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

Hoong-Kun Fun; Ching Kheng Quah; Prakash S Nayak; B Narayana; B K Sarojini

doi:10.1107/S1600536812034605

. 2012 Aug 11;68(Pt 9):o2677. doi: 10.1107/S1600536812034605

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

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, Prakash S Nayak ^b, B Narayana ^b, B K Sarojini ^c

PMCID: PMC3435699 PMID: 22969570

Abstract

In the title compound, C₂₀H₂₁N₃O₂S, the 2,3-dihydro-1H-pyrazole ring is nearly planar (r.m.s. deviation = 0.023 Å) and forms dihedral angles of 16.96 (6) and 38.93 (6)° with the benzene and phenyl rings, respectively. The dihedral angle between the benzene and phenyl rings is 55.54 (6)°. The molecular conformation is consolidated by an intramolecular C—H⋯O hydrogen bond, which forms an S(6) ring. In the crystal, inversion dimers linked by pairs of N—H⋯O_p (p = pyrazole) hydrogen bonds generate R ₂ ²(10) loops. The dimers are linked by C—H⋯O hydrogen bonds into sheets lying parallel to (100).

Related literature

For general background to the title compound and for related structures, see: Fun et al. (2011a ▶,b ▶, 2012a ▶,b ▶). For the stability of the temperature controller used in the the data collection, see: Cosier & Glazer (1986 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₀H₂₁N₃O₂S
M _r = 367.46
Monoclinic,
a = 14.9176 (8) Å
b = 6.6527 (4) Å
c = 19.5792 (10) Å
β = 110.689 (1)°
V = 1817.78 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.37 × 0.18 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.931, T _max = 0.987
19714 measured reflections
5302 independent reflections
4231 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.116
S = 1.03
5302 reflections
242 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812034605/hb6925sup1.cif

e-68-o2677-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034605/hb6925Isup2.hkl

e-68-o2677-Isup2.hkl^{(259.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812034605/hb6925Isup3.cml

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
N1—H1N1⋯O2ⁱ	0.880 (19)	1.956 (19)	2.7816 (14)	155.7 (19)
C1—H1A⋯O1	0.95	2.38	3.0185 (16)	124
C1—H1A⋯O1ⁱⁱ	0.95	2.51	3.2342 (16)	133
C7—H7A⋯O1ⁱⁱⁱ	0.99	2.57	3.4960 (16)	155
C19—H19B⋯O2^iv	0.98	2.55	3.4470 (17)	152

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

Acknowledgments

The authors would like to thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). BN also thanks the UGC, New Delhi, and the Government of India for the purchase of chemicals through the SAP–DRS-Phase 1 programme.

supplementary crystallographic information

Comment

In continuation of our work on synthesis of amides (Fun et al., 2011a, 2011b, 2012a, 2012b), we report herein the crystal structure of the title compound.

In the title molecule (Fig. 1), the 1H-pyrazol-4-yl ring (N2/N3/C9-C11) is nearly planar (r.m.s. deviation = 0.023 Å) and it forms dihedral angles of 16.96 (6) and 38.93 (6)° with the benzene (C1-C6) and phenyl (C12-C17) rings, respectively. The dihedral angle between the benzene and phenyl rings is 55.54 (6)°. Bond lengths and angles are within normal ranges and are comparable to related structures (Fun et al., 2011a, 2011b, 2012a, 2012b). The molecular structure is stabilized by intramolecular C1–H1A···O1 hydrogen bond, forming an S(6) ring motif (Bernstein et al., 1995).

In the crystal structure, Fig. 2, molecules are linked via N1–H1N1···O2, C1–H1A···O1, C7–H7A···O1 and C19–H19B···O2 hydrogen bonds (Table 1) into two-dimensional plane parallel to (100) which contains R₂² (10) ring motifs (Bernstein et al., 1995).

Experimental

[4-(Methylsulfanyl)phenyl]acetic acid (0.182 g, 1 mmol), 4-amino antipyrine (0.205 g, 1 mmol) and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (1.0 g, 0.01 mol) 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. The concoction 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). Yellow plates were grown from an acetone and toluene (1:1) solvent mixture by the slow evaporation method (m.p.: 415-418 K).