(E)-4-Chloro-N-[(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl­ene]aniline

Zhuang, Y.-G.

doi:10.1107/S1600536809035727

organic compounds

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Volume 65| Part 10| October 2009| Page o2424

doi:10.1107/S1600536809035727

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(E)-4-Chloro-N-[(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylene]aniline

Yu-Guo Zhuang ^a ^*

^aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Linhai 317000, People's Republic of China
^*Correspondence e-mail: chemsailor@126.com

(Received 2 September 2009; accepted 3 September 2009; online 9 September 2009)

In the title compound, C₁₇H₁₃Cl₂N₃, the dihedral angle between the pyrazole ring system and 4-chlorophenyl ring is 26.1 (2)°. The C=N bond linking the two aromatic rings has an E conformation.

Related literature

For the biological properties of pyrazoles, see: Pimerova & Voronina (2001 ); Selvam et al. (2005 ). For the biological activity of Schiff bases, see: Rajavel et al. (2008 ); Yu et al. (2007 ). For a related stucture, see: Sun et al. (2007 ).

Experimental

Crystal data

C₁₇H₁₃Cl₂N₃
M_r = 330.20
Orthorhombic, P c a 2₁
a = 13.6471 (6) Å
b = 15.6315 (3) Å
c = 7.3514 (6) Å
V = 1568.24 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 296 K
0.39 × 0.34 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.839, T_max = 0.960
14704 measured reflections
3558 independent reflections
2533 reflections with F² > 2σ(F²)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.099
S = 1.00
3558 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1627 Friedel pairs
Flack parameter: −0.02 (6)

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2007 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2007).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035727/rk2165sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035727/rk2165Isup2.hkl

checkCIF report

Comment top

Pyrazoles continue to attract a great deal of attention due to their extensive utilization in the pharmaceutical and agrochemical fields (Pimerova & Voronina, 2001; Selvam et al., 2005). Schiff base compounds have been used as fine chemicals and medical substrates and they are important ligands in coordination chemistry (Rajavel et al., 2008; Yu et al., 2007). As part of our studies on the synthesis and characterization of pyrazoles containing Schiff base group, we report here the molecular and crystal structure of the title compound (Fig. 1).

Bond lengths and angles of the title molecule agree with those observed in a related compound, such as (E)-N-[(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl) methylene]aniline (Sun et al., 2007). The dihedral angle between the pyrazole ring (N1/N2/C1–C3) and the substituted phenyl ring (C6–C11) is 26.1 (2)°. The C5═N3 bond linking the two aromatic rings has an E–conformation. The angles between the conjugated linkage and the pyrazole ring (C1/C2/C3/N1/N2), and between the linkage and the substituted phenyl ring (C6–C11) are 6.3 (3)° and 38.5 (2)°, respectively.

Related literature top

For the biological properties of pyrazoles, see: Pimerova & Voronina (2001); Selvam et al. (2005). For the biological activity of Schiff bases, see: Rajavel et al. (2008); Yu et al. (2007). For a related stucture, see: Sun et al. (2007).

Experimental top

A solution of 5–chloro–3–methyl–1–phenyl–4–formyl–1H–pyrazole (5 mmol) and 4–chloroaniline (5 mmol) in ethanol (20 ml) was refluxed for 2 h. After cooling, filtration and drying, the title compound was obtained (yield: 84%, m.p. 434 K). The crystal used for data collection was obtained by slow evaporation from a saturated ethanol solution at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2007).

Figures top

Fig. 1. The molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

(E)-4-Chloro-N-[(5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylene]aniline top

Crystal data top

C₁₇H₁₃Cl₂N₃	D_x = 1.399 Mg m⁻³
M_r = 330.20	Melting point: 434 K
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2c -2ac	Cell parameters from 10504 reflections
a = 13.6471 (6) Å	θ = 3.0–27.4°
b = 15.6315 (3) Å	µ = 0.41 mm⁻¹
c = 7.3514 (6) Å	T = 296 K
V = 1568.24 (15) Å³	Plate, colourless
Z = 4	0.39 × 0.34 × 0.10 mm
F(000) = 680.00

Data collection top

Rigaku R-AXIS RAPID diffractometer	2533 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.038
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −17→17
T_min = 0.839, T_max = 0.960	k = −20→20
14704 measured reflections	l = −9→9
3558 independent reflections

Refinement top

Refinement on F²	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.055P)² + 0.089P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.099	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.21 e Å⁻³
3558 reflections	Δρ_min = −0.24 e Å⁻³
201 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: Direct	Extinction coefficient: 0.0049 (8)
Secondary atom site location: Difmap	Absolute structure: Flack (1983), 1627 Friedel pairs
Hydrogen site location: Geom	Absolute structure parameter: −0.02 (6)

Crystal data top

C₁₇H₁₃Cl₂N₃	V = 1568.24 (15) Å³
M_r = 330.20	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 13.6471 (6) Å	µ = 0.41 mm⁻¹
b = 15.6315 (3) Å	T = 296 K
c = 7.3514 (6) Å	0.39 × 0.34 × 0.10 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	3558 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2533 reflections with F² > 2σ(F²)
T_min = 0.839, T_max = 0.960	R_int = 0.038
14704 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.099	Δρ_max = 0.21 e Å⁻³
S = 1.00	Δρ_min = −0.24 e Å⁻³
3558 reflections	Absolute structure: Flack (1983), 1627 Friedel pairs
201 parameters	Absolute structure parameter: −0.02 (6)

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.42986 (4)	0.48323 (3)	0.33646 (10)	0.04844 (15)
Cl2	0.32167 (6)	−0.08853 (5)	0.43233 (18)	0.0893 (3)
N1	0.71398 (12)	0.47004 (11)	0.3343 (3)	0.0478 (4)
N2	0.62562 (11)	0.51191 (10)	0.3340 (2)	0.0391 (3)
N3	0.56891 (12)	0.22175 (11)	0.3631 (3)	0.0480 (5)
C1	0.55095 (13)	0.45498 (12)	0.3464 (3)	0.0395 (4)
C2	0.58944 (14)	0.37384 (12)	0.3577 (3)	0.0411 (4)
C3	0.69251 (14)	0.38699 (14)	0.3490 (4)	0.0452 (5)
C4	0.77319 (18)	0.32253 (16)	0.3538 (5)	0.0629 (7)
C5	0.53181 (17)	0.29634 (13)	0.3730 (3)	0.0446 (5)
C6	0.50557 (16)	0.14994 (13)	0.3773 (3)	0.0436 (5)
C7	0.5429 (2)	0.07657 (16)	0.4568 (4)	0.0565 (6)
C8	0.4858 (2)	0.00375 (17)	0.4763 (4)	0.0624 (7)
C9	0.3916 (2)	0.00400 (16)	0.4118 (3)	0.0539 (6)
C10	0.35333 (17)	0.07546 (14)	0.3280 (5)	0.0548 (6)
C11	0.41003 (16)	0.14831 (14)	0.3120 (3)	0.0490 (6)
C12	0.62388 (16)	0.60273 (12)	0.3108 (3)	0.0393 (5)
C13	0.55665 (18)	0.65294 (14)	0.4025 (3)	0.0467 (5)
C14	0.55583 (19)	0.74051 (14)	0.3718 (3)	0.0539 (6)
C15	0.6222 (2)	0.77754 (17)	0.2553 (3)	0.0558 (7)
C16	0.6905 (2)	0.72688 (18)	0.1672 (3)	0.0550 (6)
C17	0.69122 (17)	0.63883 (17)	0.1930 (3)	0.0467 (5)
H5	0.4646	0.3013	0.3909	0.054*
H7	0.6073	0.0761	0.4978	0.068*
H8	0.5111	−0.0447	0.5326	0.075*
H10	0.2898	0.0746	0.2825	0.066*
H11	0.3840	0.1968	0.2569	0.059*
H13	0.5126	0.6284	0.4837	0.056*
H14	0.5098	0.7746	0.4307	0.065*
H15	0.6213	0.8363	0.2357	0.067*
H16	0.7363	0.7520	0.0901	0.066*
H17	0.7363	0.6047	0.1319	0.056*
H41	0.7578	0.2762	0.2731	0.076*
H42	0.7803	0.3010	0.4754	0.076*
H43	0.8333	0.3490	0.3160	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0317 (2)	0.0431 (2)	0.0705 (3)	−0.0001 (2)	0.0023 (3)	0.0004 (3)
Cl2	0.0752 (5)	0.0612 (4)	0.1317 (7)	−0.0261 (3)	0.0065 (5)	0.0141 (5)
N1	0.0334 (8)	0.0459 (10)	0.0642 (12)	−0.0012 (7)	−0.0001 (12)	0.0000 (13)
N2	0.0288 (8)	0.0372 (8)	0.0513 (9)	−0.0004 (6)	0.0006 (11)	0.0029 (10)
N3	0.0417 (9)	0.0363 (9)	0.0659 (14)	−0.0003 (7)	−0.0003 (10)	0.0005 (10)
C1	0.0321 (9)	0.0388 (9)	0.0476 (11)	−0.0005 (8)	0.0036 (12)	−0.0007 (12)
C2	0.0373 (10)	0.0387 (10)	0.0473 (12)	−0.0003 (8)	0.0025 (11)	0.0031 (11)
C3	0.0367 (10)	0.0467 (11)	0.0522 (12)	0.0019 (8)	−0.0021 (12)	0.0010 (12)
C4	0.0469 (13)	0.0501 (13)	0.092 (2)	0.0085 (11)	−0.0008 (16)	0.0068 (17)
C5	0.0400 (11)	0.0424 (10)	0.0515 (15)	−0.0033 (9)	0.0034 (10)	0.0036 (11)
C6	0.0409 (11)	0.0384 (10)	0.0515 (14)	0.0015 (8)	0.0012 (10)	0.0010 (10)
C7	0.0449 (13)	0.0452 (13)	0.0795 (18)	−0.0018 (10)	−0.0114 (14)	0.0083 (13)
C8	0.0650 (19)	0.0426 (13)	0.0795 (18)	−0.0026 (11)	−0.0083 (15)	0.0170 (13)
C9	0.0514 (14)	0.0456 (12)	0.0647 (15)	−0.0067 (11)	0.0055 (13)	0.0008 (12)
C10	0.0360 (10)	0.0501 (12)	0.0782 (16)	0.0023 (10)	−0.0013 (15)	−0.0023 (14)
C11	0.0445 (13)	0.0371 (11)	0.0656 (16)	0.0045 (8)	−0.0004 (13)	0.0010 (12)
C12	0.0353 (11)	0.0362 (10)	0.0463 (13)	−0.0054 (8)	−0.0049 (10)	−0.0002 (10)
C13	0.0462 (13)	0.0439 (11)	0.0501 (13)	−0.0043 (10)	0.0019 (11)	−0.0011 (10)
C14	0.0535 (14)	0.0424 (11)	0.0658 (18)	0.0032 (10)	−0.0061 (13)	−0.0073 (13)
C15	0.0620 (18)	0.0413 (13)	0.0642 (15)	−0.0111 (12)	−0.0165 (14)	0.0050 (12)
C16	0.0493 (14)	0.0580 (16)	0.0578 (14)	−0.0171 (12)	−0.0065 (12)	0.0147 (13)
C17	0.0377 (12)	0.0513 (13)	0.0510 (13)	−0.0063 (10)	−0.0009 (10)	0.0039 (11)

Geometric parameters (Å, º) top

Cl1—C1	1.7121 (19)	C12—C17	1.383 (3)
Cl2—C9	1.740 (2)	C13—C14	1.387 (3)
N1—N2	1.372 (2)	C14—C15	1.375 (3)
N1—C3	1.335 (2)	C15—C16	1.384 (3)
N2—C1	1.356 (2)	C16—C17	1.389 (3)
N2—C12	1.430 (2)	C4—H41	0.960
N3—C5	1.273 (2)	C4—H42	0.960
N3—C6	1.421 (2)	C4—H43	0.960
C1—C2	1.375 (2)	C5—H5	0.930
C2—C3	1.423 (2)	C7—H7	0.930
C2—C5	1.449 (3)	C8—H8	0.930
C3—C4	1.493 (3)	C10—H10	0.930
C6—C7	1.384 (3)	C11—H11	0.930
C6—C11	1.390 (3)	C13—H13	0.930
C7—C8	1.387 (3)	C14—H14	0.930
C8—C9	1.370 (4)	C15—H15	0.930
C9—C10	1.379 (3)	C16—H16	0.930
C10—C11	1.382 (3)	C17—H17	0.930
C12—C13	1.383 (3)

N2—N1—C3	105.73 (16)	C14—C15—C16	119.6 (2)
N1—N2—C1	110.32 (15)	C15—C16—C17	120.5 (2)
N1—N2—C12	119.23 (15)	C12—C17—C16	119.0 (2)
C1—N2—C12	130.32 (16)	C3—C4—H41	109.5
C5—N3—C6	118.52 (18)	C3—C4—H42	109.5
Cl1—C1—N2	123.59 (15)	C3—C4—H43	109.5
Cl1—C1—C2	127.52 (15)	H41—C4—H42	109.5
N2—C1—C2	108.80 (16)	H41—C4—H43	109.5
C1—C2—C3	103.98 (18)	H42—C4—H43	109.5
C1—C2—C5	124.65 (19)	N3—C5—H5	118.5
C3—C2—C5	131.37 (19)	C2—C5—H5	118.5
N1—C3—C2	111.16 (18)	C6—C7—H7	119.4
N1—C3—C4	119.75 (19)	C8—C7—H7	119.4
C2—C3—C4	129.1 (2)	C7—C8—H8	120.4
N3—C5—C2	123.1 (2)	C9—C8—H8	120.4
N3—C6—C7	117.5 (2)	C9—C10—H10	120.2
N3—C6—C11	124.1 (2)	C11—C10—H10	120.2
C7—C6—C11	118.4 (2)	C6—C11—H11	119.6
C6—C7—C8	121.1 (2)	C10—C11—H11	119.6
C7—C8—C9	119.3 (2)	C12—C13—H13	120.5
Cl2—C9—C8	118.8 (2)	C14—C13—H13	120.5
Cl2—C9—C10	120.3 (2)	C13—C14—H14	119.6
C8—C9—C10	120.8 (2)	C15—C14—H14	119.6
C9—C10—C11	119.6 (2)	C14—C15—H15	120.2
C6—C11—C10	120.7 (2)	C16—C15—H15	120.2
N2—C12—C13	121.07 (19)	C15—C16—H16	119.7
N2—C12—C17	117.95 (19)	C17—C16—H16	119.7
C13—C12—C17	121.0 (2)	C12—C17—H17	120.5
C12—C13—C14	119.1 (2)	C16—C17—H17	120.5
C13—C14—C15	120.8 (2)

N2—N1—C3—C2	0.2 (3)	C3—C2—C5—N3	−7.3 (4)
N2—N1—C3—C4	−179.9 (2)	C5—C2—C3—N1	179.7 (2)
C3—N1—N2—C1	−0.7 (3)	C5—C2—C3—C4	−0.2 (4)
C3—N1—N2—C12	−177.0 (2)	N3—C6—C7—C8	179.8 (2)
N1—N2—C1—Cl1	−176.0 (2)	N3—C6—C11—C10	178.9 (2)
N1—N2—C1—C2	0.8 (3)	C7—C6—C11—C10	0.7 (4)
N1—N2—C12—C13	−143.5 (2)	C11—C6—C7—C8	−1.9 (4)
N1—N2—C12—C17	36.8 (3)	C6—C7—C8—C9	1.6 (4)
C1—N2—C12—C13	41.0 (3)	C7—C8—C9—Cl2	178.5 (2)
C1—N2—C12—C17	−138.7 (2)	C7—C8—C9—C10	0.1 (3)
C12—N2—C1—Cl1	−0.2 (3)	Cl2—C9—C10—C11	−179.7 (2)
C12—N2—C1—C2	176.6 (2)	C8—C9—C10—C11	−1.3 (4)
C5—N3—C6—C7	−147.9 (2)	C9—C10—C11—C6	0.9 (4)
C5—N3—C6—C11	33.9 (3)	N2—C12—C13—C14	−178.2 (2)
C6—N3—C5—C2	−179.1 (2)	N2—C12—C17—C16	179.6 (2)
Cl1—C1—C2—C3	176.1 (2)	C13—C12—C17—C16	−0.1 (3)
Cl1—C1—C2—C5	−3.4 (4)	C17—C12—C13—C14	1.5 (3)
N2—C1—C2—C3	−0.6 (3)	C12—C13—C14—C15	−1.6 (3)
N2—C1—C2—C5	179.87 (19)	C13—C14—C15—C16	0.2 (4)
C1—C2—C3—N1	0.2 (3)	C14—C15—C16—C17	1.2 (4)
C1—C2—C3—C4	−179.6 (3)	C15—C16—C17—C12	−1.3 (3)
C1—C2—C5—N3	172.0 (2)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₃Cl₂N₃
M_r	330.20
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	296
a, b, c (Å)	13.6471 (6), 15.6315 (3), 7.3514 (6)
V (Å³)	1568.24 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.39 × 0.34 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.839, 0.960
No. of measured, independent and observed [F² > 2σ(F²)] reflections	14704, 3558, 2533
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.099, 1.00
No. of reflections	3558
No. of parameters	201
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24
Absolute structure	Flack (1983), 1627 Friedel pairs
Absolute structure parameter	−0.02 (6)

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku/MSC, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Acknowledgements

This work was supported by the Key Discipline Open Foundation of Zhejiang University of Technology (grant No. 20080604).

References

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