N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-di­hydro-1H-pyrazol-4-yl)-2-(4-nitro­phen­yl)acetamide

Manpreet Kaur; Jerry P Jasinski; H S Yathirajan; B Narayana; K Byrappa

doi:10.1107/S1600536814009738

. 2014 May 3;70(Pt 6):o636–o637. doi: 10.1107/S1600536814009738

N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-(4-nitrophenyl)acetamide

Manpreet Kaur ^a, Jerry P Jasinski ^b,^*, H S Yathirajan ^a, B Narayana ^c, K Byrappa ^d

PMCID: PMC4051092 PMID: 24940224

Abstract

In the title compound, C₁₉H₁₈N₄O₄, the nitrophenyl and phenyl rings are twisted by 67.0 (6) and 37.4 (4)°, respectively, with respect to the pyrazole ring plane [maximum deviation = 0.0042 (16) Å]. The dihedral angle between the mean planes of the phenyl rings is 59.3 (3)°. The amide group, with a C—N—C—C torsion angle of 177.54 (13)°, is twisted away from the plane of the pyrazole ring in an antiperiplanar conformation. In the crystal, N—H⋯O hydrogen bonds involving the carbonyl group on the pyrazole ring and the amide group, together with weak C—H⋯O interactions forming R ₂ ²(10) graph-set motifs, link the molecules into chains along [100]. Additional weak C—H⋯O interactions involving the nitrophenyl rings further link the molecules along [001], also forming R ₂ ²(10) graph-set motifs, thereby generating (010) layers.

Related literature

For the structural similarity of N-substituted 2-arylacetamides to the lateral chain of natural benzylpenicillin, see: Mijin & Marinkovic (2006 ▶); Mijin et al. (2008 ▶). For the coordination abilities of amides, see: Wu et al. (2008 ▶, 2010 ▶). For the pharmaceutical, insecticidal and non-linear properties of pyrazoles, see: Chandrakantha et al. (2013 ▶); Cheng et al. (2008 ▶); Hatton et al. (1993 ▶); Liu et al. (2010 ▶). For related structures, see: Fun et al. (2012 ▶); Butcher et al. (2013a ▶,b ▶); Kaur et al. (2013 ▶); Mahan et al. (2013 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). graphic file with name e-70-0o636-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₈N₄O₄
M _r = 366.37
Triclinic,
a = 6.7023 (6) Å
b = 8.6335 (8) Å
c = 15.8720 (13) Å
α = 76.305 (7)°
β = 84.399 (7)°
γ = 77.252 (7)°
V = 869.33 (13) Å³
Z = 2
Cu Kα radiation
μ = 0.84 mm⁻¹
T = 173 K
0.28 × 0.22 × 0.12 mm

Data collection

Agilent Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.851, T _max = 1.000
5113 measured reflections
3262 independent reflections
2913 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.129
S = 1.07
3262 reflections
247 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814009738/hg5393sup1.cif

e-70-0o636-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009738/hg5393Isup2.hkl

e-70-0o636-Isup2.hkl^{(179KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814009738/hg5393Isup3.cml

CCDC reference: 1000268

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.03	2.8658 (18)	164
C7—H7⋯O4ⁱⁱ	0.93	2.54	3.307 (2)	139
C18—H18B⋯O2ⁱⁱⁱ	0.96	2.56	3.336 (2)	138

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

Acknowledgments

MK is grateful to the CPEPA–UGC for the award of a JRF and thanks the University of Mysore for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

1. Comment

N-Substituted 2-arylacetamides are biologically active compounds because of their structural similarity to the lateral chain of natural benzylpenicillin (Mijin et al., 2006, 2008). Amides are also used as ligands due to their excellent coordination abilities (Wu et al., 2008, 2010). In a variety of biological heterocyclic compounds, N-pyrazole derivatives are of great interest because of their chemical and pharmaceutical properties (Cheng et al., 2008). Some of the N-pyrazole derivatives have been found to exhibit good insecticidal activities (Hatton et al., 1993), antifungal activities (Liu et al., 2010) and non-linear optical properties (Chandrakantha et al., 2013). Crystal structures of some related acetamide and pyrazole derivatives including: N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihrdro-1H-pyrazol-4-yl)-2- [4-(methylsulfanyl)phenyl]acetamide, (Fun et al., 2012), 2-(2,4-dichlorophenyl)-N-(1,5-dimethyl-3-oxo-2- phenyl)-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol- 4-yl)acetamide (Butcher et al., 2013a,b), 2-(3,4-Dichloro phenyl)-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl) acteamide (Mahan et al., 2013) and recently N-(1,5-Dimethyl- 3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-phenylacetamide (Kaur et al., 2013) have been reported. In view of the importance of amide derivatives of pyrazoles, this paper reports the crystal structure of the title compound (I), C₁₉H₁₈N₄O₄.

The title compound, (I), C₁₉H₁₈N₄O₄, crystallizes with one independent molecule in the asymmetric unit (Fig. 1). In the molecule, the pyrazole ring is nearly planar with C9 atom showing a maximum deviation of 0.0042 (16)Å. The mean planes of the 4-nitrophenyl and phenyl rings is twisted with respect to that of the pyrazole ring by 67.0 (6)° and 37.4 (4)°, respectively. The dihedral angle between the mean planes of the two phenyl rings is 59.3 (3)°. The amide group, with a torsion angle of 177.54° is twisted away from the plane of the pyrazole ring in an anti-periplanar conformation. Bond lengths are in normal ranges (Allen et al., 1987). Classical N—H···O intermolecular hydrogen bonds involving the pyrazole ring and the amide group along with weak C—H···O intermolecular interactions forming R₂²(10) graph set motifs link the molecules into chains along [100]. Additional weak C—H···O intermolecular interactions involving the nitrophenyl rings link the molecules further along [001] also forming R₂²(10) graph set motifs and further extending crystal packing into a 2-D supramolecular network (Fig. 2).

2. Experimental

4-Nitrophenylacetic acid (0.181 g, 1 mmol) and 4-aminoantipyrine (0.203 g, 1 mmol), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (1.0 g, 0.01 mol) and were dissolved in dichloromethane (20 mL). The mixture was stirred in presence of triethylamine at 273 K for about 3 h (Fig. 3). The reaction completion was confirmed by thin layer chormatography. The contents were poured into 100 ml of ice-cold aqueous hydrochloric acid with stirring, which was extracted thrice with dichloromethane. The organic layer was washed with a saturated NaHCO₃ solution and brine solution, dried and concentrated under reduced pressure to give the title compound, (I). Single crystals were grown from dichloromethane and and further recrystallised from methanol solution by the slow evaporation method which were subsequently used for x-ray studies.