1-(3-Phenyl­isoxazol-5-yl)cyclo­hexane-1,2-diol

Astudillo, L.; Brito, I.; Vallejos, G.; Gutíerrez, M.; López-Rodríguez, M.

doi:10.1107/S1600536809020947

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages o1509-o1510

doi:10.1107/S1600536809020947

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1-(3-Phenylisoxazol-5-yl)cyclohexane-1,2-diol

Luis Astudillo,^a Iván Brito,^b ^* Gabriel Vallejos,^c Margarita Gutíerrez ^a and Matías López-Rodríguez ^d

^aLaboratorio de Síntesis Orgánica, Instituto de Química de Recursos Naturales, Universidad de Talca, Casilla 747, Talca, Chile, ^bDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, ^cLaboratorio de Bioorgánica, Instituto de Química, Facultad de Ciencias, Universidad Austral de Chile, Casilla 567, Isla Teja S/N, Valdivia, Chile, and ^dInstituto de Bio-Orgánica `Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez N°2, La Laguna, Tenerife, Spain
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 25 May 2009; accepted 2 June 2009; online 6 June 2009)

In the title compound, C₁₅H₁₇NO₃, there are two molecules in the asymmetric unit wherein the isoxazole rings make dihedral angles of 16.16 (15) and 16.79 (13)° with the benzene rings, and the cyclohexane rings adopt chair conformations. In both molecules, the hydroxyl groups of the diol fragments are cis oriented, the O—C—C—O torsion angles being 60.76 (12) and −55.86 (11)°. The two molecules are linked by a strong O—H⋯N hydrogen bond and the crystal packing is stabilized by one O—H⋯N and two O—H⋯O hydrogen bonds. An intramolecular O—H⋯O hydrogen bond is observed in one of the molecules.

Related literature

For the uses of potassium permanganate in functional group interconversion inorganic chemistry, see: Singh & Lee (2001 ). For the use of permanganate in the preparation of natural products, see: Brown et al. (2008 ); Morris et al. (2009 ). For isoxazoles as versatile building blocks in organic synthesis, see: Melo (2005 ). For the synthesis, see: Hansen et al. (2005 ). For a related structure, see: Vallejos et al. (2009 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₅H₁₇NO₃
M_r = 259.3
Triclinic, $[P \overline 1]$
a = 9.4894 (17) Å
b = 11.5593 (15) Å
c = 14.0083 (13) Å
α = 73.02 (2)°
β = 81.62 (4)°
γ = 66.71 (5)°
V = 1349.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.21 × 0.10 × 0.09 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: none
10826 measured reflections
5863 independent reflections
4447 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.168
S = 1.14
5863 reflections
347 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.82	2.42	2.822 (2)	111
O2—H2⋯N2ⁱ	0.82	2.32	3.070 (3)	153
O3—H3⋯O5ⁱⁱ	0.82	2.27	3.054 (2)	159
O5—H5⋯O3ⁱⁱⁱ	0.82	2.12	2.923 (3)	167
O6—H6⋯N1	0.82	2.10	2.915 (3)	173
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z; (iii) x-1, y, z.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020947/pv2162sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020947/pv2162Isup2.hkl

checkCIF report

Comment top

Potassium permanganate has been used vastly in functional group interconversion inorganic chemistry, (e.g., to oxidize alcohols to carbonyl compounds, for the cleavage or oxidation of carbon-carbon double bonds, oxidation of diols to lactones, and sulfides to sulfones (Singh & Lee, 2001). Permanganate has been used for the preparation of natural products as sylvaticin (Brown et al., 2008) and membrarollin (Morris et al., 2009) among others. In our search for bioactive nitrogen-containing compounds, we decided to oxidize 5-cyclohex-1-enyl-3-phenylisoxazole utilizing permanganate to obtain the title compound, since isoxazoles are a class of heterocyclic compounds having a remarkable number of applications and have been demonstrated to be very versatile building blocks in organic synthesis (Melo, 2005). We report here the crystal structure of the title compound.

In the crystal structure of the title compound, there two molecules in the asymmetric unit (Fig. 1). The isoxazole rings in the two molecules make dihedral angles of 16.16 (15) and 16.79 (12)° with the phenyl rings. In both molecules, the hydroxyl groups of the diol fragments are cis oriented, the O—C—C—O torsion angles being 60.76 (12) and -55.86 (11)°. The cyclohexane rings in both molecules adopt chair conformations as shown by the Cremer & Pople (1975) puckering parameters: Q = 0.570 (2) and 0.571 (3) Å, θ = 1.0 (2) and 0.0 (3)°, and ϕ = 292 (19) and 279 (9)°], respectively. Both of the molecules are linked by a strong O—H···N hydrogen bond and the crystal packing is stabilized by one O—H···N and two O—H···O type hydrogen bonds. Intramolecular O—H···O hydrogen bonds are observed in one of the molecules; details of hydrogen bonding geometry have been provided in Table 1. The crystal structure of a very closely related compound to (I) has been recently reported from our laboratory (Vallejos et al., 2009).

Related literature top

For the uses of potassium permanganate in functional group

interconversion inorganic chemistry, see: Singh & Lee (2001). For the use of permanganate in the preparation of natural products, see: Brown et al. (2008); Morris et al. (2009). For isoxazoles as versatile building blocks in organic synthesis, see: Melo (2005). For the synthesis, see: Hansen et al. (2005). For a related structure, see: Vallejos et al. (2009). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

5-Cyclohex-1-enyl-3-phenylisoxazole 1 was prepared according to the procedure described by Hansen et al. (2005), from benzaldehyde (2.00 ml, 20 mmol, Merck), hydroxylamine hydrochloride (1.46 g, 21 mmol), chloramine-T trihydrate (5.9 g, 21 mmol) and 1-ethynylcyclohexene (2.25 ml, 21 mmol, Aldrich), giving off-white solid (yield 93%).

1-(3-Phenyl-5-isoxazolyl)-1,2-cyclohexanediol (II), Scheme 2: To a mixture of dichloromethane (25 ml), water (25 ml) and tetrabutylammonium bromide (1.00 g) as phase transfer catalyst, were added 5-cyclohex-1-enyl-3-phenylisoxazole 1 (1.00 g, 4.4 mmol) and KMnO₄ (2.78 g, 17.6 mmol). After dissolution, the reaction mixture was cooled at 273–283 K and vigorously stirred. Thereafter, the reaction mixture was sonicated for 30 min. The reaction was then quenched with sufficient ice cooled saturated Na₂S₂O₅ (aq)to dissolve all of the manganese salts and the aqueous layer was saturated with NaCl then extracted repeatedly using dichloromethane. The organic layer was separated and dried (Na₂SO₄), concentrated in vacuo and the resulting product was purified by column chromatography (silica gel, petroleum ether, EtOAc) to afford pure title compound, giving off-white solid (yield 32%). Yellow block-shaped crystals of the title compound suitable for X-ray analysis were grown from a hexane/EtOAc solution (1:1 v/v) at 298 K over a period of a few days.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP-3 (Farrugia, 1997) view of the two molecules in the asymmetric unit of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are drawn as small spheres of arbitrary radii and intramolecular hydrogen bonds indicated by dashed lines.
	Fig. 2. The formation of the title compound.

1-(3-Phenylisoxazol-5-yl)cyclohexane-1,2-diol top

Crystal data top

C₁₅H₁₇NO₃	Z = 4
M_r = 259.3	F(000) = 552
Triclinic, P1	D_x = 1.277 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.4894 (17) Å	Cell parameters from 5863 reflections
b = 11.5593 (15) Å	θ = 1.9–27.1°
c = 14.0083 (13) Å	µ = 0.09 mm⁻¹
α = 73.02 (2)°	T = 298 K
β = 81.62 (4)°	Block, yellow
γ = 66.71 (5)°	0.21 × 0.10 × 0.09 mm
V = 1349.0 (3) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	4447 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.074
Graphite monochromator	θ_max = 27.1°, θ_min = 2.0°
ϕ scans, and ω scans with κ offsets	h = 0→12
10826 measured reflections	k = −13→14
5863 independent reflections	l = −17→17

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0709P)² + 0.2904P] where P = (F_o² + 2F_c²)/3
5863 reflections	(Δ/σ)_max < 0.001
347 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₅H₁₇NO₃	γ = 66.71 (5)°
M_r = 259.3	V = 1349.0 (3) Å³
Triclinic, P1	Z = 4
a = 9.4894 (17) Å	Mo Kα radiation
b = 11.5593 (15) Å	µ = 0.09 mm⁻¹
c = 14.0083 (13) Å	T = 298 K
α = 73.02 (2)°	0.21 × 0.10 × 0.09 mm
β = 81.62 (4)°

Data collection top

Nonius KappaCCD area-detector diffractometer	4447 reflections with I > 2σ(I)
10826 measured reflections	R_int = 0.074
5863 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.14	Δρ_max = 0.24 e Å⁻³
5863 reflections	Δρ_min = −0.19 e Å⁻³
347 parameters

Special details top

Experimental. Melting points were recorded on an Electrothermal 9100 instrument and are uncorrected; IR spectra were obtained on a Nicolet Nexus 470-FTIR spectrometer as potassium bromide pellets and are reported in wavenumbers (cm^-1). ¹H and ¹³CNMR spectra were measured on a Bruker AM-400 spectrometer (400 MHz), using CDCl₃as solvent. TMS was used as an internal standard. Chemical shifts (d) and J values are reported in p.p.m. and Hz, respectively. Reaction progress was monitored by means of thin-layer chromatography using Merck Kieselgel 60 (230–240 mesh). All reagents were purchased from Merck, Sigma and Aldrich Chemical Co. and used without further purification. Solvents were dried and distilled prior to use.

5-Cyclohex-1-enyl-3-phenylisoxazole 1: mp 361 (2) K. RMN-¹H (CDCl₃, 400 MHz, δ): 7,82 (2H, dd, J: 8,0 and 4,0); 7,45 (1H, m); 7,45 (2H, m); 6,67 (1H, br.s); 6,39 (1H, s); 2,40 (2H, m); 2,28 (2H, m); 1,80 (2H, m); 1,70 (2H, m). RMN-¹³C (CDCl3, 100 MHz, δ): 171.65, 162.44, 130.22, 129.79, 129.49, 128.85, 128.85, 126.77, 126.77, 125.41, 96.18, 25.44, 25.24, 22.12, 21.74.

The title compound (II): mp 418 (2) K. RMN-¹H (CDCl₃, 400 MHz, δ): 7,93 (2H, m); 7,59 (3H, m); 6,82 (1H, s); 4,13 (1H, dd, J = 12 and 4); 1,97 (8H, m). RMN-¹³C (CDCl₃,100 MHz, δ): 177.83, 161.86, 129.48, 128.42, 128.35, 128.35, 126.17, 126.17, 99.13, 73.28, 71.94, 35.11, 28.96, 23.26, 19.60. FT–IR (KBr pellet, cm^-1): ν 3395, 2940, 2863, 1598, 1468, 1404.

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
O1	0.62628 (16)	0.34815 (14)	−0.02283 (11)	0.0506 (4)
O2	0.93980 (15)	0.08165 (12)	0.11711 (11)	0.0402 (4)
H2	1.0099	0.109	0.1025	0.06*
O3	0.91802 (15)	0.33990 (12)	0.08949 (10)	0.0389 (4)
H3	0.9214	0.4003	0.1072	0.058*
O4	0.26135 (18)	0.12795 (13)	−0.00370 (11)	0.0484 (4)
O5	−0.00749 (16)	0.44685 (13)	−0.11911 (10)	0.0426 (4)
H5	−0.0304	0.4079	−0.064	0.064*
O6	0.29277 (15)	0.42716 (11)	−0.16284 (10)	0.0360 (3)
H6	0.3837	0.4082	−0.1543	0.054*
N1	0.6074 (2)	0.38177 (19)	−0.12650 (14)	0.0529 (5)
N2	0.2639 (2)	0.08580 (17)	0.10155 (13)	0.0482 (5)
C1	0.7962 (2)	0.18899 (17)	0.10844 (14)	0.0323 (4)
C2	0.6772 (3)	0.1367 (2)	0.17032 (16)	0.0455 (5)
H2A	0.576	0.2048	0.1596	0.055*
H2B	0.6781	0.0648	0.1476	0.055*
C3	0.7075 (3)	0.0904 (2)	0.28125 (18)	0.0549 (6)
H3A	0.6256	0.0639	0.3177	0.066*
H3B	0.803	0.0152	0.2933	0.066*
C4	0.7175 (3)	0.1971 (3)	0.31908 (18)	0.0616 (7)
H4A	0.7444	0.1631	0.3887	0.074*
H4B	0.6182	0.2681	0.3145	0.074*
C5	0.8374 (3)	0.2482 (2)	0.25845 (16)	0.0486 (6)
H5A	0.8385	0.3189	0.2819	0.058*
H5B	0.9382	0.1791	0.268	0.058*
C6	0.8032 (2)	0.29647 (17)	0.14842 (14)	0.0334 (4)
H6A	0.7037	0.3694	0.1392	0.04*
C7	0.7557 (2)	0.24037 (17)	0.00041 (15)	0.0331 (4)
C8	0.8209 (2)	0.20197 (17)	−0.08249 (14)	0.0346 (4)
H8	0.9095	0.1303	−0.0875	0.042*
C9	0.7250 (2)	0.29443 (19)	−0.16047 (15)	0.0378 (5)
C10	0.7449 (2)	0.3044 (2)	−0.26858 (16)	0.0437 (5)
C11	0.8477 (3)	0.2006 (3)	−0.30373 (18)	0.0608 (7)
H11	0.9012	0.1227	−0.2588	0.073*
C12	0.8715 (4)	0.2119 (4)	−0.4055 (2)	0.0849 (9)
H12	0.9409	0.1421	−0.429	0.102*
C13	0.7913 (5)	0.3277 (4)	−0.4720 (2)	0.0929 (11)
H13	0.8073	0.3359	−0.5403	0.111*
C14	0.6878 (4)	0.4311 (4)	−0.4375 (2)	0.0854 (10)
H14	0.6336	0.5085	−0.4826	0.102*
C15	0.6643 (3)	0.4202 (3)	−0.3370 (2)	0.0629 (7)
H15	0.5942	0.4904	−0.3142	0.075*
C16	0.2624 (2)	0.31090 (16)	−0.14292 (14)	0.0303 (4)
C17	0.0942 (2)	0.35473 (18)	−0.17172 (14)	0.0343 (4)
H17	0.0657	0.2781	−0.1537	0.041*
C18	0.0737 (2)	0.4167 (2)	−0.28265 (15)	0.0412 (5)
H18A	0.0924	0.4972	−0.3002	0.049*
H18B	−0.0314	0.438	−0.2984	0.049*
C19	0.1827 (3)	0.3262 (2)	−0.34394 (17)	0.0520 (6)
H19A	0.1708	0.3705	−0.4144	0.062*
H19B	0.1567	0.2498	−0.3318	0.062*
C20	0.3488 (3)	0.2838 (2)	−0.31744 (16)	0.0493 (6)
H20A	0.378	0.3592	−0.336	0.059*
H20B	0.415	0.2227	−0.355	0.059*
C21	0.3705 (2)	0.22007 (19)	−0.20610 (15)	0.0407 (5)
H21A	0.4761	0.1977	−0.1908	0.049*
H21B	0.3508	0.1401	−0.1889	0.049*
C22	0.2762 (2)	0.24539 (17)	−0.03319 (14)	0.0329 (4)
C23	0.2892 (2)	0.28088 (18)	0.04736 (14)	0.0347 (4)
H23	0.301	0.3566	0.0485	0.042*
C24	0.2811 (2)	0.17773 (18)	0.13034 (15)	0.0353 (4)
C25	0.2852 (2)	0.16502 (19)	0.23812 (15)	0.0379 (5)
C26	0.2603 (3)	0.2727 (2)	0.27237 (17)	0.0526 (6)
H26	0.2419	0.3537	0.2273	0.063*
C27	0.2626 (3)	0.2598 (3)	0.37386 (18)	0.0667 (7)
H27	0.2458	0.3324	0.3965	0.08*
C28	0.2896 (3)	0.1406 (3)	0.44105 (18)	0.0661 (7)
H28	0.2912	0.1325	0.509	0.079*
C29	0.3143 (3)	0.0333 (3)	0.40761 (18)	0.0659 (7)
H29	0.3331	−0.0476	0.453	0.079*
C30	0.3113 (3)	0.0452 (2)	0.30692 (17)	0.0509 (6)
H30	0.327	−0.0277	0.285	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0387 (8)	0.0564 (9)	0.0423 (10)	0.0013 (7)	−0.0070 (7)	−0.0159 (7)
O2	0.0374 (8)	0.0297 (7)	0.0493 (9)	−0.0067 (6)	−0.0041 (7)	−0.0111 (6)
O3	0.0488 (8)	0.0377 (7)	0.0382 (8)	−0.0244 (7)	0.0061 (6)	−0.0136 (6)
O4	0.0746 (11)	0.0373 (8)	0.0361 (9)	−0.0270 (7)	−0.0048 (7)	−0.0037 (6)
O5	0.0376 (8)	0.0449 (8)	0.0347 (9)	−0.0076 (6)	0.0039 (6)	−0.0083 (6)
O6	0.0363 (7)	0.0292 (7)	0.0428 (9)	−0.0127 (6)	−0.0061 (6)	−0.0066 (6)
N1	0.0414 (11)	0.0634 (12)	0.0424 (12)	−0.0062 (9)	−0.0125 (9)	−0.0105 (9)
N2	0.0678 (13)	0.0428 (10)	0.0324 (10)	−0.0244 (9)	−0.0056 (9)	−0.0002 (8)
C1	0.0316 (10)	0.0282 (9)	0.0366 (11)	−0.0097 (8)	−0.0005 (8)	−0.0096 (8)
C2	0.0449 (12)	0.0450 (11)	0.0502 (14)	−0.0237 (10)	−0.0007 (10)	−0.0080 (10)
C3	0.0565 (14)	0.0565 (13)	0.0504 (15)	−0.0330 (12)	0.0049 (11)	0.0019 (11)
C4	0.0812 (18)	0.0710 (16)	0.0356 (14)	−0.0389 (14)	0.0104 (12)	−0.0091 (12)
C5	0.0709 (15)	0.0504 (12)	0.0323 (12)	−0.0313 (12)	−0.0010 (10)	−0.0102 (10)
C6	0.0379 (11)	0.0331 (9)	0.0303 (11)	−0.0153 (8)	0.0044 (8)	−0.0095 (8)
C7	0.0317 (10)	0.0306 (9)	0.0384 (12)	−0.0113 (8)	−0.0046 (8)	−0.0099 (8)
C8	0.0367 (11)	0.0319 (9)	0.0360 (12)	−0.0120 (8)	−0.0031 (9)	−0.0100 (8)
C9	0.0345 (11)	0.0415 (11)	0.0413 (12)	−0.0184 (9)	−0.0049 (9)	−0.0090 (9)
C10	0.0466 (12)	0.0580 (13)	0.0354 (12)	−0.0322 (11)	−0.0065 (10)	−0.0048 (10)
C11	0.0778 (18)	0.0710 (16)	0.0418 (15)	−0.0347 (14)	−0.0020 (12)	−0.0168 (12)
C12	0.116 (3)	0.112 (3)	0.0461 (18)	−0.058 (2)	0.0105 (17)	−0.0336 (18)
C13	0.138 (3)	0.140 (3)	0.0335 (17)	−0.094 (3)	−0.0026 (19)	−0.012 (2)
C14	0.111 (3)	0.106 (2)	0.0452 (18)	−0.064 (2)	−0.0234 (17)	0.0146 (17)
C15	0.0673 (17)	0.0697 (16)	0.0512 (16)	−0.0345 (14)	−0.0148 (13)	0.0040 (13)
C16	0.0343 (10)	0.0267 (9)	0.0299 (11)	−0.0122 (8)	−0.0009 (8)	−0.0060 (8)
C17	0.0353 (10)	0.0364 (10)	0.0326 (11)	−0.0153 (8)	0.0002 (8)	−0.0086 (8)
C18	0.0408 (12)	0.0500 (12)	0.0346 (12)	−0.0195 (10)	−0.0085 (9)	−0.0066 (9)
C19	0.0661 (16)	0.0640 (14)	0.0348 (13)	−0.0294 (12)	−0.0014 (11)	−0.0185 (11)
C20	0.0551 (14)	0.0544 (13)	0.0376 (13)	−0.0178 (11)	0.0100 (10)	−0.0198 (11)
C21	0.0422 (12)	0.0364 (10)	0.0413 (13)	−0.0113 (9)	0.0041 (9)	−0.0142 (9)
C22	0.0319 (10)	0.0275 (9)	0.0352 (11)	−0.0086 (8)	−0.0029 (8)	−0.0047 (8)
C23	0.0356 (11)	0.0332 (10)	0.0335 (11)	−0.0119 (8)	−0.0040 (8)	−0.0056 (8)
C24	0.0278 (10)	0.0364 (10)	0.0352 (12)	−0.0080 (8)	−0.0015 (8)	−0.0052 (8)
C25	0.0303 (10)	0.0426 (11)	0.0320 (12)	−0.0088 (9)	−0.0005 (8)	−0.0038 (9)
C26	0.0677 (16)	0.0437 (12)	0.0361 (13)	−0.0136 (11)	−0.0033 (11)	−0.0046 (10)
C27	0.095 (2)	0.0624 (15)	0.0375 (15)	−0.0225 (15)	−0.0020 (13)	−0.0152 (12)
C28	0.0800 (19)	0.0768 (18)	0.0289 (13)	−0.0212 (15)	−0.0005 (12)	−0.0077 (12)
C29	0.0844 (19)	0.0591 (15)	0.0358 (14)	−0.0216 (14)	0.0008 (13)	0.0058 (11)
C30	0.0589 (15)	0.0455 (12)	0.0404 (14)	−0.0171 (11)	−0.0002 (11)	−0.0037 (10)

Geometric parameters (Å, º) top

O1—C7	1.355 (2)	C12—C13	1.382 (5)
O1—N1	1.408 (2)	C12—H12	0.93
O2—C1	1.426 (2)	C13—C14	1.377 (5)
O2—H2	0.82	C13—H13	0.93
O3—C6	1.432 (2)	C14—C15	1.369 (4)
O3—H3	0.82	C14—H14	0.93
O4—C22	1.356 (2)	C15—H15	0.93
O4—N2	1.412 (2)	C16—C22	1.501 (3)
O5—C17	1.431 (2)	C16—C21	1.538 (3)
O5—H5	0.82	C16—C17	1.547 (3)
O6—C16	1.425 (2)	C17—C18	1.515 (3)
O6—H6	0.82	C17—H17	0.98
N1—C9	1.314 (3)	C18—C19	1.521 (3)
N2—C24	1.314 (3)	C18—H18A	0.97
C1—C7	1.501 (3)	C18—H18B	0.97
C1—C2	1.530 (3)	C19—C20	1.522 (3)
C1—C6	1.531 (2)	C19—H19A	0.97
C2—C3	1.519 (3)	C19—H19B	0.97
C2—H2A	0.97	C20—C21	1.523 (3)
C2—H2B	0.97	C20—H20A	0.97
C3—C4	1.517 (3)	C20—H20B	0.97
C3—H3A	0.97	C21—H21A	0.97
C3—H3B	0.97	C21—H21B	0.97
C4—C5	1.524 (3)	C22—C23	1.345 (3)
C4—H4A	0.97	C23—C24	1.420 (3)
C4—H4B	0.97	C23—H23	0.93
C5—C6	1.514 (3)	C24—C25	1.478 (3)
C5—H5A	0.97	C25—C26	1.385 (3)
C5—H5B	0.97	C25—C30	1.388 (3)
C6—H6A	0.98	C26—C27	1.388 (3)
C7—C8	1.343 (3)	C26—H26	0.93
C8—C9	1.415 (3)	C27—C28	1.372 (4)
C8—H8	0.93	C27—H27	0.93
C9—C10	1.475 (3)	C28—C29	1.376 (4)
C10—C11	1.383 (3)	C28—H28	0.93
C10—C15	1.397 (3)	C29—C30	1.380 (3)
C11—C12	1.386 (4)	C29—H29	0.93
C11—H11	0.93	C30—H30	0.93

C7—O1—N1	108.43 (15)	C13—C14—H14	119.9
C1—O2—H2	109.5	C14—C15—C10	120.4 (3)
C6—O3—H3	109.5	C14—C15—H15	119.8
C22—O4—N2	108.55 (14)	C10—C15—H15	119.8
C17—O5—H5	109.5	O6—C16—C22	109.15 (14)
C16—O6—H6	109.5	O6—C16—C21	110.93 (15)
C9—N1—O1	105.42 (17)	C22—C16—C21	111.75 (15)
C24—N2—O4	105.51 (15)	O6—C16—C17	106.02 (14)
O2—C1—C7	108.33 (15)	C22—C16—C17	109.02 (15)
O2—C1—C2	107.01 (15)	C21—C16—C17	109.80 (15)
C7—C1—C2	110.19 (16)	O5—C17—C18	108.31 (16)
O2—C1—C6	111.29 (15)	O5—C17—C16	110.79 (15)
C7—C1—C6	110.53 (15)	C18—C17—C16	111.75 (16)
C2—C1—C6	109.43 (16)	O5—C17—H17	108.6
C3—C2—C1	112.45 (17)	C18—C17—H17	108.6
C3—C2—H2A	109.1	C16—C17—H17	108.6
C1—C2—H2A	109.1	C17—C18—C19	111.44 (18)
C3—C2—H2B	109.1	C17—C18—H18A	109.3
C1—C2—H2B	109.1	C19—C18—H18A	109.3
H2A—C2—H2B	107.8	C17—C18—H18B	109.3
C4—C3—C2	111.14 (18)	C19—C18—H18B	109.3
C4—C3—H3A	109.4	H18A—C18—H18B	108
C2—C3—H3A	109.4	C18—C19—C20	111.25 (17)
C4—C3—H3B	109.4	C18—C19—H19A	109.4
C2—C3—H3B	109.4	C20—C19—H19A	109.4
H3A—C3—H3B	108	C18—C19—H19B	109.4
C3—C4—C5	110.92 (19)	C20—C19—H19B	109.4
C3—C4—H4A	109.5	H19A—C19—H19B	108
C5—C4—H4A	109.5	C19—C20—C21	111.04 (18)
C3—C4—H4B	109.5	C19—C20—H20A	109.4
C5—C4—H4B	109.5	C21—C20—H20A	109.4
H4A—C4—H4B	108	C19—C20—H20B	109.4
C6—C5—C4	110.94 (19)	C21—C20—H20B	109.4
C6—C5—H5A	109.5	H20A—C20—H20B	108
C4—C5—H5A	109.5	C20—C21—C16	111.55 (16)
C6—C5—H5B	109.5	C20—C21—H21A	109.3
C4—C5—H5B	109.5	C16—C21—H21A	109.3
H5A—C5—H5B	108	C20—C21—H21B	109.3
O3—C6—C5	111.89 (16)	C16—C21—H21B	109.3
O3—C6—C1	107.13 (14)	H21A—C21—H21B	108
C5—C6—C1	111.39 (15)	C23—C22—O4	109.57 (17)
O3—C6—H6A	108.8	C23—C22—C16	134.23 (16)
C5—C6—H6A	108.8	O4—C22—C16	115.99 (15)
C1—C6—H6A	108.8	C22—C23—C24	105.08 (16)
C8—C7—O1	109.78 (17)	C22—C23—H23	127.5
C8—C7—C1	133.69 (17)	C24—C23—H23	127.5
O1—C7—C1	116.53 (16)	N2—C24—C23	111.28 (17)
C7—C8—C9	104.88 (17)	N2—C24—C25	119.46 (17)
C7—C8—H8	127.6	C23—C24—C25	129.24 (17)
C9—C8—H8	127.6	C26—C25—C30	118.9 (2)
N1—C9—C8	111.47 (19)	C26—C25—C24	120.66 (18)
N1—C9—C10	119.76 (19)	C30—C25—C24	120.47 (18)
C8—C9—C10	128.74 (19)	C25—C26—C27	120.1 (2)
C11—C10—C15	119.1 (2)	C25—C26—H26	119.9
C11—C10—C9	120.4 (2)	C27—C26—H26	119.9
C15—C10—C9	120.5 (2)	C28—C27—C26	120.4 (2)
C10—C11—C12	120.4 (3)	C28—C27—H27	119.8
C10—C11—H11	119.8	C26—C27—H27	119.8
C12—C11—H11	119.8	C27—C28—C29	119.8 (2)
C13—C12—C11	119.6 (3)	C27—C28—H28	120.1
C13—C12—H12	120.2	C29—C28—H28	120.1
C11—C12—H12	120.2	C28—C29—C30	120.2 (2)
C14—C13—C12	120.4 (3)	C28—C29—H29	119.9
C14—C13—H13	119.8	C30—C29—H29	119.9
C12—C13—H13	119.8	C29—C30—C25	120.6 (2)
C15—C14—C13	120.2 (3)	C29—C30—H30	119.7
C15—C14—H14	119.9	C25—C30—H30	119.7

C7—O1—N1—C9	−0.3 (2)	C9—C10—C15—C14	177.2 (2)
C22—O4—N2—C24	−0.5 (2)	O6—C16—C17—O5	−55.87 (18)
O2—C1—C2—C3	65.7 (2)	C22—C16—C17—O5	61.51 (18)
C7—C1—C2—C3	−176.76 (16)	C21—C16—C17—O5	−175.77 (14)
C6—C1—C2—C3	−55.0 (2)	O6—C16—C17—C18	65.02 (18)
C1—C2—C3—C4	55.1 (3)	C22—C16—C17—C18	−177.60 (14)
C2—C3—C4—C5	−55.0 (3)	C21—C16—C17—C18	−54.87 (19)
C3—C4—C5—C6	56.5 (3)	O5—C17—C18—C19	177.89 (16)
C4—C5—C6—O3	−177.55 (17)	C16—C17—C18—C19	55.6 (2)
C4—C5—C6—C1	−57.7 (2)	C17—C18—C19—C20	−55.8 (2)
O2—C1—C6—O3	60.75 (19)	C18—C19—C20—C21	56.1 (2)
C7—C1—C6—O3	−59.67 (19)	C19—C20—C21—C16	−56.4 (2)
C2—C1—C6—O3	178.80 (16)	O6—C16—C21—C20	−61.6 (2)
O2—C1—C6—C5	−61.9 (2)	C22—C16—C21—C20	176.34 (15)
C7—C1—C6—C5	177.67 (16)	C17—C16—C21—C20	55.2 (2)
C2—C1—C6—C5	56.1 (2)	N2—O4—C22—C23	0.4 (2)
N1—O1—C7—C8	−0.5 (2)	N2—O4—C22—C16	−174.98 (15)
N1—O1—C7—C1	179.87 (14)	O6—C16—C22—C23	10.7 (3)
O2—C1—C7—C8	4.2 (3)	C21—C16—C22—C23	133.8 (2)
C2—C1—C7—C8	−112.5 (2)	C17—C16—C22—C23	−104.7 (2)
C6—C1—C7—C8	126.4 (2)	O6—C16—C22—O4	−175.34 (15)
O2—C1—C7—O1	−176.22 (14)	C21—C16—C22—O4	−52.3 (2)
C2—C1—C7—O1	67.0 (2)	C17—C16—C22—O4	69.3 (2)
C6—C1—C7—O1	−54.0 (2)	O4—C22—C23—C24	−0.2 (2)
O1—C7—C8—C9	1.01 (19)	C16—C22—C23—C24	174.04 (19)
C1—C7—C8—C9	−179.40 (18)	O4—N2—C24—C23	0.4 (2)
O1—N1—C9—C8	1.0 (2)	O4—N2—C24—C25	178.74 (16)
O1—N1—C9—C10	−177.26 (15)	C22—C23—C24—N2	−0.1 (2)
C7—C8—C9—N1	−1.3 (2)	C22—C23—C24—C25	−178.28 (18)
C7—C8—C9—C10	176.78 (17)	N2—C24—C25—C26	−161.9 (2)
N1—C9—C10—C11	−166.5 (2)	C23—C24—C25—C26	16.1 (3)
C8—C9—C10—C11	15.6 (3)	N2—C24—C25—C30	16.9 (3)
N1—C9—C10—C15	15.8 (3)	C23—C24—C25—C30	−165.0 (2)
C8—C9—C10—C15	−162.2 (2)	C30—C25—C26—C27	0.4 (3)
C15—C10—C11—C12	0.7 (3)	C24—C25—C26—C27	179.3 (2)
C9—C10—C11—C12	−177.1 (2)	C25—C26—C27—C28	0.0 (4)
C10—C11—C12—C13	−0.2 (4)	C26—C27—C28—C29	−0.1 (4)
C11—C12—C13—C14	−0.4 (5)	C27—C28—C29—C30	−0.3 (4)
C12—C13—C14—C15	0.5 (5)	C28—C29—C30—C25	0.7 (4)
C13—C14—C15—C10	0.0 (4)	C26—C25—C30—C29	−0.8 (3)
C11—C10—C15—C14	−0.5 (3)	C24—C25—C30—C29	−179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	2.42	2.822 (2)	111
O6—H6···N1	0.82	2.10	2.915 (3)	173
O2—H2···N2ⁱ	0.82	2.32	3.070 (3)	153
O3—H3···O5ⁱⁱ	0.82	2.27	3.054 (2)	159
O5—H5···O3ⁱⁱⁱ	0.82	2.12	2.923 (3)	167

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇NO₃
M_r	259.3
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.4894 (17), 11.5593 (15), 14.0083 (13)
α, β, γ (°)	73.02 (2), 81.62 (4), 66.71 (5)
V (Å³)	1349.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.21 × 0.10 × 0.09

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10826, 5863, 4447
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.168, 1.14
No. of reflections	5863
No. of parameters	347
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19

Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	2.42	2.822 (2)	111
O6—H6···N1	0.82	2.10	2.915 (3)	173
O2—H2···N2ⁱ	0.82	2.32	3.070 (3)	153
O3—H3···O5ⁱⁱ	0.82	2.27	3.054 (2)	159
O5—H5···O3ⁱⁱⁱ	0.82	2.12	2.923 (3)	167

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

Acknowledgements

This work was supported by grant Anillo PBCT ACT-38. MG and GV acknowledge Project PBCT (PSD-16) for postdoctoral grants. We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge licence for the CSD system.

References

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