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

In the title compound, C16H13ClFN3S, the pyrazole ring adopts an envelope conformation with the methine C atom being the flap atom. The chloro- and fluoro-benzene rings are twisted out of the plane of the pyrazole ring [dihedral angles = 15.12 (11) and 80.55 (10)°, respectively]. The amine group is orientated towards a ring N atom, forming an intra-molecular N-H⋯N hydrogen bond. This H atom also forms a hydrogen bond to the F atom, which along with N-H⋯S hydrogen bonding leads to a supra-molecular chain along the c axis. Connections between chains of the type Cl⋯π lead to a layer in the bc plane.

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: Chantrapromma et al. (2012 ▶); Abdel-Wahab et al. (2013 ▶).

Experimental

Crystal data

C16H13ClFN3S

M = 333.80

Monoclinic,

a = 14.5402 (9) Å

b = 11.2700 (8) Å

c = 9.5169 (6) Å

β = 103.850 (6)°

V = 1514.17 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.40 mm−1

T = 295 K

0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.898, T max = 1.000

10191 measured reflections

3478 independent reflections

2570 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.111

S = 1.01

3478 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.28 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/S1600536813004492/hg5293sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813004492/hg5293Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813004492/hg5293Isup3.cml

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

C16H13ClFN3S	F(000) = 688
Mr = 333.80	Dx = 1.464 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2717 reflections
a = 14.5402 (9) Å	θ = 2.9–27.5°
b = 11.2700 (8) Å	µ = 0.40 mm−1
c = 9.5169 (6) Å	T = 295 K
β = 103.850 (6)°	Prism, colourless
V = 1514.17 (17) Å3	0.40 × 0.30 × 0.20 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	3478 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2570 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.031
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.9°
ω scan	h = −15→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −14→11
Tmin = 0.898, Tmax = 1.000	l = −12→12
10191 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0432P)2 + 0.4541P] where P = (Fo2 + 2Fc2)/3
3478 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.28 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
Cl1	0.54931 (5)	0.65490 (7)	0.48095 (8)	0.0811 (3)
S1	−0.01110 (4)	1.16708 (5)	−0.15948 (5)	0.04527 (17)
F1	0.27125 (11)	1.14248 (13)	−0.60633 (13)	0.0658 (4)
N1	0.20984 (11)	1.00001 (15)	0.08010 (15)	0.0379 (4)
N2	0.13525 (11)	1.03202 (14)	−0.03592 (15)	0.0368 (4)
N3	0.10065 (13)	1.17944 (16)	0.10514 (17)	0.0463 (4)
H31	0.1483	1.1542	0.1741	0.056*
H32	0.0669	1.2407	0.1207	0.056*
C1	0.31834 (13)	0.83907 (18)	0.1544 (2)	0.0381 (4)
C2	0.37595 (15)	0.9020 (2)	0.2678 (2)	0.0498 (5)
H2	0.3661	0.9829	0.2772	0.060*
C3	0.44754 (16)	0.8454 (2)	0.3665 (2)	0.0559 (6)
H3	0.4860	0.8879	0.4419	0.067*
C4	0.46163 (14)	0.7261 (2)	0.3529 (2)	0.0505 (6)
C5	0.40755 (15)	0.6624 (2)	0.2408 (3)	0.0533 (6)
H5	0.4187	0.5819	0.2314	0.064*
C6	0.33602 (14)	0.7194 (2)	0.1414 (2)	0.0476 (5)
H6	0.2993	0.6766	0.0647	0.057*
C7	0.23925 (13)	0.89711 (18)	0.05223 (19)	0.0366 (4)
C8	0.18302 (14)	0.84371 (17)	−0.08689 (19)	0.0394 (4)
H8A	0.1424	0.7802	−0.0687	0.047*
H8B	0.2242	0.8136	−0.1452	0.047*
C9	0.12464 (13)	0.95057 (17)	−0.15998 (18)	0.0365 (4)
H9	0.0581	0.9282	−0.1966	0.044*
C10	0.16342 (12)	1.00448 (17)	−0.27969 (17)	0.0330 (4)
C11	0.23938 (13)	1.08168 (18)	−0.24895 (19)	0.0403 (5)
H11	0.2656	1.1032	−0.1534	0.048*
C12	0.27723 (14)	1.12774 (19)	−0.3580 (2)	0.0442 (5)
H12	0.3288	1.1791	−0.3370	0.053*
C13	0.23618 (15)	1.09503 (19)	−0.4978 (2)	0.0430 (5)
C14	0.16111 (15)	1.01890 (19)	−0.53370 (19)	0.0463 (5)
H14	0.1350	0.9983	−0.6296	0.056*
C15	0.12497 (14)	0.97331 (18)	−0.42252 (19)	0.0400 (4)
H15	0.0741	0.9210	−0.4442	0.048*
C16	0.07946 (13)	1.12480 (17)	−0.02300 (19)	0.0352 (4)

	U11	U22	U33	U12	U13	U23
Cl1	0.0556 (4)	0.0764 (5)	0.0967 (5)	0.0061 (3)	−0.0106 (3)	0.0318 (4)
S1	0.0410 (3)	0.0485 (4)	0.0446 (3)	0.0047 (2)	0.0067 (2)	0.0045 (2)
F1	0.0922 (10)	0.0679 (10)	0.0444 (7)	−0.0139 (8)	0.0304 (7)	0.0066 (6)
N1	0.0384 (8)	0.0440 (10)	0.0306 (7)	0.0025 (7)	0.0068 (6)	0.0007 (7)
N2	0.0406 (8)	0.0402 (10)	0.0295 (7)	0.0046 (7)	0.0080 (6)	−0.0024 (6)
N3	0.0537 (10)	0.0438 (10)	0.0409 (9)	0.0073 (8)	0.0106 (7)	−0.0069 (7)
C1	0.0368 (10)	0.0409 (12)	0.0380 (9)	0.0007 (8)	0.0116 (7)	0.0033 (8)
C2	0.0544 (13)	0.0427 (13)	0.0485 (12)	0.0034 (10)	0.0045 (9)	−0.0004 (9)
C3	0.0520 (13)	0.0587 (16)	0.0488 (12)	−0.0014 (11)	−0.0041 (10)	0.0004 (10)
C4	0.0349 (10)	0.0542 (15)	0.0606 (13)	0.0006 (10)	0.0078 (9)	0.0182 (11)
C5	0.0412 (11)	0.0397 (13)	0.0768 (15)	0.0024 (10)	0.0094 (10)	0.0066 (11)
C6	0.0400 (11)	0.0449 (13)	0.0565 (12)	−0.0026 (9)	0.0091 (9)	−0.0029 (10)
C7	0.0360 (10)	0.0397 (12)	0.0361 (9)	−0.0015 (8)	0.0129 (7)	0.0007 (8)
C8	0.0462 (11)	0.0372 (11)	0.0355 (9)	−0.0004 (9)	0.0111 (8)	−0.0002 (8)
C9	0.0364 (9)	0.0401 (11)	0.0324 (9)	−0.0022 (8)	0.0074 (7)	−0.0048 (8)
C10	0.0329 (9)	0.0343 (10)	0.0307 (8)	0.0027 (8)	0.0056 (7)	−0.0015 (7)
C11	0.0412 (10)	0.0458 (12)	0.0313 (9)	−0.0044 (9)	0.0033 (7)	−0.0028 (8)
C12	0.0431 (11)	0.0462 (13)	0.0437 (11)	−0.0074 (9)	0.0114 (8)	−0.0010 (9)
C13	0.0575 (12)	0.0397 (12)	0.0354 (10)	0.0030 (10)	0.0181 (9)	0.0038 (8)
C14	0.0605 (13)	0.0466 (13)	0.0289 (9)	−0.0014 (10)	0.0053 (8)	−0.0020 (8)
C15	0.0440 (11)	0.0380 (11)	0.0350 (9)	−0.0046 (9)	0.0037 (8)	−0.0030 (8)
C16	0.0378 (9)	0.0351 (11)	0.0358 (9)	−0.0042 (8)	0.0148 (7)	0.0024 (8)

Cl1—C4	1.735 (2)	C5—H5	0.9300
S1—C16	1.6821 (19)	C6—H6	0.9300
F1—C13	1.365 (2)	C7—C8	1.505 (2)
N1—C7	1.285 (2)	C8—C9	1.540 (3)
N1—N2	1.397 (2)	C8—H8A	0.9700
N2—C16	1.347 (2)	C8—H8B	0.9700
N2—C9	1.474 (2)	C9—C10	1.514 (3)
N3—C16	1.335 (2)	C9—H9	0.9800
N3—H31	0.8800	C10—C11	1.381 (3)
N3—H32	0.8800	C10—C15	1.386 (2)
C1—C6	1.384 (3)	C11—C12	1.386 (3)
C1—C2	1.392 (3)	C11—H11	0.9300
C1—C7	1.470 (3)	C12—C13	1.373 (3)
C2—C3	1.380 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.366 (3)
C3—C4	1.371 (3)	C14—C15	1.388 (3)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.367 (3)	C15—H15	0.9300
C5—C6	1.385 (3)
C7—N1—N2	107.67 (15)	C7—C8—H8B	111.4
C16—N2—N1	119.92 (15)	C9—C8—H8B	111.4
C16—N2—C9	127.35 (15)	H8A—C8—H8B	109.2
N1—N2—C9	112.63 (14)	N2—C9—C10	111.49 (15)
C16—N3—H31	120.0	N2—C9—C8	100.63 (13)
C16—N3—H32	120.0	C10—C9—C8	112.91 (15)
H31—N3—H32	120.0	N2—C9—H9	110.5
C6—C1—C2	118.41 (18)	C10—C9—H9	110.5
C6—C1—C7	120.48 (18)	C8—C9—H9	110.5
C2—C1—C7	121.10 (19)	C11—C10—C15	118.82 (17)
C3—C2—C1	120.5 (2)	C11—C10—C9	121.08 (15)
C3—C2—H2	119.7	C15—C10—C9	120.06 (17)
C1—C2—H2	119.7	C10—C11—C12	121.19 (17)
C4—C3—C2	119.7 (2)	C10—C11—H11	119.4
C4—C3—H3	120.2	C12—C11—H11	119.4
C2—C3—H3	120.2	C13—C12—C11	117.83 (19)
C3—C4—C5	121.16 (19)	C13—C12—H12	121.1
C3—C4—Cl1	119.23 (17)	C11—C12—H12	121.1
C5—C4—Cl1	119.61 (19)	C14—C13—F1	118.55 (17)
C4—C5—C6	119.1 (2)	C14—C13—C12	123.16 (18)
C4—C5—H5	120.4	F1—C13—C12	118.28 (19)
C6—C5—H5	120.4	C13—C14—C15	117.89 (17)
C5—C6—C1	121.1 (2)	C13—C14—H14	121.1
C5—C6—H6	119.5	C15—C14—H14	121.1
C1—C6—H6	119.5	C10—C15—C14	121.10 (18)
N1—C7—C1	120.74 (17)	C10—C15—H15	119.4
N1—C7—C8	113.88 (16)	C14—C15—H15	119.4
C1—C7—C8	125.33 (18)	N3—C16—N2	115.42 (16)
C7—C8—C9	102.08 (15)	N3—C16—S1	122.79 (16)
C7—C8—H8A	111.4	N2—C16—S1	121.78 (14)
C9—C8—H8A	111.4
C7—N1—N2—C16	167.15 (16)	C16—N2—C9—C8	−159.69 (18)
C7—N1—N2—C9	−9.4 (2)	N1—N2—C9—C8	16.59 (19)
C6—C1—C2—C3	−1.4 (3)	C7—C8—C9—N2	−16.22 (18)
C7—C1—C2—C3	177.32 (19)	C7—C8—C9—C10	102.72 (17)
C1—C2—C3—C4	−0.3 (3)	N2—C9—C10—C11	31.9 (2)
C2—C3—C4—C5	1.8 (4)	C8—C9—C10—C11	−80.5 (2)
C2—C3—C4—Cl1	−177.91 (17)	N2—C9—C10—C15	−150.42 (17)
C3—C4—C5—C6	−1.4 (4)	C8—C9—C10—C15	97.1 (2)
Cl1—C4—C5—C6	178.23 (17)	C15—C10—C11—C12	−0.1 (3)
C4—C5—C6—C1	−0.3 (3)	C9—C10—C11—C12	177.60 (18)
C2—C1—C6—C5	1.7 (3)	C10—C11—C12—C13	0.6 (3)
C7—C1—C6—C5	−177.00 (19)	C11—C12—C13—C14	−0.7 (3)
N2—N1—C7—C1	179.67 (16)	C11—C12—C13—F1	178.21 (18)
N2—N1—C7—C8	−2.9 (2)	F1—C13—C14—C15	−178.68 (19)
C6—C1—C7—N1	165.27 (18)	C12—C13—C14—C15	0.2 (3)
C2—C1—C7—N1	−13.4 (3)	C11—C10—C15—C14	−0.4 (3)
C6—C1—C7—C8	−11.9 (3)	C9—C10—C15—C14	−178.12 (18)
C2—C1—C7—C8	169.41 (19)	C13—C14—C15—C10	0.3 (3)
N1—C7—C8—C9	12.9 (2)	N1—N2—C16—N3	−0.7 (2)
C1—C7—C8—C9	−169.76 (17)	C9—N2—C16—N3	175.38 (17)
C16—N2—C9—C10	80.3 (2)	N1—N2—C16—S1	179.89 (13)
N1—N2—C9—C10	−103.38 (17)	C9—N2—C16—S1	−4.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···N1	0.88	2.24	2.617 (2)	106
N3—H31···F1i	0.88	2.41	3.257 (2)	163
N3—H32···S1ii	0.88	2.81	3.5203 (19)	139
C4—Cl1···Cg1iii	1.74 (1)	3.92 (1)	4.183 (2)	86 (1)

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H31⋯N1	0.88	2.24	2.617 (2)	106
N3—H31⋯F1i	0.88	2.41	3.257 (2)	163
N3—H32⋯S1ii	0.88	2.81	3.5203 (19)	139
C4—Cl1⋯Cg1iii	1.735 (2)	3.9240 (12)	4.183 (2)	86.17 (17)

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