N-{4-Bromo-2-[(S)-menth­yloxy]-5-oxo-2,5-dihydro-3-fur­yl}-l-valine

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

doi:10.1107/S1600536809026129

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1838

doi:10.1107/S1600536809026129

Open

access

N-{4-Bromo-2-[(S)-menthyloxy]-5-oxo-2,5-dihydro-3-furyl}-L-valine

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

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

(Received 13 June 2009; accepted 5 July 2009; online 11 July 2009)

The title compound, C₁₉H₃₀BrNO₅, was obtained via a tandem asymmetric Michael addition–elimination reaction of 3,4-dibromo-5-[(S)-L-menthyloxy]furan-2(5H)-one and L-valine in the presence of potassium hydroxide. The molecular structure contains an approximately planar (r.m.s. deviation = 0.0204 Å) five-membered furanone ring and a six-membered menthyloxy ring adopting a chair conformation. The crystal packing is stabilized by intermolecular O—H⋯O and N—H⋯O hydrogen bonding.

Related literature

For applications of chiral 5-(L-menthyloxy)-2(5H)-furanones, see: Feringa & De Jong (1988 ); De Koning et al. (1997 ); Lattmann et al. (1999 ); He et al. (2006 ); Wang et al. (2006 ). For biologically active 4-amino-2(5H)-furanones, see: Kimura et al. (2000 ); Tanoury et al. (2008 ). For related compounds, see: Wang et al. (2006); Li et al. (2009 ). For the synthesis, see: Chen & Geng (1993 ).

Experimental

Crystal data

C₁₉H₃₀BrNO₅
M_r = 432.34
Tetragonal, P 4₃ 2₁ 2
a = 10.5409 (9) Å
c = 39.388 (7) Å
V = 4376.4 (9) Å³
Z = 8
Mo Kα radiation
μ = 1.91 mm⁻¹
T = 293 K
0.30 × 0.22 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.558, T_max = 0.710
22304 measured reflections
3859 independent reflections
2726 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.085
S = 1.03
3859 reflections
241 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ), 1526 Friedel pairs
Flack parameter: −0.001 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5ⁱ	0.86	2.28	3.047 (4)	149
O4—H4⋯O2ⁱⁱ	0.82	1.83	2.615 (3)	160
Symmetry codes: (i) y-1, x+1, -z; (ii) $[-y+{\script{3\over 2}}, x+{\script{1\over 2}}, z-{\script{1\over 4}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026129/xu2542sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026129/xu2542Isup2.hkl

checkCIF report

Comment top

Chiral 5-(l-menthyloxy)-2(5H)-furanones have been utilized as key building blocks in the synthesis of supramolecules and important natural products since 1980's (Feringa & De Jong, 1988; De Koning et al., 1997; Lattmann et al., 1999), especially in asymmetric synthesis (He et al., 2006; Wang et al., 2006). At the same time, 4-amino-2(5H)-furanone is an attractive moiety in chemical, pharmaceutical and agrochemical research. 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 versatile 4-amino-2(5H)-furanones, we synthesized the title compound with chiral synthon 3,4-dibromo-5-(S)-(l-menthyloxy)-2(5H)-furanone and L-valine in the present of potassium hydroxide via the tandem asymmetric Michael addition-elimination reaction. With 2(5H)-furanone moiety and polyfunctional groups (carboxyl, amino, halo), the title compound is expected to be a biologically active product and excellent ligand.

The structure of the title compound is illustrated in Fig. 1. The title compound which has five chiral centers (C2(S), C8(S), C9(R), C10(S), C14(R)) contains a five-membered furanone ring and a six-membered menthyloxy ring connected each other via C8—O3—C9 ether bond. The furanone ring is approximately planar, whereas the cyclohexane ring displays a chair conformation with three substituents occupying equatorial positions. The bond lengths and angles in the title compound are good agreement with the expected values (Wang et al., 2006; Li et al., 2009). In the crystal structure the molecules are linked by intermolecular hydrogen bonds (Table 1).

Related literature top

Fro applications of chiral 5-(l-menthyloxy)-2(5H)-furanones, see: Feringa & De Jong (1988); De Koning et al. (1997); Lattmann et al. (1999); He et al. (2006); Wang et al. (2006). For biologically active 4-amino-2(5H)-furanones, see: Kimura et al. (2000); Tanoury et al., 2008). For related compounds, see: Wang et al. (2006); Li et al. (2009). For the synthesis, see: Chen & Geng (1993).

Experimental top

The precursor 3,4-dibromo-5-(S)-(l-menthyloxy)-2(5H)-furanone was prepared according to the literature procedure (Chen et al., 1993). An absolute ethanol solution (5 ml) of L-valine (4.5 mmol) and potassium hydroxide (5.8 mmol) was mixed with the dichloromethane solution (6 ml) of 3,4-dibromo-5-(S)-(l-menthyloxy)-2(5H)-furanone (3.0 mmol) under nitrogen atmosphere. The solution was stirred for 24 h at room temperature, and then the solvents were removed under reduced pressure. The solid residual was dissolved in dichloromethane, and pH of the solution was adjusted to 3 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) 0.9186 g (71.1%). Colorless crystals were obtained in acetone solution by slow evaporation.

Computing details top

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

Figures top

Fig. 1. Displacement ellipsoid plot (30% probability level) of the title compound.

N-{4-Bromo-2-[(S)-menthyloxy]-5-oxo-2,5-dihydro-3-furyl}-L-valine top

Crystal data top

C₁₉H₃₀BrNO₅	D_x = 1.312 Mg m⁻³
M_r = 432.34	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 3973 reflections
Hall symbol: P 4nw 2abw	θ = 2.2–19.3°
a = 10.5409 (9) Å	µ = 1.91 mm⁻¹
c = 39.388 (7) Å	T = 293 K
V = 4376.4 (9) Å³	Block, colourless
Z = 8	0.30 × 0.22 × 0.18 mm
F(000) = 1808.0

Data collection top

Bruker APEXII area-detector diffractometer	3859 independent reflections
Radiation source: fine-focus sealed tube	2726 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→12
T_min = 0.558, T_max = 0.710	k = −12→9
22304 measured reflections	l = −40→46

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0221P)² + 1.5196P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3859 reflections	Δρ_max = 0.43 e Å⁻³
241 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1526 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (11)

Crystal data top

C₁₉H₃₀BrNO₅	Z = 8
M_r = 432.34	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 1.91 mm⁻¹
a = 10.5409 (9) Å	T = 293 K
c = 39.388 (7) Å	0.30 × 0.22 × 0.18 mm
V = 4376.4 (9) Å³

Data collection top

Bruker APEXII area-detector diffractometer	3859 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2726 reflections with I > 2σ(I)
T_min = 0.558, T_max = 0.710	R_int = 0.065
22304 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.085	Δρ_max = 0.43 e Å⁻³
S = 1.03	Δρ_min = −0.40 e Å⁻³
3859 reflections	Absolute structure: Flack (1983), 1526 Friedel pairs
241 parameters	Absolute structure parameter: −0.001 (11)
0 restraints

Special details top

Experimental. Data for (I): [α]^20°_D = 63.39° (c 0.437, CH₃CH₂OH); ¹H NMR (400 MHz, CDCl₃, TMS): 0.830 (3H, d, J = 6.8 Hz, CH₃), 0.897–0.933 (7H, m, CH, 2CH₃), 0.955–1.047 (8H, m, 2CH₃, CH₂), 1.316–1.451 (2H, m, 2CH), 1.610–1.708 (2H, m, CH₂), 2.102–2.347 (3H, m, CH₂, CH), 3.519–3.610 (1H, m, CH), 4.796 (1H, s, NH), 5.160–5.260 (1H, m, CH), 5.720 (1H, s, CH), 10.720 (1H, s, COOH); ESI-MS, m/z (%): Calcd for C₁₉H₃₁BrNO₅⁺([M+H]⁺): 434.14, Found: 434.16 (95.0).

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br1	0.60721 (4)	1.06205 (6)	0.066070 (11)	0.0784 (2)
C1	0.3102 (4)	1.0150 (4)	−0.02299 (8)	0.0413 (9)
C2	0.3657 (3)	0.9857 (3)	0.01146 (8)	0.0421 (9)
H2	0.4503	1.0240	0.0126	0.051*
C3	0.3802 (4)	0.8413 (4)	0.01711 (9)	0.0599 (12)
H3	0.3900	0.8288	0.0416	0.072*
C4	0.4988 (5)	0.7874 (5)	0.00061 (13)	0.105 (2)
H4A	0.5138	0.7032	0.0090	0.157*
H4B	0.5702	0.8404	0.0060	0.157*
H4C	0.4875	0.7845	−0.0236	0.157*
C5	0.3284 (3)	1.0733 (3)	0.06891 (8)	0.0367 (8)
C6	0.4445 (3)	1.0829 (3)	0.08348 (8)	0.0447 (9)
C7	0.4303 (4)	1.1255 (3)	0.11806 (8)	0.0457 (9)
C8	0.2303 (3)	1.1000 (4)	0.09637 (7)	0.0398 (8)
H8	0.1722	1.1677	0.0894	0.048*
C9	0.0390 (3)	1.0016 (3)	0.11682 (8)	0.0410 (9)
H9	−0.0103	1.0597	0.1026	0.049*
C10	−0.0201 (4)	0.8704 (3)	0.11490 (10)	0.0522 (11)
H10	0.0288	0.8163	0.1303	0.063*
C11	−0.0114 (5)	0.8091 (4)	0.07965 (11)	0.0685 (13)
H11	0.0778	0.8134	0.0728	0.082*
C12	−0.1550 (4)	0.8779 (5)	0.12957 (12)	0.0746 (14)
H12A	−0.2064	0.9322	0.1152	0.090*
H12B	−0.1925	0.7939	0.1294	0.090*
C13	−0.1566 (4)	0.9290 (5)	0.16525 (11)	0.0748 (14)
H13A	−0.1137	0.8694	0.1801	0.090*
H13B	−0.2438	0.9361	0.1728	0.090*
C14	−0.0928 (4)	1.0580 (4)	0.16822 (9)	0.0602 (11)
H14	−0.1425	1.1186	0.1548	0.072*
C15	0.0400 (3)	1.0516 (4)	0.15277 (9)	0.0504 (10)
H15A	0.0772	1.1358	0.1529	0.061*
H15B	0.0929	0.9972	0.1667	0.061*
C16	−0.0907 (5)	1.1053 (5)	0.20473 (10)	0.0854 (15)
H16A	−0.1760	1.1192	0.2124	0.128*
H16B	−0.0441	1.1835	0.2059	0.128*
H16C	−0.0506	1.0431	0.2189	0.128*
C17	0.2621 (5)	0.7689 (5)	0.00673 (12)	0.0897 (16)
H17A	0.2539	0.7706	−0.0175	0.134*
H17B	0.1889	0.8078	0.0169	0.134*
H17C	0.2687	0.6826	0.0143	0.134*
C18	−0.0868 (5)	0.8769 (5)	0.05239 (12)	0.0987 (18)
H18A	−0.0734	0.8358	0.0309	0.148*
H18B	−0.0595	0.9636	0.0510	0.148*
H18C	−0.1754	0.8743	0.0580	0.148*
C19	−0.0465 (6)	0.6681 (5)	0.08090 (16)	0.123 (2)
H19A	−0.1369	0.6595	0.0827	0.185*
H19B	−0.0070	0.6294	0.1003	0.185*
H19C	−0.0175	0.6271	0.0606	0.185*
N1	0.2878 (3)	1.0434 (3)	0.03785 (6)	0.0450 (7)
H1	0.2098	1.0594	0.0330	0.054*
O1	0.3055 (3)	1.1382 (2)	0.12568 (5)	0.0479 (7)
O2	0.5122 (3)	1.1529 (3)	0.13854 (6)	0.0604 (8)
O3	0.1660 (2)	0.9901 (2)	0.10285 (6)	0.0429 (6)
O4	0.3943 (3)	0.9922 (4)	−0.04650 (6)	0.0843 (11)
H4	0.3630	1.0057	−0.0652	0.127*
O5	0.2048 (3)	1.0509 (3)	−0.02793 (6)	0.0596 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0465 (2)	0.1398 (5)	0.0488 (2)	0.0113 (3)	−0.0033 (2)	−0.0117 (3)
C1	0.047 (2)	0.051 (2)	0.0254 (19)	0.0110 (19)	−0.0007 (17)	−0.0051 (16)
C2	0.046 (2)	0.054 (3)	0.0255 (18)	0.0083 (18)	−0.0002 (15)	−0.0037 (16)
C3	0.093 (3)	0.058 (3)	0.029 (2)	0.023 (2)	−0.006 (2)	0.0020 (18)
C4	0.136 (5)	0.091 (4)	0.087 (4)	0.056 (4)	0.017 (4)	−0.007 (3)
C5	0.050 (2)	0.038 (2)	0.0221 (18)	0.0055 (18)	0.0006 (16)	0.0007 (15)
C6	0.052 (2)	0.057 (3)	0.0252 (17)	−0.002 (2)	−0.0005 (17)	0.0033 (16)
C7	0.061 (3)	0.050 (2)	0.0257 (18)	−0.010 (2)	−0.0028 (19)	0.0072 (17)
C8	0.051 (2)	0.044 (2)	0.0246 (18)	−0.001 (2)	0.0024 (16)	−0.0045 (18)
C9	0.042 (2)	0.047 (2)	0.034 (2)	0.004 (2)	0.0062 (17)	0.0082 (16)
C10	0.051 (3)	0.051 (3)	0.054 (2)	−0.004 (2)	−0.003 (2)	0.0120 (19)
C11	0.068 (3)	0.052 (3)	0.086 (4)	−0.004 (2)	−0.003 (3)	−0.018 (2)
C12	0.060 (3)	0.081 (3)	0.083 (4)	−0.016 (3)	0.007 (2)	0.014 (3)
C13	0.064 (3)	0.098 (4)	0.062 (3)	−0.004 (3)	0.018 (2)	0.019 (3)
C14	0.066 (3)	0.072 (3)	0.043 (2)	0.013 (3)	0.014 (2)	0.014 (2)
C15	0.058 (2)	0.058 (2)	0.035 (2)	0.000 (2)	0.0067 (18)	0.0044 (18)
C16	0.108 (4)	0.099 (4)	0.049 (3)	0.016 (4)	0.030 (3)	0.006 (3)
C17	0.132 (5)	0.068 (3)	0.070 (4)	−0.016 (3)	−0.010 (3)	−0.004 (3)
C18	0.121 (5)	0.114 (4)	0.061 (3)	0.016 (4)	−0.021 (3)	−0.026 (3)
C19	0.129 (5)	0.064 (3)	0.177 (6)	−0.020 (4)	−0.007 (4)	−0.038 (4)
N1	0.0439 (17)	0.066 (2)	0.0249 (15)	0.0106 (16)	−0.0028 (13)	−0.0058 (15)
O1	0.0584 (18)	0.0629 (19)	0.0225 (12)	−0.0081 (13)	0.0048 (12)	−0.0114 (12)
O2	0.070 (2)	0.082 (2)	0.0288 (14)	−0.0203 (15)	−0.0116 (14)	−0.0017 (13)
O3	0.0499 (15)	0.0424 (16)	0.0364 (14)	−0.0019 (13)	0.0063 (12)	−0.0002 (11)
O4	0.0685 (19)	0.158 (3)	0.0264 (14)	0.041 (2)	0.0074 (14)	0.0028 (16)
O5	0.0627 (19)	0.083 (2)	0.0334 (15)	0.0299 (17)	−0.0063 (12)	−0.0061 (14)

Geometric parameters (Å, º) top

Br1—C6	1.861 (4)	C11—C18	1.515 (6)
C1—O5	1.190 (4)	C11—C19	1.532 (6)
C1—O4	1.304 (4)	C11—H11	0.9800
C1—C2	1.509 (4)	C12—C13	1.505 (6)
C2—N1	1.458 (4)	C12—H12A	0.9700
C2—C3	1.546 (5)	C12—H12B	0.9700
C2—H2	0.9800	C13—C14	1.522 (6)
C3—C17	1.516 (6)	C13—H13A	0.9700
C3—C4	1.519 (6)	C13—H13B	0.9700
C3—H3	0.9800	C14—C16	1.522 (5)
C4—H4A	0.9600	C14—C15	1.528 (5)
C4—H4B	0.9600	C14—H14	0.9800
C4—H4C	0.9600	C15—H15A	0.9700
C5—N1	1.334 (4)	C15—H15B	0.9700
C5—C6	1.355 (5)	C16—H16A	0.9600
C5—C8	1.523 (4)	C16—H16B	0.9600
C6—C7	1.442 (4)	C16—H16C	0.9600
C7—O2	1.217 (4)	C17—H17A	0.9600
C7—O1	1.356 (4)	C17—H17B	0.9600
C8—O3	1.366 (4)	C17—H17C	0.9600
C8—O1	1.457 (4)	C18—H18A	0.9600
C8—H8	0.9800	C18—H18B	0.9600
C9—O3	1.452 (4)	C18—H18C	0.9600
C9—C15	1.511 (5)	C19—H19A	0.9600
C9—C10	1.518 (5)	C19—H19B	0.9600
C9—H9	0.9800	C19—H19C	0.9600
C10—C11	1.535 (5)	N1—H1	0.8600
C10—C12	1.537 (6)	O4—H4	0.8200
C10—H10	0.9800

O5—C1—O4	125.2 (3)	C13—C12—C10	112.3 (4)
O5—C1—C2	125.0 (3)	C13—C12—H12A	109.1
O4—C1—C2	109.7 (3)	C10—C12—H12A	109.1
N1—C2—C1	109.7 (3)	C13—C12—H12B	109.1
N1—C2—C3	111.4 (3)	C10—C12—H12B	109.1
C1—C2—C3	111.7 (3)	H12A—C12—H12B	107.9
N1—C2—H2	108.0	C12—C13—C14	112.7 (3)
C1—C2—H2	108.0	C12—C13—H13A	109.0
C3—C2—H2	108.0	C14—C13—H13A	109.0
C17—C3—C4	111.9 (4)	C12—C13—H13B	109.0
C17—C3—C2	112.0 (4)	C14—C13—H13B	109.0
C4—C3—C2	112.8 (4)	H13A—C13—H13B	107.8
C17—C3—H3	106.5	C13—C14—C16	111.8 (3)
C4—C3—H3	106.5	C13—C14—C15	109.5 (3)
C2—C3—H3	106.5	C16—C14—C15	112.2 (4)
C3—C4—H4A	109.5	C13—C14—H14	107.7
C3—C4—H4B	109.5	C16—C14—H14	107.7
H4A—C4—H4B	109.5	C15—C14—H14	107.7
C3—C4—H4C	109.5	C9—C15—C14	112.5 (3)
H4A—C4—H4C	109.5	C9—C15—H15A	109.1
H4B—C4—H4C	109.5	C14—C15—H15A	109.1
N1—C5—C6	134.1 (3)	C9—C15—H15B	109.1
N1—C5—C8	118.5 (3)	C14—C15—H15B	109.1
C6—C5—C8	107.4 (3)	H15A—C15—H15B	107.8
C5—C6—C7	109.3 (3)	C14—C16—H16A	109.5
C5—C6—Br1	131.9 (2)	C14—C16—H16B	109.5
C7—C6—Br1	118.7 (3)	H16A—C16—H16B	109.5
O2—C7—O1	121.2 (3)	C14—C16—H16C	109.5
O2—C7—C6	128.8 (4)	H16A—C16—H16C	109.5
O1—C7—C6	109.9 (3)	H16B—C16—H16C	109.5
O3—C8—O1	110.9 (3)	C3—C17—H17A	109.5
O3—C8—C5	108.3 (3)	C3—C17—H17B	109.5
O1—C8—C5	104.1 (3)	H17A—C17—H17B	109.5
O3—C8—H8	111.1	C3—C17—H17C	109.5
O1—C8—H8	111.1	H17A—C17—H17C	109.5
C5—C8—H8	111.1	H17B—C17—H17C	109.5
O3—C9—C15	112.2 (3)	C11—C18—H18A	109.5
O3—C9—C10	106.5 (3)	C11—C18—H18B	109.5
C15—C9—C10	111.6 (3)	H18A—C18—H18B	109.5
O3—C9—H9	108.9	C11—C18—H18C	109.5
C15—C9—H9	108.9	H18A—C18—H18C	109.5
C10—C9—H9	108.9	H18B—C18—H18C	109.5
C9—C10—C11	113.9 (3)	C11—C19—H19A	109.5
C9—C10—C12	108.3 (3)	C11—C19—H19B	109.5
C11—C10—C12	114.6 (4)	H19A—C19—H19B	109.5
C9—C10—H10	106.5	C11—C19—H19C	109.5
C11—C10—H10	106.5	H19A—C19—H19C	109.5
C12—C10—H10	106.5	H19B—C19—H19C	109.5
C18—C11—C19	110.7 (4)	C5—N1—C2	124.9 (3)
C18—C11—C10	114.3 (4)	C5—N1—H1	117.6
C19—C11—C10	111.4 (4)	C2—N1—H1	117.6
C18—C11—H11	106.6	C7—O1—C8	108.9 (2)
C19—C11—H11	106.6	C8—O3—C9	117.2 (2)
C10—C11—H11	106.6	C1—O4—H4	109.5

O5—C1—C2—N1	−17.4 (5)	C12—C10—C11—C18	60.0 (5)
O4—C1—C2—N1	164.1 (3)	C9—C10—C11—C19	168.0 (4)
O5—C1—C2—C3	106.6 (4)	C12—C10—C11—C19	−66.5 (5)
O4—C1—C2—C3	−71.9 (4)	C9—C10—C12—C13	−56.3 (5)
N1—C2—C3—C17	76.8 (4)	C11—C10—C12—C13	175.3 (4)
C1—C2—C3—C17	−46.2 (4)	C10—C12—C13—C14	55.7 (5)
N1—C2—C3—C4	−155.9 (3)	C12—C13—C14—C16	−177.6 (4)
C1—C2—C3—C4	81.1 (4)	C12—C13—C14—C15	−52.6 (5)
N1—C5—C6—C7	177.2 (4)	O3—C9—C15—C14	−177.3 (3)
C8—C5—C6—C7	−5.1 (4)	C10—C9—C15—C14	−57.9 (4)
N1—C5—C6—Br1	1.8 (6)	C13—C14—C15—C9	53.7 (4)
C8—C5—C6—Br1	179.5 (3)	C16—C14—C15—C9	178.5 (3)
C5—C6—C7—O2	−174.9 (4)	C6—C5—N1—C2	13.4 (6)
Br1—C6—C7—O2	1.2 (5)	C8—C5—N1—C2	−164.1 (3)
C5—C6—C7—O1	2.2 (4)	C1—C2—N1—C5	−156.4 (3)
Br1—C6—C7—O1	178.3 (2)	C3—C2—N1—C5	79.5 (4)
N1—C5—C8—O3	66.1 (4)	O2—C7—O1—C8	179.3 (3)
C6—C5—C8—O3	−112.0 (3)	C6—C7—O1—C8	1.9 (4)
N1—C5—C8—O1	−175.8 (3)	O3—C8—O1—C7	111.4 (3)
C6—C5—C8—O1	6.1 (4)	C5—C8—O1—C7	−4.8 (4)
O3—C9—C10—C11	−51.4 (4)	O1—C8—O3—C9	91.0 (3)
C15—C9—C10—C11	−174.1 (3)	C5—C8—O3—C9	−155.3 (3)
O3—C9—C10—C12	179.8 (3)	C15—C9—O3—C8	−68.8 (3)
C15—C9—C10—C12	57.1 (4)	C10—C9—O3—C8	168.9 (3)
C9—C10—C11—C18	−65.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.86	2.28	3.047 (4)	149
O4—H4···O2ⁱⁱ	0.82	1.83	2.615 (3)	160

Symmetry codes: (i) y−1, x+1, −z; (ii) −y+3/2, x+1/2, z−1/4.

Experimental details

Crystal data
Chemical formula	C₁₉H₃₀BrNO₅
M_r	432.34
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	293
a, c (Å)	10.5409 (9), 39.388 (7)
V (Å³)	4376.4 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.91
Crystal size (mm)	0.30 × 0.22 × 0.18

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.558, 0.710
No. of measured, independent and observed [I > 2σ(I)] reflections	22304, 3859, 2726
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.085, 1.03
No. of reflections	3859
No. of parameters	241
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.40
Absolute structure	Flack (1983), 1526 Friedel pairs
Absolute structure parameter	−0.001 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.86	2.28	3.047 (4)	148.6
O4—H4···O2ⁱⁱ	0.82	1.83	2.615 (3)	159.7

Symmetry codes: (i) y−1, x+1, −z; (ii) −y+3/2, 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 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, Q.-H. & Geng, Z. (1993). Acta Chim. Sin. 51, 622–624. CAS Google Scholar
De Koning, C. B., Hancock, R. D. & Van Otterlo, W. A. L. (1997). Tetrahedron Lett. 8, 1261–1264. CrossRef Google Scholar
Feringa, B. L. & De Jong, J. C. (1988). J. Org. Chem. 53, 125–127. CrossRef Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
He, L., Liu, Y.-M., Li, M. & Chen, Q.-H. (2006). Chem. J. Chin. Univ. 27, 464–467. CAS 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
Lattmann, E., Billington, D. C. & Langley, C. A. (1999). Drug Des. Discov. 16, 243–250. PubMed CAS Google Scholar
Li, Z., Song, X., Wang, Z. & Yang, K. (2009). Acta Cryst. E65, o1030. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tanoury, G. J., Chen, M.-Z., Dong, Y., Forslund, R. E. & Magdziak, D. (2008). Org. Lett. 10, 185–188. Web of Science CrossRef PubMed CAS Google Scholar
Wang, J.-P., Chen, X.-X. & Chen, Q.-H. (2006). Acta Chim. Sin. 64, 686–690. CAS Google Scholar