Crystal structure of (Z)-1-(3,4-dichlorophenyl)-3-methyl-4-[(naphthalen-1-yl­amino)(p-tolyl)methylidene]-1H-pyrazol-5(4H)-one

Naresh Sharma; Sanjay Parihar; R N Jadeja; Rajni Kant; Vivek K Gupta

doi:10.1107/S1600536814017140

. 2014 Aug 1;70(Pt 9):o955–o956. doi: 10.1107/S1600536814017140

Crystal structure of (Z)-1-(3,4-dichlorophenyl)-3-methyl-4-[(naphthalen-1-ylamino)(p-tolyl)methylidene]-1H-pyrazol-5(4H)-one

Naresh Sharma ^a, Sanjay Parihar ^b, R N Jadeja ^b, Rajni Kant ^a, Vivek K Gupta ^a,^*

PMCID: PMC4186144 PMID: 25309277

Abstract

The title Schiff base compound, C₂₈H₂₁Cl₂N₃O, was synthesized by the condensation of 1-(3,4-dichlorophenyl)-3-methyl-4-(4-methylbenzoyl)-1H-pyrazol-5(4H)-one with 1-aminonaphthalene. The p-tolyl ring is normal to the pyrazole ring, with a dihedral angle of 88.02 (14)°, and inclined to the naphthalene ring system by 78.60 (12)°. The pyrazole ring is inclined to the naphthalene ring system and the dichloro-substituted benzene ring by 63.30 (12) and 11.03 (13)°, respectively. The amino group and carbonyl oxygen atom are involved in an intramolecular N—H⋯O hydrogen bond enclosing an S(6) ring motif. There is also a short C—H⋯O contact involving the carbonyl O atom and the adjacent benzene ring. In the crystal, molecules are linked by C—H⋯π interactions, forming a three-dimensional structure.

Keywords: crystal structure, Schiff base, naphthalene, pyrazolone, pyrrole

Related literature

For the preparation and biological activity of pyrazolones and their metal complexes, see: Chiba et al. (1998 ▶); Xu et al. (2000 ▶); Casas et al. (2007 ▶); Wang et al. (2007 ▶). For Schiff bases and their diverse biological activity and exceptional chelating ability, see: Karthikeyan et al. (2006 ▶); Sinha et al. (2008 ▶); Jadeja et al. (2012a ▶,b ▶). For related structures, see: Sharma et al. (2012 ▶); Abdel-Aziz et al. (2012 ▶).

Experimental

Crystal data

C₂₈H₂₁Cl₂N₃O
M _r = 486.38
Monoclinic,
a = 11.4621 (8) Å
b = 16.9351 (11) Å
c = 12.2704 (9) Å
β = 97.478 (6)°
V = 2361.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur, Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.850, T _max = 1.000
10634 measured reflections
4621 independent reflections
2763 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.137
S = 1.03
4621 reflections
309 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814017140/su2756sup1.cif

e-70-0o955-sup1.cif^{(30.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017140/su2756Isup2.hkl

e-70-0o955-Isup2.hkl^{(221.8KB, hkl)}

Click here for additional data file.^{(8.8KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814017140/su2756Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S1600536814017140/su2756fig1.tif

A view of the molecular structure of the title molecule, with atom labelling. The displacement ellipsoids are drawn at the 40% probability level.

Click here for additional data file.^{(1.6MB, tif)}

a . DOI: 10.1107/S1600536814017140/su2756fig2.tif

The crystal packing of the title compound viewed along the a axis.

CCDC reference: 1013619

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg3, Cg5 are the centroids of rings N1/N2/C3–C5, C14–C19 and C24–C29, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13⋯O5	0.86	1.98	2.702 (3)	141
C7—H7⋯O5	0.93	2.32	2.937 (4)	124
C8—H8⋯Cg3ⁱ	0.93	2.71	3.639 (3)	176
C15—H15⋯Cg1ⁱⁱ	0.93	2.97	3.825 (3)	154
C23—H23⋯Cg5ⁱⁱⁱ	0.93	2.77	3.679 (3)	165

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

Acknowledgments

RK acknowledges the Department of Science and Technology for funding the single-crystal X-ray diffractometer sanctioned as a National Facility under Project No. SR/S2/CMP-47/2003.

supplementary crystallographic information

S1. Synthesis and crystallization

1-(3,4-Dichlorophenyl)-3-methyl-4-(4-methylbenzoyl)-1H-pyrazol-5(4H)-one (0.360 g, 1 mmol) was dissolved in a minimum amount of absolute ethanol. To this solution, a solution of 1-aminonaphthalene (0.143 g, 1 mmol) in 10 ml absolute ethanol was added dropwise. The reaction mixture was refluxed for 8 h. After completion of the reaction, it was allowed to cool and then filtered. The filtrate was kept for slow evaporation giving block-like yellow crystals of the title compound in 2–3 days (yield 0.325, 67%). ¹H NMR (400 MHz,CDCl3, TMS): δ 1.61 (s, 3H), 2.48 (s, 3H), 6.87 (d, 1H), 7.09–7.20 (m, 5H), 7.47 (d, 1H), 7.55–7.59 (m, 1H), 7.62–7.68 (m, 2H), 7.85 (d, 1H), 8.05–8.08 (dd, 1H), 8.22 (d, 1H), 8.33 (d, 1H), 13.12 (s, 1H). Elemental analysis calculated for C₂₈H₂₁Cl₂N₃O: C 69.14, H 4.35, N 8.64; found: C 69.18, H 4.41, 8.65.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All the H atoms were fixed geometrically and allowed to ride on their parent atoms: N—H = 0.86 Å, C—H =0.93–0.96 Å with U_iso(H) = 1.5U_eq(C-methyl) and = 1.2U_eq(N,C) for other H atoms.