5-(2,4-Di­chloro­phen­oxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

Kumar, S.M.; Manju, N.; Asma; Kalluraya, B.; Byrappa, K.; Warad, I.

doi:10.1107/S2414314616011111

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161111

https://doi.org/10.1107/S2414314616011111

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5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde

S. Madan Kumar,^a N. Manju,^b Asma,^b Balakrishna Kalluraya,^b K. Byrappa ^c and Ismail Warad ^d ^*

^aPURSE Lab, Mangalagangotri, Mangalore University, Mangaluru 574 199, India, ^bDepartment of Post-Graduate and Research In Chemistry, Mangalagangori, Mangalore University, India, ^cDepartment of Material Science, Mangalore University, Mangaluru 574 199, India, and ^dDepartment of Chemistry, Faculty of Science, An-Najah National University, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: khalil.i@najah.edu

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 6 July 2016; accepted 8 July 2016; online 22 July 2016)

In the crystal structure of the title compound, C₁₇H₁₂Cl₂N₂O₂, the pyrazole ring makes dihedral angles of 65.0 (2) and 43.9 (2)° with the dichlorophenyl and phenyl rings, respectively. The dihedral angle between the chlorophenyl and phenyl rings is 59.1 (2)°. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds and weak C—Cl⋯π and C—H⋯π interactions, generating a three-dimensional network.

Keywords: crystal structure; pyrazole; intermolecular hydrogen bonds.

CCDC reference: 1491572

Structure description

As part of a research project on the synthesis and crystal structure determination of pyrazole derivatives, the structure of 5-(2,4-dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde is reported (Fig. 1).

Figure 1
A view of the title molecule, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The pyrazole (C1–C3/N1/N2) ring makes dihedral angles of 65.0 (2) and 43.9 (2)° with the dichlorophenyl (C12–C17) and phenyl (C4–C9) rings, respectively. The chlorophenyl ring makes a dihedral angle of 59.1 (2)° with the phenyl ring. In the crystal (Fig. 2), molecules are connected via C8—H8⋯O2ⁱ hydrogen bonds (Table 1). In addition, weak C—H⋯π interactions are observed [C13—H13⋯Cg2ⁱⁱ, with H13⋯Cg2ⁱⁱ = 2.95 Å, and C15—Cl2⋯Cg1ⁱⁱⁱ, with Cl2⋯Cg1ⁱⁱⁱ = 3.582 (4) Å; Cg1 and Cg2 are the centroids of the C1–C3/N1/N2 and C4–C9 rings, respectively; symmetry codes: (ii) −x + 1, −y − 1, −z + 1; (iii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.93	2.50	3.297 (6)	144
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view along the c axis of the crystal packing of the title compound. Hydrogen bonds are drawn as dashed lines.

Synthesis and crystallization

5-Chloro-4-formyl-3-methyl-1-phenyl-1H-pyrazole (0.1 mmol) and 2,4-dichlorophenol (0.1 mmol) were dissolved in dimethyl sulfoxide in a round-bottomed flask and the solution refluxed for 4 h. After completion of the reaction, the reaction mixture was poured into crushed ice. The solid obtained was recrystallized from ethanol solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₂Cl₂N₂O₂
M_r	347.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.113 (8), 13.278 (10), 12.224 (10)
β (°)	102.219 (15)
V (Å³)	1604 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.42
Crystal size (mm)	0.32 × 0.23 × 0.21

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Multi-scan (NUMABS; Rigaku 1999 )
T_min, T_max	0.891, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	12776, 2911, 2127
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.182, 1.21
No. of reflections	2911
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20
Computer programs: CrystalClear SM Expert (Rigaku, 2011 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1491572

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011111/vm4011sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011111/vm4011Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616011111/vm4011Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear SM Expert (Rigaku, 2011); cell refinement: CrystalClear SM Expert (Rigaku, 2011); data reduction: CrystalClear SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde top

Crystal data top

C₁₇H₁₂Cl₂N₂O₂	F(000) = 712
M_r = 347.19	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
a = 10.113 (8) Å	Cell parameters from 2911 reflections
b = 13.278 (10) Å	θ = 3.1–25.3°
c = 12.224 (10) Å	µ = 0.42 mm⁻¹
β = 102.219 (15)°	T = 293 K
V = 1604 (2) Å³	Block, brown
Z = 4	0.32 × 0.23 × 0.21 mm

Data collection top

Rigaku Saturn724+ diffractometer	R_int = 0.059
profile data from ω–scans	θ_max = 25.3°, θ_min = 3.1°
Absorption correction: multi-scan (NUMABS; Rigaku 1999)	h = −12→12
T_min = 0.891, T_max = 0.916	k = −15→15
12776 measured reflections	l = −14→14
2911 independent reflections	2911 standard reflections
2127 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.072	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + (0.0764P)²] where P = (F_o² + 2F_c²)/3
S = 1.21	(Δ/σ)_max < 0.001
2911 reflections	Δρ_max = 0.22 e Å⁻³
209 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq
Cl1	−0.00103 (11)	0.17058 (9)	0.30659 (9)	0.0662 (4)
Cl2	−0.06627 (12)	0.10625 (11)	0.72543 (11)	0.0819 (5)
O1	0.2843 (2)	0.1852 (2)	0.4076 (2)	0.0520 (8)
O2	0.2891 (4)	0.3853 (3)	0.5424 (3)	0.0861 (11)
N1	0.6373 (3)	0.2049 (3)	0.4479 (3)	0.0514 (9)
N2	0.5120 (3)	0.1601 (2)	0.4098 (3)	0.0442 (8)
C1	0.6133 (4)	0.2838 (3)	0.5059 (3)	0.0506 (10)
C2	0.4743 (4)	0.2941 (3)	0.5058 (3)	0.0459 (10)
C3	0.4154 (3)	0.2133 (3)	0.4444 (3)	0.0439 (10)
C4	0.4995 (3)	0.0817 (3)	0.3285 (3)	0.0428 (9)
C5	0.4137 (3)	0.0008 (3)	0.3318 (3)	0.0500 (10)
H5	0.3665	−0.0048	0.3891	0.060*
C6	0.3992 (4)	−0.0712 (3)	0.2491 (4)	0.0563 (11)
H6	0.3414	−0.1254	0.2502	0.068*
C7	0.4700 (4)	−0.0635 (4)	0.1646 (4)	0.0579 (11)
H7	0.4590	−0.1120	0.1085	0.070*
C8	0.5571 (4)	0.0161 (3)	0.1633 (3)	0.0540 (11)
H8	0.6058	0.0208	0.1069	0.065*
C9	0.5721 (4)	0.0887 (3)	0.2453 (3)	0.0496 (10)
H9	0.6311	0.1424	0.2446	0.060*
C10	0.7282 (4)	0.3492 (4)	0.5623 (4)	0.0782 (15)
H10A	0.8122	0.3203	0.5532	0.117*
H10B	0.7279	0.3543	0.6406	0.117*
H10C	0.7182	0.4151	0.5292	0.117*
C11	0.4077 (5)	0.3774 (4)	0.5475 (3)	0.0631 (12)
H11	0.4624	0.4297	0.5816	0.076*
C12	0.2070 (3)	0.1646 (3)	0.4873 (3)	0.0423 (9)
C13	0.2603 (4)	0.1510 (3)	0.5986 (3)	0.0590 (12)
H13	0.3535	0.1543	0.6250	0.071*
C14	0.1764 (4)	0.1322 (4)	0.6723 (4)	0.0595 (12)
H14	0.2128	0.1238	0.7483	0.071*
C15	0.0396 (4)	0.1260 (3)	0.6325 (4)	0.0506 (10)
C16	−0.0160 (4)	0.1374 (3)	0.5201 (3)	0.0477 (10)
H16	−0.1090	0.1326	0.4936	0.057*
C17	0.0686 (4)	0.1561 (3)	0.4475 (3)	0.0403 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0528 (7)	0.0950 (9)	0.0438 (6)	−0.0045 (6)	−0.0053 (5)	−0.0044 (6)
Cl2	0.0684 (8)	0.1111 (11)	0.0782 (9)	−0.0020 (7)	0.0425 (7)	0.0116 (7)
O1	0.0324 (14)	0.086 (2)	0.0388 (15)	0.0022 (13)	0.0103 (12)	−0.0021 (14)
O2	0.078 (2)	0.101 (3)	0.082 (3)	0.036 (2)	0.022 (2)	−0.0045 (19)
N1	0.0301 (17)	0.062 (2)	0.059 (2)	−0.0052 (16)	0.0033 (15)	−0.0077 (18)
N2	0.0282 (16)	0.056 (2)	0.0470 (19)	−0.0018 (14)	0.0037 (14)	−0.0067 (16)
C1	0.045 (2)	0.055 (3)	0.049 (2)	−0.003 (2)	0.003 (2)	0.000 (2)
C2	0.046 (2)	0.055 (2)	0.036 (2)	0.006 (2)	0.0070 (18)	−0.0007 (19)
C3	0.0322 (19)	0.061 (3)	0.039 (2)	0.0055 (19)	0.0094 (17)	0.006 (2)
C4	0.0347 (19)	0.050 (2)	0.044 (2)	0.0021 (18)	0.0087 (18)	0.0028 (19)
C5	0.032 (2)	0.064 (3)	0.056 (3)	−0.0037 (19)	0.0126 (19)	0.008 (2)
C6	0.041 (2)	0.054 (3)	0.073 (3)	−0.006 (2)	0.010 (2)	−0.009 (2)
C7	0.050 (2)	0.069 (3)	0.051 (3)	0.006 (2)	0.005 (2)	−0.008 (2)
C8	0.054 (2)	0.063 (3)	0.049 (3)	0.006 (2)	0.018 (2)	0.006 (2)
C9	0.046 (2)	0.051 (2)	0.056 (3)	−0.0064 (19)	0.020 (2)	0.004 (2)
C10	0.063 (3)	0.075 (3)	0.093 (4)	−0.015 (2)	0.008 (3)	−0.016 (3)
C11	0.073 (3)	0.075 (3)	0.040 (2)	0.009 (3)	0.010 (2)	0.004 (2)
C12	0.0315 (19)	0.055 (2)	0.042 (2)	0.0054 (17)	0.0122 (17)	−0.0004 (19)
C13	0.032 (2)	0.095 (3)	0.048 (3)	0.006 (2)	0.0052 (19)	0.009 (2)
C14	0.046 (2)	0.088 (3)	0.046 (2)	0.008 (2)	0.014 (2)	0.012 (2)
C15	0.048 (2)	0.056 (3)	0.054 (3)	0.007 (2)	0.025 (2)	0.006 (2)
C16	0.032 (2)	0.051 (2)	0.062 (3)	0.0007 (18)	0.013 (2)	−0.004 (2)
C17	0.038 (2)	0.042 (2)	0.040 (2)	0.0042 (17)	0.0074 (17)	−0.0027 (17)

Geometric parameters (Å, º) top

Cl1—C17	1.728 (4)	C7—H7	0.9300
Cl2—C15	1.737 (4)	C7—C8	1.378 (6)
O1—C3	1.359 (4)	C8—H8	0.9300
O1—C12	1.399 (4)	C8—C9	1.376 (6)
O2—C11	1.193 (5)	C9—H9	0.9300
N1—N2	1.387 (4)	C10—H10A	0.9600
N1—C1	1.316 (5)	C10—H10B	0.9600
N2—C3	1.344 (4)	C10—H10C	0.9600
N2—C4	1.426 (5)	C11—H11	0.9300
C1—C2	1.411 (5)	C12—C13	1.366 (5)
C1—C10	1.498 (6)	C12—C17	1.385 (5)
C2—C3	1.371 (5)	C13—H13	0.9300
C2—C11	1.443 (6)	C13—C14	1.385 (5)
C4—C5	1.387 (5)	C14—H14	0.9300
C4—C9	1.378 (5)	C14—C15	1.369 (6)
C5—H5	0.9300	C15—C16	1.379 (6)
C5—C6	1.376 (6)	C16—H16	0.9300
C6—H6	0.9300	C16—C17	1.380 (5)
C6—C7	1.379 (6)

C3—O1—C12	118.2 (3)	C8—C9—C4	119.8 (4)
C1—N1—N2	105.2 (3)	C8—C9—H9	120.1
N1—N2—C4	119.1 (3)	C1—C10—H10A	109.5
C3—N2—N1	110.0 (3)	C1—C10—H10B	109.5
C3—N2—C4	129.8 (3)	C1—C10—H10C	109.5
N1—C1—C2	112.0 (3)	H10A—C10—H10B	109.5
N1—C1—C10	119.8 (4)	H10A—C10—H10C	109.5
C2—C1—C10	128.3 (4)	H10B—C10—H10C	109.5
C1—C2—C11	127.8 (4)	O2—C11—C2	126.1 (5)
C3—C2—C1	104.0 (3)	O2—C11—H11	117.0
C3—C2—C11	127.7 (4)	C2—C11—H11	117.0
O1—C3—C2	132.6 (3)	C13—C12—O1	124.0 (3)
N2—C3—O1	118.3 (3)	C13—C12—C17	119.7 (3)
N2—C3—C2	108.8 (3)	C17—C12—O1	116.3 (3)
C5—C4—N2	120.6 (3)	C12—C13—H13	119.8
C9—C4—N2	118.8 (3)	C12—C13—C14	120.3 (4)
C9—C4—C5	120.5 (4)	C14—C13—H13	119.8
C4—C5—H5	120.4	C13—C14—H14	120.3
C6—C5—C4	119.1 (4)	C15—C14—C13	119.5 (4)
C6—C5—H5	120.4	C15—C14—H14	120.3
C5—C6—H6	119.8	C14—C15—Cl2	119.5 (3)
C5—C6—C7	120.5 (4)	C14—C15—C16	121.0 (4)
C7—C6—H6	119.8	C16—C15—Cl2	119.4 (3)
C6—C7—H7	120.0	C15—C16—H16	120.5
C8—C7—C6	120.0 (4)	C15—C16—C17	118.9 (3)
C8—C7—H7	120.0	C17—C16—H16	120.5
C7—C8—H8	119.9	C12—C17—Cl1	120.6 (3)
C9—C8—C7	120.1 (4)	C16—C17—Cl1	118.9 (3)
C9—C8—H8	119.9	C16—C17—C12	120.5 (4)
C4—C9—H9	120.1

Cl2—C15—C16—C17	178.1 (3)	C4—N2—C3—O1	7.3 (6)
O1—C12—C13—C14	179.1 (4)	C4—N2—C3—C2	−167.6 (4)
O1—C12—C17—Cl1	0.0 (5)	C4—C5—C6—C7	0.5 (6)
O1—C12—C17—C16	−179.0 (3)	C5—C4—C9—C8	1.5 (6)
N1—N2—C3—O1	174.9 (3)	C5—C6—C7—C8	0.7 (6)
N1—N2—C3—C2	0.0 (4)	C6—C7—C8—C9	−0.9 (6)
N1—N2—C4—C5	143.8 (4)	C7—C8—C9—C4	−0.2 (6)
N1—N2—C4—C9	−37.6 (5)	C9—C4—C5—C6	−1.6 (6)
N1—C1—C2—C3	1.2 (4)	C10—C1—C2—C3	−178.6 (4)
N1—C1—C2—C11	−171.3 (4)	C10—C1—C2—C11	8.9 (7)
N2—N1—C1—C2	−1.1 (4)	C11—C2—C3—O1	−2.0 (7)
N2—N1—C1—C10	178.6 (4)	C11—C2—C3—N2	171.8 (4)
N2—C4—C5—C6	177.0 (3)	C12—O1—C3—N2	124.8 (3)
N2—C4—C9—C8	−177.2 (3)	C12—O1—C3—C2	−61.9 (5)
C1—N1—N2—C3	0.7 (4)	C12—C13—C14—C15	0.9 (7)
C1—N1—N2—C4	169.8 (3)	C13—C12—C17—Cl1	−178.8 (3)
C1—C2—C3—O1	−174.5 (4)	C13—C12—C17—C16	2.3 (6)
C1—C2—C3—N2	−0.7 (4)	C13—C14—C15—Cl2	−178.0 (3)
C1—C2—C11—O2	177.0 (4)	C13—C14—C15—C16	0.5 (7)
C3—O1—C12—C13	−13.8 (5)	C14—C15—C16—C17	−0.5 (6)
C3—O1—C12—C17	167.5 (3)	C15—C16—C17—Cl1	−179.9 (3)
C3—N2—C4—C5	−49.5 (6)	C15—C16—C17—C12	−0.9 (5)
C3—N2—C4—C9	129.1 (4)	C17—C12—C13—C14	−2.2 (6)
C3—C2—C11—O2	6.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.50	3.297 (6)	144

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Acknowledgements

Authors thank DST–PURSE, Mangalore University, Mangaluru, for providing the single-crystal X-ray diffraction facility.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2011). CrystalClear SM Expert. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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