036*
C6	0.3483 (3)	0.0884 (3)	0.67452 (11)	0.0237 (5)
C7	0.4492 (3)	0.0034 (3)	0.63269 (11)	0.0230 (5)
C8	0.5724 (3)	0.0676 (3)	0.59991 (11)	0.0231 (5)
C9	0.6426 (3)	−0.0531 (3)	0.56744 (11)	0.0273 (6)
C10	0.7810 (4)	−0.0464 (4)	0.52519 (14)	0.0400 (7)
H10A	0.8020	−0.1507	0.5094	0.060*	0.50
H10B	0.8771	−0.0083	0.5465	0.060*	0.50
H10C	0.7547	0.0243	0.4921	0.060*	0.50
H10D	0.8205	0.0609	0.5226	0.060*	0.50
H10E	0.7454	−0.0815	0.4855	0.060*	0.50
H10F	0.8679	−0.1141	0.5399	0.060*	0.50
C11	0.5531 (4)	0.3344 (3)	0.55871 (12)	0.0354 (7)
H11A	0.5831	0.2970	0.5189	0.053*
H11B	0.5968	0.4391	0.5650	0.053*
H11C	0.4355	0.3375	0.5616	0.053*
C12	0.3618 (3)	−0.2766 (3)	0.64581 (11)	0.0268 (6)
H12A	0.3318	−0.2465	0.6870	0.032*
H12B	0.4325	−0.3692	0.6487	0.032*
C13	0.2108 (3)	−0.3195 (3)	0.61103 (12)	0.0289 (6)
C14	−0.0120 (4)	−0.4933 (5)	0.61234 (15)	0.0498 (9)
H14A	−0.0681	−0.4125	0.5884	0.060*
H14B	−0.0871	−0.5311	0.6432	0.060*
C15	0.0347 (4)	−0.6243 (4)	0.57295 (16)	0.0516 (9)
H15A	−0.0622	−0.6712	0.5552	0.077*
H15B	0.0930	−0.7027	0.5966	0.077*
H15C	0.1042	−0.5855	0.5411	0.077*

	U11	U22	U33	U12	U13	U23
S1	0.0218 (3)	0.0242 (3)	0.0228 (3)	−0.0016 (3)	0.0000 (2)	−0.0012 (3)
O1	0.0321 (10)	0.0244 (10)	0.0339 (10)	−0.0043 (8)	0.0013 (8)	−0.0057 (8)
O2	0.0242 (9)	0.0367 (11)	0.0276 (9)	0.0017 (8)	−0.0034 (7)	0.0017 (8)
O3	0.0440 (12)	0.0537 (15)	0.0330 (11)	−0.0269 (11)	0.0023 (9)	0.0034 (10)
O4	0.0597 (15)	0.0542 (16)	0.0466 (14)	−0.0224 (12)	−0.0224 (12)	0.0196 (12)
N1	0.0263 (11)	0.0227 (11)	0.0210 (10)	−0.0037 (9)	0.0032 (8)	−0.0002 (9)
N2	0.0313 (11)	0.0237 (12)	0.0204 (10)	−0.0042 (9)	0.0045 (9)	−0.0025 (9)
N3	0.0361 (12)	0.0298 (13)	0.0231 (11)	−0.0019 (10)	0.0093 (9)	−0.0039 (10)
C1	0.0232 (12)	0.0264 (13)	0.0198 (12)	0.0043 (10)	0.0011 (9)	0.0015 (10)
C2	0.0317 (14)	0.0263 (15)	0.0287 (14)	0.0032 (11)	0.0035 (11)	−0.0015 (11)
C3	0.0338 (15)	0.0379 (17)	0.0381 (16)	0.0142 (13)	0.0132 (12)	0.0002 (14)
C4	0.0221 (13)	0.0428 (18)	0.0408 (16)	0.0041 (12)	0.0078 (11)	0.0069 (14)
C5	0.0249 (13)	0.0311 (15)	0.0342 (15)	−0.0011 (12)	0.0007 (11)	0.0007 (12)
C6	0.0220 (12)	0.0270 (14)	0.0219 (12)	0.0015 (10)	−0.0008 (10)	0.0019 (10)
C7	0.0234 (12)	0.0256 (13)	0.0200 (12)	−0.0018 (10)	−0.0012 (10)	−0.0006 (10)
C8	0.0249 (12)	0.0238 (13)	0.0206 (12)	−0.0034 (10)	0.0010 (10)	0.0000 (10)
C9	0.0327 (14)	0.0275 (14)	0.0217 (13)	−0.0016 (12)	0.0066 (11)	−0.0007 (11)
C10	0.0475 (18)	0.0366 (17)	0.0362 (16)	−0.0020 (14)	0.0200 (14)	−0.0044 (14)
C11	0.0515 (18)	0.0303 (16)	0.0244 (14)	−0.0047 (14)	−0.0019 (12)	0.0074 (12)
C12	0.0332 (14)	0.0236 (13)	0.0234 (13)	−0.0036 (11)	0.0003 (11)	0.0028 (11)
C13	0.0323 (14)	0.0284 (15)	0.0260 (14)	−0.0043 (12)	0.0016 (11)	−0.0004 (11)
C14	0.0363 (17)	0.063 (2)	0.050 (2)	−0.0272 (17)	0.0035 (15)	−0.0070 (18)
C15	0.052 (2)	0.047 (2)	0.055 (2)	−0.0165 (17)	−0.0085 (17)	−0.0043 (18)

S1—O1	1.429 (2)	C6—C7	1.458 (3)
S1—O2	1.4312 (19)	C7—C8	1.381 (3)
S1—N1	1.646 (2)	C8—C9	1.397 (4)
S1—C1	1.767 (3)	C9—C10	1.497 (4)
O3—C13	1.321 (3)	C10—H10A	0.9800
O3—C14	1.462 (3)	C10—H10B	0.9800
O4—C13	1.195 (3)	C10—H10C	0.9800
N1—C8	1.435 (3)	C10—H10D	0.9800
N1—C11	1.481 (3)	C10—H10E	0.9800
N2—C7	1.358 (3)	C10—H10F	0.9800
N2—N3	1.365 (3)	C11—H11A	0.9800
N2—C12	1.443 (3)	C11—H11B	0.9800
N3—C9	1.333 (3)	C11—H11C	0.9800
C1—C2	1.387 (4)	C12—C13	1.513 (4)
C1—C6	1.405 (4)	C12—H12A	0.9900
C2—C3	1.384 (4)	C12—H12B	0.9900
C2—H2	0.9500	C14—C15	1.483 (5)
C3—C4	1.381 (4)	C14—H14A	0.9900
C3—H3	0.9500	C14—H14B	0.9900
C4—C5	1.381 (4)	C15—H15A	0.9800
C4—H4	0.9500	C15—H15B	0.9800
C5—C6	1.399 (4)	C15—H15C	0.9800
C5—H5	0.9500
O1—S1—O2	119.04 (12)	H10A—C10—H10C	109.5
O1—S1—N1	108.32 (12)	H10B—C10—H10C	109.5
O2—S1—N1	107.12 (11)	C9—C10—H10D	109.5
O1—S1—C1	109.24 (12)	H10A—C10—H10D	141.1
O2—S1—C1	107.91 (12)	H10B—C10—H10D	56.3
N1—S1—C1	104.22 (11)	H10C—C10—H10D	56.3
C13—O3—C14	117.3 (2)	C9—C10—H10E	109.5
C8—N1—C11	116.1 (2)	H10A—C10—H10E	56.3
C8—N1—S1	109.67 (17)	H10B—C10—H10E	141.1
C11—N1—S1	117.25 (18)	H10C—C10—H10E	56.3
C7—N2—N3	112.1 (2)	H10D—C10—H10E	109.5
C7—N2—C12	129.2 (2)	C9—C10—H10F	109.5
N3—N2—C12	118.2 (2)	H10A—C10—H10F	56.3
C9—N3—N2	105.6 (2)	H10B—C10—H10F	56.3
C2—C1—C6	122.2 (2)	H10C—C10—H10F	141.1
C2—C1—S1	119.3 (2)	H10D—C10—H10F	109.5
C6—C1—S1	118.50 (19)	H10E—C10—H10F	109.5
C3—C2—C1	118.4 (3)	N1—C11—H11A	109.5
C3—C2—H2	120.8	N1—C11—H11B	109.5
C1—C2—H2	120.8	H11A—C11—H11B	109.5
C4—C3—C2	120.7 (3)	N1—C11—H11C	109.5
C4—C3—H3	119.7	H11A—C11—H11C	109.5
C2—C3—H3	119.7	H11B—C11—H11C	109.5
C5—C4—C3	120.6 (3)	N2—C12—C13	113.1 (2)
C5—C4—H4	119.7	N2—C12—H12A	109.0
C3—C4—H4	119.7	C13—C12—H12A	109.0
C4—C5—C6	120.5 (3)	N2—C12—H12B	109.0
C4—C5—H5	119.8	C13—C12—H12B	109.0
C6—C5—H5	119.8	H12A—C12—H12B	107.8
C5—C6—C1	117.5 (2)	O4—C13—O3	125.6 (3)
C5—C6—C7	126.2 (2)	O4—C13—C12	125.4 (3)
C1—C6—C7	116.1 (2)	O3—C13—C12	109.0 (2)
N2—C7—C8	105.2 (2)	O3—C14—C15	110.2 (3)
N2—C7—C6	129.7 (2)	O3—C14—H14A	109.6
C8—C7—C6	125.1 (2)	C15—C14—H14A	109.6
C7—C8—C9	107.2 (2)	O3—C14—H14B	109.6
C7—C8—N1	123.0 (2)	C15—C14—H14B	109.6
C9—C8—N1	129.6 (2)	H14A—C14—H14B	108.1
N3—C9—C8	109.9 (2)	C14—C15—H15A	109.5
N3—C9—C10	121.3 (3)	C14—C15—H15B	109.5
C8—C9—C10	128.8 (3)	H15A—C15—H15B	109.5
C9—C10—H10A	109.5	C14—C15—H15C	109.5
C9—C10—H10B	109.5	H15A—C15—H15C	109.5
H10A—C10—H10B	109.5	H15B—C15—H15C	109.5
C9—C10—H10C	109.5
O1—S1—N1—C8	−167.65 (16)	N3—N2—C7—C6	−177.6 (2)
O2—S1—N1—C8	62.78 (19)	C12—N2—C7—C6	−6.1 (4)
C1—S1—N1—C8	−51.42 (19)	C5—C6—C7—N2	−27.8 (4)
O1—S1—N1—C11	−32.5 (2)	C1—C6—C7—N2	156.1 (3)
O2—S1—N1—C11	−162.02 (19)	C5—C6—C7—C8	155.4 (3)
C1—S1—N1—C11	83.8 (2)	C1—C6—C7—C8	−20.7 (4)
C7—N2—N3—C9	0.2 (3)	N2—C7—C8—C9	0.2 (3)
C12—N2—N3—C9	−172.2 (2)	C6—C7—C8—C9	177.6 (2)
O1—S1—C1—C2	−28.1 (2)	N2—C7—C8—N1	−175.4 (2)
O2—S1—C1—C2	102.6 (2)	C6—C7—C8—N1	2.1 (4)
N1—S1—C1—C2	−143.7 (2)	C11—N1—C8—C7	−98.0 (3)
O1—S1—C1—C6	152.79 (19)	S1—N1—C8—C7	37.7 (3)
O2—S1—C1—C6	−76.4 (2)	C11—N1—C8—C9	87.5 (3)
N1—S1—C1—C6	37.2 (2)	S1—N1—C8—C9	−136.7 (3)
C6—C1—C2—C3	1.2 (4)	N2—N3—C9—C8	−0.1 (3)
S1—C1—C2—C3	−177.9 (2)	N2—N3—C9—C10	179.6 (2)
C1—C2—C3—C4	−2.2 (4)	C7—C8—C9—N3	0.0 (3)
C2—C3—C4—C5	0.5 (4)	N1—C8—C9—N3	175.1 (2)
C3—C4—C5—C6	2.3 (4)	C7—C8—C9—C10	−179.7 (3)
C4—C5—C6—C1	−3.2 (4)	N1—C8—C9—C10	−4.6 (5)
C4—C5—C6—C7	−179.2 (3)	C7—N2—C12—C13	97.8 (3)
C2—C1—C6—C5	1.5 (4)	N3—N2—C12—C13	−91.2 (3)
S1—C1—C6—C5	−179.50 (19)	C14—O3—C13—O4	4.4 (5)
C2—C1—C6—C7	177.9 (2)	C14—O3—C13—C12	−174.7 (3)
S1—C1—C6—C7	−3.1 (3)	N2—C12—C13—O4	6.1 (4)
N3—N2—C7—C8	−0.2 (3)	N2—C12—C13—O3	−174.8 (2)
C12—N2—C7—C8	171.2 (2)	C13—O3—C14—C15	85.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2i	0.99	2.43	3.338 (3)	152
C12—H12B···O1ii	0.99	2.29	3.255 (3)	165
C4—H4···O2iii	0.95	2.58	3.290 (3)	132
C10—H10C···O4iv	0.98	2.51	3.369 (4)	147
C14—H14B···O1v	0.99	2.55	3.424 (4)	147
C11—H11B···O1	0.98	2.51	2.872 (3)	102

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O2i	0.99	2.43	3.338 (3)	152
C12—H12B⋯O1ii	0.99	2.29	3.255 (3)	165
C4—H4⋯O2iii	0.95	2.58	3.290 (3)	132
C10—H10C⋯O4iv	0.98	2.51	3.369 (4)	147
C14—H14B⋯O1v	0.99	2.55	3.424 (4)	147

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