Diethyl 1-(4-methyl­phen­yl)-3-phenyl-5-oxopyrrolidine-2,2-dicarboxyl­ate

Jayanta Kumar Ray; Gopa Barman; M Canle L; M I Fernández P; J A Santaballa

doi:10.1107/S1600536810028552

. 2010 Jul 24;66(Pt 8):o2104–o2105. doi: 10.1107/S1600536810028552

Diethyl 1-(4-methylphenyl)-3-phenyl-5-oxopyrrolidine-2,2-dicarboxylate

Jayanta Kumar Ray ^a, Gopa Barman ^a, M Canle L ^b, M I Fernández P ^b, J A Santaballa ^b,^*

PMCID: PMC3007313 PMID: 21588396

Abstract

In the title compound, C₂₃H₂₅NO₅, the lactam ring adopts an envelope conformation and both ethoxycarbonyl side chains show an s-cis conformation: one is nearly planar, the dihedral angle between CO₂ and OCH₂CH₃ groups being 7.95 (14)° and the other is almost orthogonal, the C—O—C—C torsion angle being 85.33 (9)°. Dimers related by inversion symmetry are stabilized by C—H⋯O hydrogen bonds. The crystal structure is consolidated by weak intermolecular C—H⋯O interactions. Weak intramolecular interactions of the same kind also occur.

Related literature

The title compound may show antibacterial activity as has been found in other γ-lactam derivatives. For related structures see: Nigam et al. (1989 ▶); Ray et al. (1994 ▶, 1998 ▶, 2004 ▶, 2010 ▶); Kandasamy et al. (1995 ▶). For conformational analysis, see: Cremer & Pople (1975 ▶); Rao et al. (1981 ▶). For hydrogen bonding, see: Desiraju (2005 ▶).

Experimental

Crystal data

C₂₃H₂₅NO₅
M _r = 395.44
Triclinic,
a = 9.4905 (2) Å
b = 10.6167 (2) Å
c = 10.8198 (2) Å
α = 93.014 (1)°
β = 95.167 (1)°
γ = 110.537 (1)°
V = 1012.60 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.42 × 0.30 × 0.12 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.964, T _max = 0.996
14991 measured reflections
3672 independent reflections
3331 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.091
S = 1.87
3672 reflections
362 parameters
All H-atom parameters refined
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810028552/rn2065sup1.cif

e-66-o2104-sup1.cif^{(24.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028552/rn2065Isup2.hkl

e-66-o2104-Isup2.hkl^{(180KB, 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
C2—H2A⋯O2ⁱ	0.985 (14)	2.529 (14)	3.5096 (14)	173.4 (10)
C3—H3⋯O4	0.984 (13)	2.369 (13)	2.8814 (14)	111.7 (9)
C6—H6⋯O2	0.955 (15)	2.573 (14)	3.3143 (14)	134.7 (11)
C13—H13⋯O2ⁱ	0.975 (14)	2.453 (14)	3.4128 (14)	168.3 (12)
C15—H15⋯O1ⁱⁱ	0.987 (15)	2.462 (15)	3.2184 (15)	133.2 (10)
C22—H22A⋯O1ⁱⁱⁱ	0.963 (13)	2.513 (14)	3.2100 (15)	129.2 (9)
C22—H22B⋯O4^iv	0.983 (13)	2.579 (13)	3.2426 (14)	124.9 (10)

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

Acknowledgments

JKR thanks the Ministerio de Educación y Ciencia for funding a short sabbatical visit (SAB2006–0199) to the Universidade da Coruña. The authors wish to thank Dr Ana Isabel Balana Gracia (SAI-UDC technician) for her helpful comments and are indebted to the CESGA (Xunta de Galicia - Spain) for the use of the Cambridge Structural Database. Funds were provided by the Xunta de Galicia through the project PGIDIT05TAM10301PR.

supplementary crystallographic information

Comment

In addition to the γ-lactam unit (N1/C1—C4), the title compound contains two phenyl rings (C5—C10) and (C12—C17), and two ethoxycarbonyl side chains, with bond distances and angles within typical values. The asymmetric unit of the title compound with our numbering scheme is in Figure 1. The γ-lactam unit (N1/C1—C4) adopts an envelope conformation. Atom C3 deviates 0.4804 (11)Å from the mean plane passing through the remaining atoms in the ring (r.m.s. 0.026 Å). In the envelope the atom C3 is the flap, with puckering parameters q2 = 0.3030 (12)Å and φ₂ = 291.9 (2)° (Cremer & Pople, 1975), and a pseudo-rotation angle P = 90.0 (1)°, and a maximum torsion angle τ_m = 30.6 (1)° (Rao et al., 1981) when the bond reference is N1—C1. The planar portion of the γ-lactam unit (N1—C1—C2—C4) forms dihedral angles of 69.53 (7)° and 67.61 (7)° with rings (C5—C10) and (C12—C17) respectively, and the dihedral angle between them is 56.66 (6)°. The ethoxycarbonyl side chain involving O2—C18—O3—C19—C20 adopts a s-cis conformation, with atoms of the group being nearly co-planar, the dihedral angle between CO₂ and OCH₂CH₃ moieties being 7.95 (14)°; the other ethoxycarbonyl chain (O4—C21—O5—C22—C23) is also s-cis, the ethyl and the carboxylate moieties in a gauche relationship, the torsion angle of C21—O5—C22—C23 being 85.33 (9)°. The geometry of the title compound is similar to that of pirrolidinones (Nigam et al. 1989), (Ray et al., 2004), (Ray et al., 2010), (Kandasamy et al., 1995). The crystal structure contains van der Waals and C—H···O weak interactions, the latter are listed in Table 1. Carbonyl O atoms O1, O2 and O4 interact with two H atoms; such intermolecular interactions could be classified as supportive (Desiraju, 2005). Inversion dimers are formed involving oxygen atoms O2 and O4; in the first case, the same pair of molecules are linked, each oxygen O2 of one molecule interacting with H atoms H2a and H13 of the other (symmetry code: -x, 1 - y, 2 - z). When oxygen O4 is considered, three molecules participate; there is an inversion dimer due to the intermolecular interactions between oxygen O4 and hydrogen H2b (symmetry code: -x, 1 - y, 1 - z), and the same applies for O4 and H22b (symmetry code: 1 - x, 1 - y, 1 - z). In addition to those dimers, the interaction of oxygen O1 with H atoms H15 (symmetry code: x, 1 + y, z) and H22a (symmetry code: -1 + x, y, z) results in sheets propagating in the ab plane. The angle between the two C—H..O hydrogen bonds bifurcated at O1 (C15—H15—O1 and C22—H22a—O1) is almost a right angle (86.7°).

Experimental

The title compound was synthesized via an intermolecular Michael addition reaction, followed by an intramolecular amidification reaction, between diethyl 4-methylanilinomalonate (synthesized by the condensation reaction between 4-methylaniline and diethyl bromomalonate) in the presence of triethylamine, using dry benzene as solvent. Single crystals were grown by slow evaporation at room temperature of a solution of the resulting compound in 2-propanol. Yield 79%. Colourless solid [m.p. 401–402 K (ethyl acetate-petroleum ether)]; ν_max(liquid film)/cm^-1 1727.75, 1638.76; δH (200 MHz; CDCl₃; Me₄Si) 0.79 (3H, t, J 7.04, OCH₂CH₃), 0.94 (3H, t, J 7.24, OCH₂CH₃), 2.34 (3H, s, ArCH₃), 2.98–3.05 (2H, dd, J 5.2 and J 9.15, NCOCH₂), 3.47–3.56 (1H, m, OCH₂CH₃), 3.81–4.16 (3H, m, OCH₂CH₃), 4.6 (1H, t, J 9.44, C(3)HPh), 7.19–7.25 (4H, m, ArH), 7.3–7.37 (5H, m, ArH). δC (100 MHz; CDCl₃; Me₄Si) 13.36, 13.47 (2× OCH₂CH₃), 21.18 (ArCH₃), 35.12 (C(4)H₂), 45.21 (C(3)HPh), 61.80, 62.28 (2×OCH₂CH₃), 79.34 (C(2)), 128.12 (C_P), 128.45(2C_b), 128.49 (2C_n), 128.54 (2C_o), 129.62 (2C_c), 134.17 (C_d), 136.65 (C_a), 138.29 (C_m), 167.06, 167.31 (2× COOCH₂CH₃), 174.90 (NCO).