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

Aneeka Mahan; Ray J Butcher; Prakash S Nayak; B Narayana; H S Yathirajan

doi:10.1107/S1600536813002341

. 2013 Feb 20;69(Pt 3):o402–o403. doi: 10.1107/S1600536813002341

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

Aneeka Mahan ^a, Ray J Butcher ^b,^*, Prakash S Nayak ^c, B Narayana ^c, H S Yathirajan ^d

PMCID: PMC3588482 PMID: 23476584

Abstract

In the title compound, C₁₉H₁₇Cl₂N₃O₂, there are three molecules (A, B and C) in the asymmetric unit and each differs in the conformation adopted. As a result of steric repulsion, the amide group is rotated with respect to both the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings, making dihedral angles of 44.5 (2) and 56.2 (2)°, respectively in A, 51.1 (2) and 54.1 (2)° in B, and 53.8 (2) and 54.6 (2)° in C. The dihedral angles between the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings are 54.8 (2), 76.2 (2) and 77.5 (2)° in molecules A, B and C, respectively, while the 2,3-dihydro-1H-pyrazol-4-yl and phenyl rings make dihedral angles of 45.3 (2), 51.2 (2) and 42.8 (2)°, respectively. In the crystal, two of the molecules are linked through N—H⋯O hydrogen bonding to an adjoining molecule, forming dimers of the R ₂ ²(10) type, while the third molecule forms such dimers with itself. C—H⋯O interactions link the dimers.

Related literature

For graph-set description of hydrogen-bonding patterns, see: Bernstein et al. (1995 ▶). For related structures, see: Fun et al. (2011a ▶,b ▶, 2012a ▶,b ▶). For similar structures but with differing dichloro substitution, see: Butcher et al. (2013a ▶,b ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For the biological activity of N-substituted 2-arylacetamides, see: Mijin & Marinkovic (2006 ▶); Mijin et al. (2008 ▶). For the coordination abilities of amides, see: Wu et al. (2008 ▶, 2010 ▶). graphic file with name e-69-0o402-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₇Cl₂N₃O₂
M _r = 390.26
Monoclinic,
a = 17.2064 (8) Å
b = 20.7984 (9) Å
c = 15.6102 (7) Å
β = 101.213 (4)°
V = 5479.7 (4) Å³
Z = 12
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 123 K
0.51 × 0.34 × 0.10 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2011 ▶) based on expressions derived by Clark & Reid (1995 ▶)] T _min = 0.743, T _max = 0.932
54403 measured reflections
27521 independent reflections
11938 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.119
wR(F ²) = 0.345
S = 1.02
27521 reflections
709 parameters
H-atom parameters constrained
Δρ_max = 3.46 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(41.8KB, cif)}

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813002341/hg5286sup1.cif

e-69-0o402-sup1.cif^{(41.8KB, cif)}

Click here for additional data file.^{(1.3MB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813002341/hg5286Isup2.hkl

e-69-0o402-Isup2.hkl^{(1.3MB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O2A ⁱ	0.88	1.98	2.820 (3)	159
N1B—H1BA⋯O2C	0.88	2.01	2.849 (3)	159
N1C—H1CA⋯O2B	0.88	1.96	2.795 (3)	158
C11A—H11C⋯O2B ⁱⁱ	0.98	2.39	3.344 (4)	163
C11C—H11H⋯O2A ⁱⁱⁱ	0.98	2.45	3.377 (4)	158
C12C—H12G⋯O2A ⁱⁱⁱ	0.98	2.44	3.186 (4)	133
C12C—H12H⋯O1B ⁱⁱⁱ	0.98	2.51	3.178 (4)	125
C12A—H12A⋯O2B ⁱⁱ	0.98	2.50	3.273 (4)	136
C11B—H11F⋯O2C ^iv	0.98	2.42	3.364 (4)	163
C12B—H12D⋯O2C ^iv	0.98	2.46	3.282 (4)	142
C17B—H17B⋯Cl1B ^v	0.95	2.89	3.705 (4)	144

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

Acknowledgments

RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer.

supplementary crystallographic information

Comment

N-Substituted 2-arylacetamides are very interesting 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). Crystal structures of some acetamide derivatives viz., (2E)-1-(2,5-dimethoxyphenyl)-3-(3-nitrophenyl)prop-2-en-1-one, N-(4-bromophenyl)-2-(naphthalen-1-yl)acetamide, N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-[4-(methylsulfanyl)phenyl]acetamide, N-(4-bromophenyl)-2-(4-chlorophenyl)acetamide (Fun et al., 2011a, 2011b, 2012a, 2012b) have been reported. Two related molecules with different dichloro substitution patterns have recently been published (Butcher et al., 2013a, 2013b). In view of the importance of amides we report herein the crystal structure of the title compound (I).

In the title compound, C₁₉H₁₇Cl₂N₃O₂, there are three molecules in the asymmetric unit and each differs in the comformation adopted. In each molecule the amide group is planar but two of the molecules (B and C) are linked through N—H···O hydrogen bonding to an adjoining molecule forming dimers of the R₂²(10) type (Bernstein et al., 1995) while molecule A forms such dimers with itself. The major conformational difference between three molecules is seen in the dihedral angles between the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings which are 54.8 (2)°, 76.2 (2),° and 77.5 (2)° for A, B, and C, respectively. Due to steric repulsion the amide group is rotated with respect to both the dichlorophenyl and 2,3-dihydro-1H-pyrazol-4-yl rings with dihedral angles of 44.5 (2)° and 56.2 (2)° for A; 51.1 (2) and 54.1 (2) for B; and 53.8 (2) and 54.6 (2) for C. All other metrical parameters are in the normal ranges (Allen, 2002).

Experimental

3,4-Dichlorophenylacetic acid (0.240 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. 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 saturated NaHCO₃ solution and brine solution, dried and concentrated under reduced pressure to give the title compound (I). Single crystals were grown from methylene chloride by the slow evaporation method (m.p.: 473–475 K).