1-(4-Fluoro-phen-yl)-3-methyl-4-phenyl-sulfanyl-1H-pyrazol-5(4H)-one.

The title compound, C(16)H(13)FN(2)OS, has undergone enol-to-keto tautomerism during the crystallization process. The 1H-pyrazole-5-one ring [maximum deviation = 0.0198 (11) Å] is inclined at angles of 33.10 (5) and 79.57 (5)° with respect to the fluoro-phenyl [maximum deviation = 0.0090 (12) Å] and phenyl-thiol [maximum deviation = 0.0229 (3) Å] rings attached to it. In the crystal, neighbouring mol-ecules are linked into inversion dimers, generating R(2) (2)(8) ring motifs. These dimers are further linked into two-dimensional arrays parallel to the bc plane via inter-molecular N-H⋯O, C-H⋯F and C-H⋯O hydrogen bonds. The crystal is further stabilized by weak π-π [centroid-centroid distance = 3.6921 (7) Å] and C-H⋯π inter-actions.

Related literature

For pyrazole derivatives and their microbial activity, see: Ragavan et al. (2009 ▶, 2010 ▶). For related structures, see: Shahani et al. (2009 ▶, 2010a ▶,b ▶,c ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C16H13FN2OS

M = 300.34

Monoclinic,

a = 17.2628 (3) Å

b = 7.28340 (1) Å

c = 11.4877 (2) Å

β = 91.138 (1)°

V = 1444.09 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 100 K

0.37 × 0.17 × 0.14 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.918, T max = 0.968

21517 measured reflections

5704 independent reflections

4543 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.113

S = 1.03

5704 reflections

195 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040596/hb5673sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040596/hb5673Isup2.hkl

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

C16H13FN2OS	F(000) = 624
Mr = 300.34	Dx = 1.381 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5911 reflections
a = 17.2628 (3) Å	θ = 2.4–33.6°
b = 7.28340 (1) Å	µ = 0.24 mm−1
c = 11.4877 (2) Å	T = 100 K
β = 91.138 (1)°	Needle, colourless
V = 1444.09 (4) Å3	0.37 × 0.17 × 0.14 mm
Z = 4

Bruker SMART APEXII CCD diffractometer	5704 independent reflections
Radiation source: fine-focus sealed tube	4543 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 33.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −25→26
Tmin = 0.918, Tmax = 0.968	k = −9→11
21517 measured reflections	l = −17→17

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.527P] where P = (Fo2 + 2Fc2)/3
5704 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.287633 (16)	0.50655 (4)	0.76602 (2)	0.01812 (7)
F1	0.01268 (6)	−0.41073 (14)	0.38015 (8)	0.0433 (3)
O1	0.17691 (5)	0.14246 (12)	0.74551 (7)	0.02106 (17)
N1	0.17513 (6)	0.18952 (13)	0.54527 (8)	0.01725 (18)
N2	0.20721 (6)	0.31449 (14)	0.46958 (8)	0.01727 (18)
C1	0.13682 (7)	−0.12951 (16)	0.56378 (10)	0.0193 (2)
H1A	0.1672	−0.1386	0.6313	0.023*
C2	0.09597 (7)	−0.28107 (18)	0.52250 (11)	0.0231 (2)
H2A	0.0978	−0.3924	0.5621	0.028*
C3	0.05246 (8)	−0.2620 (2)	0.42099 (11)	0.0271 (3)
C4	0.04640 (7)	−0.1000 (2)	0.36073 (10)	0.0285 (3)
H4A	0.0161	−0.0924	0.2930	0.034*
C5	0.08635 (7)	0.05268 (19)	0.40275 (10)	0.0226 (2)
H5A	0.0826	0.1646	0.3641	0.027*
C6	0.13208 (6)	0.03598 (16)	0.50366 (9)	0.0166 (2)
C7	0.24940 (6)	0.43573 (15)	0.53067 (9)	0.01692 (19)
C8	0.24443 (6)	0.39363 (15)	0.64842 (9)	0.01656 (19)
C9	0.19702 (6)	0.23394 (15)	0.65843 (9)	0.01662 (19)
C10	0.36501 (6)	0.35655 (15)	0.80605 (9)	0.01676 (19)
C11	0.39018 (7)	0.21470 (17)	0.73533 (10)	0.0211 (2)
H11A	0.3652	0.1923	0.6643	0.025*
C12	0.45278 (7)	0.10600 (18)	0.77057 (11)	0.0238 (2)
H12A	0.4694	0.0114	0.7228	0.029*
C13	0.49050 (7)	0.13786 (18)	0.87642 (11)	0.0231 (2)
H13A	0.5329	0.0666	0.8991	0.028*
C14	0.46437 (7)	0.27724 (17)	0.94827 (10)	0.0220 (2)
H14A	0.4890	0.2980	1.0198	0.026*
C15	0.40165 (7)	0.38605 (17)	0.91402 (10)	0.0199 (2)
H15A	0.3842	0.4783	0.9629	0.024*
C16	0.29242 (7)	0.58417 (17)	0.47078 (10)	0.0228 (2)
H16A	0.2592	0.6404	0.4130	0.034*
H16B	0.3370	0.5331	0.4340	0.034*
H16C	0.3088	0.6748	0.5267	0.034*
H1N2	0.1992 (11)	0.314 (3)	0.3895 (18)	0.049 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.02393 (14)	0.01636 (13)	0.01404 (12)	0.00137 (10)	−0.00028 (9)	−0.00369 (9)
F1	0.0523 (6)	0.0484 (6)	0.0292 (4)	−0.0311 (5)	−0.0029 (4)	−0.0083 (4)
O1	0.0323 (4)	0.0221 (4)	0.0089 (3)	−0.0046 (3)	0.0013 (3)	0.0002 (3)
N1	0.0241 (4)	0.0185 (4)	0.0092 (4)	−0.0017 (3)	0.0003 (3)	0.0006 (3)
N2	0.0237 (4)	0.0192 (4)	0.0090 (4)	0.0002 (3)	0.0013 (3)	0.0012 (3)
C1	0.0193 (5)	0.0206 (5)	0.0179 (5)	0.0009 (4)	−0.0019 (4)	−0.0015 (4)
C2	0.0234 (5)	0.0226 (5)	0.0232 (5)	−0.0027 (4)	0.0001 (4)	−0.0022 (4)
C3	0.0268 (6)	0.0346 (7)	0.0200 (5)	−0.0133 (5)	0.0019 (4)	−0.0074 (5)
C4	0.0260 (6)	0.0451 (8)	0.0143 (5)	−0.0124 (5)	−0.0026 (4)	0.0009 (5)
C5	0.0215 (5)	0.0331 (6)	0.0132 (5)	−0.0032 (5)	−0.0020 (4)	0.0028 (4)
C6	0.0168 (4)	0.0212 (5)	0.0118 (4)	0.0002 (4)	0.0007 (3)	−0.0026 (4)
C7	0.0212 (5)	0.0166 (5)	0.0130 (4)	0.0022 (4)	0.0018 (3)	0.0002 (4)
C8	0.0221 (5)	0.0163 (5)	0.0114 (4)	0.0009 (4)	0.0009 (3)	−0.0011 (4)
C9	0.0225 (5)	0.0182 (5)	0.0092 (4)	0.0009 (4)	−0.0002 (3)	−0.0015 (3)
C10	0.0198 (5)	0.0173 (5)	0.0131 (4)	−0.0018 (4)	0.0015 (3)	0.0000 (4)
C11	0.0246 (5)	0.0244 (5)	0.0144 (5)	0.0027 (4)	0.0011 (4)	−0.0037 (4)
C12	0.0273 (6)	0.0255 (6)	0.0189 (5)	0.0056 (5)	0.0037 (4)	−0.0023 (4)
C13	0.0227 (5)	0.0271 (6)	0.0196 (5)	0.0021 (4)	0.0018 (4)	0.0051 (4)
C14	0.0245 (5)	0.0257 (6)	0.0158 (5)	−0.0033 (4)	−0.0015 (4)	0.0031 (4)
C15	0.0252 (5)	0.0210 (5)	0.0134 (4)	−0.0027 (4)	0.0008 (4)	−0.0013 (4)
C16	0.0295 (6)	0.0205 (5)	0.0186 (5)	−0.0013 (4)	0.0052 (4)	0.0030 (4)

S1—C8	1.7371 (11)	C5—H5A	0.9300
S1—C10	1.7790 (11)	C7—C8	1.3913 (15)
F1—C3	1.3613 (15)	C7—C16	1.4879 (17)
O1—C9	1.2567 (13)	C8—C9	1.4280 (16)
N1—N2	1.3821 (13)	C10—C11	1.3894 (16)
N1—C9	1.3848 (13)	C10—C15	1.3977 (15)
N1—C6	1.4203 (14)	C11—C12	1.3933 (17)
N2—C7	1.3351 (14)	C11—H11A	0.9300
N2—H1N2	0.93 (2)	C12—C13	1.3873 (17)
C1—C2	1.3884 (16)	C12—H12A	0.9300
C1—C6	1.3908 (16)	C13—C14	1.3893 (18)
C1—H1A	0.9300	C13—H13A	0.9300
C2—C3	1.3814 (17)	C14—C15	1.3922 (17)
C2—H2A	0.9300	C14—H14A	0.9300
C3—C4	1.371 (2)	C15—H15A	0.9300
C4—C5	1.3898 (18)	C16—H16A	0.9600
C4—H4A	0.9300	C16—H16B	0.9600
C5—C6	1.3948 (15)	C16—H16C	0.9600
C8—S1—C10	102.64 (5)	C7—C8—S1	128.16 (9)
N2—N1—C9	109.36 (9)	C9—C8—S1	124.12 (8)
N2—N1—C6	121.35 (8)	O1—C9—N1	123.29 (10)
C9—N1—C6	129.13 (9)	O1—C9—C8	131.59 (10)
C7—N2—N1	109.03 (9)	N1—C9—C8	105.12 (9)
C7—N2—H1N2	126.2 (13)	C11—C10—C15	119.47 (11)
N1—N2—H1N2	124.7 (13)	C11—C10—S1	123.19 (8)
C2—C1—C6	119.67 (10)	C15—C10—S1	117.34 (9)
C2—C1—H1A	120.2	C10—C11—C12	120.16 (10)
C6—C1—H1A	120.2	C10—C11—H11A	119.9
C3—C2—C1	118.17 (12)	C12—C11—H11A	119.9
C3—C2—H2A	120.9	C13—C12—C11	120.50 (11)
C1—C2—H2A	120.9	C13—C12—H12A	119.8
F1—C3—C4	118.56 (11)	C11—C12—H12A	119.8
F1—C3—C2	118.22 (13)	C12—C13—C14	119.39 (11)
C4—C3—C2	123.22 (12)	C12—C13—H13A	120.3
C3—C4—C5	118.73 (11)	C14—C13—H13A	120.3
C3—C4—H4A	120.6	C13—C14—C15	120.52 (10)
C5—C4—H4A	120.6	C13—C14—H14A	119.7
C4—C5—C6	119.19 (12)	C15—C14—H14A	119.7
C4—C5—H5A	120.4	C14—C15—C10	119.94 (11)
C6—C5—H5A	120.4	C14—C15—H15A	120.0
C1—C6—C5	121.00 (11)	C10—C15—H15A	120.0
C1—C6—N1	119.34 (9)	C7—C16—H16A	109.5
C5—C6—N1	119.66 (11)	C7—C16—H16B	109.5
N2—C7—C8	108.77 (10)	H16A—C16—H16B	109.5
N2—C7—C16	120.64 (10)	C7—C16—H16C	109.5
C8—C7—C16	130.59 (10)	H16A—C16—H16C	109.5
C7—C8—C9	107.72 (9)	H16B—C16—H16C	109.5
C9—N1—N2—C7	0.64 (12)	C16—C7—C8—S1	0.70 (19)
C6—N1—N2—C7	−175.10 (10)	C10—S1—C8—C7	−104.41 (11)
C6—C1—C2—C3	0.90 (18)	C10—S1—C8—C9	74.55 (10)
C1—C2—C3—F1	179.69 (12)	N2—N1—C9—O1	−179.24 (10)
C1—C2—C3—C4	−1.5 (2)	C6—N1—C9—O1	−3.94 (18)
F1—C3—C4—C5	179.41 (12)	N2—N1—C9—C8	0.04 (12)
C2—C3—C4—C5	0.6 (2)	C6—N1—C9—C8	175.35 (11)
C3—C4—C5—C6	0.9 (2)	C7—C8—C9—O1	178.53 (12)
C2—C1—C6—C5	0.50 (18)	S1—C8—C9—O1	−0.61 (19)
C2—C1—C6—N1	−178.88 (11)	C7—C8—C9—N1	−0.68 (12)
C4—C5—C6—C1	−1.40 (18)	S1—C8—C9—N1	−179.82 (8)
C4—C5—C6—N1	177.98 (11)	C8—S1—C10—C11	14.04 (11)
N2—N1—C6—C1	144.74 (11)	C8—S1—C10—C15	−166.31 (9)
C9—N1—C6—C1	−30.08 (17)	C15—C10—C11—C12	−1.69 (18)
N2—N1—C6—C5	−34.65 (16)	S1—C10—C11—C12	177.96 (10)
C9—N1—C6—C5	150.54 (12)	C10—C11—C12—C13	0.10 (19)
N1—N2—C7—C8	−1.07 (12)	C11—C12—C13—C14	1.21 (19)
N1—N2—C7—C16	178.48 (10)	C12—C13—C14—C15	−0.93 (19)
N2—C7—C8—C9	1.09 (13)	C13—C14—C15—C10	−0.66 (18)
C16—C7—C8—C9	−178.40 (11)	C11—C10—C15—C14	1.97 (17)
N2—C7—C8—S1	−179.82 (9)	S1—C10—C15—C14	−177.70 (9)

Cg1 and Cg3 are the centroids of the pyrazol (N1/N2/C7–C9) and benzene ring (C10–C15) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1i	0.93 (2)	1.72 (2)	2.6352 (12)	168 (2)
C2—H2A···F1ii	0.93	2.49	3.1450 (16)	128
C4—H4A···F1iii	0.93	2.43	3.2381 (15)	145
C5—H5A···O1i	0.93	2.56	3.2786 (15)	134
C2—H2A···Cg1iv	0.93	2.94	3.6300 (14)	132
C12—H12A···Cg3v	0.93	2.74	3.5928 (14)	153
C16—H16B···Cg3vi	0.96	2.79	3.6826 (13)	155

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg3 are the centroids of the pyrazol (N1/N2/C7–C9) and benzene (C10–C15) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1i	0.93 (2)	1.72 (2)	2.6352 (12)	168 (2)
C2—H2A⋯F1ii	0.93	2.49	3.1450 (16)	128
C4—H4A⋯F1iii	0.93	2.43	3.2381 (15)	145
C5—H5A⋯O1i	0.93	2.56	3.2786 (15)	134
C2—H2A⋯Cg1iv	0.93	2.94	3.6300 (14)	132
C12—H12A⋯Cg3v	0.93	2.74	3.5928 (14)	153
C16—H16B⋯Cg3vi	0.96	2.79	3.6826 (13)	155

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