(Z)-Ethyl 2-oxo-3-(1,2-dihydroquinolin-2-yl­idene)propano­ate

Valkonen, A.; Kolehmainen, E.; Ośmiałowski, B.; Gawinecki, R.

doi:10.1107/S160053681002324X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages o1746-o1747

doi:10.1107/S160053681002324X

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(Z)-Ethyl 2-oxo-3-(1,2-dihydroquinolin-2-ylidene)propanoate

Arto Valkonen,^a ^* Erkki Kolehmainen,^a Borys Ośmiałowski ^b and Ryszard Gawinecki ^b

^aDepartment of Chemistry, University of Jyväskylä, PO Box 35, FIN-40014 Jyväskylä, Finland, and ^bDepartment of Chemistry, University of Technology and Life Sciences, Seminaryjna 3, PL-85-326 Bydgoszcz, Poland
^*Correspondence e-mail: arto.m.valkonen@jyu.fi

(Received 9 June 2010; accepted 16 June 2010; online 23 June 2010)

Both independent molecules in the asymmetric unit of the tautomeric title compound, C₁₄H₁₃NO₃, a synthetic product obtained from 2-lithiomethylquinoline and diethyl oxalate, crystallize in the enaminone form with a Z configuration around the double bond. Intramolecular N—H⋯O hydrogen bonds occur, generating an S(6) graph-set motif. In the crystal, weak intermolecular C—H⋯O and π–π stacking interactions [centroid–centroid distances = 3.7020 (14)–3.7429 (13)Å] define a three-dimensional supramolecular network.

Related literature

The enaminone form is predominant in the crystalline state for 2-substituted quinolines, see: Kolehmainen et al. (2000 ); Loghmani-Khouzani et al. (2006 ). The enaminone form has been found to be the only tautomeric form present in a chloroform solution, see: More O'Ferrall & Murray (1994 ); Greenhill (1990 ). For the synthesis, see: Kolehmainen et al. (2000); Ośmiałowski et al. (2002 , 2003 ). For its melting point, see: Stock et al. (1958 ); Leonard & Boyer (1950 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For π–π stacking interactions, see: Meyer et al. (2003 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₃NO₃
M_r = 243.25
Monoclinic, P 2₁ /n
a = 7.8367 (3) Å
b = 11.9726 (6) Å
c = 25.3156 (13) Å
β = 99.019 (3)°
V = 2345.89 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.15 × 0.15 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
12368 measured reflections
4210 independent reflections
2528 reflections with I > 2σ(I)
R_int = 0.084

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.124
S = 1.01
4210 reflections
331 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O12	0.92 (2)	1.78 (2)	2.582 (2)	144 (2)
N1A—H1A⋯O12A	0.91 (2)	1.87 (2)	2.633 (2)	141 (2)
C7—H7⋯O13A	0.95	2.50	3.203 (3)	131
C8—H8⋯O12A	0.95	2.51	3.456 (3)	172
C8A—H8A⋯O12	0.95	2.52	3.412 (3)	156
C16A—H16D⋯O13ⁱ	0.98	2.46	3.379 (3)	156
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Bruker, 2002 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and Mercury (Macrae et al., 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002324X/jj2040sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002324X/jj2040Isup2.hkl

checkCIF report

Comment top

In 2-subtituted quinolines, in which the substituent contains a carbonyl group at the β-position, the enaminone form is predominant in the crystalline state, particularily at temperatures far below 0 °C (Kolehmainen et al., 2000; Loghmani-Khouzani et al., 2006). The title compound, (I), C₁₄H₁₃NO₃, (Fig. 1) exhibits similar behavior. Early studies were not able to determine whether the enaminone, form (I, Fig. 2) or enol,form ((Z)-ethyl 2-hydroxy-3-(quinolin-2-yl) acrylate (II)), was pesent in a methanol solution (Stock et al., 1958). However, the enaminone form (I) has been found to be the only tautomeric form present in a chloroform solution (More O'Ferrall & Murray, 1994; Greenhill, 1990). Since the enol form, (Z)-ethyl 2-hydroxy-3-(pyridin-2-yl)acrylate (III), was the only tautomer detected in the chloroform solution of a pyridinyl derivative (More O'Ferrall & Murray, 1994), this suggests that benzo-annulation may be responsible for the higher stability of the enaminone form (I) over the enol form (II).

In the title compound, (I), the (Z)-configuration around double bond is observed in each of the two independent molecules in the asymmetric unit (Fig. 1) with only small deviations in the side chain dihedral angles. Intramolecular N—H···O hydrogen bonds (Table 1), generating an S(6) graph set motif (Bernstein et al., 1995) are observed resulting from a (Z) configuration around C2═C11. The double-bonded O atoms are located on the same side of the C—C bond between carbonyl groups (s-cis conformation). Bond distances and angles are in normal ranges (Allen et al., 1987). In addition, weak intermolecular C—H···O interactions (Table 1) as well as π–π stacking interactions with reasonable closest C···C distances (about 3.4 Å, Meyer et al., 2003) are found and contribute to crystal structure stabilization.

Related literature top

The enaminone form is predominant in the crystalline state for 2-substituted quinolines, see: Kolehmainen et al. (2000); Loghmani-Khouzani et al. (2006). The enaminone form has been found to be the only tautomeric form present in a chloroform solution, see: More O'Ferrall & Murray (1994); Greenhill (1990). For the synthesis, see: Kolehmainen et al. (2000); Ośmiałowski et al. (2002, 2003). For its melting point, see: Stock et al. (1958); Leonard & Boyer (1950). For hydrogen-bond motifs, see: Bernstein et al. (1995). For π–π stacking interactions, see: Meyer et al. (2003). For bond-length data, see: Allen et al. (1987).

Experimental top

(Z)-Ethyl 2-oxo-3-(quinolin-2(1H)-ylidene)propanoate was obtained from equimolar starting quantities of 2-lithiomethylquinoline and diethyl oxalate following procedures described (Kolehmainen et al., 2000; Ośmiałowski et al., 2002; Ośmiałowski et al., 2003). The product melts at 132–134 °C (EtOH) [lit. mp 130.8–131.6 °C (Stock et al., 1958); 132 °C (Leonard & Boyer, 1950)]. Suitable single crystals for X-ray diffraction were obtained by very slow evaporation of analytical sample from NMR-tube, where CDCl₃ was used as a solvent.

Computing details top

Data collection: COLLECT (Bruker, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Figures top

	Fig. 1. View of the asymmetric unit of title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
	Fig. 2. Chemical formula and structural diagrams for (Z)-Ethyl 2-oxo-3-(quinolin-2(1H)-ylidene)propanoate (I), (Z)-ethyl 2-hydroxy-3-(quinolin-2-yl)acrylate (II) and (Z)-ethyl 2-hydroxy-3-(pyridin-2-yl)acrylate (III).
	Fig. 3. Packing diagram of the title compound showing the non-covalent N—H···O and C—H···O interactions.

(Z)-Ethyl 2-oxo-3-(1,2-dihydroquinolin-2-ylidene)propanoate top

Crystal data top

C₁₄H₁₃NO₃	F(000) = 1024
M_r = 243.25	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6418 reflections
a = 7.8367 (3) Å	θ = 0.4–26.0°
b = 11.9726 (6) Å	µ = 0.10 mm⁻¹
c = 25.3156 (13) Å	T = 173 K
β = 99.019 (3)°	Block, orange
V = 2345.89 (19) Å³	0.15 × 0.15 × 0.10 mm
Z = 8

Data collection top

Bruker–Nonius KappaCCD diffractometer	2528 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.084
Graphite monochromator	θ_max = 25.3°, θ_min = 2.4°
Detector resolution: 9 pixels mm^-1	h = −8→9
ϕ and ω scans	k = −14→14
12368 measured reflections	l = −28→30
4210 independent reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0505P)² + 0.2151P] where P = (F_o² + 2F_c²)/3
4210 reflections	(Δ/σ)_max < 0.001
331 parameters	Δρ_max = 0.19 e Å⁻³
2 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₄H₁₃NO₃	V = 2345.89 (19) Å³
M_r = 243.25	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.8367 (3) Å	µ = 0.10 mm⁻¹
b = 11.9726 (6) Å	T = 173 K
c = 25.3156 (13) Å	0.15 × 0.15 × 0.10 mm
β = 99.019 (3)°

Data collection top

Bruker–Nonius KappaCCD diffractometer	2528 reflections with I > 2σ(I)
12368 measured reflections	R_int = 0.084
4210 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	2 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.19 e Å⁻³
4210 reflections	Δρ_min = −0.20 e Å⁻³
331 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
O12	0.48192 (19)	0.58816 (12)	0.21420 (6)	0.0317 (4)
O13	0.3793 (2)	0.59651 (14)	0.10532 (7)	0.0421 (5)
O14	0.32200 (19)	0.77845 (12)	0.11502 (6)	0.0312 (4)
N1	0.6755 (2)	0.68740 (15)	0.29211 (8)	0.0258 (5)
H1	0.614 (3)	0.6287 (15)	0.2746 (9)	0.031*
C2	0.6575 (3)	0.78169 (18)	0.26243 (9)	0.0249 (5)
C3	0.7474 (3)	0.87881 (18)	0.28434 (9)	0.0269 (5)
H3	0.7378	0.9465	0.2645	0.032*
C4	0.8464 (3)	0.87531 (18)	0.33324 (9)	0.0287 (6)
H4	0.9037	0.9410	0.3476	0.034*
C5	0.9698 (3)	0.76496 (19)	0.41398 (9)	0.0292 (6)
H5	1.0306	0.8285	0.4296	0.035*
C6	0.9840 (3)	0.6654 (2)	0.44071 (10)	0.0337 (6)
H6	1.0558	0.6598	0.4745	0.040*
C7	0.8932 (3)	0.57168 (19)	0.41838 (10)	0.0335 (6)
H7	0.9026	0.5032	0.4376	0.040*
C8	0.7908 (3)	0.57718 (19)	0.36916 (9)	0.0293 (6)
H8	0.7298	0.5132	0.3542	0.035*
C9	0.7778 (3)	0.67895 (18)	0.34137 (9)	0.0239 (5)
C10	0.8656 (3)	0.77435 (18)	0.36343 (9)	0.0239 (5)
C11	0.5546 (3)	0.77913 (18)	0.21150 (9)	0.0268 (6)
H11	0.5380	0.8460	0.1911	0.032*
C12	0.4772 (3)	0.68116 (19)	0.19047 (9)	0.0268 (5)
C13	0.3875 (3)	0.67949 (19)	0.13238 (9)	0.0274 (6)
C15	0.2399 (3)	0.7798 (2)	0.05944 (9)	0.0368 (6)
H15A	0.1482	0.7223	0.0533	0.044*
H15B	0.3260	0.7639	0.0357	0.044*
C16	0.1634 (3)	0.8941 (2)	0.04784 (11)	0.0440 (7)
H16A	0.1069	0.8977	0.0105	0.066*
H16B	0.2552	0.9504	0.0540	0.066*
H16C	0.0781	0.9089	0.0715	0.066*
O12A	0.53371 (19)	0.35331 (12)	0.32136 (6)	0.0321 (4)
O13A	0.7560 (2)	0.31949 (14)	0.41590 (7)	0.0503 (5)
O14A	0.67498 (19)	0.14041 (13)	0.41249 (6)	0.0329 (4)
N1A	0.3651 (2)	0.25757 (16)	0.23504 (7)	0.0252 (5)
H1A	0.408 (3)	0.3175 (15)	0.2546 (8)	0.030*
C2A	0.4166 (3)	0.15861 (18)	0.25803 (9)	0.0244 (5)
C3A	0.3623 (3)	0.05969 (18)	0.22881 (9)	0.0280 (5)
H3A	0.3991	−0.0111	0.2433	0.034*
C4A	0.2594 (3)	0.06522 (19)	0.18088 (9)	0.0291 (6)
H4A	0.2233	−0.0018	0.1623	0.035*
C5A	0.0960 (3)	0.1818 (2)	0.10830 (9)	0.0302 (6)
H5A	0.0552	0.1170	0.0886	0.036*
C6A	0.0484 (3)	0.2854 (2)	0.08803 (10)	0.0325 (6)
H6A	−0.0277	0.2920	0.0550	0.039*
C7A	0.1120 (3)	0.38156 (19)	0.11605 (9)	0.0320 (6)
H7A	0.0812	0.4532	0.1014	0.038*
C8A	0.2188 (3)	0.37321 (18)	0.16452 (9)	0.0288 (6)
H8A	0.2626	0.4385	0.1832	0.035*
C9A	0.2620 (3)	0.26763 (18)	0.18590 (9)	0.0237 (5)
C10A	0.2041 (3)	0.17018 (18)	0.15768 (9)	0.0242 (5)
C11A	0.5169 (3)	0.15734 (19)	0.30907 (9)	0.0269 (5)
H11A	0.5509	0.0873	0.3250	0.032*
C12A	0.5685 (3)	0.25474 (18)	0.33731 (9)	0.0261 (5)
C13A	0.6777 (3)	0.24376 (19)	0.39235 (10)	0.0292 (6)
C15A	0.7745 (3)	0.12443 (19)	0.46547 (9)	0.0333 (6)
H15C	0.7326	0.1753	0.4915	0.040*
H15D	0.8981	0.1404	0.4649	0.040*
C16A	0.7511 (3)	0.0051 (2)	0.48090 (10)	0.0416 (7)
H16D	0.8166	−0.0088	0.5166	0.062*
H16E	0.7933	−0.0444	0.4549	0.062*
H16F	0.6283	−0.0096	0.4813	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O12	0.0432 (10)	0.0213 (9)	0.0289 (10)	−0.0031 (7)	0.0007 (7)	−0.0004 (8)
O13	0.0670 (12)	0.0272 (10)	0.0301 (11)	0.0047 (8)	0.0012 (9)	−0.0086 (8)
O14	0.0386 (9)	0.0263 (9)	0.0260 (10)	0.0032 (7)	−0.0032 (7)	−0.0021 (7)
N1	0.0286 (10)	0.0194 (11)	0.0290 (12)	−0.0041 (8)	0.0038 (9)	−0.0044 (9)
C2	0.0268 (12)	0.0195 (13)	0.0299 (14)	0.0006 (9)	0.0093 (10)	−0.0025 (10)
C3	0.0329 (13)	0.0161 (12)	0.0322 (14)	−0.0017 (10)	0.0062 (10)	0.0007 (10)
C4	0.0324 (13)	0.0216 (13)	0.0326 (15)	−0.0031 (10)	0.0065 (11)	−0.0062 (11)
C5	0.0315 (13)	0.0269 (14)	0.0288 (14)	−0.0041 (10)	0.0038 (10)	−0.0068 (11)
C6	0.0376 (14)	0.0344 (15)	0.0283 (15)	−0.0009 (11)	0.0026 (11)	0.0000 (12)
C7	0.0410 (14)	0.0273 (14)	0.0329 (15)	−0.0010 (11)	0.0083 (11)	0.0051 (12)
C8	0.0325 (13)	0.0245 (13)	0.0315 (15)	−0.0015 (10)	0.0072 (10)	−0.0025 (11)
C9	0.0247 (11)	0.0244 (13)	0.0236 (13)	0.0011 (9)	0.0066 (9)	−0.0026 (11)
C10	0.0238 (11)	0.0233 (13)	0.0257 (14)	−0.0013 (9)	0.0075 (10)	−0.0021 (10)
C11	0.0321 (12)	0.0201 (13)	0.0278 (14)	0.0014 (10)	0.0032 (10)	−0.0007 (10)
C12	0.0284 (12)	0.0249 (14)	0.0278 (14)	0.0024 (10)	0.0065 (10)	−0.0018 (11)
C13	0.0315 (13)	0.0228 (13)	0.0285 (14)	0.0000 (10)	0.0063 (10)	−0.0011 (11)
C15	0.0466 (15)	0.0375 (15)	0.0237 (14)	0.0065 (12)	−0.0019 (11)	−0.0029 (12)
C16	0.0548 (17)	0.0366 (16)	0.0371 (16)	0.0038 (13)	−0.0035 (13)	0.0012 (13)
O12A	0.0420 (9)	0.0223 (9)	0.0301 (10)	0.0008 (7)	−0.0001 (7)	0.0032 (8)
O13A	0.0767 (13)	0.0298 (10)	0.0369 (12)	−0.0185 (9)	−0.0147 (10)	0.0029 (9)
O14A	0.0446 (10)	0.0260 (10)	0.0241 (10)	−0.0024 (7)	−0.0072 (7)	0.0031 (7)
N1A	0.0299 (11)	0.0231 (11)	0.0218 (11)	−0.0021 (8)	0.0019 (8)	−0.0017 (9)
C2A	0.0285 (12)	0.0220 (13)	0.0237 (13)	−0.0001 (10)	0.0080 (10)	0.0012 (10)
C3A	0.0379 (13)	0.0195 (13)	0.0274 (14)	−0.0002 (10)	0.0081 (10)	−0.0001 (11)
C4A	0.0352 (13)	0.0238 (13)	0.0287 (14)	−0.0055 (10)	0.0061 (10)	−0.0044 (11)
C5A	0.0281 (12)	0.0332 (15)	0.0285 (14)	−0.0037 (10)	0.0024 (10)	−0.0057 (11)
C6A	0.0313 (13)	0.0353 (15)	0.0285 (14)	0.0024 (11)	−0.0026 (10)	−0.0032 (12)
C7A	0.0378 (14)	0.0252 (14)	0.0314 (15)	0.0054 (11)	0.0001 (11)	0.0033 (11)
C8A	0.0333 (13)	0.0233 (13)	0.0287 (14)	0.0008 (10)	0.0015 (10)	−0.0036 (11)
C9A	0.0224 (12)	0.0252 (13)	0.0241 (13)	−0.0009 (9)	0.0056 (9)	0.0015 (10)
C10A	0.0229 (11)	0.0244 (13)	0.0260 (14)	−0.0023 (9)	0.0061 (10)	−0.0034 (10)
C11A	0.0364 (13)	0.0207 (13)	0.0232 (13)	0.0005 (10)	0.0032 (10)	0.0018 (10)
C12A	0.0308 (13)	0.0231 (13)	0.0243 (13)	−0.0001 (10)	0.0040 (10)	0.0013 (11)
C13A	0.0385 (14)	0.0225 (13)	0.0268 (14)	−0.0017 (11)	0.0054 (10)	0.0029 (11)
C15A	0.0407 (14)	0.0339 (15)	0.0217 (14)	−0.0022 (11)	−0.0062 (10)	0.0025 (11)
C16A	0.0559 (17)	0.0354 (15)	0.0291 (15)	0.0009 (12)	−0.0065 (12)	0.0053 (12)

Geometric parameters (Å, º) top

O12—C12	1.263 (3)	O12A—C12A	1.263 (3)
O13—C13	1.203 (3)	O13A—C13A	1.199 (3)
O14—C13	1.338 (3)	O14A—C13A	1.340 (3)
O14—C15	1.453 (3)	O14A—C15A	1.454 (2)
N1—C2	1.351 (3)	N1A—C2A	1.353 (3)
N1—C9	1.376 (3)	N1A—C9A	1.378 (3)
N1—H1	0.924 (15)	N1A—H1A	0.905 (15)
C2—C11	1.410 (3)	C2A—C11A	1.403 (3)
C2—C3	1.426 (3)	C2A—C3A	1.426 (3)
C3—C4	1.355 (3)	C3A—C4A	1.349 (3)
C3—H3	0.9500	C3A—H3A	0.9500
C4—C10	1.425 (3)	C4A—C10A	1.426 (3)
C4—H4	0.9500	C4A—H4A	0.9500
C5—C6	1.367 (3)	C5A—C6A	1.371 (3)
C5—C10	1.410 (3)	C5A—C10A	1.403 (3)
C5—H5	0.9500	C5A—H5A	0.9500
C6—C7	1.400 (3)	C6A—C7A	1.403 (3)
C6—H6	0.9500	C6A—H6A	0.9500
C7—C8	1.374 (3)	C7A—C8A	1.376 (3)
C7—H7	0.9500	C7A—H7A	0.9500
C8—C9	1.403 (3)	C8A—C9A	1.396 (3)
C8—H8	0.9500	C8A—H8A	0.9500
C9—C10	1.403 (3)	C9A—C10A	1.406 (3)
C11—C12	1.388 (3)	C11A—C12A	1.394 (3)
C11—H11	0.9500	C11A—H11A	0.9500
C12—C13	1.528 (3)	C12A—C13A	1.523 (3)
C15—C16	1.505 (3)	C15A—C16A	1.500 (3)
C15—H15A	0.9900	C15A—H15C	0.9900
C15—H15B	0.9900	C15A—H15D	0.9900
C16—H16A	0.9800	C16A—H16D	0.9800
C16—H16B	0.9800	C16A—H16E	0.9800
C16—H16C	0.9800	C16A—H16F	0.9800

C13—O14—C15	114.65 (17)	C13A—O14A—C15A	115.73 (17)
C2—N1—C9	124.10 (19)	C2A—N1A—C9A	123.90 (19)
C2—N1—H1	111.6 (14)	C2A—N1A—H1A	113.6 (14)
C9—N1—H1	124.3 (14)	C9A—N1A—H1A	122.5 (14)
N1—C2—C11	119.05 (19)	N1A—C2A—C11A	119.5 (2)
N1—C2—C3	117.6 (2)	N1A—C2A—C3A	117.3 (2)
C11—C2—C3	123.4 (2)	C11A—C2A—C3A	123.2 (2)
C4—C3—C2	120.5 (2)	C4A—C3A—C2A	120.9 (2)
C4—C3—H3	119.8	C4A—C3A—H3A	119.5
C2—C3—H3	119.8	C2A—C3A—H3A	119.5
C3—C4—C10	120.9 (2)	C3A—C4A—C10A	120.9 (2)
C3—C4—H4	119.6	C3A—C4A—H4A	119.5
C10—C4—H4	119.6	C10A—C4A—H4A	119.5
C6—C5—C10	120.6 (2)	C6A—C5A—C10A	121.0 (2)
C6—C5—H5	119.7	C6A—C5A—H5A	119.5
C10—C5—H5	119.7	C10A—C5A—H5A	119.5
C5—C6—C7	120.2 (2)	C5A—C6A—C7A	119.9 (2)
C5—C6—H6	119.9	C5A—C6A—H6A	120.0
C7—C6—H6	119.9	C7A—C6A—H6A	120.0
C8—C7—C6	121.0 (2)	C8A—C7A—C6A	120.7 (2)
C8—C7—H7	119.5	C8A—C7A—H7A	119.7
C6—C7—H7	119.5	C6A—C7A—H7A	119.7
C7—C8—C9	118.9 (2)	C7A—C8A—C9A	119.2 (2)
C7—C8—H8	120.6	C7A—C8A—H8A	120.4
C9—C8—H8	120.6	C9A—C8A—H8A	120.4
N1—C9—C8	120.3 (2)	N1A—C9A—C8A	120.1 (2)
N1—C9—C10	118.7 (2)	N1A—C9A—C10A	118.89 (19)
C8—C9—C10	121.0 (2)	C8A—C9A—C10A	121.0 (2)
C9—C10—C5	118.3 (2)	C5A—C10A—C9A	118.2 (2)
C9—C10—C4	118.2 (2)	C5A—C10A—C4A	123.8 (2)
C5—C10—C4	123.5 (2)	C9A—C10A—C4A	117.98 (19)
C12—C11—C2	121.5 (2)	C12A—C11A—C2A	122.6 (2)
C12—C11—H11	119.3	C12A—C11A—H11A	118.7
C2—C11—H11	119.3	C2A—C11A—H11A	118.7
O12—C12—C11	125.8 (2)	O12A—C12A—C11A	125.9 (2)
O12—C12—C13	114.90 (19)	O12A—C12A—C13A	115.81 (19)
C11—C12—C13	119.2 (2)	C11A—C12A—C13A	118.2 (2)
O13—C13—O14	124.1 (2)	O13A—C13A—O14A	123.1 (2)
O13—C13—C12	122.3 (2)	O13A—C13A—C12A	124.1 (2)
O14—C13—C12	113.55 (19)	O14A—C13A—C12A	112.81 (18)
O14—C15—C16	107.56 (19)	O14A—C15A—C16A	107.21 (18)
O14—C15—H15A	110.2	O14A—C15A—H15C	110.3
C16—C15—H15A	110.2	C16A—C15A—H15C	110.3
O14—C15—H15B	110.2	O14A—C15A—H15D	110.3
C16—C15—H15B	110.2	C16A—C15A—H15D	110.3
H15A—C15—H15B	108.5	H15C—C15A—H15D	108.5
C15—C16—H16A	109.5	C15A—C16A—H16D	109.5
C15—C16—H16B	109.5	C15A—C16A—H16E	109.5
H16A—C16—H16B	109.5	H16D—C16A—H16E	109.5
C15—C16—H16C	109.5	C15A—C16A—H16F	109.5
H16A—C16—H16C	109.5	H16D—C16A—H16F	109.5
H16B—C16—H16C	109.5	H16E—C16A—H16F	109.5

C9—N1—C2—C11	177.4 (2)	C9A—N1A—C2A—C11A	−177.9 (2)
C9—N1—C2—C3	−1.5 (3)	C9A—N1A—C2A—C3A	1.0 (3)
N1—C2—C3—C4	−0.2 (3)	N1A—C2A—C3A—C4A	−1.9 (3)
C11—C2—C3—C4	−179.0 (2)	C11A—C2A—C3A—C4A	177.0 (2)
C2—C3—C4—C10	1.2 (4)	C2A—C3A—C4A—C10A	1.0 (3)
C10—C5—C6—C7	−0.8 (4)	C10A—C5A—C6A—C7A	1.9 (4)
C5—C6—C7—C8	1.0 (4)	C5A—C6A—C7A—C8A	−1.6 (4)
C6—C7—C8—C9	−0.2 (4)	C6A—C7A—C8A—C9A	−0.6 (4)
C2—N1—C9—C8	−179.1 (2)	C2A—N1A—C9A—C8A	−178.3 (2)
C2—N1—C9—C10	2.0 (3)	C2A—N1A—C9A—C10A	0.8 (3)
C7—C8—C9—N1	−179.7 (2)	C7A—C8A—C9A—N1A	−178.3 (2)
C7—C8—C9—C10	−0.8 (3)	C7A—C8A—C9A—C10A	2.7 (3)
N1—C9—C10—C5	179.9 (2)	C6A—C5A—C10A—C9A	0.1 (3)
C8—C9—C10—C5	1.0 (3)	C6A—C5A—C10A—C4A	−179.6 (2)
N1—C9—C10—C4	−0.9 (3)	N1A—C9A—C10A—C5A	178.5 (2)
C8—C9—C10—C4	−179.7 (2)	C8A—C9A—C10A—C5A	−2.4 (3)
C6—C5—C10—C9	−0.2 (3)	N1A—C9A—C10A—C4A	−1.7 (3)
C6—C5—C10—C4	−179.4 (2)	C8A—C9A—C10A—C4A	177.3 (2)
C3—C4—C10—C9	−0.7 (3)	C3A—C4A—C10A—C5A	−179.4 (2)
C3—C4—C10—C5	178.6 (2)	C3A—C4A—C10A—C9A	0.9 (3)
N1—C2—C11—C12	−2.5 (3)	N1A—C2A—C11A—C12A	−0.9 (3)
C3—C2—C11—C12	176.3 (2)	C3A—C2A—C11A—C12A	−179.7 (2)
C2—C11—C12—O12	3.6 (4)	C2A—C11A—C12A—O12A	−0.2 (4)
C2—C11—C12—C13	−171.9 (2)	C2A—C11A—C12A—C13A	−179.8 (2)
C15—O14—C13—O13	−0.9 (3)	C15A—O14A—C13A—O13A	−0.2 (3)
C15—O14—C13—C12	178.48 (19)	C15A—O14A—C13A—C12A	−179.0 (2)
O12—C12—C13—O13	−26.2 (3)	O12A—C12A—C13A—O13A	−14.1 (4)
C11—C12—C13—O13	149.7 (2)	C11A—C12A—C13A—O13A	165.5 (2)
O12—C12—C13—O14	154.39 (19)	O12A—C12A—C13A—O14A	164.6 (2)
C11—C12—C13—O14	−29.7 (3)	C11A—C12A—C13A—O14A	−15.7 (3)
C13—O14—C15—C16	176.16 (19)	C13A—O14A—C15A—C16A	178.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12	0.92 (2)	1.78 (2)	2.582 (2)	144 (2)
N1A—H1A···O12A	0.91 (2)	1.87 (2)	2.633 (2)	141 (2)
C7—H7···O13A	0.95	2.50	3.203 (3)	131
C8—H8···O12A	0.95	2.51	3.456 (3)	172
C8A—H8A···O12	0.95	2.52	3.412 (3)	156
C16A—H16D···O13ⁱ	0.98	2.46	3.379 (3)	156

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO₃
M_r	243.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	7.8367 (3), 11.9726 (6), 25.3156 (13)
β (°)	99.019 (3)
V (Å³)	2345.89 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12368, 4210, 2528
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.124, 1.01
No. of reflections	4210
No. of parameters	331
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20

Computer programs: COLLECT (Bruker, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O12	0.924 (15)	1.776 (18)	2.582 (2)	144 (2)
N1A—H1A···O12A	0.905 (15)	1.870 (18)	2.633 (2)	140.6 (19)
C7—H7···O13A	0.95	2.50	3.203 (3)	130.6
C8—H8···O12A	0.95	2.51	3.456 (3)	171.8
C8A—H8A···O12	0.95	2.52	3.412 (3)	156.3
C16A—H16D···O13ⁱ	0.98	2.46	3.379 (3)	156.2

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

Academy Professor Kari Rissanen and the Academy of Finland (project No. 212588) are thanked for financial support to AV.

References

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