5-(4-Fluoro-phen-yl)-3-(4-methyl-phen-yl)-4,5-dihydro-1H-pyrazole-1-carbothio-amide.

The central pyrazole ring in the title compound, C17H16FN3S, adopts an envelope conformation with the methine C atom bearing the 4-fluoro-phenyl substituent as the flap atom. Whereas the tolyl ring is slightly twisted out of the least-squares plane through the pyrazole ring [dihedral angle = 13.51 (11)°], the fluoro-benzene ring is almost perpendicular [dihedral angle = 80.21 (11)°]. The thio-amide group is almost coplanar with the N-N bond of the ring [N-N-C-N torsion angle = 1.2 (3)°] and the amine group forms an intra-molecular hydrogen bond with a ring N atom. In the crystal, supra-molecular double layers in the bc plane are formed via N-H⋯S, N-H⋯F and C-H⋯F inter-actions.

Related literature

For the biological activity of pyrazolin-1-yl­thia­zoles, see: Abdel-Wahab et al. (2009 ▶, 2012 ▶); Chimenti et al. (2010 ▶). For related structures, see: Nonthason et al. (2011 ▶); Chantra­promma et al. (2012 ▶).

Experimental

Crystal data

C17H16FN3S

M = 313.39

Monoclinic,

a = 14.4154 (10) Å

b = 11.3197 (9) Å

c = 9.5575 (8) Å

β = 103.991 (8)°

V = 1513.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 295 K

0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.772, T max = 1.000

9303 measured reflections

3500 independent reflections

2370 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.122

S = 1.04

3500 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.26 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 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813004194/hg5291sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813004194/hg5291Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813004194/hg5291Isup3.cml

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

C17H16FN3S	F(000) = 656
Mr = 313.39	Dx = 1.376 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2000 reflections
a = 14.4154 (10) Å	θ = 2.9–27.5°
b = 11.3197 (9) Å	µ = 0.22 mm−1
c = 9.5575 (8) Å	T = 295 K
β = 103.991 (8)°	Prism, colourless
V = 1513.3 (2) Å3	0.30 × 0.20 × 0.10 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	3500 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2370 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.038
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.9°
ω scan	h = −18→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→14
Tmin = 0.772, Tmax = 1.000	l = −12→12
9303 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0448P)2 + 0.2973P] where P = (Fo2 + 2Fc2)/3
3500 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.26 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	0.48991 (4)	0.33372 (5)	0.33938 (6)	0.04739 (19)
F1	0.76993 (11)	0.35963 (12)	−0.10409 (14)	0.0659 (4)
N1	0.63664 (12)	0.46879 (14)	0.46526 (17)	0.0384 (4)
N2	0.71143 (11)	0.50005 (15)	0.58117 (17)	0.0391 (4)
N3	0.60198 (14)	0.32075 (15)	0.60342 (19)	0.0491 (5)
H31	0.6497	0.3462	0.6727	0.059*
H32	0.5684	0.2591	0.6181	0.059*
C1	0.73573 (16)	0.40770 (19)	0.0050 (2)	0.0445 (5)
C2	0.77815 (16)	0.3771 (2)	0.1434 (2)	0.0483 (6)
H2	0.8306	0.3266	0.1637	0.058*
C3	0.74165 (14)	0.42262 (19)	0.2528 (2)	0.0435 (5)
H3	0.7697	0.4024	0.3479	0.052*
C4	0.66378 (13)	0.49796 (17)	0.2226 (2)	0.0341 (4)
C5	0.62418 (15)	0.52828 (18)	0.0812 (2)	0.0416 (5)
H5	0.5728	0.5804	0.0602	0.050*
C6	0.65938 (16)	0.48273 (19)	−0.0307 (2)	0.0469 (5)
H6	0.6320	0.5025	−0.1262	0.056*
C7	0.62560 (14)	0.55094 (17)	0.3424 (2)	0.0376 (5)
H7	0.5584	0.5736	0.3066	0.045*
C8	0.68480 (15)	0.65640 (18)	0.4168 (2)	0.0406 (5)
H8A	0.7267	0.6865	0.3594	0.049*
H8B	0.6439	0.7198	0.4347	0.049*
C9	0.74100 (14)	0.60325 (18)	0.5553 (2)	0.0378 (5)
C10	0.82031 (14)	0.65987 (18)	0.6583 (2)	0.0381 (5)
C11	0.87678 (15)	0.5981 (2)	0.7726 (2)	0.0486 (6)
H11	0.8658	0.5179	0.7826	0.058*
C12	0.94914 (17)	0.6537 (2)	0.8718 (3)	0.0526 (6)
H12	0.9867	0.6101	0.9470	0.063*
C13	0.96669 (15)	0.7734 (2)	0.8614 (2)	0.0470 (5)
C14	0.91224 (16)	0.8339 (2)	0.7453 (3)	0.0519 (6)
H14	0.9243	0.9136	0.7342	0.062*
C15	0.83985 (15)	0.7787 (2)	0.6447 (2)	0.0470 (5)
H15	0.8041	0.8216	0.5673	0.056*
C16	1.04181 (18)	0.8345 (2)	0.9752 (3)	0.0673 (8)
H16A	1.0751	0.8910	0.9303	0.101*
H16B	1.0864	0.7772	1.0264	0.101*
H16C	1.0119	0.8744	1.0414	0.101*
C17	0.58067 (14)	0.37547 (17)	0.4763 (2)	0.0365 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0422 (3)	0.0508 (3)	0.0468 (3)	−0.0061 (3)	0.0063 (2)	−0.0054 (3)
F1	0.0882 (10)	0.0730 (9)	0.0427 (8)	0.0155 (8)	0.0279 (7)	−0.0051 (7)
N1	0.0401 (9)	0.0438 (10)	0.0305 (8)	−0.0056 (8)	0.0071 (7)	−0.0003 (7)
N2	0.0387 (9)	0.0462 (10)	0.0315 (9)	−0.0038 (8)	0.0066 (7)	−0.0025 (8)
N3	0.0545 (11)	0.0474 (10)	0.0437 (10)	−0.0086 (9)	0.0088 (9)	0.0077 (8)
C1	0.0549 (13)	0.0448 (12)	0.0370 (11)	−0.0018 (11)	0.0170 (10)	−0.0035 (10)
C2	0.0448 (12)	0.0556 (13)	0.0442 (12)	0.0135 (11)	0.0099 (10)	0.0022 (11)
C3	0.0438 (11)	0.0547 (13)	0.0296 (10)	0.0095 (11)	0.0043 (9)	0.0018 (10)
C4	0.0342 (10)	0.0357 (10)	0.0315 (10)	−0.0021 (9)	0.0062 (8)	0.0008 (8)
C5	0.0433 (11)	0.0431 (11)	0.0346 (11)	0.0075 (10)	0.0020 (9)	0.0040 (9)
C6	0.0594 (14)	0.0487 (12)	0.0283 (10)	0.0028 (11)	0.0023 (10)	0.0040 (9)
C7	0.0360 (10)	0.0428 (11)	0.0325 (10)	0.0030 (9)	0.0056 (8)	0.0044 (9)
C8	0.0455 (11)	0.0403 (11)	0.0360 (11)	0.0006 (10)	0.0100 (9)	−0.0010 (9)
C9	0.0370 (10)	0.0422 (11)	0.0359 (10)	0.0003 (10)	0.0124 (9)	−0.0027 (9)
C10	0.0362 (10)	0.0427 (11)	0.0372 (11)	−0.0007 (9)	0.0124 (9)	−0.0038 (9)
C11	0.0509 (13)	0.0447 (12)	0.0469 (13)	−0.0063 (11)	0.0052 (11)	−0.0013 (10)
C12	0.0521 (13)	0.0542 (14)	0.0449 (13)	0.0011 (12)	−0.0010 (11)	−0.0012 (11)
C13	0.0385 (11)	0.0510 (13)	0.0509 (13)	0.0004 (10)	0.0098 (10)	−0.0134 (11)
C14	0.0434 (12)	0.0413 (12)	0.0695 (16)	−0.0045 (11)	0.0106 (12)	−0.0052 (11)
C15	0.0423 (12)	0.0465 (12)	0.0513 (13)	0.0009 (10)	0.0093 (10)	0.0026 (11)
C16	0.0527 (14)	0.0653 (16)	0.0745 (18)	−0.0040 (13)	−0.0025 (13)	−0.0231 (14)
C17	0.0384 (10)	0.0378 (11)	0.0365 (11)	0.0033 (9)	0.0151 (9)	−0.0034 (9)

S1—C17	1.679 (2)	C7—C8	1.538 (3)
F1—C1	1.369 (2)	C7—H7	0.9800
N1—C17	1.349 (2)	C8—C9	1.501 (3)
N1—N2	1.392 (2)	C8—H8A	0.9700
N1—C7	1.476 (2)	C8—H8B	0.9700
N2—C9	1.288 (3)	C9—C10	1.464 (3)
N3—C17	1.332 (2)	C10—C11	1.383 (3)
N3—H31	0.8800	C10—C15	1.386 (3)
N3—H32	0.8800	C11—C12	1.381 (3)
C1—C2	1.361 (3)	C11—H11	0.9300
C1—C6	1.367 (3)	C12—C13	1.386 (3)
C2—C3	1.379 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.377 (3)
C3—C4	1.383 (3)	C13—C16	1.505 (3)
C3—H3	0.9300	C14—C15	1.385 (3)
C4—C5	1.377 (3)	C14—H14	0.9300
C4—C7	1.509 (3)	C15—H15	0.9300
C5—C6	1.389 (3)	C16—H16A	0.9600
C5—H5	0.9300	C16—H16B	0.9600
C6—H6	0.9300	C16—H16C	0.9600
C17—N1—N2	119.99 (16)	C9—C8—H8B	111.3
C17—N1—C7	127.16 (16)	C7—C8—H8B	111.3
N2—N1—C7	112.76 (15)	H8A—C8—H8B	109.2
C9—N2—N1	107.83 (16)	N2—C9—C10	120.57 (18)
C17—N3—H31	120.0	N2—C9—C8	113.58 (17)
C17—N3—H32	120.0	C10—C9—C8	125.81 (18)
H31—N3—H32	120.0	C11—C10—C15	118.05 (19)
C2—C1—F1	118.6 (2)	C11—C10—C9	121.63 (19)
C2—C1—C6	123.1 (2)	C15—C10—C9	120.31 (19)
F1—C1—C6	118.25 (19)	C12—C11—C10	121.0 (2)
C1—C2—C3	118.5 (2)	C12—C11—H11	119.5
C1—C2—H2	120.7	C10—C11—H11	119.5
C3—C2—H2	120.7	C11—C12—C13	121.1 (2)
C2—C3—C4	120.74 (19)	C11—C12—H12	119.4
C2—C3—H3	119.6	C13—C12—H12	119.4
C4—C3—H3	119.6	C14—C13—C12	117.8 (2)
C5—C4—C3	118.76 (18)	C14—C13—C16	121.6 (2)
C5—C4—C7	120.31 (17)	C12—C13—C16	120.6 (2)
C3—C4—C7	120.86 (17)	C13—C14—C15	121.5 (2)
C4—C5—C6	121.39 (19)	C13—C14—H14	119.3
C4—C5—H5	119.3	C15—C14—H14	119.3
C6—C5—H5	119.3	C14—C15—C10	120.6 (2)
C1—C6—C5	117.44 (19)	C14—C15—H15	119.7
C1—C6—H6	121.3	C10—C15—H15	119.7
C5—C6—H6	121.3	C13—C16—H16A	109.5
N1—C7—C4	111.36 (16)	C13—C16—H16B	109.5
N1—C7—C8	100.38 (15)	H16A—C16—H16B	109.5
C4—C7—C8	113.31 (16)	C13—C16—H16C	109.5
N1—C7—H7	110.5	H16A—C16—H16C	109.5
C4—C7—H7	110.5	H16B—C16—H16C	109.5
C8—C7—H7	110.5	N3—C17—N1	115.16 (18)
C9—C8—C7	102.56 (16)	N3—C17—S1	122.98 (16)
C9—C8—H8A	111.3	N1—C17—S1	121.85 (15)
C7—C8—H8A	111.3
C17—N1—N2—C9	−167.33 (17)	N1—N2—C9—C10	−179.64 (16)
C7—N1—N2—C9	9.5 (2)	N1—N2—C9—C8	2.3 (2)
F1—C1—C2—C3	−177.94 (19)	C7—C8—C9—N2	−12.1 (2)
C6—C1—C2—C3	0.9 (3)	C7—C8—C9—C10	169.92 (18)
C1—C2—C3—C4	−0.2 (3)	N2—C9—C10—C11	11.6 (3)
C2—C3—C4—C5	−1.0 (3)	C8—C9—C10—C11	−170.55 (19)
C2—C3—C4—C7	−178.1 (2)	N2—C9—C10—C15	−167.37 (19)
C3—C4—C5—C6	1.5 (3)	C8—C9—C10—C15	10.5 (3)
C7—C4—C5—C6	178.58 (19)	C15—C10—C11—C12	1.4 (3)
C2—C1—C6—C5	−0.4 (3)	C9—C10—C11—C12	−177.6 (2)
F1—C1—C6—C5	178.42 (19)	C10—C11—C12—C13	0.9 (4)
C4—C5—C6—C1	−0.8 (3)	C11—C12—C13—C14	−2.7 (4)
C17—N1—C7—C4	−79.3 (2)	C11—C12—C13—C16	176.3 (2)
N2—N1—C7—C4	104.12 (18)	C12—C13—C14—C15	2.3 (3)
C17—N1—C7—C8	160.42 (18)	C16—C13—C14—C15	−176.7 (2)
N2—N1—C7—C8	−16.1 (2)	C13—C14—C15—C10	−0.1 (3)
C5—C4—C7—N1	149.56 (18)	C11—C10—C15—C14	−1.8 (3)
C3—C4—C7—N1	−33.4 (2)	C9—C10—C15—C14	177.28 (19)
C5—C4—C7—C8	−98.2 (2)	N2—N1—C17—N3	1.2 (3)
C3—C4—C7—C8	78.8 (2)	C7—N1—C17—N3	−175.12 (18)
N1—C7—C8—C9	15.56 (19)	N2—N1—C17—S1	−179.70 (14)
C4—C7—C8—C9	−103.26 (18)	C7—N1—C17—S1	4.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···N2	0.88	2.23	2.611 (3)	106
N3—H31···F1i	0.88	2.41	3.255 (2)	162
N3—H32···S1ii	0.88	2.83	3.538 (2)	138
C16—H16B···F1iii	0.96	2.55	3.478 (3)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H31⋯N2	0.88	2.23	2.611 (3)	106
N3—H31⋯F1i	0.88	2.41	3.255 (2)	162
N3—H32⋯S1ii	0.88	2.83	3.538 (2)	138
C16—H16B⋯F1iii	0.96	2.55	3.478 (3)	163

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