2-(3,4-Dimethyl-5,5-dioxo-2H,4H-pyrazolo-[4,3-c][1,2]benzothia-zin-2-yl)-N-(2-fluoro-benz-yl)acetamide.

In the title mol-ecule, C(20)H(19)FN(4)O(3)S, the heterocyclic thia-zine ring adopts a half-chair conformation with the S atom displaced by 0.668 (4) Å from the mean plane formed by the remaining ring atoms. The mean planes of the benzene and pyrazole rings are inclined with respect to each other at a dihedral angle of 17.4 (3)°. The acetamide chain (O/N/C/C/C) linking the pyrazole and 2-fluoro-benzyl rings is essentially planar (r.m.s. deviation = 0.030 Å) and forms dihedral angles with the mean planes of these rings of 78.8 (2) and 78.89 (14)°, respectively. The crystal structure is stabilized by N-H⋯O and C-H⋯O hydrogen-bonding inter-actions, resulting in a six-membered ring with an R(2) (1)(6) motif, while C-H⋯O and C-H⋯F hydrogen-bonding inter-actions result in chains of mol-ecules lying along the c axis in a zigzag fashion.

Related literature

For biological activities of benzothia­zine derivatives, see: Turck et al. (1996 ▶); Silverstein et al. (2000 ▶); Lombardino et al. (1973 ▶); Zinnes et al. (1973 ▶); Ahmad, Siddiqui, Ahmad et al. (2010 ▶); Ahmad, Siddiqui, Zia-ur-Rehman & Parvez (2010 ▶). For related crystal structures, see: Siddiqui et al. (2008 ▶, 2009 ▶). For graph-set notations, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C20H19FN4O3S

M = 414.45

Orthorhombic,

a = 27.4331 (15) Å

b = 7.4519 (5) Å

c = 9.2598 (6) Å

V = 1893.0 (2) Å3

Z = 4

Cu Kα radiation

μ = 1.88 mm−1

T = 173 K

0.12 × 0.06 × 0.05 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.806, T max = 0.912

17539 measured reflections

3009 independent reflections

2730 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.146

S = 1.09

3009 reflections

264 parameters

1 restraint

H-atom parameters constrained

Δρmax = 1.05 e Å−3

Δρmin = −0.45 e Å−3

Absolute structure: Flack (1983 ▶), 1207 Friedel pairs

Flack parameter: 0.05 (3)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); 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/S160053681203187X/qm2076sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203187X/qm2076Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681203187X/qm2076Isup3.cml

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

C20H19FN4O3S	F(000) = 864
Mr = 414.45	Dx = 1.454 Mg m−3
Orthorhombic, Pna21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 8539 reflections
a = 27.4331 (15) Å	θ = 3.2–67.4°
b = 7.4519 (5) Å	µ = 1.88 mm−1
c = 9.2598 (6) Å	T = 173 K
V = 1893.0 (2) Å3	Needle, colorless
Z = 4	0.12 × 0.06 × 0.05 mm

Bruker SMART APEXII CCD diffractometer	3009 independent reflections
Radiation source: fine-focus sealed tube	2730 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and φ scans	θmax = 68.1°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −32→32
Tmin = 0.806, Tmax = 0.912	k = −8→8
17539 measured reflections	l = −10→8

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049	H-atom parameters constrained
wR(F2) = 0.146	w = 1/[σ2(Fo2) + (0.0785P)2 + 2.144P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
3009 reflections	Δρmax = 1.05 e Å−3
264 parameters	Δρmin = −0.45 e Å−3
1 restraint	Absolute structure: Flack (1983), 1207 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.05 (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
C1	0.18005 (14)	0.5585 (5)	0.5621 (5)	0.0298 (9)
C2	0.19683 (14)	0.6653 (6)	0.4508 (5)	0.0366 (10)
H2	0.2306	0.6695	0.4286	0.044*
C3	0.16385 (16)	0.7660 (6)	0.3722 (6)	0.0410 (11)
H3	0.1747	0.8363	0.2928	0.049*
C4	0.11472 (16)	0.7642 (5)	0.4095 (6)	0.0411 (11)
H4	0.0925	0.8391	0.3589	0.049*
C5	0.09785 (14)	0.6551 (5)	0.5191 (5)	0.0330 (10)
H5	0.0642	0.6552	0.5433	0.040*
C6	0.12980 (13)	0.5455 (5)	0.5939 (5)	0.0276 (8)
C7	0.11436 (12)	0.4057 (5)	0.6914 (5)	0.0279 (8)
C8	0.14419 (13)	0.2643 (5)	0.7402 (5)	0.0294 (9)
C9	0.21028 (17)	0.0897 (7)	0.6235 (6)	0.0487 (13)
H9A	0.1937	−0.0172	0.6608	0.073*
H9B	0.2456	0.0742	0.6326	0.073*
H9C	0.2018	0.1066	0.5216	0.073*
C10	0.11529 (13)	0.1512 (5)	0.8186 (5)	0.0309 (9)
C11	0.12523 (17)	−0.0203 (6)	0.8981 (6)	0.0402 (11)
H11A	0.1037	−0.0283	0.9824	0.060*
H11B	0.1593	−0.0221	0.9301	0.060*
H11C	0.1192	−0.1225	0.8340	0.060*
C12	0.02597 (14)	0.1619 (5)	0.8796 (5)	0.0336 (9)
H12A	−0.0003	0.2517	0.8664	0.040*
H12B	0.0315	0.1467	0.9845	0.040*
C13	0.00996 (13)	−0.0174 (5)	0.8142 (5)	0.0265 (8)
C14	−0.02579 (14)	−0.3102 (5)	0.8631 (5)	0.0317 (9)
H14A	−0.0295	−0.3838	0.9515	0.038*
H14B	0.0014	−0.3620	0.8063	0.038*
C15	−0.07211 (15)	−0.3255 (5)	0.7752 (5)	0.0321 (9)
C16	−0.07666 (19)	−0.4367 (6)	0.6583 (6)	0.0504 (13)
C17	−0.1212 (2)	−0.4580 (7)	0.5805 (6)	0.0593 (16)
H17	−0.1236	−0.5374	0.5006	0.071*
C18	−0.1600 (2)	−0.3605 (8)	0.6252 (8)	0.0618 (16)
H18	−0.1898	−0.3701	0.5735	0.074*
C19	−0.15798 (19)	−0.2509 (9)	0.7397 (8)	0.0635 (16)
H19	−0.1864	−0.1850	0.7649	0.076*
C20	−0.11537 (14)	−0.2278 (8)	0.8259 (9)	0.077 (2)
H20	−0.1150	−0.1547	0.9099	0.093*
F1	−0.03977 (13)	−0.5300 (6)	0.6187 (5)	0.0875 (13)
N1	0.19490 (11)	0.2479 (4)	0.7068 (4)	0.0341 (9)
N2	0.06857 (10)	0.3820 (4)	0.7375 (4)	0.0281 (7)
N3	0.07015 (11)	0.2262 (4)	0.8123 (4)	0.0294 (7)
N4	−0.01247 (11)	−0.1285 (5)	0.9057 (4)	0.0304 (8)
H4A	−0.0193	−0.0912	0.9936	0.036*
O1	0.22202 (11)	0.5389 (4)	0.8089 (4)	0.0455 (8)
O2	0.26539 (10)	0.4115 (5)	0.5993 (4)	0.0522 (9)
O3	0.01791 (9)	−0.0534 (4)	0.6870 (4)	0.0345 (6)
S1	0.22083 (3)	0.44366 (14)	0.67509 (13)	0.0366 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0245 (19)	0.035 (2)	0.030 (3)	−0.0034 (15)	−0.0003 (17)	−0.0045 (17)
C2	0.0277 (19)	0.041 (2)	0.041 (3)	−0.0089 (16)	0.0123 (19)	−0.003 (2)
C3	0.045 (2)	0.039 (2)	0.038 (3)	−0.0113 (19)	0.003 (2)	0.008 (2)
C4	0.037 (2)	0.032 (2)	0.055 (3)	−0.0024 (17)	−0.004 (2)	0.007 (2)
C5	0.0247 (18)	0.0297 (19)	0.044 (3)	−0.0011 (15)	−0.0004 (18)	−0.0020 (19)
C6	0.0256 (18)	0.0299 (18)	0.027 (2)	−0.0046 (15)	0.0001 (17)	−0.0017 (17)
C7	0.0202 (15)	0.0357 (19)	0.028 (2)	−0.0012 (13)	0.0007 (17)	−0.0018 (19)
C8	0.0192 (16)	0.041 (2)	0.028 (2)	−0.0003 (15)	−0.0001 (17)	−0.0041 (17)
C9	0.038 (2)	0.057 (3)	0.051 (3)	0.011 (2)	0.004 (2)	−0.014 (2)
C10	0.0257 (18)	0.0307 (19)	0.036 (3)	0.0002 (14)	−0.0043 (17)	−0.0015 (18)
C11	0.038 (2)	0.042 (2)	0.041 (3)	0.0007 (18)	−0.006 (2)	0.010 (2)
C12	0.0290 (19)	0.038 (2)	0.033 (3)	−0.0057 (16)	0.0026 (18)	−0.0058 (19)
C13	0.0202 (17)	0.036 (2)	0.023 (2)	0.0010 (14)	0.0011 (16)	0.0009 (18)
C14	0.0278 (18)	0.0296 (19)	0.038 (3)	−0.0008 (15)	0.0007 (18)	0.0023 (18)
C15	0.037 (2)	0.035 (2)	0.024 (2)	−0.0099 (16)	−0.0015 (17)	0.0037 (17)
C16	0.058 (3)	0.050 (3)	0.044 (3)	−0.003 (2)	0.004 (3)	0.003 (2)
C17	0.092 (4)	0.056 (3)	0.030 (3)	−0.029 (3)	−0.018 (3)	0.006 (2)
C18	0.047 (3)	0.070 (4)	0.069 (4)	−0.018 (3)	−0.008 (3)	0.022 (3)
C19	0.043 (3)	0.074 (4)	0.073 (5)	−0.004 (3)	−0.011 (3)	0.015 (4)
C20	0.019 (2)	0.072 (3)	0.141 (7)	−0.013 (2)	−0.021 (3)	0.068 (4)
F1	0.063 (2)	0.117 (3)	0.082 (3)	0.011 (2)	−0.0018 (19)	−0.036 (3)
N1	0.0213 (14)	0.0416 (18)	0.039 (2)	0.0041 (12)	0.0043 (15)	0.0026 (17)
N2	0.0225 (14)	0.0303 (17)	0.032 (2)	−0.0024 (12)	0.0031 (14)	−0.0018 (14)
N3	0.0235 (15)	0.0333 (16)	0.032 (2)	−0.0056 (12)	0.0006 (14)	0.0017 (15)
N4	0.0254 (15)	0.0374 (17)	0.028 (2)	−0.0041 (14)	0.0007 (14)	−0.0031 (15)
O1	0.0400 (17)	0.059 (2)	0.038 (2)	−0.0167 (13)	−0.0096 (15)	−0.0051 (17)
O2	0.0200 (13)	0.077 (2)	0.060 (2)	0.0022 (14)	0.0048 (15)	0.007 (2)
O3	0.0364 (14)	0.0427 (15)	0.0243 (17)	−0.0059 (11)	−0.0004 (14)	0.0020 (13)
S1	0.0184 (4)	0.0516 (6)	0.0399 (7)	−0.0042 (4)	−0.0017 (4)	0.0012 (5)

C1—C2	1.381 (6)	C12—C13	1.531 (6)
C1—C6	1.413 (5)	C12—H12A	0.9900
C1—S1	1.755 (4)	C12—H12B	0.9900
C2—C3	1.383 (7)	C13—O3	1.227 (5)
C2—H2	0.9500	C13—N4	1.335 (5)
C3—C4	1.391 (6)	C14—N4	1.457 (5)
C3—H3	0.9500	C14—C15	1.514 (6)
C4—C5	1.380 (7)	C14—H14A	0.9900
C4—H4	0.9500	C14—H14B	0.9900
C5—C6	1.384 (6)	C15—C16	1.369 (7)
C5—H5	0.9500	C15—C20	1.469 (7)
C6—C7	1.443 (6)	C16—F1	1.282 (6)
C7—N2	1.339 (5)	C16—C17	1.428 (8)
C7—C8	1.408 (5)	C17—C18	1.354 (9)
C8—C10	1.366 (6)	C17—H17	0.9500
C8—N1	1.430 (5)	C18—C19	1.340 (9)
C9—N1	1.471 (6)	C18—H18	0.9500
C9—H9A	0.9800	C19—C20	1.425 (8)
C9—H9B	0.9800	C19—H19	0.9500
C9—H9C	0.9800	C20—H20	0.9500
C10—N3	1.360 (5)	N1—S1	1.650 (3)
C10—C11	1.500 (6)	N2—N3	1.353 (5)
C11—H11A	0.9800	N4—H4A	0.8800
C11—H11B	0.9800	O1—S1	1.429 (4)
C11—H11C	0.9800	O2—S1	1.430 (3)
C12—N3	1.444 (5)
C2—C1—C6	121.3 (4)	H12A—C12—H12B	108.0
C2—C1—S1	120.9 (3)	O3—C13—N4	123.7 (4)
C6—C1—S1	117.7 (3)	O3—C13—C12	121.3 (4)
C1—C2—C3	119.2 (4)	N4—C13—C12	115.0 (4)
C1—C2—H2	120.4	N4—C14—C15	115.2 (3)
C3—C2—H2	120.4	N4—C14—H14A	108.5
C2—C3—C4	119.8 (4)	C15—C14—H14A	108.5
C2—C3—H3	120.1	N4—C14—H14B	108.5
C4—C3—H3	120.1	C15—C14—H14B	108.5
C5—C4—C3	120.9 (4)	H14A—C14—H14B	107.5
C5—C4—H4	119.6	C16—C15—C20	118.6 (5)
C3—C4—H4	119.6	C16—C15—C14	123.2 (4)
C4—C5—C6	120.2 (4)	C20—C15—C14	118.0 (4)
C4—C5—H5	119.9	F1—C16—C15	118.9 (5)
C6—C5—H5	119.9	F1—C16—C17	118.1 (5)
C5—C6—C1	118.3 (4)	C15—C16—C17	123.0 (5)
C5—C6—C7	123.6 (3)	C18—C17—C16	117.4 (5)
C1—C6—C7	117.8 (3)	C18—C17—H17	121.3
N2—C7—C8	110.2 (3)	C16—C17—H17	121.3
N2—C7—C6	124.8 (3)	C19—C18—C17	122.4 (6)
C8—C7—C6	124.8 (3)	C19—C18—H18	118.8
C10—C8—C7	107.1 (3)	C17—C18—H18	118.8
C10—C8—N1	128.8 (4)	C18—C19—C20	123.4 (6)
C7—C8—N1	124.1 (4)	C18—C19—H19	118.3
N1—C9—H9A	109.5	C20—C19—H19	118.3
N1—C9—H9B	109.5	C19—C20—C15	115.1 (7)
H9A—C9—H9B	109.5	C19—C20—H20	122.5
N1—C9—H9C	109.5	C15—C20—H20	122.5
H9A—C9—H9C	109.5	C8—N1—C9	117.5 (3)
H9B—C9—H9C	109.5	C8—N1—S1	112.4 (3)
N3—C10—C8	104.6 (3)	C9—N1—S1	119.5 (3)
N3—C10—C11	122.4 (4)	C7—N2—N3	104.3 (3)
C8—C10—C11	132.9 (4)	N2—N3—C10	113.8 (3)
C10—C11—H11A	109.5	N2—N3—C12	118.6 (3)
C10—C11—H11B	109.5	C10—N3—C12	127.6 (3)
H11A—C11—H11B	109.5	C13—N4—C14	121.3 (4)
C10—C11—H11C	109.5	C13—N4—H4A	119.3
H11A—C11—H11C	109.5	C14—N4—H4A	119.3
H11B—C11—H11C	109.5	O1—S1—O2	119.3 (2)
N3—C12—C13	111.1 (3)	O1—S1—N1	107.15 (19)
N3—C12—H12A	109.4	O2—S1—N1	107.9 (2)
C13—C12—H12A	109.4	O1—S1—C1	106.9 (2)
N3—C12—H12B	109.4	O2—S1—C1	109.5 (2)
C13—C12—H12B	109.4	N1—S1—C1	105.23 (17)
C6—C1—C2—C3	2.2 (7)	C17—C18—C19—C20	−0.7 (9)
S1—C1—C2—C3	−174.3 (3)	C18—C19—C20—C15	3.6 (8)
C1—C2—C3—C4	2.6 (7)	C16—C15—C20—C19	−4.1 (7)
C2—C3—C4—C5	−3.7 (7)	C14—C15—C20—C19	−178.8 (4)
C3—C4—C5—C6	0.1 (7)	C10—C8—N1—C9	60.7 (6)
C4—C5—C6—C1	4.5 (6)	C7—C8—N1—C9	−117.5 (5)
C4—C5—C6—C7	−168.7 (4)	C10—C8—N1—S1	−154.7 (4)
C2—C1—C6—C5	−5.7 (6)	C7—C8—N1—S1	27.0 (5)
S1—C1—C6—C5	170.9 (3)	C8—C7—N2—N3	−0.8 (5)
C2—C1—C6—C7	167.9 (4)	C6—C7—N2—N3	173.4 (4)
S1—C1—C6—C7	−15.5 (5)	C7—N2—N3—C10	1.3 (5)
C5—C6—C7—N2	−10.3 (7)	C7—N2—N3—C12	179.1 (4)
C1—C6—C7—N2	176.5 (4)	C8—C10—N3—N2	−1.3 (5)
C5—C6—C7—C8	163.0 (4)	C11—C10—N3—N2	179.0 (4)
C1—C6—C7—C8	−10.2 (6)	C8—C10—N3—C12	−178.9 (4)
N2—C7—C8—C10	0.0 (5)	C11—C10—N3—C12	1.5 (7)
C6—C7—C8—C10	−174.1 (4)	C13—C12—N3—N2	116.5 (4)
N2—C7—C8—N1	178.6 (4)	C13—C12—N3—C10	−66.1 (6)
C6—C7—C8—N1	4.5 (7)	O3—C13—N4—C14	5.2 (6)
C7—C8—C10—N3	0.8 (5)	C12—C13—N4—C14	−174.2 (3)
N1—C8—C10—N3	−177.8 (4)	C15—C14—N4—C13	−80.3 (5)
C7—C8—C10—C11	−179.7 (5)	C8—N1—S1—O1	68.7 (3)
N1—C8—C10—C11	1.8 (8)	C9—N1—S1—O1	−147.5 (4)
N3—C12—C13—O3	−31.9 (5)	C8—N1—S1—O2	−161.6 (3)
N3—C12—C13—N4	147.6 (3)	C9—N1—S1—O2	−17.8 (4)
N4—C14—C15—C16	138.4 (4)	C8—N1—S1—C1	−44.7 (3)
N4—C14—C15—C20	−47.1 (5)	C9—N1—S1—C1	99.0 (4)
C20—C15—C16—F1	−176.0 (5)	C2—C1—S1—O1	104.4 (4)
C14—C15—C16—F1	−1.6 (7)	C6—C1—S1—O1	−72.2 (3)
C20—C15—C16—C17	2.0 (7)	C2—C1—S1—O2	−26.1 (4)
C14—C15—C16—C17	176.4 (4)	C6—C1—S1—O2	157.2 (3)
F1—C16—C17—C18	179.0 (5)	C2—C1—S1—N1	−141.9 (4)
C15—C16—C17—C18	0.9 (8)	C6—C1—S1—N1	41.5 (4)
C16—C17—C18—C19	−1.6 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O3i	0.88	2.09	2.940 (5)	162
C3—H3···O2ii	0.95	2.50	3.366 (6)	152
C14—H14A···F1iii	0.99	2.53	3.202 (6)	125
C12—H12B···O3i	0.99	2.42	3.195 (6)	135
C14—H14B···F1	0.99	2.42	2.820 (6)	103

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O3i	0.88	2.09	2.940 (5)	162
C3—H3⋯O2ii	0.95	2.50	3.366 (6)	152
C14—H14A⋯F1iii	0.99	2.53	3.202 (6)	125
C12—H12B⋯O3i	0.99	2.42	3.195 (6)	135
C14—H14B⋯F1	0.99	2.42	2.820 (6)	103

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