N-[(2S)-4-Chloro-2-(l-menth­yloxy)-5-oxo-2,5-dihydro­furan-3-yl]-l-valine

Song, X.-M.; Li, Z.-Y.; Wang, Z.-Y.; Li, J.-X.

doi:10.1107/S1600536809022120

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1585

doi:10.1107/S1600536809022120

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N-[(2S)-4-Chloro-2-(L-menthyloxy)-5-oxo-2,5-dihydrofuran-3-yl]-L-valine

Xiu-Mei Song,^a Zhao-Yang Li,^a Zhao-Yang Wang ^a ^* and Jian-Xiao Li ^a

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: wangwangzhaoyang@tom.com

(Received 7 April 2009; accepted 10 June 2009; online 17 June 2009)

The title compound, C₁₉H₃₀ClNO₅, was obtained by the tandem asymmetric Michael addition–elimination reaction of (5S)-3,4-dichloro-5-(L-menthyloxy)furan-2(5H)-one and L-valine in the presence of potassium hydroxide. The furanone unit is approximately planar (r.m.s. deviation = 0.0204 Å) and the six-membered cyclohexane ring adopts a chair conformation. The crystal structure is stabilized by a network of O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For biologically active 4-amino-2(5H)-furanones, see: Kimura et al. (2000 ); Tanoury et al., 2008 ). For the synthesis of the precursor, (5S)-3,4-dichloro-5-(L-menthyloxy)furan-2(5H)-one, see: Chen & Geng (1993 ).

Experimental

Crystal data

C₁₉H₃₀ClNO₅
M_r = 387.89
Tetragonal, P 4₃ 2₁ 2
a = 10.4540 (4) Å
c = 39.300 (3) Å
V = 4294.9 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.30 × 0.23 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.769, T_max = 0.867 (expected range = 0.860–0.970)
22031 measured reflections
3796 independent reflections
2868 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.091
S = 1.04
3796 reflections
242 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack, (1983 ), 1499 Friedel pairs
Flack parameter: −0.03 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.25	3.019 (3)	148
O1—H1A⋯O3ⁱⁱ	0.82	1.83	2.617 (2)	160
Symmetry codes: (i) y+1, x-1, -z; (ii) $[-y+{\script{1\over 2}}, x-{\script{1\over 2}}, z-{\script{1\over 4}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022120/gk2204sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022120/gk2204Isup2.hkl

checkCIF report

Comment top

Many 4-amino-2(5H)-furanones have been patented as prodrugs or insecticides and herbicides (Kimura et al., 2000; Tanoury et al., 2008). Attracted by versatility of 4-amino-2(5H)-furanones, we synthesized the title molecule with chiral synthon 3,4-dichloro-5-(S)-(l-menthyloxy)-2(5H)-furanone and L-valine in the presence of potassium hydroxide via the tandem asymmetric Michael addition-elimination reaction. With 2(5H)-furanone moiety and polyfunctional groups (carboxyl, amino, halogeno), the title compound is expected to be a biologically active product and an excellent ligand.

The structure of the title compound is illustrated in Fig. 1. The five-membered furane ring and the six-membered cyclohexane ring are connected via C10—O2—C11 ether bond. The configuration of chiral centers is following: C4(S), C10(S), C11(R), C12(S), C17(R)). The furanone unit is approximately planar, whereas the cyclohexane ring shows a chair conformation with three substituents occupying equatorial positions. The molecules are linked by O4—H6···O3 and N1—H1···O5 hydrogen bonds forming a three-dimensional network (Table. 1 and Fig. 2).

Related literature top

For biologically active 4-amino-2(5H)-furanones, see: Kimura et al. (2000); Tanoury et al., 2008). For the synthesis of the precursor, (5S)-3,4-dichloro-5-(L-menthyloxy)furan-2(5H)-one, see: Chen & Geng (1993).

Experimental top

The precursor, 3,4-dichloro-5-(S)-(L-menthyloxy)-2(5H)-furanone, was prepared according to the literature procedure (Chen et al., 1993).

After the mixture of L-valine (4.5 mmol) and potassium hydroxide (5.8 mmol) was dissolved in absolute ethyl alcohol under nitrogen atmosphere, dichloromethane solution of 3,4-dichloro-5-(S)-(l-menthyloxy)-2(5H)-furanone (3.0 mmol) was added. The reaction was carried out under the stirring at room temperature for 24 h. Once the reaction was complete, the solvents were removed under reduced pressure. The residual solid was dissolved in dichloromethane, and pH of the solution was adjusted to 3–4 with 15% of aqueous HCl solution. Then the combined organic layers from extraction were concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography with the gradient mixture of petroleum ether and ethyl acetate to give the product yielding (I) 0.6891 g (59.2%). Data for (I): [α]^20°_D = 47.616° (c 0.481, CH₃CH₂OH); ¹H NMR (400 MHz, CDCl₃, TMS): 0.832 (3H, d, J = 6.0 Hz, CH₃), 0.904–0.935 (7H, m, CH, 2CH₃), 0.955–1.057 (8H, m, 2CH₃, CH₂), 1.312–1.457 (2H, m, 2CH), 1.605–1.710 (2H, m, CH₂), 2.100–2.350 (3H, m, CH₂, CH), 3.505–3.609 (1H, m, CH), 4.726 (1H, s, NH), 5.116–5.138 (1H, d, J = 8.8 Hz, CH), 5.700 (1H, s, CH), 10.212 (1H, s, COOH); ESI-MS, m/z (%): Calcd for C₁₉H₃₁ClNO₅⁺([M+H]⁺): 388.19, Found: 388.15 (100.0)

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids shown at the 30% probability level.
	Fig. 2. Perspective view of the crystal packing. Dashed lines represent hydrogen bonds.

N-[(2S)-4-Chloro-2-(L-menthyloxy)-5-oxo-2,5-dihydrofuran-3-yl]- L-valine top

Crystal data top

C₁₉H₃₀ClNO₅	D_x = 1.200 Mg m⁻³
M_r = 387.89	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 3405 reflections
Hall symbol: P 4nw 2abw	θ = 2.2–19.1°
a = 10.4540 (4) Å	µ = 0.20 mm⁻¹
c = 39.300 (3) Å	T = 293 K
V = 4294.9 (4) Å³	Block, colourless
Z = 8	0.30 × 0.23 × 0.15 mm
F(000) = 1664.0

Data collection top

Bruker APEXII CCD area-detector diffractometer	3796 independent reflections
Radiation source: fine-focus sealed tube	2868 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 0 pixels mm^-1	θ_max = 25.0°, θ_min = 2.0°
ϕ and ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −11→12
T_min = 0.769, T_max = 0.867	l = −46→46
22031 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0329P)² + 0.7758P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.18 e Å⁻³
3796 reflections	Δρ_min = −0.23 e Å⁻³
242 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^
0 restraints	Extinction coefficient: 0.0020 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack, (1983), 1499 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.03 (8)

Crystal data top

C₁₉H₃₀ClNO₅	Z = 8
M_r = 387.89	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 0.20 mm⁻¹
a = 10.4540 (4) Å	T = 293 K
c = 39.300 (3) Å	0.30 × 0.23 × 0.15 mm
V = 4294.9 (4) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3796 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2868 reflections with I > 2σ(I)
T_min = 0.769, T_max = 0.867	R_int = 0.053
22031 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.091	Δρ_max = 0.18 e Å⁻³
S = 1.04	Δρ_min = −0.23 e Å⁻³
3796 reflections	Absolute structure: Flack, (1983), 1499 Friedel pairs
242 parameters	Absolute structure parameter: −0.03 (8)
0 restraints

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
C1	0.6886 (3)	−0.0142 (2)	−0.02302 (5)	0.0457 (6)
C2	0.6349 (2)	0.0184 (2)	0.01161 (5)	0.0434 (6)
H2	0.5486	−0.0178	0.0132	0.052*
C3	0.6252 (3)	0.1638 (3)	0.01705 (6)	0.0645 (8)
H3	0.6169	0.1771	0.0416	0.077*
C4	0.5046 (4)	0.2198 (3)	0.00080 (9)	0.1066 (14)
H4A	0.4929	0.3061	0.0085	0.160*
H4B	0.4318	0.1692	0.0072	0.160*
H4C	0.5135	0.2191	−0.0235	0.160*
C5	0.7443 (4)	0.2337 (3)	0.00618 (8)	0.0901 (11)
H5A	0.8180	0.1926	0.0158	0.135*
H5B	0.7403	0.3207	0.0140	0.135*
H5C	0.7507	0.2325	−0.0182	0.135*
C6	0.6726 (2)	−0.0701 (2)	0.06900 (5)	0.0420 (6)
C7	0.5557 (2)	−0.0781 (2)	0.08334 (5)	0.0478 (6)
C8	0.5677 (3)	−0.1196 (2)	0.11793 (5)	0.0489 (6)
C9	0.7698 (2)	−0.0992 (2)	0.09642 (5)	0.0429 (6)
H9	0.8263	−0.1695	0.0896	0.052*
C10	0.9662 (2)	−0.0054 (2)	0.11656 (5)	0.0445 (6)
H10	1.0136	−0.0663	0.1024	0.053*
C11	0.9624 (2)	−0.0546 (3)	0.15302 (5)	0.0529 (7)
H11A	0.9221	−0.1381	0.1534	0.063*
H11B	0.9112	0.0029	0.1668	0.063*
C12	1.0967 (3)	−0.0645 (3)	0.16813 (6)	0.0596 (7)
H12	1.1447	−0.1278	0.1549	0.072*
C13	1.0913 (3)	−0.1106 (3)	0.20518 (6)	0.0868 (10)
H13A	1.0524	−0.0458	0.2191	0.130*
H13B	1.1764	−0.1271	0.2132	0.130*
H13C	1.0416	−0.1877	0.2065	0.130*
C14	1.1649 (3)	0.0631 (3)	0.16501 (7)	0.0753 (9)
H14A	1.1233	0.1250	0.1797	0.090*
H14B	1.2525	0.0534	0.1727	0.090*
C15	1.1654 (3)	0.1133 (3)	0.12899 (7)	0.0723 (9)
H15A	1.2151	0.0562	0.1147	0.087*
H15B	1.2062	0.1966	0.1286	0.087*
C16	1.0302 (2)	0.1249 (2)	0.11446 (6)	0.0522 (7)
H16	0.9828	0.1814	0.1299	0.063*
C17	1.0229 (3)	0.1862 (3)	0.07910 (7)	0.0698 (8)
H17	0.9327	0.1846	0.0723	0.084*
C18	1.0627 (4)	0.3269 (3)	0.08046 (11)	0.1295 (16)
H18A	1.0213	0.3678	0.0993	0.194*
H18B	1.0380	0.3685	0.0597	0.194*
H18C	1.1538	0.3325	0.0832	0.194*
C19	1.0969 (4)	0.1145 (4)	0.05192 (7)	0.1001 (12)
H19A	1.1866	0.1177	0.0571	0.150*
H19B	1.0818	0.1534	0.0302	0.150*
H19C	1.0692	0.0270	0.0514	0.150*
Cl1	0.40649 (7)	−0.05720 (10)	0.066293 (16)	0.0818 (3)
N1	0.71379 (18)	−0.0411 (2)	0.03775 (4)	0.0463 (5)
H1	0.7919	−0.0586	0.0327	0.056*
O1	0.60255 (18)	0.0096 (2)	−0.04637 (4)	0.0835 (7)
H1A	0.6322	−0.0068	−0.0652	0.125*
O2	0.79397 (18)	−0.05167 (19)	−0.02856 (4)	0.0633 (5)
O3	0.48370 (18)	−0.14530 (18)	0.13838 (4)	0.0625 (5)
O4	0.69263 (17)	−0.13404 (16)	0.12582 (3)	0.0515 (5)
O5	0.83805 (15)	0.01070 (15)	0.10286 (4)	0.0472 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0580 (17)	0.0518 (16)	0.0274 (11)	0.0057 (12)	−0.0053 (11)	0.0020 (11)
C2	0.0501 (15)	0.0544 (16)	0.0259 (10)	0.0075 (12)	−0.0023 (10)	0.0030 (10)
C3	0.095 (2)	0.0608 (18)	0.0382 (13)	0.0207 (17)	0.0001 (14)	−0.0027 (13)
C4	0.135 (4)	0.086 (3)	0.099 (2)	0.056 (2)	−0.020 (2)	0.002 (2)
C5	0.132 (3)	0.067 (2)	0.072 (2)	−0.014 (2)	0.006 (2)	0.0021 (17)
C6	0.0515 (15)	0.0469 (15)	0.0276 (11)	0.0046 (11)	−0.0012 (11)	−0.0033 (10)
C7	0.0480 (15)	0.0655 (17)	0.0301 (11)	0.0041 (13)	0.0008 (11)	0.0020 (11)
C8	0.0632 (19)	0.0531 (16)	0.0303 (11)	−0.0084 (13)	0.0000 (12)	−0.0034 (11)
C9	0.0542 (15)	0.0481 (15)	0.0265 (11)	−0.0019 (12)	−0.0016 (10)	0.0020 (11)
C10	0.0485 (15)	0.0488 (15)	0.0361 (12)	0.0063 (12)	−0.0051 (11)	−0.0040 (11)
C11	0.0620 (17)	0.0601 (17)	0.0365 (12)	0.0011 (14)	−0.0035 (12)	−0.0009 (12)
C12	0.0670 (18)	0.070 (2)	0.0418 (13)	0.0108 (15)	−0.0119 (13)	−0.0125 (13)
C13	0.106 (3)	0.108 (3)	0.0464 (16)	0.017 (2)	−0.0248 (17)	−0.0055 (17)
C14	0.070 (2)	0.092 (3)	0.0641 (18)	−0.0008 (18)	−0.0196 (15)	−0.0204 (17)
C15	0.064 (2)	0.073 (2)	0.079 (2)	−0.0123 (17)	−0.0053 (16)	−0.0122 (17)
C16	0.0554 (17)	0.0466 (16)	0.0545 (15)	0.0019 (12)	0.0008 (13)	−0.0082 (12)
C17	0.074 (2)	0.0622 (19)	0.0737 (19)	−0.0058 (16)	0.0041 (16)	0.0165 (15)
C18	0.153 (4)	0.071 (3)	0.164 (4)	−0.030 (3)	0.003 (3)	0.035 (3)
C19	0.119 (3)	0.123 (3)	0.0585 (18)	0.011 (3)	0.014 (2)	0.019 (2)
Cl1	0.0488 (4)	0.1483 (8)	0.0483 (4)	0.0136 (5)	0.0026 (3)	0.0132 (4)
N1	0.0460 (12)	0.0683 (14)	0.0247 (9)	0.0099 (10)	0.0023 (8)	0.0061 (9)
O1	0.0698 (13)	0.151 (2)	0.0296 (8)	0.0369 (14)	−0.0086 (9)	−0.0045 (11)
O2	0.0639 (13)	0.0890 (15)	0.0369 (9)	0.0293 (11)	0.0062 (8)	0.0049 (9)
O3	0.0717 (13)	0.0841 (14)	0.0317 (8)	−0.0182 (10)	0.0114 (9)	0.0017 (8)
O4	0.0601 (12)	0.0674 (12)	0.0270 (8)	−0.0094 (9)	−0.0030 (8)	0.0084 (7)
O5	0.0530 (11)	0.0463 (11)	0.0422 (9)	0.0000 (8)	−0.0070 (8)	0.0009 (8)

Geometric parameters (Å, º) top

C1—O2	1.189 (3)	C11—C12	1.528 (3)
C1—O1	1.309 (3)	C11—H11A	0.9700
C1—C2	1.511 (3)	C11—H11B	0.9700
C2—N1	1.456 (3)	C12—C14	1.517 (4)
C2—C3	1.538 (3)	C12—C13	1.534 (3)
C2—H2	0.9800	C12—H12	0.9800
C3—C5	1.506 (4)	C13—H13A	0.9600
C3—C4	1.530 (4)	C13—H13B	0.9600
C3—H3	0.9800	C13—H13C	0.9600
C4—H4A	0.9600	C14—C15	1.510 (4)
C4—H4B	0.9600	C14—H14A	0.9700
C4—H4C	0.9600	C14—H14B	0.9700
C5—H5A	0.9600	C15—C16	1.529 (4)
C5—H5B	0.9600	C15—H15A	0.9700
C5—H5C	0.9600	C15—H15B	0.9700
C6—N1	1.336 (3)	C16—C17	1.532 (3)
C6—C7	1.348 (3)	C16—H16	0.9800
C6—C9	1.511 (3)	C17—C19	1.518 (4)
C7—C8	1.432 (3)	C17—C18	1.529 (4)
C7—Cl1	1.712 (2)	C17—H17	0.9800
C8—O3	1.220 (3)	C18—H18A	0.9600
C8—O4	1.351 (3)	C18—H18B	0.9600
C9—O5	1.376 (3)	C18—H18C	0.9600
C9—O4	1.455 (3)	C19—H19A	0.9600
C9—H9	0.9800	C19—H19B	0.9600
C10—O5	1.454 (3)	C19—H19C	0.9600
C10—C16	1.520 (3)	N1—H1	0.8600
C10—C11	1.523 (3)	O1—H1A	0.8200
C10—H10	0.9800

O2—C1—O1	124.8 (2)	C14—C12—C11	109.9 (2)
O2—C1—C2	125.7 (2)	C14—C12—C13	111.7 (2)
O1—C1—C2	109.5 (2)	C11—C12—C13	110.9 (2)
N1—C2—C1	109.21 (18)	C14—C12—H12	108.1
N1—C2—C3	111.14 (19)	C11—C12—H12	108.1
C1—C2—C3	111.9 (2)	C13—C12—H12	108.1
N1—C2—H2	108.2	C12—C13—H13A	109.5
C1—C2—H2	108.2	C12—C13—H13B	109.5
C3—C2—H2	108.2	H13A—C13—H13B	109.5
C5—C3—C4	112.2 (3)	C12—C13—H13C	109.5
C5—C3—C2	112.7 (2)	H13A—C13—H13C	109.5
C4—C3—C2	112.0 (2)	H13B—C13—H13C	109.5
C5—C3—H3	106.5	C15—C14—C12	112.5 (2)
C4—C3—H3	106.5	C15—C14—H14A	109.1
C2—C3—H3	106.5	C12—C14—H14A	109.1
C3—C4—H4A	109.5	C15—C14—H14B	109.1
C3—C4—H4B	109.5	C12—C14—H14B	109.1
H4A—C4—H4B	109.5	H14A—C14—H14B	107.8
C3—C4—H4C	109.5	C14—C15—C16	112.0 (2)
H4A—C4—H4C	109.5	C14—C15—H15A	109.2
H4B—C4—H4C	109.5	C16—C15—H15A	109.2
C3—C5—H5A	109.5	C14—C15—H15B	109.2
C3—C5—H5B	109.5	C16—C15—H15B	109.2
H5A—C5—H5B	109.5	H15A—C15—H15B	107.9
C3—C5—H5C	109.5	C10—C16—C15	108.4 (2)
H5A—C5—H5C	109.5	C10—C16—C17	113.7 (2)
H5B—C5—H5C	109.5	C15—C16—C17	114.7 (2)
N1—C6—C7	133.7 (2)	C10—C16—H16	106.5
N1—C6—C9	119.0 (2)	C15—C16—H16	106.5
C7—C6—C9	107.34 (18)	C17—C16—H16	106.5
C6—C7—C8	109.7 (2)	C19—C17—C18	111.2 (3)
C6—C7—Cl1	130.86 (17)	C19—C17—C16	114.0 (2)
C8—C7—Cl1	119.30 (18)	C18—C17—C16	110.9 (3)
O3—C8—O4	121.3 (2)	C19—C17—H17	106.8
O3—C8—C7	129.0 (2)	C18—C17—H17	106.8
O4—C8—C7	109.6 (2)	C16—C17—H17	106.8
O5—C9—O4	110.51 (17)	C17—C18—H18A	109.5
O5—C9—C6	108.15 (19)	C17—C18—H18B	109.5
O4—C9—C6	104.14 (18)	H18A—C18—H18B	109.5
O5—C9—H9	111.3	C17—C18—H18C	109.5
O4—C9—H9	111.3	H18A—C18—H18C	109.5
C6—C9—H9	111.3	H18B—C18—H18C	109.5
O5—C10—C16	106.35 (18)	C17—C19—H19A	109.5
O5—C10—C11	111.29 (19)	C17—C19—H19B	109.5
C16—C10—C11	111.45 (19)	H19A—C19—H19B	109.5
O5—C10—H10	109.2	C17—C19—H19C	109.5
C16—C10—H10	109.2	H19A—C19—H19C	109.5
C11—C10—H10	109.2	H19B—C19—H19C	109.5
C10—C11—C12	111.4 (2)	C6—N1—C2	124.25 (19)
C10—C11—H11A	109.4	C6—N1—H1	117.9
C12—C11—H11A	109.4	C2—N1—H1	117.9
C10—C11—H11B	109.4	C1—O1—H1A	109.5
C12—C11—H11B	109.4	C8—O4—C9	109.00 (16)
H11A—C11—H11B	108.0	C9—O5—C10	116.73 (18)

O2—C1—C2—N1	−18.5 (4)	C13—C12—C14—C15	−177.1 (3)
O1—C1—C2—N1	163.8 (2)	C12—C14—C15—C16	56.1 (3)
O2—C1—C2—C3	105.0 (3)	O5—C10—C16—C15	179.41 (19)
O1—C1—C2—C3	−72.8 (3)	C11—C10—C16—C15	58.0 (3)
N1—C2—C3—C5	76.6 (3)	O5—C10—C16—C17	−51.8 (3)
C1—C2—C3—C5	−45.8 (3)	C11—C10—C16—C17	−173.2 (2)
N1—C2—C3—C4	−155.9 (2)	C14—C15—C16—C10	−56.8 (3)
C1—C2—C3—C4	81.8 (3)	C14—C15—C16—C17	175.0 (2)
N1—C6—C7—C8	177.3 (3)	C10—C16—C17—C19	−65.7 (3)
C9—C6—C7—C8	−4.1 (3)	C15—C16—C17—C19	59.8 (3)
N1—C6—C7—Cl1	1.9 (4)	C10—C16—C17—C18	167.9 (3)
C9—C6—C7—Cl1	−179.5 (2)	C15—C16—C17—C18	−66.5 (4)
C6—C7—C8—O3	−175.2 (3)	C7—C6—N1—C2	14.1 (4)
Cl1—C7—C8—O3	0.9 (4)	C9—C6—N1—C2	−164.4 (2)
C6—C7—C8—O4	1.9 (3)	C1—C2—N1—C6	−155.7 (2)
Cl1—C7—C8—O4	177.94 (17)	C3—C2—N1—C6	80.5 (3)
N1—C6—C9—O5	66.0 (3)	O3—C8—O4—C9	178.6 (2)
C7—C6—C9—O5	−112.9 (2)	C7—C8—O4—C9	1.3 (3)
N1—C6—C9—O4	−176.5 (2)	O5—C9—O4—C8	112.3 (2)
C7—C6—C9—O4	4.7 (3)	C6—C9—O4—C8	−3.6 (2)
O5—C10—C11—C12	−176.8 (2)	O4—C9—O5—C10	92.0 (2)
C16—C10—C11—C12	−58.3 (3)	C6—C9—O5—C10	−154.55 (17)
C10—C11—C12—C14	54.4 (3)	C16—C10—O5—C9	168.55 (17)
C10—C11—C12—C13	178.4 (2)	C11—C10—O5—C9	−69.9 (2)
C11—C12—C14—C15	−53.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.25	3.019 (3)	148
O1—H1A···O3ⁱⁱ	0.82	1.83	2.617 (2)	160

Symmetry codes: (i) y+1, x−1, −z; (ii) −y+1/2, x−1/2, z−1/4.

Experimental details

Crystal data
Chemical formula	C₁₉H₃₀ClNO₅
M_r	387.89
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	293
a, c (Å)	10.4540 (4), 39.300 (3)
V (Å³)	4294.9 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.30 × 0.23 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.769, 0.867
No. of measured, independent and observed [I > 2σ(I)] reflections	22031, 3796, 2868
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.091, 1.04
No. of reflections	3796
No. of parameters	242
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23
Absolute structure	Flack, (1983), 1499 Friedel pairs
Absolute structure parameter	−0.03 (8)

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.25	3.019 (3)	148
O1—H1A···O3ⁱⁱ	0.82	1.83	2.617 (2)	160

Symmetry codes: (i) y+1, x−1, −z; (ii) −y+1/2, x−1/2, z−1/4.

Acknowledgements

The work was supported by the National Natural Science Foundation of China (grant No. 20772035) and the Natural Science Foundation of Guangdong Province, China (grant No. 5300082).

References

Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, Q. H. & Geng, Z. (1993). Acta Chim. Sin. 51, 622–624. CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kimura, Y., Mizuno, T., Kawano, T., Okada, K. & Shimad, A. (2000). Phytochemistry, 53, 829–831. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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