4-{(4Z)-4-[(2Z)-3-(4-Fluoro-anilino)-1-hy-droxy-but-2-en-1-yl-idene]-3-methyl-5-oxo-4,5-dihydro-1H-pyrazol-1-yl}-benzene-sulfonamide.

In the title compound, C(20)H(19)FN(4)O(4)S, the pyrazole and benzene-sulfonamide rings are coplanar [dihedral angle = 5.02 (15)°] but this planarity does not extend over the entire mol-ecule, the dihedral angle between the terminal six-membered rings being 33.24 (14)°. Intra-molecular hy-droxy-hy-droxy O-H⋯O and amine-hy-droxy N-H⋯O hydrogen bonds, as a well as a tight C-H⋯O(carbon-yl) inter-action, lead to a sequence of three fused S(6) rings. Supra-molecular chains along the a axis feature in the crystal packing; these chains are stabilized by amine-sulfonamide N-H⋯O and amine-pyrazole N-H⋯N hydrogen bonds.

Related literature

For background to the synthesis, see: Gelin et al. (1983 ▶); Bendaas et al. (1999 ▶). For related structures, see: Asiri, Al-Youbi, Alamry et al. (2011 ▶); Asiri, Al-Youbi, Faidallah et al. (2011 ▶).

Experimental

Crystal data

C20H19FN4O4S

M = 430.45

Triclinic,

a = 7.8121 (5) Å

b = 10.0137 (8) Å

c = 12.6003 (9) Å

α = 97.950 (6)°

β = 104.632 (6)°

γ = 98.394 (6)°

V = 927.58 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 100 K

0.25 × 0.10 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.946, T max = 0.996

6559 measured reflections

4240 independent reflections

2935 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.146

S = 1.01

4240 reflections

287 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812006502/hg5177sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006502/hg5177Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812006502/hg5177Isup3.cml

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

C20H19FN4O4S	Z = 2
Mr = 430.45	F(000) = 448
Triclinic, P1	Dx = 1.541 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8121 (5) Å	Cell parameters from 1846 reflections
b = 10.0137 (8) Å	θ = 2.4–27.5°
c = 12.6003 (9) Å	µ = 0.22 mm−1
α = 97.950 (6)°	T = 100 K
β = 104.632 (6)°	Prism, yellow
γ = 98.394 (6)°	0.25 × 0.10 × 0.02 mm
V = 927.58 (12) Å3

Agilent SuperNova Dual diffractometer with an Atlas detector	4240 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2935 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.041
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.4°
ω scan	h = −10→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→13
Tmin = 0.946, Tmax = 0.996	l = −16→16
6559 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0548P)2 + 0.375P] where P = (Fo2 + 2Fc2)/3
4240 reflections	(Δ/σ)max = 0.001
287 parameters	Δρmax = 0.47 e Å−3
4 restraints	Δρmin = −0.36 e Å−3

	x	y	z	Uiso*/Ueq
S1	1.14758 (9)	0.18251 (7)	0.13099 (5)	0.01909 (19)
F1	0.3342 (3)	0.78774 (18)	1.20106 (14)	0.0361 (5)
O1	0.7345 (3)	0.41000 (19)	0.53049 (16)	0.0245 (5)
O2	0.5322 (3)	0.4509 (2)	0.65439 (16)	0.0267 (5)
H1	0.608 (4)	0.457 (4)	0.617 (3)	0.057 (12)*
O3	1.0480 (3)	0.17118 (19)	0.01577 (15)	0.0218 (5)
O4	1.2886 (3)	0.2998 (2)	0.18161 (16)	0.0262 (5)
N1	0.6195 (3)	0.2035 (2)	0.39856 (18)	0.0181 (5)
N2	0.4693 (3)	0.0958 (2)	0.37289 (18)	0.0194 (5)
N3	0.3372 (3)	0.4895 (2)	0.7974 (2)	0.0246 (6)
H3	0.429 (3)	0.519 (3)	0.772 (2)	0.026 (9)*
N4	1.2349 (3)	0.0473 (2)	0.13729 (19)	0.0214 (5)
H41	1.299 (3)	0.047 (3)	0.2055 (13)	0.026*
H42	1.156 (3)	−0.025 (2)	0.098 (2)	0.026*
C1	0.7495 (4)	0.1957 (3)	0.3386 (2)	0.0184 (6)
C2	0.8925 (4)	0.3055 (3)	0.3569 (2)	0.0207 (6)
H2	0.9062	0.3844	0.4119	0.025*
C3	1.0138 (4)	0.2982 (3)	0.2943 (2)	0.0208 (6)
H3A	1.1116	0.3725	0.3067	0.025*
C4	0.9944 (4)	0.1833 (3)	0.2133 (2)	0.0183 (6)
C5	0.8533 (4)	0.0721 (3)	0.1959 (2)	0.0198 (6)
H5	0.8402	−0.0066	0.1409	0.024*
C6	0.7327 (4)	0.0778 (3)	0.2596 (2)	0.0185 (6)
H6	0.6385	0.0016	0.2498	0.022*
C7	0.6167 (4)	0.3021 (3)	0.4854 (2)	0.0190 (6)
C8	0.4559 (4)	0.2561 (3)	0.5145 (2)	0.0191 (6)
C9	0.3752 (4)	0.1281 (3)	0.4419 (2)	0.0194 (6)
C10	0.2070 (4)	0.0316 (3)	0.4376 (2)	0.0224 (6)
H10A	0.1031	0.0764	0.4172	0.034*
H10B	0.2166	0.0062	0.5110	0.034*
H10C	0.1914	−0.0512	0.3819	0.034*
C11	0.4130 (4)	0.3362 (3)	0.6027 (2)	0.0215 (6)
C12	0.2592 (4)	0.3066 (3)	0.6396 (2)	0.0252 (7)
H12	0.1707	0.2292	0.5978	0.030*
C13	0.2232 (4)	0.3787 (3)	0.7311 (2)	0.0233 (6)
C14	0.0456 (4)	0.3322 (3)	0.7541 (3)	0.0316 (8)
H14A	−0.0467	0.2940	0.6834	0.047*
H14B	0.0101	0.4107	0.7929	0.047*
H14C	0.0581	0.2617	0.8008	0.047*
C15	0.3261 (4)	0.5620 (3)	0.9014 (2)	0.0273 (7)
C16	0.2655 (4)	0.4976 (3)	0.9798 (3)	0.0288 (7)
H16	0.2238	0.4011	0.9648	0.035*
C17	0.2665 (4)	0.5744 (3)	1.0786 (2)	0.0281 (7)
H17	0.2213	0.5319	1.1315	0.034*
C18	0.3323 (4)	0.7119 (3)	1.1012 (2)	0.0252 (7)
C19	0.3989 (4)	0.7777 (3)	1.0272 (2)	0.0280 (7)
H19	0.4477	0.8733	1.0453	0.034*
C20	0.3932 (4)	0.7016 (3)	0.9259 (2)	0.0257 (7)
H20	0.4356	0.7454	0.8727	0.031*

	U11	U22	U33	U12	U13	U23
S1	0.0177 (4)	0.0186 (4)	0.0193 (4)	−0.0007 (3)	0.0069 (3)	−0.0013 (3)
F1	0.0487 (12)	0.0327 (10)	0.0289 (10)	0.0100 (9)	0.0165 (9)	−0.0006 (8)
O1	0.0214 (11)	0.0215 (10)	0.0259 (11)	−0.0032 (9)	0.0089 (9)	−0.0082 (8)
O2	0.0252 (12)	0.0268 (11)	0.0250 (11)	−0.0012 (10)	0.0107 (9)	−0.0059 (9)
O3	0.0224 (10)	0.0235 (11)	0.0189 (10)	0.0035 (9)	0.0055 (8)	0.0029 (8)
O4	0.0244 (11)	0.0233 (11)	0.0281 (11)	−0.0044 (9)	0.0119 (9)	−0.0040 (8)
N1	0.0169 (12)	0.0174 (12)	0.0177 (12)	0.0004 (10)	0.0053 (9)	−0.0020 (9)
N2	0.0171 (12)	0.0186 (12)	0.0197 (12)	−0.0013 (10)	0.0044 (10)	0.0000 (9)
N3	0.0236 (14)	0.0240 (13)	0.0243 (13)	0.0026 (11)	0.0092 (11)	−0.0042 (10)
N4	0.0205 (13)	0.0233 (13)	0.0170 (12)	0.0033 (11)	0.0022 (10)	−0.0009 (10)
C1	0.0181 (14)	0.0220 (14)	0.0156 (13)	0.0053 (12)	0.0053 (11)	0.0018 (11)
C2	0.0246 (15)	0.0169 (14)	0.0172 (14)	0.0033 (12)	0.0045 (12)	−0.0047 (10)
C3	0.0188 (14)	0.0181 (14)	0.0231 (15)	0.0003 (12)	0.0052 (12)	−0.0001 (11)
C4	0.0160 (14)	0.0200 (14)	0.0192 (14)	0.0029 (12)	0.0063 (11)	0.0023 (11)
C5	0.0208 (15)	0.0174 (14)	0.0182 (14)	0.0027 (12)	0.0030 (11)	−0.0018 (10)
C6	0.0164 (14)	0.0174 (14)	0.0185 (14)	−0.0013 (11)	0.0036 (11)	0.0000 (10)
C7	0.0213 (15)	0.0195 (14)	0.0146 (13)	0.0029 (12)	0.0042 (11)	−0.0002 (10)
C8	0.0177 (14)	0.0209 (14)	0.0175 (14)	0.0028 (12)	0.0044 (11)	0.0010 (11)
C9	0.0179 (14)	0.0203 (14)	0.0186 (14)	0.0023 (12)	0.0039 (11)	0.0019 (11)
C10	0.0239 (15)	0.0200 (14)	0.0214 (15)	−0.0005 (12)	0.0070 (12)	0.0012 (11)
C11	0.0226 (15)	0.0211 (14)	0.0176 (14)	0.0021 (12)	0.0036 (12)	−0.0008 (11)
C12	0.0251 (16)	0.0254 (16)	0.0222 (15)	0.0021 (13)	0.0059 (12)	−0.0011 (12)
C13	0.0245 (15)	0.0252 (15)	0.0215 (15)	0.0072 (13)	0.0074 (12)	0.0041 (12)
C14	0.0278 (17)	0.0327 (18)	0.0347 (18)	0.0034 (15)	0.0146 (14)	−0.0008 (13)
C15	0.0244 (16)	0.0315 (17)	0.0254 (16)	0.0072 (14)	0.0083 (13)	−0.0006 (12)
C16	0.0314 (17)	0.0256 (16)	0.0308 (17)	0.0067 (14)	0.0105 (14)	0.0048 (13)
C17	0.0290 (17)	0.0287 (17)	0.0284 (17)	0.0074 (14)	0.0110 (14)	0.0037 (13)
C18	0.0260 (16)	0.0307 (16)	0.0207 (15)	0.0123 (14)	0.0077 (12)	0.0014 (12)
C19	0.0263 (16)	0.0247 (16)	0.0302 (17)	0.0003 (14)	0.0090 (13)	−0.0016 (12)
C20	0.0203 (15)	0.0287 (16)	0.0285 (16)	0.0021 (13)	0.0096 (13)	0.0039 (13)

S1—O4	1.4353 (19)	C6—H6	0.9500
S1—O3	1.4437 (19)	C7—C8	1.427 (4)
S1—N4	1.605 (3)	C8—C11	1.417 (4)
S1—C4	1.770 (3)	C8—C9	1.423 (4)
F1—C18	1.372 (3)	C9—C10	1.497 (4)
O1—C7	1.270 (3)	C10—H10A	0.9800
O2—C11	1.336 (3)	C10—H10B	0.9800
O2—H1	0.848 (10)	C10—H10C	0.9800
N1—C7	1.375 (3)	C11—C12	1.402 (4)
N1—N2	1.410 (3)	C12—C13	1.387 (4)
N1—C1	1.415 (3)	C12—H12	0.9500
N2—C9	1.311 (4)	C13—C14	1.508 (4)
N3—C13	1.342 (4)	C14—H14A	0.9800
N3—C15	1.436 (4)	C14—H14B	0.9800
N3—H3	0.881 (10)	C14—H14C	0.9800
N4—H41	0.878 (10)	C15—C20	1.382 (4)
N4—H42	0.875 (10)	C15—C16	1.393 (4)
C1—C2	1.397 (4)	C16—C17	1.368 (4)
C1—C6	1.401 (4)	C16—H16	0.9500
C2—C3	1.381 (4)	C17—C18	1.361 (4)
C2—H2	0.9500	C17—H17	0.9500
C3—C4	1.391 (4)	C18—C19	1.375 (4)
C3—H3A	0.9500	C19—C20	1.380 (4)
C4—C5	1.398 (4)	C19—H19	0.9500
C5—C6	1.386 (4)	C20—H20	0.9500
C5—H5	0.9500
O4—S1—O3	118.53 (11)	N2—C9—C10	119.3 (2)
O4—S1—N4	108.00 (13)	C8—C9—C10	128.9 (3)
O3—S1—N4	106.03 (12)	C9—C10—H10A	109.5
O4—S1—C4	106.19 (12)	C9—C10—H10B	109.5
O3—S1—C4	108.51 (13)	H10A—C10—H10B	109.5
N4—S1—C4	109.38 (13)	C9—C10—H10C	109.5
C11—O2—H1	105 (3)	H10A—C10—H10C	109.5
C7—N1—N2	111.1 (2)	H10B—C10—H10C	109.5
C7—N1—C1	129.7 (2)	O2—C11—C12	117.8 (3)
N2—N1—C1	119.2 (2)	O2—C11—C8	115.8 (2)
C9—N2—N1	106.2 (2)	C12—C11—C8	126.4 (2)
C13—N3—C15	127.8 (2)	C13—C12—C11	126.6 (3)
C13—N3—H3	114 (2)	C13—C12—H12	116.7
C15—N3—H3	118 (2)	C11—C12—H12	116.7
S1—N4—H41	111 (2)	N3—C13—C12	122.7 (3)
S1—N4—H42	110 (2)	N3—C13—C14	119.2 (3)
H41—N4—H42	121 (3)	C12—C13—C14	118.1 (3)
C2—C1—C6	120.2 (2)	C13—C14—H14A	109.5
C2—C1—N1	120.2 (2)	C13—C14—H14B	109.5
C6—C1—N1	119.6 (2)	H14A—C14—H14B	109.5
C3—C2—C1	119.3 (3)	C13—C14—H14C	109.5
C3—C2—H2	120.3	H14A—C14—H14C	109.5
C1—C2—H2	120.3	H14B—C14—H14C	109.5
C2—C3—C4	120.7 (2)	C20—C15—C16	119.7 (3)
C2—C3—H3A	119.6	C20—C15—N3	116.5 (2)
C4—C3—H3A	119.6	C16—C15—N3	123.6 (3)
C3—C4—C5	120.2 (3)	C17—C16—C15	119.5 (3)
C3—C4—S1	118.9 (2)	C17—C16—H16	120.2
C5—C4—S1	120.9 (2)	C15—C16—H16	120.2
C6—C5—C4	119.4 (2)	C18—C17—C16	119.9 (3)
C6—C5—H5	120.3	C18—C17—H17	120.0
C4—C5—H5	120.3	C16—C17—H17	120.0
C5—C6—C1	120.1 (2)	C17—C18—F1	119.4 (2)
C5—C6—H6	120.0	C17—C18—C19	122.0 (3)
C1—C6—H6	120.0	F1—C18—C19	118.6 (3)
O1—C7—N1	126.8 (2)	C18—C19—C20	118.4 (3)
O1—C7—C8	127.7 (2)	C18—C19—H19	120.8
N1—C7—C8	105.5 (2)	C20—C19—H19	120.8
C11—C8—C9	134.9 (3)	C19—C20—C15	120.4 (3)
C11—C8—C7	119.6 (2)	C19—C20—H20	119.8
C9—C8—C7	105.5 (2)	C15—C20—H20	119.8
N2—C9—C8	111.8 (2)
C7—N1—N2—C9	0.5 (3)	N1—C7—C8—C9	1.2 (3)
C1—N1—N2—C9	178.6 (2)	N1—N2—C9—C8	0.3 (3)
C7—N1—C1—C2	−7.0 (4)	N1—N2—C9—C10	−178.6 (2)
N2—N1—C1—C2	175.4 (2)	C11—C8—C9—N2	−179.4 (3)
C7—N1—C1—C6	173.8 (3)	C7—C8—C9—N2	−1.0 (3)
N2—N1—C1—C6	−3.8 (4)	C11—C8—C9—C10	−0.6 (6)
C6—C1—C2—C3	1.8 (4)	C7—C8—C9—C10	177.8 (3)
N1—C1—C2—C3	−177.4 (3)	C9—C8—C11—O2	177.0 (3)
C1—C2—C3—C4	0.3 (4)	C7—C8—C11—O2	−1.2 (4)
C2—C3—C4—C5	−1.4 (4)	C9—C8—C11—C12	−3.1 (6)
C2—C3—C4—S1	177.1 (2)	C7—C8—C11—C12	178.6 (3)
O4—S1—C4—C3	10.3 (3)	O2—C11—C12—C13	−5.5 (5)
O3—S1—C4—C3	−118.1 (2)	C8—C11—C12—C13	174.7 (3)
N4—S1—C4—C3	126.6 (2)	C15—N3—C13—C12	−171.6 (3)
O4—S1—C4—C5	−171.2 (2)	C15—N3—C13—C14	10.4 (5)
O3—S1—C4—C5	60.3 (3)	C11—C12—C13—N3	−0.2 (5)
N4—S1—C4—C5	−54.9 (3)	C11—C12—C13—C14	177.9 (3)
C3—C4—C5—C6	0.3 (4)	C13—N3—C15—C20	−148.1 (3)
S1—C4—C5—C6	−178.1 (2)	C13—N3—C15—C16	37.0 (5)
C4—C5—C6—C1	1.8 (4)	C20—C15—C16—C17	2.6 (5)
C2—C1—C6—C5	−2.9 (4)	N3—C15—C16—C17	177.3 (3)
N1—C1—C6—C5	176.3 (3)	C15—C16—C17—C18	−2.3 (5)
N2—N1—C7—O1	178.0 (3)	C16—C17—C18—F1	−179.4 (3)
C1—N1—C7—O1	0.2 (5)	C16—C17—C18—C19	0.0 (5)
N2—N1—C7—C8	−1.1 (3)	C17—C18—C19—C20	1.9 (5)
C1—N1—C7—C8	−178.9 (3)	F1—C18—C19—C20	−178.6 (3)
O1—C7—C8—C11	0.9 (5)	C18—C19—C20—C15	−1.6 (5)
N1—C7—C8—C11	179.9 (2)	C16—C15—C20—C19	−0.6 (5)
O1—C7—C8—C9	−177.8 (3)	N3—C15—C20—C19	−175.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O1	0.85 (1)	1.71 (2)	2.522 (3)	161 (4)
N3—H3···O2	0.88 (1)	1.95 (2)	2.662 (3)	137 (3)
C2—H2···O1	0.95	2.26	2.917 (4)	126
N4—H41···N2i	0.88 (1)	2.14 (1)	2.999 (3)	167 (3)
N4—H42···O3ii	0.88 (1)	2.08 (1)	2.943 (3)	169 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1⋯O1	0.85 (1)	1.71 (2)	2.522 (3)	161 (4)
N3—H3⋯O2	0.88 (1)	1.95 (2)	2.662 (3)	137 (3)
C2—H2⋯O1	0.95	2.26	2.917 (4)	126
N4—H41⋯N2i	0.88 (1)	2.14 (1)	2.999 (3)	167 (3)
N4—H42⋯O3ii	0.88 (1)	2.08 (1)	2.943 (3)	169 (3)

Symmetry codes: (i) ; (ii) .