3-(3-Chloro-anilino)-1-(3,5-dimethyl-1H-pyrazol-1-yl)propan-1-one.

In the mol-ecule of the title compound, C(14)H(16)ClN(3)O, the benzene and pyrazole rings are oriented at a dihedral angle of 3.50 (3)°. In the crystal structure, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into chains. A π-π contact between the benzene and pyrazole rings [centroid-centroid distance = 3.820 (3) Å] may further stabilize the structure.

Related literature

For general background to 1,3,5-tris­ubstituted pyrazoles, see: Elguero & Goya (2002 ▶). The n class="Chemical">pyrazole chemotype is the structural motif of several highly potent inhibitors against coagulation factor Xa, see: Penning & Talley (1997 ▶); Eriksson & Quinlan (2006 ▶); Escolar et al. (2006 ▶). Pyrazole 3-carboxyl­ates have been identified as selective antagonist subtype 1PGE2 receptors (Akarca, 2005 ▶) and pyrazole-based mat­erials have been used as co-polymers for electroluminescent applications (Mella & Fagnoni, 1997 ▶). For the synthesis, see: Saeed & Mumtaz (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C14H16ClN3O

M = 277.75

Monoclinic,

a = 14.5389 (8) Å

b = 7.8731 (6) Å

c = 12.1411 (7) Å

β = 102.566 (5)°

V = 1356.46 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 173 K

0.35 × 0.33 × 0.33 mm

Data collection

Stoe IPDS II two-circle diffractometer

Absorption correction: multi-scan (MULABS; Blessing, 1995 ▶) T min = 0.909, T max = 0.914

8907 measured reflections

2528 independent reflections

2192 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.086

S = 1.06

2528 reflections

179 parameters

H atoms treated by a mixture of independent and n class="Chemical">constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.23 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-RED (Stoe & Cie, 2001 ▶); data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATOn class="Chemical">N (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016250/hk2680sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016250/hk2680Isup2.hkl

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

C14H16ClN3O	F(000) = 584
Mr = 277.75	Dx = 1.360 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8296 reflections
a = 14.5389 (8) Å	θ = 3.5–25.9°
b = 7.8731 (6) Å	µ = 0.28 mm−1
c = 12.1411 (7) Å	T = 173 K
β = 102.566 (5)°	Block, orange
V = 1356.46 (15) Å3	0.35 × 0.33 × 0.33 mm
Z = 4

Stoe IPDS II two-circle diffractometer	2528 independent reflections
Radiation source: fine-focus sealed tube	2192 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 25.6°, θmin = 3.4°
Absorption correction: multi-scan (MULABS; Blessing, 1995)	h = −17→16
Tmin = 0.909, Tmax = 0.914	k = −9→8
8907 measured reflections	l = −14→14

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086	w = 1/[σ2(Fo2) + (0.0525P)2 + 0.155P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2528 reflections	Δρmax = 0.22 e Å−3
179 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0118 (15)

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	0.09245 (2)	0.19275 (5)	0.40578 (3)	0.03790 (14)
O1	0.56854 (7)	0.37061 (15)	0.32982 (8)	0.0338 (3)
N1	0.44533 (8)	0.16939 (17)	0.58746 (10)	0.0303 (3)
H1	0.4841 (13)	0.165 (2)	0.6485 (15)	0.035 (4)*
C1	0.47221 (8)	0.24939 (17)	0.49191 (10)	0.0230 (3)
H1A	0.4458	0.3656	0.4810	0.028*
H1B	0.4478	0.1831	0.4224	0.028*
C2	0.57897 (9)	0.25608 (17)	0.51596 (10)	0.0224 (3)
H2A	0.6019	0.3236	0.5853	0.027*
H2B	0.6041	0.1394	0.5304	0.027*
C3	0.61688 (9)	0.33260 (16)	0.42090 (10)	0.0218 (3)
C11	0.35323 (9)	0.13937 (17)	0.59318 (10)	0.0224 (3)
C12	0.27731 (9)	0.18284 (17)	0.50608 (10)	0.0232 (3)
H12	0.2873	0.2407	0.4410	0.028*
C13	0.18671 (9)	0.13994 (18)	0.51620 (11)	0.0261 (3)
C14	0.16813 (10)	0.0571 (2)	0.60922 (12)	0.0319 (3)
H14	0.1056	0.0281	0.6135	0.038*
C15	0.24443 (10)	0.01754 (19)	0.69646 (12)	0.0321 (3)
H15	0.2337	−0.0378	0.7620	0.039*
C16	0.33520 (10)	0.05718 (18)	0.68943 (11)	0.0270 (3)
H16	0.3862	0.0289	0.7500	0.032*
N21	0.71440 (8)	0.35624 (14)	0.44523 (8)	0.0211 (2)
N22	0.76632 (8)	0.30431 (14)	0.54929 (9)	0.0234 (2)
C23	0.85436 (9)	0.33838 (17)	0.54618 (11)	0.0252 (3)
C24	0.86089 (9)	0.41270 (18)	0.44162 (11)	0.0261 (3)
H24	0.9170	0.4479	0.4201	0.031*
C25	0.77205 (9)	0.42387 (16)	0.37845 (10)	0.0228 (3)
C26	0.93179 (10)	0.3031 (2)	0.64623 (13)	0.0374 (4)
H26A	0.9551	0.4104	0.6828	0.056*
H26B	0.9833	0.2441	0.6219	0.056*
H26C	0.9078	0.2315	0.6998	0.056*
C27	0.73737 (10)	0.49322 (19)	0.26314 (11)	0.0310 (3)
H27A	0.7888	0.5528	0.2390	0.046*
H27B	0.6855	0.5726	0.2636	0.046*
H27C	0.7149	0.3999	0.2107	0.046*

	U11	U22	U33	U12	U13	U23
Cl1	0.01956 (19)	0.0532 (3)	0.0377 (2)	0.00375 (15)	−0.00099 (14)	−0.00656 (16)
O1	0.0241 (5)	0.0519 (7)	0.0233 (5)	−0.0005 (5)	0.0006 (4)	0.0057 (4)
N1	0.0177 (6)	0.0487 (8)	0.0228 (6)	−0.0042 (5)	0.0009 (5)	0.0071 (5)
C1	0.0182 (6)	0.0276 (7)	0.0228 (6)	−0.0011 (5)	0.0033 (5)	0.0014 (5)
C2	0.0181 (6)	0.0255 (7)	0.0227 (6)	−0.0010 (5)	0.0029 (5)	0.0007 (5)
C3	0.0197 (6)	0.0242 (7)	0.0209 (6)	0.0003 (5)	0.0030 (5)	−0.0023 (5)
C11	0.0203 (6)	0.0229 (6)	0.0243 (6)	−0.0023 (5)	0.0056 (5)	−0.0041 (5)
C12	0.0211 (6)	0.0259 (7)	0.0229 (6)	−0.0003 (5)	0.0055 (5)	−0.0026 (5)
C13	0.0194 (6)	0.0290 (7)	0.0292 (6)	0.0005 (5)	0.0038 (5)	−0.0078 (5)
C14	0.0234 (7)	0.0352 (8)	0.0401 (8)	−0.0051 (6)	0.0135 (6)	−0.0043 (6)
C15	0.0331 (8)	0.0337 (8)	0.0328 (7)	−0.0028 (6)	0.0145 (6)	0.0030 (6)
C16	0.0274 (7)	0.0286 (7)	0.0250 (6)	−0.0010 (6)	0.0058 (5)	0.0015 (5)
N21	0.0197 (5)	0.0255 (6)	0.0183 (5)	−0.0011 (4)	0.0044 (4)	0.0000 (4)
N22	0.0195 (5)	0.0299 (6)	0.0199 (5)	0.0003 (5)	0.0021 (4)	0.0019 (4)
C23	0.0193 (6)	0.0296 (7)	0.0263 (6)	0.0005 (5)	0.0042 (5)	−0.0025 (5)
C24	0.0222 (6)	0.0303 (7)	0.0279 (7)	−0.0047 (6)	0.0102 (5)	−0.0028 (5)
C25	0.0261 (6)	0.0215 (6)	0.0231 (6)	−0.0031 (5)	0.0104 (5)	−0.0032 (5)
C26	0.0199 (7)	0.0555 (10)	0.0345 (8)	0.0007 (7)	0.0012 (6)	0.0059 (7)
C27	0.0347 (7)	0.0370 (8)	0.0226 (6)	−0.0034 (6)	0.0090 (6)	0.0028 (6)

Cl1—C13	1.7461 (14)	C14—H14	0.9500
O1—C3	1.2116 (16)	C15—C16	1.3767 (19)
N1—C11	1.3762 (17)	C15—H15	0.9500
N1—C1	1.4466 (16)	C16—H16	0.9500
N1—H1	0.828 (18)	N21—N22	1.3850 (15)
C1—C2	1.5165 (17)	N21—C25	1.3925 (16)
C1—H1A	0.9900	N22—C23	1.3164 (17)
C1—H1B	0.9900	C23—C24	1.4197 (18)
C2—C3	1.5085 (17)	C23—C26	1.4916 (19)
C2—H2A	0.9900	C24—C25	1.3540 (19)
C2—H2B	0.9900	C24—H24	0.9500
C3—N21	1.3964 (17)	C25—C27	1.4850 (18)
C11—C12	1.3950 (18)	C26—H26A	0.9800
C11—C16	1.4093 (18)	C26—H26B	0.9800
C12—C13	1.3909 (19)	C26—H26C	0.9800
C12—H12	0.9500	C27—H27A	0.9800
C13—C14	1.381 (2)	C27—H27B	0.9800
C14—C15	1.392 (2)	C27—H27C	0.9800
C11—N1—C1	123.43 (12)	C16—C15—H15	119.4
C11—N1—H1	115.4 (12)	C14—C15—H15	119.4
C1—N1—H1	119.0 (12)	C15—C16—C11	120.61 (13)
N1—C1—C2	107.73 (10)	C15—C16—H16	119.7
N1—C1—H1A	110.2	C11—C16—H16	119.7
C2—C1—H1A	110.2	N22—N21—C25	111.49 (10)
N1—C1—H1B	110.2	N22—N21—C3	118.72 (10)
C2—C1—H1B	110.2	C25—N21—C3	129.78 (11)
H1A—C1—H1B	108.5	C23—N22—N21	104.72 (10)
C3—C2—C1	113.30 (10)	N22—C23—C24	111.36 (11)
C3—C2—H2A	108.9	N22—C23—C26	120.32 (12)
C1—C2—H2A	108.9	C24—C23—C26	128.29 (12)
C3—C2—H2B	108.9	C25—C24—C23	106.98 (11)
C1—C2—H2B	108.9	C25—C24—H24	126.5
H2A—C2—H2B	107.7	C23—C24—H24	126.5
O1—C3—N21	121.39 (11)	C24—C25—N21	105.44 (11)
O1—C3—C2	124.12 (12)	C24—C25—C27	130.10 (12)
N21—C3—C2	114.49 (10)	N21—C25—C27	124.45 (12)
N1—C11—C12	122.53 (12)	C23—C26—H26A	109.5
N1—C11—C16	118.64 (12)	C23—C26—H26B	109.5
C12—C11—C16	118.81 (12)	H26A—C26—H26B	109.5
C13—C12—C11	118.80 (12)	C23—C26—H26C	109.5
C13—C12—H12	120.6	H26A—C26—H26C	109.5
C11—C12—H12	120.6	H26B—C26—H26C	109.5
C14—C13—C12	122.99 (13)	C25—C27—H27A	109.5
C14—C13—Cl1	118.68 (11)	C25—C27—H27B	109.5
C12—C13—Cl1	118.33 (11)	H27A—C27—H27B	109.5
C13—C14—C15	117.55 (13)	C25—C27—H27C	109.5
C13—C14—H14	121.2	H27A—C27—H27C	109.5
C15—C14—H14	121.2	H27B—C27—H27C	109.5
C16—C15—C14	121.21 (13)
C11—N1—C1—C2	−178.65 (12)	O1—C3—N21—N22	−177.55 (12)
N1—C1—C2—C3	178.34 (11)	C2—C3—N21—N22	1.99 (16)
C1—C2—C3—O1	−6.68 (19)	O1—C3—N21—C25	1.0 (2)
C1—C2—C3—N21	173.80 (11)	C2—C3—N21—C25	−179.47 (12)
C1—N1—C11—C12	0.5 (2)	C25—N21—N22—C23	−0.40 (14)
C1—N1—C11—C16	178.65 (13)	C3—N21—N22—C23	178.39 (11)
N1—C11—C12—C13	176.66 (12)	N21—N22—C23—C24	0.26 (15)
C16—C11—C12—C13	−1.49 (19)	N21—N22—C23—C26	178.52 (12)
C11—C12—C13—C14	0.5 (2)	N22—C23—C24—C25	−0.02 (16)
C11—C12—C13—Cl1	−179.22 (10)	C26—C23—C24—C25	−178.12 (14)
C12—C13—C14—C15	0.7 (2)	C23—C24—C25—N21	−0.22 (14)
Cl1—C13—C14—C15	−179.52 (11)	C23—C24—C25—C27	179.06 (13)
C13—C14—C15—C16	−1.0 (2)	N22—N21—C25—C24	0.39 (14)
C14—C15—C16—C11	0.0 (2)	C3—N21—C25—C24	−178.23 (12)
N1—C11—C16—C15	−176.98 (13)	N22—N21—C25—C27	−178.94 (12)
C12—C11—C16—C15	1.2 (2)	C3—N21—C25—C27	2.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.828 (18)	2.293 (19)	3.1101 (15)	169.1 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.828 (18)	2.293 (19)	3.1101 (15)	169.1 (16)

Symmetry code: (i) .