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

Ray, J.K.; Barman, G.; Canle L., M.; Fernández P., M.I.; Santaballa, J.A.

doi:10.1107/S1600536810028552

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages o2104-o2105

https://doi.org/10.1107/S1600536810028552

Open

access

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 and J. A. Santaballa ^b ^*

^aDepartment of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India, and ^bDepartamento de Química Física e Enxeñería Química I, Facultade de Ciencias, Universidade da Coruña, Rúa Alejandro de la Sota 1, E-15008 A Coruña, Spain
^*Correspondence e-mail: arturo@udc.es

(Received 1 November 2009; accepted 16 July 2010; online 24 July 2010)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.031
wR(F²) = 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

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)
Symmetry codes: (i) -x, -y+1, -z+2; (ii) x, y-1, z; (iii) x+1, y, z; (iv) -x+1, -y+1, -z+1.

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.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028552/rn2065Isup2.hkl

checkCIF report

Comment top

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°).

Related literature top

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 top

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).

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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: PLEASE SUPPLY.

Figures top

Fig. 1. View of the title compound showing the atomic numbering and 50% probability displacement ellipsoids. H atoms are not shown for clarity.

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

Crystal data top

C₂₃H₂₅NO₅	Z = 2
M_r = 395.44	F(000) = 420
Triclinic, P1	D_x = 1.297 Mg m⁻³
Hall symbol: -P 1	Melting point: 401 K
a = 9.4905 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6167 (2) Å	Cell parameters from 9079 reflections
c = 10.8198 (2) Å	θ = 2.5–28.2°
α = 93.014 (1)°	µ = 0.09 mm⁻¹
β = 95.167 (1)°	T = 100 K
γ = 110.537 (1)°	Block, colourless
V = 1012.60 (3) Å³	0.42 × 0.30 × 0.12 mm

Data collection top

Bruker APEXII area-detector diffractometer	3672 independent reflections
Radiation source: fine-focus sealed tube	3331 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
phi and ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.964, T_max = 0.996	k = −12→12
14991 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	All H-atom parameters refined
S = 1.87	w = 1/[σ²(F_o²) + (0.0352P)²] where P = (F_o² + 2F_c²)/3
3672 reflections	(Δ/σ)_max = 0.001
362 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₃H₂₅NO₅	γ = 110.537 (1)°
M_r = 395.44	V = 1012.60 (3) Å³
Triclinic, P1	Z = 2
a = 9.4905 (2) Å	Mo Kα radiation
b = 10.6167 (2) Å	µ = 0.09 mm⁻¹
c = 10.8198 (2) Å	T = 100 K
α = 93.014 (1)°	0.42 × 0.30 × 0.12 mm
β = 95.167 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	3672 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3331 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.996	R_int = 0.020
14991 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.091	All H-atom parameters refined
S = 1.87	Δρ_max = 0.22 e Å⁻³
3672 reflections	Δρ_min = −0.22 e Å⁻³
362 parameters

Special details top

Experimental. Data was collected using a X8 APEX II BRUKER-Nonius diffractometer equipped with an KRYOFLEX low-temperature apparatus operating at 100 K. A suitable crystal was chosen and mounted on a glass fiber using grease. Data were measured using omega scans of 0.5° per frame for 10 s, such that a total of 2870 frames were collected in a optimized strategy and with a final resolution of 0.75 Å. Data integration and reduction was performed using the APEX2 (Bruker, 2009) software suite. Absorption corrections were applied using SADABS (Bruker, 2009). The structures are solved by direct methods using the SHELX97 program and refined by least squares on F² SHELXL97, incorporated in the Apex2 software suite.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

All non-hydrogen atoms were refined anisotropically. Hydrogen were found in subsequent difference Fourier maps and included as isotropic atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	−0.06859 (8)	0.71231 (8)	0.72064 (8)	0.0250 (2)
O2	0.19397 (9)	0.56920 (8)	0.97081 (7)	0.0205 (2)
O3	0.28043 (8)	0.41475 (7)	0.88942 (6)	0.01674 (18)
O4	0.27852 (9)	0.49468 (9)	0.55611 (7)	0.0247 (2)
O5	0.43697 (8)	0.59245 (8)	0.72998 (6)	0.01664 (18)
N1	0.13851 (9)	0.64837 (9)	0.73404 (8)	0.0144 (2)
C1	−0.01411 (11)	0.62475 (11)	0.72555 (9)	0.0162 (2)
C2	−0.09624 (12)	0.47497 (11)	0.72503 (11)	0.0169 (2)
H2A	−0.1303 (14)	0.4554 (13)	0.8076 (13)	0.026 (3)*
H2B	−0.1846 (14)	0.4437 (13)	0.6609 (12)	0.022 (3)*
C3	0.02044 (11)	0.41224 (11)	0.69452 (10)	0.0150 (2)
H3	0.0252 (13)	0.4114 (12)	0.6039 (12)	0.017 (3)*
C4	0.17508 (11)	0.52637 (10)	0.74648 (9)	0.0140 (2)
C5	0.24744 (11)	0.78151 (11)	0.73057 (9)	0.0146 (2)
C6	0.34323 (13)	0.85116 (12)	0.83513 (10)	0.0215 (3)
H6	0.3365 (15)	0.8085 (14)	0.9110 (14)	0.035 (4)*
C7	0.44489 (13)	0.98064 (12)	0.82749 (11)	0.0244 (3)
H7	0.5146 (15)	1.0322 (14)	0.8986 (13)	0.031 (3)*
C8	0.45132 (12)	1.04361 (11)	0.71799 (10)	0.0204 (3)
C9	0.35414 (12)	0.97144 (12)	0.61366 (10)	0.0218 (3)
H9	0.3578 (15)	1.0138 (14)	0.5335 (13)	0.033 (4)*
C10	0.25387 (12)	0.84142 (11)	0.61952 (10)	0.0196 (3)
H10	0.1856 (16)	0.7897 (14)	0.5467 (13)	0.030 (3)*
C11	0.55881 (16)	1.18611 (13)	0.71308 (13)	0.0290 (3)
H11A	0.6210 (17)	1.2226 (15)	0.7902 (14)	0.037 (4)*
H11B	0.5053 (18)	1.2474 (17)	0.6996 (15)	0.048 (4)*
H11C	0.6186 (19)	1.1952 (16)	0.6448 (15)	0.048 (4)*
C12	−0.00523 (11)	0.27271 (11)	0.73582 (10)	0.0163 (2)
C13	−0.06002 (12)	0.23452 (11)	0.84876 (11)	0.0197 (2)
H13	−0.0828 (14)	0.2983 (13)	0.9043 (12)	0.025 (3)*
C14	−0.08302 (13)	0.10562 (12)	0.88368 (12)	0.0247 (3)
H14	−0.1211 (16)	0.0818 (14)	0.9631 (13)	0.033 (4)*
C15	−0.05170 (14)	0.01258 (12)	0.80671 (12)	0.0283 (3)
H15	−0.0677 (15)	−0.0789 (15)	0.8318 (12)	0.033 (4)*
C16	0.00369 (14)	0.04957 (13)	0.69484 (12)	0.0277 (3)
H16	0.0251 (16)	−0.0136 (15)	0.6414 (13)	0.035 (4)*
C17	0.02681 (13)	0.17826 (12)	0.65939 (11)	0.0216 (3)
H17	0.0627 (15)	0.2023 (13)	0.5821 (13)	0.029 (3)*
C18	0.21958 (11)	0.50969 (10)	0.88294 (9)	0.0140 (2)
C19	0.30418 (13)	0.37111 (12)	1.01290 (10)	0.0198 (3)
H19A	0.2082 (14)	0.3496 (12)	1.0498 (11)	0.019 (3)*
H19B	0.3819 (13)	0.4486 (13)	1.0648 (11)	0.017 (3)*
C20	0.35183 (15)	0.25173 (13)	0.99354 (12)	0.0266 (3)
H20A	0.2751 (19)	0.1811 (17)	0.9407 (15)	0.045 (4)*
H20B	0.3660 (15)	0.2159 (14)	1.0749 (13)	0.034 (4)*
H20C	0.4514 (17)	0.2762 (14)	0.9584 (13)	0.037 (4)*
C21	0.30183 (11)	0.53278 (11)	0.66516 (9)	0.0148 (2)
C22	0.56966 (12)	0.61488 (13)	0.66233 (10)	0.0194 (3)
H22A	0.6495 (14)	0.6216 (12)	0.7267 (11)	0.017 (3)*
H22B	0.5482 (13)	0.5336 (13)	0.6052 (11)	0.018 (3)*
C23	0.60496 (15)	0.74321 (15)	0.60006 (13)	0.0299 (3)
H23A	0.6205 (15)	0.8196 (15)	0.6628 (13)	0.030 (4)*
H23B	0.6949 (17)	0.7600 (15)	0.5572 (13)	0.038 (4)*
H23C	0.5222 (17)	0.7335 (15)	0.5358 (14)	0.042 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0162 (4)	0.0157 (4)	0.0452 (5)	0.0083 (3)	0.0031 (3)	0.0041 (4)
O2	0.0276 (4)	0.0211 (4)	0.0159 (4)	0.0115 (3)	0.0066 (3)	0.0013 (3)
O3	0.0205 (4)	0.0187 (4)	0.0145 (4)	0.0108 (3)	0.0027 (3)	0.0044 (3)
O4	0.0195 (4)	0.0374 (5)	0.0148 (4)	0.0078 (4)	0.0034 (3)	−0.0028 (3)
O5	0.0119 (4)	0.0237 (4)	0.0151 (4)	0.0070 (3)	0.0034 (3)	0.0015 (3)
N1	0.0122 (4)	0.0123 (5)	0.0191 (5)	0.0048 (4)	0.0016 (3)	0.0026 (4)
C1	0.0141 (5)	0.0177 (6)	0.0177 (5)	0.0067 (4)	0.0021 (4)	0.0019 (4)
C2	0.0129 (5)	0.0153 (6)	0.0224 (6)	0.0048 (4)	0.0014 (4)	0.0027 (4)
C3	0.0144 (5)	0.0148 (5)	0.0150 (5)	0.0047 (4)	0.0013 (4)	0.0007 (4)
C4	0.0142 (5)	0.0139 (5)	0.0150 (5)	0.0063 (4)	0.0025 (4)	0.0008 (4)
C5	0.0122 (5)	0.0130 (5)	0.0200 (5)	0.0057 (4)	0.0033 (4)	0.0021 (4)
C6	0.0264 (6)	0.0183 (6)	0.0170 (6)	0.0048 (5)	0.0007 (5)	0.0038 (5)
C7	0.0267 (6)	0.0198 (6)	0.0200 (6)	0.0017 (5)	−0.0030 (5)	0.0003 (5)
C8	0.0178 (6)	0.0171 (6)	0.0253 (6)	0.0045 (5)	0.0037 (4)	0.0037 (5)
C9	0.0216 (6)	0.0214 (6)	0.0211 (6)	0.0052 (5)	0.0022 (5)	0.0072 (5)
C10	0.0177 (6)	0.0191 (6)	0.0189 (6)	0.0036 (5)	−0.0017 (4)	0.0022 (5)
C11	0.0287 (7)	0.0215 (7)	0.0289 (7)	−0.0006 (6)	0.0007 (6)	0.0051 (5)
C12	0.0122 (5)	0.0143 (6)	0.0210 (5)	0.0036 (4)	−0.0006 (4)	0.0002 (4)
C13	0.0186 (6)	0.0172 (6)	0.0241 (6)	0.0070 (5)	0.0035 (4)	0.0020 (5)
C14	0.0234 (6)	0.0208 (6)	0.0300 (7)	0.0070 (5)	0.0043 (5)	0.0079 (5)
C15	0.0283 (7)	0.0149 (6)	0.0410 (7)	0.0080 (5)	−0.0018 (5)	0.0044 (5)
C16	0.0297 (7)	0.0191 (6)	0.0353 (7)	0.0125 (5)	−0.0013 (5)	−0.0066 (5)
C17	0.0206 (6)	0.0216 (6)	0.0228 (6)	0.0088 (5)	0.0011 (5)	−0.0024 (5)
C18	0.0112 (5)	0.0135 (5)	0.0169 (5)	0.0030 (4)	0.0038 (4)	0.0026 (4)
C19	0.0224 (6)	0.0224 (6)	0.0147 (5)	0.0077 (5)	0.0005 (5)	0.0058 (5)
C20	0.0312 (7)	0.0267 (7)	0.0259 (7)	0.0152 (6)	0.0003 (5)	0.0081 (5)
C21	0.0156 (5)	0.0148 (5)	0.0156 (5)	0.0070 (4)	0.0022 (4)	0.0032 (4)
C22	0.0128 (5)	0.0298 (7)	0.0181 (6)	0.0094 (5)	0.0058 (4)	0.0041 (5)
C23	0.0211 (6)	0.0374 (8)	0.0338 (7)	0.0104 (6)	0.0099 (6)	0.0143 (6)

Geometric parameters (Å, º) top

O1—C1	1.2132 (13)	C9—H9	0.996 (14)
O2—C18	1.2035 (12)	C10—H10	0.977 (15)
O3—C18	1.3278 (12)	C11—H11A	0.955 (16)
O3—C19	1.4611 (12)	C11—H11B	0.965 (17)
O4—C21	1.2019 (13)	C11—H11C	0.960 (17)
O5—C21	1.3264 (13)	C12—C13	1.3952 (15)
O5—C22	1.4671 (12)	C12—C17	1.3978 (16)
N1—C1	1.3741 (13)	C13—C14	1.3867 (16)
N1—C5	1.4337 (13)	C13—H13	0.974 (13)
N1—C4	1.4633 (13)	C14—C15	1.3862 (18)
C1—C2	1.5049 (15)	C14—H14	0.974 (14)
C2—C3	1.5294 (14)	C15—C16	1.3840 (18)
C2—H2A	0.985 (13)	C15—H15	0.986 (14)
C2—H2B	0.985 (13)	C16—C17	1.3862 (17)
C3—C12	1.5131 (15)	C16—H16	0.949 (15)
C3—C4	1.5716 (14)	C17—H17	0.945 (14)
C3—H3	0.985 (12)	C19—C20	1.4987 (17)
C4—C18	1.5353 (14)	C19—H19A	0.985 (13)
C4—C21	1.5380 (14)	C19—H19B	0.994 (13)
C5—C6	1.3813 (15)	C20—H20A	0.957 (17)
C5—C10	1.3851 (15)	C20—H20B	0.994 (14)
C6—C7	1.3867 (16)	C20—H20C	1.004 (15)
C6—H6	0.955 (15)	C22—C23	1.4964 (17)
C7—C8	1.3865 (16)	C22—H22A	0.963 (12)
C7—H7	0.969 (14)	C22—H22B	0.983 (13)
C8—C9	1.3920 (16)	C23—H23A	0.990 (15)
C8—C11	1.5059 (16)	C23—H23B	0.974 (15)
C9—C10	1.3833 (16)	C23—H23C	0.974 (16)

C18—O3—C19	116.52 (8)	H11B—C11—H11C	104.4 (13)
C21—O5—C22	117.09 (8)	C13—C12—C17	118.39 (10)
C1—N1—C5	121.50 (9)	C13—C12—C3	122.07 (9)
C1—N1—C4	113.50 (8)	C17—C12—C3	119.54 (10)
C5—N1—C4	125.00 (8)	C14—C13—C12	120.68 (11)
O1—C1—N1	124.33 (10)	C14—C13—H13	119.0 (8)
O1—C1—C2	127.73 (9)	C12—C13—H13	120.3 (8)
N1—C1—C2	107.93 (9)	C15—C14—C13	120.39 (12)
C1—C2—C3	104.67 (8)	C15—C14—H14	120.7 (8)
C1—C2—H2A	108.8 (8)	C13—C14—H14	118.9 (8)
C3—C2—H2A	112.7 (7)	C16—C15—C14	119.46 (11)
C1—C2—H2B	110.5 (8)	C16—C15—H15	120.2 (8)
C3—C2—H2B	110.7 (7)	C14—C15—H15	120.3 (8)
H2A—C2—H2B	109.5 (10)	C15—C16—C17	120.41 (11)
C12—C3—C2	116.32 (9)	C15—C16—H16	120.0 (9)
C12—C3—C4	116.64 (8)	C17—C16—H16	119.6 (9)
C2—C3—C4	102.81 (8)	C16—C17—C12	120.67 (11)
C12—C3—H3	110.1 (7)	C16—C17—H17	120.0 (8)
C2—C3—H3	107.7 (7)	C12—C17—H17	119.3 (8)
C4—C3—H3	102.0 (7)	O2—C18—O3	125.34 (9)
N1—C4—C18	111.92 (8)	O2—C18—C4	124.12 (9)
N1—C4—C21	108.16 (8)	O3—C18—C4	110.40 (8)
C18—C4—C21	111.84 (8)	O3—C19—C20	106.36 (9)
N1—C4—C3	101.81 (8)	O3—C19—H19A	107.5 (7)
C18—C4—C3	110.42 (8)	C20—C19—H19A	113.3 (7)
C21—C4—C3	112.27 (8)	O3—C19—H19B	107.9 (7)
C6—C5—C10	119.81 (10)	C20—C19—H19B	113.4 (7)
C6—C5—N1	121.64 (9)	H19A—C19—H19B	108.1 (10)
C10—C5—N1	118.54 (9)	C19—C20—H20A	110.4 (9)
C5—C6—C7	119.44 (10)	C19—C20—H20B	109.6 (8)
C5—C6—H6	118.6 (9)	H20A—C20—H20B	107.7 (12)
C7—C6—H6	122.0 (9)	C19—C20—H20C	112.2 (8)
C8—C7—C6	121.76 (11)	H20A—C20—H20C	110.3 (12)
C8—C7—H7	116.5 (8)	H20B—C20—H20C	106.5 (11)
C6—C7—H7	121.8 (8)	O4—C21—O5	125.77 (10)
C7—C8—C9	117.84 (10)	O4—C21—C4	123.35 (9)
C7—C8—C11	120.84 (10)	O5—C21—C4	110.77 (8)
C9—C8—C11	121.31 (10)	O5—C22—C23	110.51 (9)
C10—C9—C8	120.96 (10)	O5—C22—H22A	103.6 (7)
C10—C9—H9	119.6 (8)	C23—C22—H22A	110.8 (7)
C8—C9—H9	119.4 (8)	O5—C22—H22B	106.9 (7)
C9—C10—C5	120.17 (10)	C23—C22—H22B	114.4 (7)
C9—C10—H10	121.6 (8)	H22A—C22—H22B	109.9 (10)
C5—C10—H10	118.2 (8)	C22—C23—H23A	109.7 (8)
C8—C11—H11A	112.6 (9)	C22—C23—H23B	110.8 (9)
C8—C11—H11B	111.6 (10)	H23A—C23—H23B	110.0 (12)
H11A—C11—H11B	103.5 (13)	C22—C23—H23C	108.9 (9)
C8—C11—H11C	112.7 (10)	H23A—C23—H23C	111.5 (12)
H11A—C11—H11C	111.4 (13)	H23B—C23—H23C	106.0 (12)

C5—N1—C1—O1	−3.65 (16)	C6—C5—C10—C9	−1.04 (16)
C4—N1—C1—O1	176.36 (10)	N1—C5—C10—C9	177.92 (10)
C5—N1—C1—C2	176.93 (9)	C2—C3—C12—C13	−38.01 (14)
C4—N1—C1—C2	−3.06 (11)	C4—C3—C12—C13	83.65 (12)
O1—C1—C2—C3	163.95 (11)	C2—C3—C12—C17	142.13 (10)
N1—C1—C2—C3	−16.65 (11)	C4—C3—C12—C17	−96.21 (12)
C1—C2—C3—C12	156.77 (9)	C17—C12—C13—C14	−0.44 (16)
C1—C2—C3—C4	28.05 (10)	C3—C12—C13—C14	179.69 (10)
C1—N1—C4—C18	−97.26 (10)	C12—C13—C14—C15	0.05 (17)
C5—N1—C4—C18	82.75 (11)	C13—C14—C15—C16	0.39 (18)
C1—N1—C4—C21	139.09 (9)	C14—C15—C16—C17	−0.44 (18)
C5—N1—C4—C21	−40.89 (12)	C15—C16—C17—C12	0.04 (18)
C1—N1—C4—C3	20.66 (10)	C13—C12—C17—C16	0.40 (16)
C5—N1—C4—C3	−159.32 (9)	C3—C12—C17—C16	−179.73 (10)
C12—C3—C4—N1	−157.57 (8)	C19—O3—C18—O2	6.15 (14)
C2—C3—C4—N1	−29.05 (10)	C19—O3—C18—C4	−169.70 (8)
C12—C3—C4—C18	−38.57 (12)	N1—C4—C18—O2	16.45 (14)
C2—C3—C4—C18	89.95 (9)	C21—C4—C18—O2	138.00 (10)
C12—C3—C4—C21	86.98 (11)	C3—C4—C18—O2	−96.21 (12)
C2—C3—C4—C21	−144.51 (8)	N1—C4—C18—O3	−167.65 (8)
C1—N1—C5—C6	109.35 (12)	C21—C4—C18—O3	−46.09 (11)
C4—N1—C5—C6	−70.67 (14)	C3—C4—C18—O3	79.70 (10)
C1—N1—C5—C10	−69.59 (13)	C18—O3—C19—C20	172.04 (9)
C4—N1—C5—C10	110.40 (11)	C22—O5—C21—O4	0.53 (16)
C10—C5—C6—C7	0.02 (16)	C22—O5—C21—C4	−175.69 (8)
N1—C5—C6—C7	−178.91 (10)	N1—C4—C21—O4	−85.80 (12)
C5—C6—C7—C8	1.25 (18)	C18—C4—C21—O4	150.51 (10)
C6—C7—C8—C9	−1.45 (17)	C3—C4—C21—O4	25.74 (14)
C6—C7—C8—C11	177.81 (12)	N1—C4—C21—O5	90.53 (10)
C7—C8—C9—C10	0.40 (17)	C18—C4—C21—O5	−33.16 (12)
C11—C8—C9—C10	−178.86 (11)	C3—C4—C21—O5	−157.93 (8)
C8—C9—C10—C5	0.83 (17)	C21—O5—C22—C23	84.62 (12)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₅NO₅
M_r	395.44
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.4905 (2), 10.6167 (2), 10.8198 (2)
α, β, γ (°)	93.014 (1), 95.167 (1), 110.537 (1)
V (Å³)	1012.60 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.30 × 0.12

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.964, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	14991, 3672, 3331
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.091, 1.87
No. of reflections	3672
No. of parameters	362
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), PLEASE SUPPLY.

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, y−1, z; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1.

Acknowledgements

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.

References

Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Desiraju, G. M. (2005). Chem. Commun. pp. 2995–3001. Web of Science CrossRef Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kandasamy, S., Fun, H.-K., Ray, J. K., Roy, B. C. & Nigam, G. D. (1995). Acta Cryst. C51, 1942–1944. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Nigam, G. D., Mattern, G. & Frohlich, R. (1989). Z. Kristallogr. 189, 293. CrossRef Google Scholar
Rao, S. T., Westhof, E. & Sundaralingam, M. (1981). Acta Cryst. A37, 421–425. CrossRef CAS IUCr Journals Web of Science Google Scholar
Ray, J. K., Chakraborty, A., Adhikari, S. D., Chinnakali, K. & Fun, H.-K. (1998). Acta Cryst. C54, 368–370. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ray, J. K., Haldar, P., Canle L., M., Fernández P., M. I. & Santaballa, J. A. (2010). Acta Cryst. E66, o2103. Google Scholar
Ray, J. K., Haldar, P., Canle L., M., Santaballa, J. A. & Mahía, J. (2004). Acta Cryst. C60, o163–o165. Google Scholar
Ray, J. K., Sami, I., Kar, G. K., Roy, B. C. & Brahma, N. K. (1994). Bioorg. Med. Chem. 2, 1417–1421. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar