1-(2,4-Dichloro-phen-yl)-5-(2-nitro-anilino)-1H-pyrazole-4-carbonitrile.

In the title compound, C(16)H(9)Cl(2)N(5)O(2), the folded mol-ecular conformation is characterized by a dihedral angle between the two benzene rings of 74.03 (5)°. An intra-molecular N-H⋯O hydrogen bond is observed between the H atom of the amide group and a nitro-group O atom. Inter-molecular C-H⋯O and N-H⋯N hydrogen bonds feature in the crystal packing.

Related literature

For general background to N-1-diaryl-1H-pyrazol-5-amine derivatives as synthetic inter­mediates in the preparation of medicinal compounds and the synthesis of the title compound, see: Markwalder et al. (2004 ▶); Mehdi et al. (2010 ▶). For the pharmacological activity of the 5-amino­pyrazole nucleus, see: Nils et al. (2010 ▶); Aymn et al. (2005 ▶).

Experimental

Crystal data

C16H9Cl2N5O2

M = 374.18

Orthorhombic,

a = 13.878 (3) Å

b = 13.475 (3) Å

c = 17.421 (4) Å

V = 3257.7 (11) Å3

Z = 8

Mo Kα radiation

μ = 0.42 mm−1

T = 293 K

0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn724 CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) ▶ T min = 0.921, T max = 0.951

31011 measured reflections

3888 independent reflections

2738 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.142

S = 1.04

3888 reflections

231 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.24 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2005) ▶; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812011506/kp2396sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011506/kp2396Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812011506/kp2396Isup3.cml

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

C16H9Cl2N5O2	F(000) = 1520
Mr = 374.18	Dx = 1.526 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2n2ab	Cell parameters from 7017 reflections
a = 13.878 (3) Å	θ = 2.4–28.0°
b = 13.475 (3) Å	µ = 0.42 mm−1
c = 17.421 (4) Å	T = 293 K
V = 3257.7 (11) Å3	Prism, yellow
Z = 8	0.20 × 0.18 × 0.12 mm

Rigaku Saturn724 CCD diffractometer	3888 independent reflections
Radiation source: rotating anode	2738 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.050
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 2.3°
ω scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −17→16
Tmin = 0.921, Tmax = 0.951	l = −22→22
31011 measured reflections

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)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142	w = 1/[σ2(Fo2) + (0.0759P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
3888 reflections	Δρmax = 0.24 e Å−3
231 parameters	Δρmin = −0.24 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: 0.0166 (13)

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	0.15552 (5)	0.60779 (4)	0.46994 (4)	0.0673 (2)
Cl2	−0.14562 (5)	0.48959 (6)	0.30041 (5)	0.0881 (3)
O1	0.35014 (15)	0.63038 (12)	0.30863 (12)	0.0858 (6)
O2	0.41521 (15)	0.62525 (14)	0.19700 (10)	0.0914 (6)
N1	0.20172 (14)	0.33598 (13)	0.53423 (10)	0.0540 (5)
N2	0.20985 (13)	0.39203 (11)	0.46920 (9)	0.0467 (4)
N3	0.54146 (17)	0.37889 (14)	0.51865 (12)	0.0667 (5)
N4	0.32727 (13)	0.46781 (13)	0.38776 (9)	0.0477 (4)
N5	0.37959 (14)	0.58365 (14)	0.25298 (11)	0.0609 (5)
C1	0.09266 (15)	0.51444 (13)	0.42412 (12)	0.0481 (5)
C2	0.00946 (15)	0.53705 (15)	0.38503 (13)	0.0558 (6)
H2A	−0.0128	0.6021	0.3830	0.067*
C3	−0.04013 (16)	0.46247 (16)	0.34907 (13)	0.0556 (6)
C4	−0.00852 (16)	0.36558 (16)	0.35107 (13)	0.0575 (6)
H4A	−0.0428	0.3158	0.3261	0.069*
C5	0.07443 (15)	0.34366 (14)	0.39045 (12)	0.0521 (5)
H5	0.0962	0.2785	0.3925	0.063*
C6	0.12581 (15)	0.41746 (14)	0.42708 (11)	0.0446 (5)
C7	0.30239 (15)	0.41365 (13)	0.45245 (11)	0.0438 (5)
C8	0.35782 (15)	0.37153 (15)	0.50928 (12)	0.0476 (5)
C9	0.29092 (16)	0.32434 (15)	0.55794 (11)	0.0536 (5)
H9	0.3079	0.2890	0.6018	0.064*
C10	0.45966 (19)	0.37500 (15)	0.51458 (12)	0.0516 (5)
C11	0.34423 (13)	0.42402 (14)	0.31790 (11)	0.0407 (4)
C12	0.33508 (16)	0.32211 (15)	0.30894 (12)	0.0559 (6)
H12	0.3164	0.2838	0.3508	0.067*
C13	0.35285 (19)	0.27656 (18)	0.24013 (15)	0.0735 (7)
H13	0.3455	0.2082	0.2360	0.088*
C14	0.3815 (2)	0.3305 (2)	0.17670 (14)	0.0750 (7)
H14	0.3942	0.2988	0.1304	0.090*
C15	0.39084 (16)	0.4299 (2)	0.18286 (12)	0.0608 (6)
H15	0.4098	0.4670	0.1404	0.073*
C16	0.37242 (14)	0.47708 (15)	0.25204 (11)	0.0453 (5)
H4	0.3360 (18)	0.528 (2)	0.3926 (15)	0.077 (8)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0852 (5)	0.0448 (3)	0.0719 (4)	−0.0062 (3)	−0.0050 (3)	−0.0152 (3)
Cl2	0.0593 (4)	0.1038 (6)	0.1013 (6)	0.0108 (3)	−0.0192 (4)	−0.0065 (4)
O1	0.1372 (18)	0.0455 (10)	0.0746 (13)	−0.0036 (9)	0.0066 (11)	0.0082 (9)
O2	0.1296 (16)	0.0868 (13)	0.0577 (11)	−0.0414 (11)	−0.0163 (11)	0.0338 (9)
N1	0.0691 (13)	0.0515 (10)	0.0413 (9)	−0.0029 (8)	0.0045 (8)	0.0103 (7)
N2	0.0577 (11)	0.0429 (9)	0.0394 (9)	−0.0014 (7)	0.0013 (7)	0.0059 (6)
N3	0.0697 (15)	0.0613 (12)	0.0691 (14)	0.0055 (10)	−0.0084 (10)	0.0057 (9)
N4	0.0668 (11)	0.0363 (9)	0.0401 (9)	−0.0063 (8)	0.0028 (8)	0.0020 (7)
N5	0.0745 (13)	0.0594 (12)	0.0488 (12)	−0.0166 (10)	−0.0150 (10)	0.0172 (9)
C1	0.0547 (13)	0.0399 (10)	0.0499 (12)	−0.0017 (9)	0.0047 (10)	−0.0043 (8)
C2	0.0593 (14)	0.0464 (12)	0.0617 (14)	0.0075 (10)	0.0046 (11)	−0.0014 (10)
C3	0.0485 (13)	0.0607 (14)	0.0576 (14)	0.0001 (10)	0.0000 (10)	0.0011 (10)
C4	0.0570 (14)	0.0552 (13)	0.0603 (14)	−0.0137 (11)	0.0003 (11)	−0.0063 (10)
C5	0.0603 (13)	0.0374 (10)	0.0586 (13)	−0.0049 (9)	0.0041 (11)	−0.0001 (9)
C6	0.0504 (12)	0.0412 (10)	0.0421 (11)	−0.0031 (8)	0.0036 (9)	0.0022 (8)
C7	0.0556 (13)	0.0383 (10)	0.0375 (10)	0.0000 (8)	0.0012 (9)	0.0007 (7)
C8	0.0616 (14)	0.0411 (10)	0.0400 (11)	0.0023 (9)	−0.0034 (9)	−0.0011 (8)
C9	0.0733 (16)	0.0472 (12)	0.0401 (11)	0.0021 (10)	−0.0014 (10)	0.0068 (8)
C10	0.0625 (16)	0.0450 (11)	0.0472 (12)	0.0066 (10)	−0.0054 (10)	0.0006 (8)
C11	0.0394 (10)	0.0420 (10)	0.0406 (10)	−0.0025 (8)	−0.0020 (8)	0.0023 (8)
C12	0.0729 (14)	0.0439 (11)	0.0511 (13)	−0.0054 (10)	0.0077 (11)	−0.0017 (9)
C13	0.097 (2)	0.0552 (15)	0.0684 (17)	−0.0038 (12)	0.0093 (14)	−0.0156 (12)
C14	0.0862 (18)	0.0849 (19)	0.0540 (15)	−0.0084 (15)	0.0118 (13)	−0.0203 (13)
C15	0.0567 (14)	0.0836 (17)	0.0422 (12)	−0.0094 (12)	0.0042 (10)	0.0003 (11)
C16	0.0428 (11)	0.0514 (11)	0.0419 (11)	−0.0071 (9)	−0.0053 (8)	0.0061 (8)

Cl1—C1	1.726 (2)	C4—C5	1.372 (3)
Cl2—C3	1.731 (2)	C4—H4A	0.9300
O1—N5	1.226 (3)	C5—C6	1.380 (3)
O2—N5	1.229 (2)	C5—H5	0.9300
N1—C9	1.314 (3)	C7—C8	1.376 (3)
N1—N2	1.366 (2)	C8—C9	1.409 (3)
N2—C7	1.349 (3)	C8—C10	1.417 (3)
N2—C6	1.420 (3)	C9—H9	0.9300
N3—C10	1.139 (3)	C11—C12	1.388 (3)
N4—C11	1.373 (2)	C11—C16	1.407 (3)
N4—C7	1.386 (2)	C12—C13	1.369 (3)
N4—H4	0.82 (3)	C12—H12	0.9300
N5—C16	1.440 (3)	C13—C14	1.381 (3)
C1—C2	1.375 (3)	C13—H13	0.9300
C1—C6	1.386 (3)	C14—C15	1.350 (3)
C2—C3	1.370 (3)	C14—H14	0.9300
C2—H2A	0.9300	C15—C16	1.386 (3)
C3—C4	1.378 (3)	C15—H15	0.9300
C9—N1—N2	104.40 (16)	N2—C7—C8	106.71 (18)
C7—N2—N1	112.17 (16)	N2—C7—N4	121.77 (18)
C7—N2—C6	128.19 (16)	C8—C7—N4	131.51 (19)
N1—N2—C6	119.60 (17)	C7—C8—C9	104.52 (19)
C11—N4—C7	122.49 (17)	C7—C8—C10	126.21 (19)
C11—N4—H4	119.2 (18)	C9—C8—C10	129.26 (19)
C7—N4—H4	118.1 (18)	N1—C9—C8	112.19 (18)
O1—N5—O2	121.8 (2)	N1—C9—H9	123.9
O1—N5—C16	119.88 (18)	C8—C9—H9	123.9
O2—N5—C16	118.3 (2)	N3—C10—C8	179.2 (2)
C2—C1—C6	120.40 (18)	N4—C11—C12	120.61 (17)
C2—C1—Cl1	119.47 (15)	N4—C11—C16	123.50 (17)
C6—C1—Cl1	120.13 (17)	C12—C11—C16	115.88 (18)
C3—C2—C1	119.08 (19)	C13—C12—C11	121.7 (2)
C3—C2—H2A	120.5	C13—C12—H12	119.1
C1—C2—H2A	120.5	C11—C12—H12	119.1
C2—C3—C4	121.6 (2)	C12—C13—C14	121.1 (2)
C2—C3—Cl2	119.61 (17)	C12—C13—H13	119.5
C4—C3—Cl2	118.80 (17)	C14—C13—H13	119.5
C5—C4—C3	118.9 (2)	C15—C14—C13	119.1 (2)
C5—C4—H4A	120.5	C15—C14—H14	120.4
C3—C4—H4A	120.5	C13—C14—H14	120.4
C4—C5—C6	120.63 (19)	C14—C15—C16	120.4 (2)
C4—C5—H5	119.7	C14—C15—H15	119.8
C6—C5—H5	119.7	C16—C15—H15	119.8
C5—C6—C1	119.4 (2)	C15—C16—C11	121.82 (19)
C5—C6—N2	119.31 (17)	C15—C16—N5	117.01 (19)
C1—C6—N2	121.28 (17)	C11—C16—N5	121.12 (18)
C9—N1—N2—C7	0.7 (2)	N4—C7—C8—C9	−178.5 (2)
C9—N1—N2—C6	178.77 (16)	N2—C7—C8—C10	179.56 (19)
C6—C1—C2—C3	0.0 (3)	N4—C7—C8—C10	0.3 (4)
Cl1—C1—C2—C3	−179.77 (17)	N2—N1—C9—C8	−0.3 (2)
C1—C2—C3—C4	−0.1 (3)	C7—C8—C9—N1	−0.3 (2)
C1—C2—C3—Cl2	179.38 (17)	C10—C8—C9—N1	−179.1 (2)
C2—C3—C4—C5	0.3 (3)	C7—C8—C10—N3	45 (19)
Cl2—C3—C4—C5	−179.17 (17)	C9—C8—C10—N3	−136 (19)
C3—C4—C5—C6	−0.4 (3)	C7—N4—C11—C12	1.3 (3)
C4—C5—C6—C1	0.3 (3)	C7—N4—C11—C16	−177.99 (18)
C4—C5—C6—N2	178.21 (19)	N4—C11—C12—C13	−179.1 (2)
C2—C1—C6—C5	−0.1 (3)	C16—C11—C12—C13	0.2 (3)
Cl1—C1—C6—C5	179.68 (16)	C11—C12—C13—C14	0.5 (4)
C2—C1—C6—N2	−177.94 (18)	C12—C13—C14—C15	−0.8 (4)
Cl1—C1—C6—N2	1.8 (3)	C13—C14—C15—C16	0.3 (4)
C7—N2—C6—C5	110.9 (2)	C14—C15—C16—C11	0.4 (3)
N1—N2—C6—C5	−66.7 (2)	C14—C15—C16—N5	−177.1 (2)
C7—N2—C6—C1	−71.2 (3)	N4—C11—C16—C15	178.6 (2)
N1—N2—C6—C1	111.1 (2)	C12—C11—C16—C15	−0.7 (3)
N1—N2—C7—C8	−0.9 (2)	N4—C11—C16—N5	−3.9 (3)
C6—N2—C7—C8	−178.74 (17)	C12—C11—C16—N5	176.78 (18)
N1—N2—C7—N4	178.39 (17)	O1—N5—C16—C15	168.9 (2)
C6—N2—C7—N4	0.6 (3)	O2—N5—C16—C15	−10.8 (3)
C11—N4—C7—N2	−88.3 (2)	O1—N5—C16—C11	−8.7 (3)
C11—N4—C7—C8	90.8 (3)	O2—N5—C16—C11	171.6 (2)
N2—C7—C8—C9	0.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O2i	0.93	2.51	3.050 (3)	117
C5—H5···O1ii	0.93	2.58	3.374 (3)	143
N4—H4···N3iii	0.82 (3)	2.62 (3)	3.201 (3)	129 (2)
N4—H4···O1	0.82 (3)	2.02 (3)	2.608 (2)	128 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O2i	0.93	2.51	3.050 (3)	117
C5—H5⋯O1ii	0.93	2.58	3.374 (3)	143
N4—H4⋯N3iii	0.82 (3)	2.62 (3)	3.201 (3)	129 (2)
N4—H4⋯O1	0.82 (3)	2.02 (3)	2.608 (2)	128 (2)

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