1-{[5-(4-Chloro-phen-yl)-1-(4-fluoro-phen-yl)-1H-pyrazol-3-yl]carbon-yl]}piperidin-4-one.

In the title compound, C(21)H(17)ClFN(3)O(2), the 1H-pyrazole ring makes dihedral angles of 36.73 (7), 18.73 (7) and 60.88 (8)°, respectively, with the mean planes of the chloro-phenyl, 4-oxo-piperidine and fluoro-phenyl rings. The mol-ecular structure is stabilized by an intra-molecular C-H⋯N hydrogen bond, which forms an S(6) ring motif. In the crystal, inter-molecular C-H⋯O hydrogen bonds link mol-ecules into chains along [101]. In addition, inter-molecular C-H⋯F hydrogen bonds with an R(2) (1)(7) ring motif connect neighbouring chains into layers parallel to the ac plane.

Related literature

For pyrazole derivatives and their microbial activities, see: Ragavan et al. (2009 ▶, 2010 ▶). For a related structure, see: Shahani et al. (2010 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). 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

C21H17ClFN3O2

M = 397.83

Triclinic,

a = 6.0341 (2) Å

b = 8.2500 (3) Å

c = 10.2448 (3) Å

α = 108.837 (1)°

β = 104.782 (1)°

γ = 92.792 (1)°

V = 461.90 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.24 mm−1

T = 100 K

0.77 × 0.21 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.837, T max = 0.974

10178 measured reflections

3646 independent reflections

3596 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.062

S = 1.05

3646 reflections

253 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 1556 Friedel pairs

Flack parameter: 0.06 (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/S1600536810047215/is2632sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047215/is2632Isup2.hkl

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

C21H17ClFN3O2	Z = 1
Mr = 397.83	F(000) = 206
Triclinic, P1	Dx = 1.430 Mg m−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0341 (2) Å	Cell parameters from 9510 reflections
b = 8.2500 (3) Å	θ = 2.2–35.0°
c = 10.2448 (3) Å	µ = 0.24 mm−1
α = 108.837 (1)°	T = 100 K
β = 104.782 (1)°	Needle, colourless
γ = 92.792 (1)°	0.77 × 0.21 × 0.11 mm
V = 461.90 (3) Å3

Bruker SMART APEXII CCD area-detector diffractometer	3646 independent reflections
Radiation source: fine-focus sealed tube	3596 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.837, Tmax = 0.974	k = −10→10
10178 measured reflections	l = −13→13

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)] = 0.024	H-atom parameters constrained
wR(F2) = 0.062	w = 1/[σ2(Fo2) + (0.0375P)2 + 0.0616P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3646 reflections	Δρmax = 0.17 e Å−3
253 parameters	Δρmin = −0.21 e Å−3
3 restraints	Absolute structure: Flack (1983), 1556 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.06 (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
Cl1	−0.18751 (5)	−0.56629 (4)	−0.09987 (4)	0.02699 (9)
F1	0.47475 (18)	−0.01865 (15)	−0.50052 (9)	0.0397 (3)
O1	1.11635 (17)	0.26727 (13)	0.53957 (10)	0.0225 (2)
O2	1.85032 (19)	0.66828 (16)	0.41014 (12)	0.0326 (3)
N1	0.73866 (19)	0.06297 (14)	0.07455 (11)	0.0160 (2)
N2	0.92725 (19)	0.18040 (14)	0.16028 (11)	0.0171 (2)
N3	1.27132 (19)	0.41856 (15)	0.42751 (11)	0.0197 (2)
C1	0.4556 (2)	0.08181 (18)	−0.13442 (14)	0.0192 (3)
H1A	0.3585	0.1228	−0.0774	0.023*
C2	0.3886 (3)	0.06260 (19)	−0.27928 (14)	0.0235 (3)
H2A	0.2462	0.0894	−0.3215	0.028*
C3	0.5399 (3)	0.00258 (19)	−0.35841 (14)	0.0254 (3)
C4	0.7542 (3)	−0.03780 (19)	−0.30190 (14)	0.0243 (3)
H4A	0.8525	−0.0754	−0.3587	0.029*
C5	0.8185 (2)	−0.02049 (18)	−0.15695 (14)	0.0200 (3)
H5A	0.9602	−0.0487	−0.1154	0.024*
C6	0.6687 (2)	0.03934 (16)	−0.07542 (13)	0.0161 (2)
C7	0.2588 (2)	−0.14175 (17)	0.15655 (13)	0.0173 (3)
H7A	0.2749	−0.0537	0.2437	0.021*
C8	0.0689 (2)	−0.27130 (18)	0.10073 (14)	0.0190 (3)
H8A	−0.0413	−0.2705	0.1498	0.023*
C9	0.0469 (2)	−0.40181 (17)	−0.02954 (15)	0.0192 (3)
C10	0.2091 (3)	−0.40594 (18)	−0.10451 (15)	0.0199 (3)
H10A	0.1914	−0.4943	−0.1918	0.024*
C11	0.3994 (2)	−0.27583 (17)	−0.04738 (14)	0.0188 (3)
H11A	0.5098	−0.2778	−0.0966	0.023*
C12	0.4254 (2)	−0.14175 (16)	0.08395 (13)	0.0160 (3)
C13	0.6292 (2)	−0.00678 (16)	0.15007 (13)	0.0151 (2)
C14	0.7564 (2)	0.07058 (17)	0.29276 (13)	0.0172 (3)
H14A	0.7284	0.0510	0.3719	0.021*
C15	0.9368 (2)	0.18496 (17)	0.29308 (13)	0.0164 (3)
C16	1.1168 (2)	0.29506 (17)	0.42851 (13)	0.0168 (3)
C17	1.2640 (2)	0.49206 (18)	0.31390 (14)	0.0202 (3)
H17A	1.2384	0.6119	0.3472	0.024*
H17B	1.1365	0.4287	0.2296	0.024*
C18	1.4914 (3)	0.48167 (19)	0.27422 (15)	0.0225 (3)
H18A	1.5073	0.3614	0.2298	0.027*
H18B	1.4901	0.5391	0.2051	0.027*
C19	1.6952 (3)	0.56654 (19)	0.40686 (15)	0.0240 (3)
C20	1.6883 (2)	0.5158 (2)	0.53511 (15)	0.0239 (3)
H20A	1.8015	0.5955	0.6202	0.029*
H20B	1.7320	0.4010	0.5200	0.029*
C21	1.4500 (2)	0.51622 (19)	0.56187 (14)	0.0203 (3)
H21A	1.4476	0.4642	0.6341	0.024*
H21B	1.4190	0.6344	0.5975	0.024*

	U11	U22	U33	U12	U13	U23
Cl1	0.02313 (16)	0.01987 (16)	0.03408 (18)	−0.00462 (12)	0.00415 (13)	0.00849 (13)
F1	0.0393 (5)	0.0625 (7)	0.0143 (4)	−0.0089 (5)	0.0024 (4)	0.0159 (4)
O1	0.0247 (5)	0.0267 (5)	0.0153 (4)	0.0003 (4)	0.0023 (4)	0.0092 (4)
O2	0.0231 (5)	0.0389 (6)	0.0328 (6)	−0.0016 (5)	0.0122 (4)	0.0060 (5)
N1	0.0171 (5)	0.0171 (5)	0.0133 (5)	−0.0006 (4)	0.0035 (4)	0.0058 (4)
N2	0.0162 (5)	0.0173 (5)	0.0150 (5)	−0.0008 (4)	0.0013 (4)	0.0048 (4)
N3	0.0203 (6)	0.0210 (6)	0.0139 (5)	−0.0026 (5)	−0.0014 (4)	0.0065 (4)
C1	0.0194 (6)	0.0214 (7)	0.0187 (6)	−0.0005 (5)	0.0056 (5)	0.0097 (5)
C2	0.0222 (7)	0.0291 (8)	0.0196 (7)	−0.0038 (6)	0.0001 (5)	0.0145 (6)
C3	0.0308 (7)	0.0295 (8)	0.0129 (6)	−0.0090 (6)	0.0024 (5)	0.0085 (5)
C4	0.0281 (7)	0.0243 (7)	0.0183 (6)	−0.0055 (6)	0.0098 (6)	0.0033 (5)
C5	0.0199 (6)	0.0182 (6)	0.0196 (6)	−0.0016 (5)	0.0057 (5)	0.0041 (5)
C6	0.0197 (6)	0.0160 (6)	0.0127 (5)	−0.0023 (5)	0.0040 (5)	0.0062 (4)
C7	0.0203 (6)	0.0173 (6)	0.0151 (6)	0.0034 (5)	0.0039 (5)	0.0075 (5)
C8	0.0187 (6)	0.0213 (7)	0.0206 (6)	0.0038 (5)	0.0061 (5)	0.0114 (5)
C9	0.0175 (6)	0.0159 (6)	0.0244 (7)	−0.0009 (5)	0.0019 (5)	0.0109 (5)
C10	0.0240 (7)	0.0165 (6)	0.0182 (6)	0.0011 (5)	0.0051 (5)	0.0055 (5)
C11	0.0211 (6)	0.0174 (6)	0.0184 (6)	0.0012 (5)	0.0062 (5)	0.0068 (5)
C12	0.0179 (6)	0.0149 (6)	0.0155 (5)	0.0021 (5)	0.0017 (5)	0.0081 (5)
C13	0.0174 (6)	0.0142 (6)	0.0154 (5)	0.0035 (5)	0.0055 (5)	0.0065 (5)
C14	0.0206 (6)	0.0178 (6)	0.0138 (6)	0.0028 (5)	0.0045 (5)	0.0065 (5)
C15	0.0182 (6)	0.0161 (6)	0.0147 (6)	0.0035 (5)	0.0031 (5)	0.0060 (5)
C16	0.0172 (6)	0.0172 (6)	0.0151 (6)	0.0044 (5)	0.0027 (5)	0.0055 (5)
C17	0.0202 (6)	0.0202 (6)	0.0195 (6)	−0.0005 (5)	0.0022 (5)	0.0090 (5)
C18	0.0258 (7)	0.0229 (7)	0.0192 (6)	0.0035 (6)	0.0074 (5)	0.0070 (5)
C19	0.0196 (7)	0.0237 (7)	0.0260 (7)	0.0062 (6)	0.0086 (5)	0.0033 (6)
C20	0.0190 (7)	0.0258 (7)	0.0218 (7)	0.0029 (6)	0.0021 (5)	0.0047 (5)
C21	0.0192 (6)	0.0224 (7)	0.0144 (6)	−0.0004 (5)	0.0011 (5)	0.0032 (5)

Cl1—C9	1.7387 (14)	C8—C9	1.3877 (19)
F1—C3	1.3570 (14)	C8—H8A	0.9300
O1—C16	1.2317 (16)	C9—C10	1.385 (2)
O2—C19	1.2130 (19)	C10—C11	1.394 (2)
N1—N2	1.3558 (15)	C10—H10A	0.9300
N1—C13	1.3701 (17)	C11—C12	1.4045 (18)
N1—C6	1.4299 (15)	C11—H11A	0.9300
N2—C15	1.3352 (16)	C12—C13	1.4714 (18)
N3—C16	1.3515 (18)	C13—C14	1.3823 (17)
N3—C21	1.4657 (15)	C14—C15	1.4039 (19)
N3—C17	1.4684 (17)	C14—H14A	0.9300
C1—C6	1.3875 (19)	C15—C16	1.5004 (17)
C1—C2	1.3881 (18)	C17—C18	1.526 (2)
C1—H1A	0.9300	C17—H17A	0.9700
C2—C3	1.378 (2)	C17—H17B	0.9700
C2—H2A	0.9300	C18—C19	1.516 (2)
C3—C4	1.379 (2)	C18—H18A	0.9700
C4—C5	1.3927 (18)	C18—H18B	0.9700
C4—H4A	0.9300	C19—C20	1.511 (2)
C5—C6	1.3862 (18)	C20—C21	1.531 (2)
C5—H5A	0.9300	C20—H20A	0.9700
C7—C8	1.3903 (19)	C20—H20B	0.9700
C7—C12	1.3951 (19)	C21—H21A	0.9700
C7—H7A	0.9300	C21—H21B	0.9700
N2—N1—C13	112.88 (10)	C7—C12—C13	119.32 (11)
N2—N1—C6	118.05 (11)	C11—C12—C13	121.72 (12)
C13—N1—C6	128.81 (11)	N1—C13—C14	105.49 (12)
C15—N2—N1	104.32 (11)	N1—C13—C12	124.42 (11)
C16—N3—C21	118.56 (11)	C14—C13—C12	130.04 (12)
C16—N3—C17	128.10 (11)	C13—C14—C15	105.57 (12)
C21—N3—C17	112.47 (11)	C13—C14—H14A	127.2
C6—C1—C2	119.43 (13)	C15—C14—H14A	127.2
C6—C1—H1A	120.3	N2—C15—C14	111.75 (11)
C2—C1—H1A	120.3	N2—C15—C16	125.60 (12)
C3—C2—C1	117.83 (13)	C14—C15—C16	122.64 (11)
C3—C2—H2A	121.1	O1—C16—N3	122.03 (11)
C1—C2—H2A	121.1	O1—C16—C15	116.83 (12)
F1—C3—C2	118.27 (13)	N3—C16—C15	121.13 (11)
F1—C3—C4	117.82 (13)	N3—C17—C18	110.09 (11)
C2—C3—C4	123.90 (12)	N3—C17—H17A	109.6
C3—C4—C5	117.84 (13)	C18—C17—H17A	109.6
C3—C4—H4A	121.1	N3—C17—H17B	109.6
C5—C4—H4A	121.1	C18—C17—H17B	109.6
C6—C5—C4	119.19 (12)	H17A—C17—H17B	108.2
C6—C5—H5A	120.4	C19—C18—C17	110.61 (11)
C4—C5—H5A	120.4	C19—C18—H18A	109.5
C5—C6—C1	121.79 (12)	C17—C18—H18A	109.5
C5—C6—N1	119.07 (11)	C19—C18—H18B	109.5
C1—C6—N1	119.11 (12)	C17—C18—H18B	109.5
C8—C7—C12	121.09 (12)	H18A—C18—H18B	108.1
C8—C7—H7A	119.5	O2—C19—C20	122.68 (13)
C12—C7—H7A	119.5	O2—C19—C18	122.62 (14)
C9—C8—C7	118.83 (13)	C20—C19—C18	114.69 (13)
C9—C8—H8A	120.6	C19—C20—C21	113.13 (11)
C7—C8—H8A	120.6	C19—C20—H20A	109.0
C10—C9—C8	121.64 (13)	C21—C20—H20A	109.0
C10—C9—Cl1	118.91 (10)	C19—C20—H20B	109.0
C8—C9—Cl1	119.45 (11)	C21—C20—H20B	109.0
C9—C10—C11	119.11 (12)	H20A—C20—H20B	107.8
C9—C10—H10A	120.4	N3—C21—C20	109.72 (11)
C11—C10—H10A	120.4	N3—C21—H21A	109.7
C10—C11—C12	120.45 (13)	C20—C21—H21A	109.7
C10—C11—H11A	119.8	N3—C21—H21B	109.7
C12—C11—H11A	119.8	C20—C21—H21B	109.7
C7—C12—C11	118.89 (13)	H21A—C21—H21B	108.2
C13—N1—N2—C15	−0.07 (13)	C6—N1—C13—C12	8.4 (2)
C6—N1—N2—C15	174.57 (11)	C7—C12—C13—N1	−146.36 (12)
C6—C1—C2—C3	−0.5 (2)	C11—C12—C13—N1	36.75 (19)
C1—C2—C3—F1	179.21 (13)	C7—C12—C13—C14	36.9 (2)
C1—C2—C3—C4	−0.6 (2)	C11—C12—C13—C14	−140.04 (14)
F1—C3—C4—C5	−178.30 (12)	N1—C13—C14—C15	0.40 (14)
C2—C3—C4—C5	1.5 (2)	C12—C13—C14—C15	177.65 (12)
C3—C4—C5—C6	−1.3 (2)	N1—N2—C15—C14	0.34 (14)
C4—C5—C6—C1	0.3 (2)	N1—N2—C15—C16	179.57 (11)
C4—C5—C6—N1	−177.75 (12)	C13—C14—C15—N2	−0.47 (15)
C2—C1—C6—C5	0.6 (2)	C13—C14—C15—C16	−179.73 (11)
C2—C1—C6—N1	178.67 (12)	C21—N3—C16—O1	2.92 (18)
N2—N1—C6—C5	62.36 (15)	C17—N3—C16—O1	−165.56 (13)
C13—N1—C6—C5	−123.97 (15)	C21—N3—C16—C15	−177.10 (11)
N2—N1—C6—C1	−115.72 (14)	C17—N3—C16—C15	14.4 (2)
C13—N1—C6—C1	57.94 (19)	N2—C15—C16—O1	−171.13 (13)
C12—C7—C8—C9	−0.09 (18)	C14—C15—C16—O1	8.02 (18)
C7—C8—C9—C10	0.12 (19)	N2—C15—C16—N3	8.88 (19)
C7—C8—C9—Cl1	179.22 (10)	C14—C15—C16—N3	−171.97 (12)
C8—C9—C10—C11	0.13 (19)	C16—N3—C17—C18	−127.53 (14)
Cl1—C9—C10—C11	−178.98 (10)	C21—N3—C17—C18	63.42 (14)
C9—C10—C11—C12	−0.41 (19)	N3—C17—C18—C19	−54.44 (15)
C8—C7—C12—C11	−0.19 (18)	C17—C18—C19—O2	−132.83 (14)
C8—C7—C12—C13	−177.17 (11)	C17—C18—C19—C20	46.56 (16)
C10—C11—C12—C7	0.44 (19)	O2—C19—C20—C21	134.59 (15)
C10—C11—C12—C13	177.34 (12)	C18—C19—C20—C21	−44.80 (16)
N2—N1—C13—C14	−0.21 (14)	C16—N3—C21—C20	129.76 (13)
C6—N1—C13—C14	−174.15 (12)	C17—N3—C21—C20	−60.04 (15)
N2—N1—C13—C12	−177.66 (11)	C19—C20—C21—N3	49.66 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1i	0.93	2.38	3.1196 (19)	136
C7—H7A···F1ii	0.93	2.50	3.2099 (15)	133
C14—H14A···F1ii	0.93	2.41	3.2614 (17)	153
C17—H17B···N2	0.97	2.16	2.9091 (18)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1i	0.93	2.38	3.1196 (19)	136
C7—H7A⋯F1ii	0.93	2.50	3.2099 (15)	133
C14—H14A⋯F1ii	0.93	2.41	3.2614 (17)	153
C17—H17B⋯N2	0.97	2.16	2.9091 (18)	133

Symmetry codes: (i) ; (ii) .