Ethyl (2E)-[1-(4-methoxy­phen­yl)­pyrrolidin-2-yl­idene]acetate

Fernandes, M.A.; Michael, J.P.; Perry, C.B.

doi:10.1107/S1600536807023689

Ethyl (2E)-[1-(4-methoxyphenyl)pyrrolidin-2-ylidene]acetate

M. A. Fernandes, J. P. Michael and C. B. Perry

The title compound, C₁₅H₁₉NO₃, crystallizes with two conformationally similar molecules, A and B, in the asymmetric unit. The structure contains several C—H

O interactions, two of which link molecules A and B in a pseudo-centrosymmetric fashion to form dimers described by the graph set R²₂(24). In addition, a C—H

π interaction between a benzene H atom of a B molecule and the benzene ring of an A molecule further link these dimers to form a ribbon of molecules running parallel to the [100] direction. The remaining C—H

O interactions between molecules A and B, A and A, and B and B provide additional stabilization for the structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023689/si2016sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023689/si2016Isup2.hkl Contains datablock I

CCDC reference: 654901

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R factor = 0.047
wR factor = 0.120
Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4A    ..  O1B     ..       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7C    ..  O1B     ..       2.71 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H15E   ..  O2A     ..       2.64 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

N-Arylenaminones such as (I) can be prepared in various ways, including by the Eschenmoser sulfide contraction and by reaction of suitable anilines with ethyl 6-chloro-3-oxohexanoate (Michael et al., 1988). Our interest in these compounds stems from their ready cyclization in hot polyphosphoric acid (a variant of the classic Conrad-Limpach reaction) to give tricyclic analogues of the quinolone antibacterial agents (Michael et al., 2001).

Compound (I) crystallizes in the space group P-1 with two molecules in the asymmetric unit (Z' = 2, Fig. 1). The two molecules are conformationally similar, with the major differences between the two being the degree of rotation around the C9—N1 and C12—O3 bonds (Table 1). In both cases, the closest pucker descriptor of the pyrrolidine rings is twisted on C5A—C6A and C5B—C6B for molecules A and B, respectively. The Cremer & Pople puckering parameters (Cremer & Pople, 1975) for the pyrrolidine ring of molecule A are q₂ = 0.2204 (19) Å and φ₂ = 118.9 (5)°, and for molecule B are q₂ = 0.2935 (19) Å and φ₂ = 118.3 (3)°.

The structure contains several C—H···O interactions (Table 2). Two of these, C15A—H15B···O2B and C15B—H15E···O2A, link molecules A and B in a pseudo-centrosymmetric fashion, forming dimers described by the graph set R²₂(24) (Etter et al., 1990; Bernstein et al., 1995). In addition, a C—H···π interaction between the H13B atom of a B molecule and the phenyl ring of an A molecule (Fig. 1) further links these dimers to form a ribbon of molecules running parallel to the [100] direction (Fig. 2). The remaining C—H···O interactions between molecules A and B, A and A, and B and B provide additional stabilization for the structure (Table 2). Three of these C—H···O interactions are flagged by PLATON (Spek, 2003) as slightly long, but have C···O distances and other geometric characteristics well within the limits defined by Desiraju et al. (Desiraju, 1996; Steiner & Desiraju, 1998).

Related literature top

For details of the preparation and use of the title compound, see: Michael et al. (1988, 2001). For hydrogen-bonding motifs, see: Etter et al. (1990); Bernstein et al. (1995). For discussion of C—H···O interactions, see: Desiraju (1996); Steiner & Desiraju (1998). For definition of ring-puckering parameters, see: Cremer & Pople (1975).

Experimental top

Ethyl (2E)-[1-(4-methoxyphenyl)pyrrolidin-2-ylidene]acetate (I) was prepared in 65% yield from 4-methoxyaniline and ethyl 6-chloro-3-oxohexanoate, as described previously (Michael et al., 1988). Crystals suitable for X-ray crystallography were obtained as colourless needles by recrystallization from hexane–ethyl acetate (ca 1:2).

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The intermolecular C—H···π interaction is shown with a dashed bond.
	Fig. 2. Part of the crystal structure of (I) showing the intermolecular C—H···O (dashed purple lines), and C—H···π interactions (dashed orange lines). All hydrogen atoms not involved in these interactions have been omitted for clarity.

Ethyl (2E)-[1-(4-methoxyphenyl)pyrrolidin-2-ylidene]acetate top

Crystal data top

C₁₅H₁₉NO₃	Z = 4
M_r = 261.31	F(000) = 560
Triclinic, P1	D_x = 1.254 Mg m⁻³ D_m = 1.254 Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Melting point = 345.5–346.5 K
a = 9.7056 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7763 (3) Å	Cell parameters from 2637 reflections
c = 15.0413 (5) Å	θ = 0.0–0.0°
α = 93.126 (2)°	µ = 0.09 mm⁻¹
β = 92.987 (2)°	T = 173 K
γ = 103.301 (2)°	Needle, colourless
V = 1383.77 (9) Å³	0.54 × 0.21 × 0.14 mm

Data collection top

Bruker APEX II CCD area-detector diffractometer	3779 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 28.0°, θ_min = 1.4°
phi and ω scans	h = −12→12
11703 measured reflections	k = −12→12
6666 independent reflections	l = −19→18

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0507P)²] where P = (F_o² + 2F_c²)/3
6666 reflections	(Δ/σ)_max < 0.001
347 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₅H₁₉NO₃	γ = 103.301 (2)°
M_r = 261.31	V = 1383.77 (9) Å³
Triclinic, P1	Z = 4
a = 9.7056 (4) Å	Mo Kα radiation
b = 9.7763 (3) Å	µ = 0.09 mm⁻¹
c = 15.0413 (5) Å	T = 173 K
α = 93.126 (2)°	0.54 × 0.21 × 0.14 mm
β = 92.987 (2)°

Data collection top

Bruker APEX II CCD area-detector diffractometer	3779 reflections with I > 2σ(I)
11703 measured reflections	R_int = 0.041
6666 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 0.94	Δρ_max = 0.19 e Å⁻³
6666 reflections	Δρ_min = −0.22 e Å⁻³
347 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1A	0.17022 (17)	0.52626 (17)	0.85839 (11)	0.0295 (4)
C2A	0.23671 (16)	0.46291 (16)	0.78914 (10)	0.0287 (4)
H2A	0.1999	0.4615	0.7292	0.034*
C3A	0.34824 (17)	0.40551 (16)	0.80472 (11)	0.0279 (4)
C4A	0.42096 (18)	0.39177 (19)	0.89320 (11)	0.0372 (4)
H4A	0.3577	0.3240	0.9283	0.045*
H4B	0.4483	0.4840	0.9279	0.045*
C5A	0.5506 (2)	0.3393 (2)	0.87207 (12)	0.0500 (5)
H5A	0.5653	0.2677	0.9133	0.060*
H5B	0.6362	0.4179	0.8769	0.060*
C6A	0.52023 (19)	0.2757 (2)	0.77750 (12)	0.0414 (5)
H6B	0.6069	0.2959	0.7439	0.050*
H6A	0.4829	0.1725	0.7763	0.050*
C7A	−0.02277 (19)	0.62950 (19)	0.88806 (12)	0.0406 (5)
H7A	0.0422	0.7115	0.9212	0.049*
H7B	−0.0634	0.5612	0.9314	0.049*
C8A	−0.1382 (2)	0.6755 (2)	0.83749 (15)	0.0582 (6)
H8A	−0.0967	0.7464	0.7968	0.087*
H8B	−0.1944	0.7163	0.8793	0.087*
H8C	−0.1996	0.5942	0.8030	0.087*
C9A	0.35464 (16)	0.30970 (17)	0.65066 (11)	0.0276 (4)
C10A	0.35809 (18)	0.41127 (17)	0.58982 (11)	0.0339 (4)
H10A	0.3991	0.5073	0.6078	0.041*
C11A	0.30246 (18)	0.37437 (17)	0.50308 (11)	0.0346 (4)
H11A	0.3043	0.4451	0.4620	0.041*
C12A	0.24384 (17)	0.23381 (17)	0.47590 (11)	0.0294 (4)
C13A	0.23974 (17)	0.13206 (17)	0.53626 (11)	0.0332 (4)
H13A	0.1994	0.0359	0.5183	0.040*
C14A	0.29465 (17)	0.17055 (17)	0.62314 (11)	0.0323 (4)
H14A	0.2911	0.1001	0.6646	0.039*
C15A	0.1331 (2)	0.06410 (19)	0.35860 (12)	0.0476 (5)
H15A	0.2034	0.0076	0.3677	0.071*
H15B	0.1027	0.0582	0.2951	0.071*
H15C	0.0508	0.0281	0.3929	0.071*
N1A	0.41348 (14)	0.34435 (14)	0.74039 (9)	0.0315 (3)
O1A	0.20722 (13)	0.54574 (13)	0.93772 (8)	0.0433 (3)
O2A	0.05333 (12)	0.56466 (11)	0.82451 (7)	0.0327 (3)
O3A	0.19482 (13)	0.20770 (12)	0.38803 (8)	0.0403 (3)
C1B	0.83658 (17)	−0.02700 (16)	0.12391 (11)	0.0290 (4)
C2B	0.79144 (16)	0.05642 (16)	0.19314 (10)	0.0267 (4)
H2B	0.8452	0.0749	0.2489	0.032*
C3B	0.67510 (16)	0.10985 (16)	0.18201 (10)	0.0264 (4)
C4B	0.58101 (17)	0.09749 (18)	0.09807 (11)	0.0335 (4)
H4C	0.5236	−0.0001	0.0859	0.040*
H4D	0.6381	0.1243	0.0464	0.040*
C5B	0.48628 (19)	0.19869 (19)	0.11569 (12)	0.0390 (5)
H5C	0.5274	0.2925	0.0944	0.047*
H5D	0.3902	0.1620	0.0862	0.047*
C6B	0.48175 (17)	0.2060 (2)	0.21622 (12)	0.0387 (5)
H6C	0.4716	0.2996	0.2395	0.046*
H6D	0.4026	0.1325	0.2353	0.046*
C7B	1.00681 (18)	−0.15775 (18)	0.08914 (12)	0.0392 (5)
H7C	1.0163	−0.1161	0.0306	0.047*
H7D	0.9389	−0.2507	0.0808	0.047*
C8B	1.1469 (2)	−0.1744 (2)	0.12535 (14)	0.0581 (6)
H8D	1.2157	−0.0833	0.1282	0.087*
H8E	1.1794	−0.2425	0.0863	0.087*
H8F	1.1380	−0.2084	0.1854	0.087*
C9B	0.66910 (16)	0.20555 (16)	0.33754 (10)	0.0254 (4)
C10B	0.81081 (16)	0.26330 (16)	0.36328 (11)	0.0274 (4)
H10B	0.8771	0.2863	0.3190	0.033*
C11B	0.85713 (16)	0.28796 (16)	0.45265 (10)	0.0276 (4)
H11B	0.9549	0.3255	0.4693	0.033*
C12B	0.76065 (17)	0.25783 (16)	0.51795 (11)	0.0294 (4)
C13B	0.61861 (17)	0.20185 (17)	0.49247 (11)	0.0340 (4)
H13B	0.5518	0.1817	0.5367	0.041*
C14B	0.57365 (17)	0.17523 (17)	0.40377 (11)	0.0319 (4)
H14B	0.4762	0.1356	0.3874	0.038*
C15B	0.9377 (2)	0.3441 (2)	0.63622 (12)	0.0549 (6)
H15D	0.9989	0.2822	0.6176	0.082*
H15E	0.9464	0.3598	0.7014	0.082*
H15F	0.9667	0.4345	0.6094	0.082*
N1B	0.61959 (13)	0.18097 (14)	0.24637 (9)	0.0281 (3)
O1B	0.77983 (13)	−0.06314 (13)	0.04944 (8)	0.0420 (3)
O2B	0.95603 (12)	−0.06652 (12)	0.15178 (7)	0.0351 (3)
O3B	0.79418 (12)	0.27977 (13)	0.60753 (8)	0.0434 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.0285 (9)	0.0320 (9)	0.0274 (10)	0.0064 (7)	0.0024 (7)	−0.0002 (7)
C2A	0.0305 (9)	0.0343 (9)	0.0210 (9)	0.0087 (7)	−0.0010 (7)	−0.0025 (7)
C3A	0.0273 (9)	0.0290 (8)	0.0253 (9)	0.0032 (7)	0.0014 (7)	−0.0001 (7)
C4A	0.0380 (10)	0.0438 (10)	0.0301 (10)	0.0127 (9)	−0.0062 (8)	−0.0012 (8)
C5A	0.0446 (12)	0.0706 (14)	0.0398 (12)	0.0250 (11)	−0.0039 (9)	0.0040 (10)
C6A	0.0346 (10)	0.0516 (11)	0.0431 (12)	0.0215 (9)	−0.0014 (9)	0.0032 (9)
C7A	0.0415 (11)	0.0458 (11)	0.0392 (11)	0.0179 (9)	0.0167 (9)	−0.0022 (9)
C8A	0.0495 (13)	0.0694 (14)	0.0678 (15)	0.0337 (11)	0.0179 (11)	0.0119 (12)
C9A	0.0260 (9)	0.0332 (9)	0.0260 (9)	0.0118 (7)	0.0064 (7)	−0.0013 (7)
C10A	0.0431 (11)	0.0267 (8)	0.0332 (10)	0.0108 (8)	0.0056 (8)	−0.0015 (7)
C11A	0.0454 (11)	0.0329 (9)	0.0286 (10)	0.0144 (8)	0.0051 (8)	0.0046 (7)
C12A	0.0274 (9)	0.0378 (9)	0.0248 (9)	0.0110 (8)	0.0059 (7)	−0.0021 (7)
C13A	0.0329 (10)	0.0300 (9)	0.0347 (10)	0.0028 (8)	0.0069 (8)	−0.0017 (8)
C14A	0.0346 (10)	0.0325 (9)	0.0308 (10)	0.0078 (8)	0.0082 (8)	0.0065 (8)
C15A	0.0421 (11)	0.0533 (12)	0.0400 (12)	0.0010 (10)	−0.0034 (9)	−0.0130 (10)
N1A	0.0321 (8)	0.0394 (8)	0.0263 (8)	0.0158 (7)	0.0007 (6)	−0.0002 (6)
O1A	0.0464 (8)	0.0643 (9)	0.0223 (7)	0.0217 (7)	−0.0004 (6)	−0.0059 (6)
O2A	0.0317 (6)	0.0424 (7)	0.0272 (6)	0.0155 (5)	0.0046 (5)	−0.0025 (5)
O3A	0.0460 (8)	0.0445 (7)	0.0289 (7)	0.0099 (6)	−0.0019 (6)	−0.0031 (6)
C1B	0.0268 (9)	0.0292 (9)	0.0290 (10)	0.0029 (7)	0.0030 (7)	0.0002 (7)
C2B	0.0278 (9)	0.0290 (8)	0.0220 (8)	0.0049 (7)	0.0014 (7)	−0.0021 (7)
C3B	0.0260 (9)	0.0261 (8)	0.0240 (9)	0.0004 (7)	0.0023 (7)	−0.0016 (7)
C4B	0.0308 (9)	0.0388 (10)	0.0283 (9)	0.0050 (8)	−0.0044 (8)	−0.0006 (8)
C5B	0.0329 (10)	0.0479 (11)	0.0362 (11)	0.0133 (9)	−0.0083 (8)	−0.0041 (9)
C6B	0.0260 (9)	0.0524 (11)	0.0385 (11)	0.0145 (8)	−0.0052 (8)	−0.0060 (9)
C7B	0.0428 (11)	0.0367 (10)	0.0406 (11)	0.0143 (8)	0.0125 (9)	−0.0070 (8)
C8B	0.0571 (14)	0.0749 (15)	0.0543 (14)	0.0385 (12)	0.0123 (11)	0.0020 (12)
C9B	0.0261 (8)	0.0254 (8)	0.0256 (9)	0.0092 (7)	0.0015 (7)	−0.0033 (7)
C10B	0.0259 (8)	0.0288 (8)	0.0263 (9)	0.0037 (7)	0.0051 (7)	−0.0015 (7)
C11B	0.0226 (8)	0.0290 (8)	0.0282 (9)	0.0020 (7)	−0.0011 (7)	−0.0036 (7)
C12B	0.0322 (9)	0.0309 (9)	0.0238 (9)	0.0067 (7)	0.0018 (7)	−0.0048 (7)
C13B	0.0285 (9)	0.0421 (10)	0.0309 (10)	0.0065 (8)	0.0101 (8)	−0.0029 (8)
C14B	0.0221 (8)	0.0374 (9)	0.0345 (10)	0.0053 (7)	0.0037 (7)	−0.0068 (8)
C15B	0.0474 (12)	0.0733 (14)	0.0296 (11)	−0.0108 (11)	−0.0074 (9)	−0.0083 (10)
N1B	0.0225 (7)	0.0364 (8)	0.0256 (7)	0.0092 (6)	−0.0005 (6)	−0.0044 (6)
O1B	0.0428 (7)	0.0528 (8)	0.0296 (7)	0.0144 (6)	−0.0030 (6)	−0.0137 (6)
O2B	0.0354 (7)	0.0399 (7)	0.0326 (7)	0.0156 (6)	0.0045 (6)	−0.0076 (5)
O3B	0.0385 (7)	0.0611 (8)	0.0242 (7)	0.0003 (6)	0.0025 (6)	−0.0050 (6)

Geometric parameters (Å, º) top

C1A—O1A	1.2199 (18)	C1B—O1B	1.2189 (18)
C1A—O2A	1.358 (2)	C1B—O2B	1.357 (2)
C1A—C2A	1.438 (2)	C1B—C2B	1.436 (2)
C2A—C3A	1.345 (2)	C2B—C3B	1.355 (2)
C2A—H2A	0.9500	C2B—H2B	0.9500
C3A—N1A	1.3675 (19)	C3B—N1B	1.3653 (18)
C3A—C4A	1.501 (2)	C3B—C4B	1.502 (2)
C4A—C5A	1.506 (2)	C4B—C5B	1.520 (2)
C4A—H4A	0.9900	C4B—H4C	0.9900
C4A—H4B	0.9900	C4B—H4D	0.9900
C5A—C6A	1.507 (2)	C5B—C6B	1.513 (2)
C5A—H5A	0.9900	C5B—H5C	0.9900
C5A—H5B	0.9900	C5B—H5D	0.9900
C6A—N1A	1.461 (2)	C6B—N1B	1.468 (2)
C6A—H6B	0.9900	C6B—H6C	0.9900
C6A—H6A	0.9900	C6B—H6D	0.9900
C7A—O2A	1.4437 (18)	C7B—O2B	1.4440 (17)
C7A—C8A	1.489 (3)	C7B—C8B	1.485 (3)
C7A—H7A	0.9900	C7B—H7C	0.9900
C7A—H7B	0.9900	C7B—H7D	0.9900
C8A—H8A	0.9800	C8B—H8D	0.9800
C8A—H8B	0.9800	C8B—H8E	0.9800
C8A—H8C	0.9800	C8B—H8F	0.9800
C9A—C14A	1.382 (2)	C9B—C10B	1.387 (2)
C9A—C10A	1.383 (2)	C9B—C14B	1.393 (2)
C9A—N1A	1.429 (2)	C9B—N1B	1.4183 (19)
C10A—C11A	1.382 (2)	C10B—C11B	1.385 (2)
C10A—H10A	0.9500	C10B—H10B	0.9500
C11A—C12A	1.391 (2)	C11B—C12B	1.389 (2)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—O3A	1.3712 (19)	C12B—O3B	1.3632 (18)
C12A—C13A	1.378 (2)	C12B—C13B	1.386 (2)
C13A—C14A	1.384 (2)	C13B—C14B	1.374 (2)
C13A—H13A	0.9500	C13B—H13B	0.9500
C14A—H14A	0.9500	C14B—H14B	0.9500
C15A—O3A	1.4295 (19)	C15B—O3B	1.424 (2)
C15A—H15A	0.9800	C15B—H15D	0.9800
C15A—H15B	0.9800	C15B—H15E	0.9800
C15A—H15C	0.9800	C15B—H15F	0.9800

O1A—C1A—O2A	121.46 (15)	O1B—C1B—O2B	121.40 (15)
O1A—C1A—C2A	127.81 (17)	O1B—C1B—C2B	127.75 (17)
O2A—C1A—C2A	110.73 (14)	O2B—C1B—C2B	110.84 (14)
C3A—C2A—C1A	123.46 (16)	C3B—C2B—C1B	122.52 (15)
C3A—C2A—H2A	118.3	C3B—C2B—H2B	118.7
C1A—C2A—H2A	118.3	C1B—C2B—H2B	118.7
C2A—C3A—N1A	124.80 (15)	C2B—C3B—N1B	125.93 (15)
C2A—C3A—C4A	127.71 (15)	C2B—C3B—C4B	126.49 (14)
N1A—C3A—C4A	107.46 (15)	N1B—C3B—C4B	107.55 (14)
C3A—C4A—C5A	105.81 (14)	C3B—C4B—C5B	104.97 (13)
C3A—C4A—H4A	110.6	C3B—C4B—H4C	110.8
C5A—C4A—H4A	110.6	C5B—C4B—H4C	110.8
C3A—C4A—H4B	110.6	C3B—C4B—H4D	110.8
C5A—C4A—H4B	110.6	C5B—C4B—H4D	110.8
H4A—C4A—H4B	108.7	H4C—C4B—H4D	108.8
C4A—C5A—C6A	104.88 (15)	C6B—C5B—C4B	103.25 (15)
C4A—C5A—H5A	110.8	C6B—C5B—H5C	111.1
C6A—C5A—H5A	110.8	C4B—C5B—H5C	111.1
C4A—C5A—H5B	110.8	C6B—C5B—H5D	111.1
C6A—C5A—H5B	110.8	C4B—C5B—H5D	111.1
H5A—C5A—H5B	108.8	H5C—C5B—H5D	109.1
N1A—C6A—C5A	103.85 (14)	N1B—C6B—C5B	102.98 (13)
N1A—C6A—H6B	111.0	N1B—C6B—H6C	111.2
C5A—C6A—H6B	111.0	C5B—C6B—H6C	111.2
N1A—C6A—H6A	111.0	N1B—C6B—H6D	111.2
C5A—C6A—H6A	111.0	C5B—C6B—H6D	111.2
H6B—C6A—H6A	109.0	H6C—C6B—H6D	109.1
O2A—C7A—C8A	107.74 (15)	O2B—C7B—C8B	108.21 (14)
O2A—C7A—H7A	110.2	O2B—C7B—H7C	110.1
C8A—C7A—H7A	110.2	C8B—C7B—H7C	110.1
O2A—C7A—H7B	110.2	O2B—C7B—H7D	110.1
C8A—C7A—H7B	110.2	C8B—C7B—H7D	110.1
H7A—C7A—H7B	108.5	H7C—C7B—H7D	108.4
C7A—C8A—H8A	109.5	C7B—C8B—H8D	109.5
C7A—C8A—H8B	109.5	C7B—C8B—H8E	109.5
H8A—C8A—H8B	109.5	H8D—C8B—H8E	109.5
C7A—C8A—H8C	109.5	C7B—C8B—H8F	109.5
H8A—C8A—H8C	109.5	H8D—C8B—H8F	109.5
H8B—C8A—H8C	109.5	H8E—C8B—H8F	109.5
C14A—C9A—C10A	118.80 (15)	C10B—C9B—C14B	118.39 (15)
C14A—C9A—N1A	119.30 (15)	C10B—C9B—N1B	121.71 (14)
C10A—C9A—N1A	121.89 (14)	C14B—C9B—N1B	119.87 (14)
C11A—C10A—C9A	120.61 (15)	C11B—C10B—C9B	120.96 (15)
C11A—C10A—H10A	119.7	C11B—C10B—H10B	119.5
C9A—C10A—H10A	119.7	C9B—C10B—H10B	119.5
C10A—C11A—C12A	120.06 (17)	C10B—C11B—C12B	120.00 (15)
C10A—C11A—H11A	120.0	C10B—C11B—H11B	120.0
C12A—C11A—H11A	120.0	C12B—C11B—H11B	120.0
O3A—C12A—C13A	124.77 (14)	O3B—C12B—C13B	115.89 (14)
O3A—C12A—C11A	115.60 (16)	O3B—C12B—C11B	124.90 (14)
C13A—C12A—C11A	119.63 (16)	C13B—C12B—C11B	119.21 (15)
C12A—C13A—C14A	119.74 (15)	C14B—C13B—C12B	120.54 (15)
C12A—C13A—H13A	120.1	C14B—C13B—H13B	119.7
C14A—C13A—H13A	120.1	C12B—C13B—H13B	119.7
C9A—C14A—C13A	121.15 (17)	C13B—C14B—C9B	120.88 (15)
C9A—C14A—H14A	119.4	C13B—C14B—H14B	119.6
C13A—C14A—H14A	119.4	C9B—C14B—H14B	119.6
O3A—C15A—H15A	109.5	O3B—C15B—H15D	109.5
O3A—C15A—H15B	109.5	O3B—C15B—H15E	109.5
H15A—C15A—H15B	109.5	H15D—C15B—H15E	109.5
O3A—C15A—H15C	109.5	O3B—C15B—H15F	109.5
H15A—C15A—H15C	109.5	H15D—C15B—H15F	109.5
H15B—C15A—H15C	109.5	H15E—C15B—H15F	109.5
C3A—N1A—C9A	123.25 (14)	C3B—N1B—C9B	126.00 (14)
C3A—N1A—C6A	112.78 (14)	C3B—N1B—C6B	112.13 (13)
C9A—N1A—C6A	120.97 (13)	C9B—N1B—C6B	120.75 (13)
C1A—O2A—C7A	115.79 (13)	C1B—O2B—C7B	115.68 (13)
C12A—O3A—C15A	116.68 (14)	C12B—O3B—C15B	117.54 (13)

O1A—C1A—C2A—C3A	4.9 (3)	O1B—C1B—C2B—C3B	−1.4 (3)
O2A—C1A—C2A—C3A	−174.83 (14)	O2B—C1B—C2B—C3B	179.57 (14)
C1A—C2A—C3A—N1A	179.86 (14)	C1B—C2B—C3B—N1B	174.85 (14)
C1A—C2A—C3A—C4A	1.9 (3)	C1B—C2B—C3B—C4B	−2.8 (2)
C2A—C3A—C4A—C5A	−172.15 (17)	C2B—C3B—C4B—C5B	−169.03 (16)
N1A—C3A—C4A—C5A	9.64 (18)	N1B—C3B—C4B—C5B	12.94 (17)
C3A—C4A—C5A—C6A	−20.0 (2)	C3B—C4B—C5B—C6B	−26.37 (17)
C4A—C5A—C6A—N1A	22.6 (2)	C4B—C5B—C6B—N1B	29.56 (17)
C14A—C9A—C10A—C11A	0.1 (3)	C14B—C9B—C10B—C11B	1.2 (2)
N1A—C9A—C10A—C11A	178.92 (15)	N1B—C9B—C10B—C11B	179.33 (14)
C9A—C10A—C11A—C12A	−0.8 (3)	C9B—C10B—C11B—C12B	−1.5 (2)
C10A—C11A—C12A—O3A	−178.39 (15)	C10B—C11B—C12B—O3B	−179.01 (15)
C10A—C11A—C12A—C13A	1.0 (3)	C10B—C11B—C12B—C13B	0.6 (2)
O3A—C12A—C13A—C14A	178.91 (15)	O3B—C12B—C13B—C14B	−179.77 (15)
C11A—C12A—C13A—C14A	−0.4 (3)	C11B—C12B—C13B—C14B	0.6 (3)
C10A—C9A—C14A—C13A	0.5 (2)	C12B—C13B—C14B—C9B	−0.9 (3)
N1A—C9A—C14A—C13A	−178.36 (15)	C10B—C9B—C14B—C13B	0.0 (2)
C12A—C13A—C14A—C9A	−0.4 (3)	N1B—C9B—C14B—C13B	−178.17 (15)
C2A—C3A—N1A—C9A	−12.4 (2)	C2B—C3B—N1B—C9B	−3.5 (2)
C4A—C3A—N1A—C9A	165.84 (14)	C4B—C3B—N1B—C9B	174.58 (14)
C2A—C3A—N1A—C6A	−172.96 (16)	C2B—C3B—N1B—C6B	−171.40 (15)
C4A—C3A—N1A—C6A	5.32 (18)	C4B—C3B—N1B—C6B	6.66 (18)
C14A—C9A—N1A—C3A	−104.94 (18)	C10B—C9B—N1B—C3B	51.5 (2)
C10A—C9A—N1A—C3A	76.2 (2)	C14B—C9B—N1B—C3B	−130.39 (16)
C14A—C9A—N1A—C6A	54.0 (2)	C10B—C9B—N1B—C6B	−141.55 (16)
C10A—C9A—N1A—C6A	−124.82 (18)	C14B—C9B—N1B—C6B	36.6 (2)
C5A—C6A—N1A—C3A	−17.92 (19)	C5B—C6B—N1B—C3B	−23.41 (18)
C5A—C6A—N1A—C9A	−178.93 (14)	C5B—C6B—N1B—C9B	167.95 (14)
O1A—C1A—O2A—C7A	0.1 (2)	O1B—C1B—O2B—C7B	−2.4 (2)
C2A—C1A—O2A—C7A	179.90 (13)	C2B—C1B—O2B—C7B	176.66 (13)
C8A—C7A—O2A—C1A	174.90 (15)	C8B—C7B—O2B—C1B	172.56 (15)
C13A—C12A—O3A—C15A	1.2 (2)	C13B—C12B—O3B—C15B	−176.74 (16)
C11A—C12A—O3A—C15A	−179.54 (15)	C11B—C12B—O3B—C15B	2.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4A—H4A···O1Bⁱ	0.99	2.64	3.530 (2)	150
C7A—H7B···O1Aⁱⁱ	0.99	2.60	3.546 (2)	160
C15A—H15B···O2Bⁱⁱⁱ	0.98	2.60	3.501 (2)	153
C5B—H5D···O1B^iv	0.99	2.55	3.463 (2)	153
C7B—H7C···O1B^v	0.99	2.71	3.490 (2)	137
C15B—H15E···O2A^vi	0.98	2.64	3.438 (2)	139
C13B—H13B···Cg	0.95	2.83	3.531 (2)	131

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₉NO₃
M_r	261.31
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.7056 (4), 9.7763 (3), 15.0413 (5)
α, β, γ (°)	93.126 (2), 92.987 (2), 103.301 (2)
V (Å³)	1383.77 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.54 × 0.21 × 0.14

Data collection
Diffractometer	Bruker APEX II CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11703, 6666, 3779
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.120, 0.94
No. of reflections	6666
No. of parameters	347
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.22

Computer programs: APEX2 (Bruker, 2005), APEX2, SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Selected torsion angles (º) top

C10A—C9A—N1A—C3A	76.2 (2)	C10B—C9B—N1B—C3B	51.5 (2)
C13A—C12A—O3A—C15A	1.2 (2)	C13B—C12B—O3B—C15B	−176.74 (16)