Paraherquamide E

Aree, T.; Antia, B.S.; Ekpa, O.D.; Kittakoop, P.

doi:10.1107/S1600536810030795

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2227

https://doi.org/10.1107/S1600536810030795

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Paraherquamide E

Thammarat Aree,^a ^* Bassey S. Antia,^b Okon D. Ekpa ^b and Prasat Kittakoop ^c

^aDepartment of Chemistry, Faculty of Science, Chulalongkorn University, Phyathai Road, Pathumwan, Bangkok 10330, Thailand, ^bDepartment of Pure and Applied Chemistry, University of Calabar, Calabar, Nigeria, and ^cChulabhorn Research Institute and Chulabhorn Graduate Institute, Chemical Biology Program, Vibhavadi-Rangsit Highway, Bangkok 10210, Thailand
^*Correspondence e-mail: thammarat.aree@gmail.com

(Received 30 July 2010; accepted 2 August 2010; online 11 August 2010)

In the title compound, C₂₈H₃₅N₃O₄, also known as 14-deoxyparaherquamide A,the two pyrrolidine rings adopt envelope conformations. The piperazine ring of the diazabicyclo[2.2.2]octan-3-one unit adopts a boat conformation whereas the two piperidine rings are in distorted boat conformations. Intramolecular C—H⋯O hydrogen bonds are observed. In the crystal, the molecules are linked into chains along the b axis by intermolecular N—H⋯O hydrogen bonds.

Related literature

For the structure determination of paraherquamides, see: Liesch & Wichmann (1990 ). For the crystal structure of paraherquamide A, see: Yamazaki et al. (1981 ). For the antinematodal and antiparasitic activities of paraherquamides, see: Ondeyka et al. (1990 ). For their anthelmintic activity, see: Blanchflower et al. (1991 ) and for their insecticidal activity, see: Lopez-Gresa et al. (2006 ). For reviews on the total synthesis and biosynthesis of paraherquamides, see: Williams (2002 ); Williams & Cox (2003 ).

Experimental

Crystal data

C₂₈H₃₅N₃O₄
M_r = 477.59
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.5069 (2) Å
b = 16.0351 (8) Å
c = 23.9713 (11) Å
V = 2501.14 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.40 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.946, T_max = 0.954
8444 measured reflections
2889 independent reflections
1746 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.102
S = 0.98
2889 reflections
322 parameters
H-atom parameters constrained
Δρ_max = 0.16 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⋯O4ⁱ	0.86	2.21	2.968 (4)	147
C17—H17A⋯O4	0.96	2.39	3.016 (5)	123
C20—H20⋯O1	0.98	2.44	3.126 (4)	126
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: Mercury (Macrae et al. 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810030795/ci5149sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030795/ci5149Isup2.hkl

checkCIF report

Comment top

The title compound, paraherquamide E (Fig. 1), was isolated from the marine-derived fungus Aspergillus aculeatus. In the family of the paraherquamides A–I, only the crystal structure of paraherquamide A has been reported thus far (Yamazaki et al., 1981). We report here the crystal structure of paraherquamide E.

The molecular structure of the title compound comprises one diazabicyclo[2.2.2]octan-3-one unit, one cyclopentane ring, one 1,4-dioxepine ring and two pyrrolidine rings one in the middle and the other in the left end of the molecule. The two pyrrolidine rings adopt envelope conformations with atoms C3 and C13 as flaps. The piperazine ring of the diazabicyclo[2.2.2]octan-3-one unit adopts a boat conformation whereas the two piperidine rings are in distorted boat conformations.

The molecular structures of paraherquamide A and E are very similar and can be superimposed with r.m.s. deviation of superposition 0.15 Å (all H-atoms are excluded from the calculation).

In the crystal, the molecules are linked into chains along the b-axis by intermolecular N1—H···O4 hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For the structure determination of paraherquamides, see: Liesch & Wichmann (1990). For the crystal structure of paraherquamide A, see: Yamazaki et al. (1981). For the antinematodal and antiparasitic activities of paraherquamides, see: Ondeyka et al. (1990). For their anthelmintic activity, see: Blanchflower et al. (1991) and for their insecticidal activity, see: Lopez-Gresa et al. (2006). For reviews on the total synthesis and biosynthesis of paraherquamides, see: Williams (2002); Williams & Cox (2003).

Experimental top

The title compound was isolated from the marine-derived fungus Aspergillus aculeatus and the single crystals were obtained by slow evaporation of a methanol–hexane (9:1, v/v) solution at room temperature.

Structure description top

The molecular structures of paraherquamide A and E are very similar and can be superimposed with r.m.s. deviation of superposition 0.15 Å (all H-atoms are excluded from the calculation).

In the crystal, the molecules are linked into chains along the b-axis by intermolecular N1—H···O4 hydrogen bonds (Table 1 and Fig. 2).

For the structure determination of paraherquamides, see: Liesch & Wichmann (1990). For the crystal structure of paraherquamide A, see: Yamazaki et al. (1981). For the antinematodal and antiparasitic activities of paraherquamides, see: Ondeyka et al. (1990). For their anthelmintic activity, see: Blanchflower et al. (1991) and for their insecticidal activity, see: Lopez-Gresa et al. (2006). For reviews on the total synthesis and biosynthesis of paraherquamides, see: Williams (2002); Williams & Cox (2003).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al. 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atomic numbering scheme and 30% probability displacement ellipsoids.
	Fig. 2. A view of the N—H···O hydrogen-bonded (dotted lines) chains of paraherquamide molecules along the b axis.

Paraherquamide E top

Crystal data top

C₂₈H₃₅N₃O₄	D_x = 1.268 Mg m⁻³
M_r = 477.59	Melting point: not measured K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1372 reflections
a = 6.5069 (2) Å	θ = 2.5–19.7°
b = 16.0351 (8) Å	µ = 0.09 mm⁻¹
c = 23.9713 (11) Å	T = 298 K
V = 2501.14 (19) Å³	Needle, colourless
Z = 4	0.40 × 0.10 × 0.10 mm
F(000) = 1024

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2889 independent reflections
Radiation source: fine-focus sealed tube	1746 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
φ and ω scans	θ_max = 28.2°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −5→8
T_min = 0.946, T_max = 0.954	k = −20→15
8444 measured reflections	l = −31→26

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0463P)²] where P = (F_o² + 2F_c²)/3
2889 reflections	(Δ/σ)_max = 0.001
322 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₈H₃₅N₃O₄	V = 2501.14 (19) Å³
M_r = 477.59	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.5069 (2) Å	µ = 0.09 mm⁻¹
b = 16.0351 (8) Å	T = 298 K
c = 23.9713 (11) Å	0.40 × 0.10 × 0.10 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2889 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1746 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.954	R_int = 0.049
8444 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 0.98	Δρ_max = 0.16 e Å⁻³
2889 reflections	Δρ_min = −0.20 e Å⁻³
322 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
N1	0.0595 (4)	0.84401 (16)	0.16792 (11)	0.0366 (7)
H1	−0.0514	0.8699	0.1769	0.044*
N2	0.6009 (5)	0.47354 (18)	0.15605 (13)	0.0452 (8)
N3	0.3520 (4)	0.54738 (18)	0.23432 (11)	0.0353 (7)
O1	−0.0133 (4)	0.71770 (14)	0.20826 (10)	0.0510 (7)
O2	0.4573 (4)	1.06380 (14)	0.07563 (9)	0.0421 (7)
O3	0.0828 (4)	1.01425 (14)	0.13216 (10)	0.0468 (7)
O4	0.2499 (4)	0.41513 (15)	0.25453 (10)	0.0543 (7)
C2	0.0988 (6)	0.7623 (2)	0.17997 (14)	0.0364 (9)
C3	0.3025 (5)	0.73668 (19)	0.15236 (13)	0.0293 (8)
C4	0.5582 (5)	0.8436 (2)	0.10529 (14)	0.0387 (9)
H4	0.6645	0.8054	0.1007	0.046*
C5	0.5796 (5)	0.9252 (2)	0.08689 (14)	0.0396 (9)
H5	0.7014	0.9414	0.0697	0.047*
C6	0.4235 (5)	0.9831 (2)	0.09359 (13)	0.0336 (8)
C7	0.2432 (6)	0.9606 (2)	0.12015 (14)	0.0327 (8)
C8	0.2239 (5)	0.8798 (2)	0.13901 (14)	0.0314 (8)
C9	0.3764 (5)	0.8200 (2)	0.13052 (13)	0.0321 (8)
C10	0.4413 (6)	0.6932 (2)	0.19609 (14)	0.0393 (9)
H10A	0.5828	0.7110	0.1916	0.047*
H10B	0.3968	0.7074	0.2335	0.047*
C11	0.4239 (5)	0.5991 (2)	0.18678 (12)	0.0308 (8)
C12	0.6319 (5)	0.5608 (2)	0.17134 (15)	0.0434 (10)
H12A	0.6918	0.5910	0.1403	0.052*
H12B	0.7252	0.5646	0.2028	0.052*
C13	0.3851 (5)	0.4474 (2)	0.16074 (14)	0.0353 (9)
C14	0.4053 (6)	0.3551 (2)	0.14645 (17)	0.0553 (11)
H14	0.4357	0.3520	0.1065	0.066*
C15	0.6035 (8)	0.3309 (3)	0.1771 (2)	0.0952 (18)
H15A	0.5717	0.3047	0.2126	0.114*
H15B	0.6839	0.2923	0.1549	0.114*
C16	0.7211 (7)	0.4117 (3)	0.1863 (2)	0.0831 (16)
H16A	0.7289	0.4254	0.2256	0.100*
H16B	0.8593	0.4078	0.1713	0.100*
C17	0.2264 (8)	0.2967 (2)	0.15698 (19)	0.0720 (14)
H17A	0.1929	0.2970	0.1960	0.108*
H17B	0.2634	0.2412	0.1458	0.108*
H17C	0.1094	0.3149	0.1358	0.108*
C18	0.3167 (5)	0.4666 (2)	0.22117 (14)	0.0377 (9)
C19	0.2626 (6)	0.50045 (19)	0.11950 (13)	0.0371 (9)
H19A	0.1244	0.4786	0.1156	0.045*
H19B	0.3282	0.4998	0.0832	0.045*
C20	0.2558 (5)	0.58959 (18)	0.14247 (12)	0.0282 (8)
H20	0.1259	0.5933	0.1630	0.034*
C21	0.2623 (5)	0.66842 (19)	0.10578 (13)	0.0311 (8)
C22	0.4342 (6)	0.6665 (2)	0.06154 (14)	0.0441 (10)
H22A	0.5655	0.6642	0.0798	0.066*
H22B	0.4266	0.7159	0.0390	0.066*
H22C	0.4175	0.6182	0.0383	0.066*
C23	0.0595 (6)	0.6830 (2)	0.07491 (15)	0.0463 (10)
H23A	0.0437	0.6417	0.0462	0.069*
H23B	0.0603	0.7375	0.0584	0.069*
H23C	−0.0527	0.6788	0.1008	0.069*
C24	0.0153 (6)	1.0726 (2)	0.09430 (16)	0.0498 (10)
H24	−0.1173	1.0923	0.1003	0.060*
C25	0.1105 (6)	1.1046 (2)	0.05100 (17)	0.0523 (11)
H25	0.0318	1.1411	0.0298	0.063*
C26	0.3240 (6)	1.0919 (2)	0.03039 (14)	0.0456 (10)
C27	0.4195 (8)	1.1744 (2)	0.0128 (2)	0.0788 (15)
H27A	0.4292	1.2107	0.0446	0.118*
H27B	0.3351	1.2001	−0.0152	0.118*
H27C	0.5543	1.1646	−0.0021	0.118*
C28	0.3285 (7)	1.0286 (3)	−0.01689 (16)	0.0696 (14)
H28A	0.4682	1.0189	−0.0280	0.104*
H28B	0.2518	1.0497	−0.0480	0.104*
H28C	0.2685	0.9771	−0.0044	0.104*
C29	0.3185 (8)	0.5797 (3)	0.28994 (15)	0.0709 (14)
H29A	0.2896	0.5344	0.3149	0.106*
H29B	0.2042	0.6175	0.2895	0.106*
H29C	0.4394	0.6086	0.3023	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0304 (16)	0.0298 (18)	0.0497 (17)	0.0040 (13)	0.0168 (14)	0.0009 (14)
N2	0.0426 (19)	0.0366 (19)	0.056 (2)	0.0087 (16)	0.0165 (16)	0.0203 (16)
N3	0.0423 (18)	0.0410 (19)	0.0227 (14)	−0.0021 (14)	0.0018 (13)	0.0055 (13)
O1	0.0489 (17)	0.0379 (16)	0.0663 (17)	−0.0022 (12)	0.0272 (14)	0.0053 (13)
O2	0.0468 (16)	0.0336 (15)	0.0457 (15)	−0.0107 (12)	−0.0008 (13)	0.0057 (12)
O3	0.0510 (16)	0.0383 (15)	0.0513 (15)	0.0103 (13)	0.0191 (13)	0.0106 (13)
O4	0.0655 (18)	0.0513 (16)	0.0460 (16)	−0.0100 (15)	0.0173 (14)	0.0181 (14)
C2	0.037 (2)	0.032 (2)	0.040 (2)	−0.0045 (18)	0.0061 (18)	−0.0024 (17)
C3	0.0302 (19)	0.0281 (19)	0.0296 (18)	−0.0024 (15)	0.0045 (16)	0.0010 (15)
C4	0.027 (2)	0.037 (2)	0.052 (2)	−0.0009 (16)	0.0052 (18)	−0.0025 (18)
C5	0.027 (2)	0.042 (2)	0.050 (2)	−0.0092 (19)	0.0052 (18)	−0.0007 (18)
C6	0.037 (2)	0.029 (2)	0.0343 (19)	−0.0059 (18)	0.0019 (18)	0.0009 (16)
C7	0.036 (2)	0.025 (2)	0.0365 (19)	0.0032 (17)	0.0030 (17)	−0.0035 (15)
C8	0.0300 (19)	0.031 (2)	0.0329 (19)	−0.0055 (16)	0.0043 (16)	−0.0063 (16)
C9	0.032 (2)	0.032 (2)	0.0316 (18)	−0.0039 (17)	0.0001 (17)	−0.0014 (16)
C10	0.035 (2)	0.043 (2)	0.040 (2)	−0.0051 (17)	−0.0061 (17)	−0.0005 (17)
C11	0.0298 (19)	0.035 (2)	0.0275 (17)	−0.0047 (16)	−0.0012 (16)	0.0076 (15)
C12	0.029 (2)	0.051 (3)	0.050 (2)	0.0013 (17)	−0.0004 (18)	0.0189 (19)
C13	0.039 (2)	0.029 (2)	0.038 (2)	0.0025 (16)	0.0131 (18)	0.0098 (17)
C14	0.069 (3)	0.034 (2)	0.063 (3)	0.010 (2)	0.024 (2)	0.011 (2)
C15	0.083 (4)	0.055 (3)	0.148 (5)	0.026 (3)	0.021 (4)	0.048 (3)
C16	0.056 (3)	0.065 (3)	0.129 (4)	0.022 (3)	0.012 (3)	0.046 (3)
C17	0.093 (4)	0.040 (2)	0.083 (3)	−0.002 (2)	0.023 (3)	0.002 (2)
C18	0.032 (2)	0.042 (2)	0.040 (2)	0.0033 (17)	0.0061 (17)	0.0121 (19)
C19	0.052 (2)	0.031 (2)	0.0282 (18)	0.0012 (18)	0.0014 (18)	0.0000 (16)
C20	0.0256 (17)	0.0321 (19)	0.0269 (18)	−0.0008 (15)	0.0028 (15)	0.0017 (15)
C21	0.0311 (19)	0.035 (2)	0.0272 (18)	−0.0002 (16)	−0.0017 (16)	0.0050 (15)
C22	0.055 (3)	0.041 (2)	0.036 (2)	0.005 (2)	0.0101 (19)	0.0052 (17)
C23	0.046 (2)	0.043 (2)	0.050 (2)	0.000 (2)	−0.0187 (19)	0.0070 (18)
C24	0.047 (2)	0.038 (2)	0.065 (3)	0.0089 (19)	0.015 (2)	0.007 (2)
C25	0.053 (3)	0.049 (3)	0.055 (2)	0.008 (2)	0.005 (2)	0.013 (2)
C26	0.051 (2)	0.045 (2)	0.040 (2)	0.0019 (19)	0.010 (2)	0.0102 (19)
C27	0.084 (4)	0.052 (3)	0.100 (4)	−0.003 (3)	0.019 (3)	0.037 (3)
C28	0.081 (4)	0.087 (3)	0.041 (2)	0.016 (3)	0.003 (2)	−0.003 (2)
C29	0.120 (4)	0.064 (3)	0.029 (2)	−0.019 (3)	0.012 (2)	0.004 (2)

Geometric parameters (Å, º) top

N1—C2	1.366 (4)	C14—C15	1.534 (6)
N1—C8	1.398 (4)	C14—H14	0.98
N1—H1	0.86	C15—C16	1.521 (7)
N2—C16	1.456 (5)	C15—H15A	0.97
N2—C12	1.460 (4)	C15—H15B	0.97
N2—C13	1.470 (5)	C16—H16A	0.97
N3—C18	1.353 (4)	C16—H16B	0.97
N3—C29	1.447 (4)	C17—H17A	0.96
N3—C11	1.485 (4)	C17—H17B	0.96
O1—C2	1.226 (4)	C17—H17C	0.96
O2—C6	1.382 (4)	C19—C20	1.532 (4)
O2—C26	1.460 (4)	C19—H19A	0.97
O3—C24	1.376 (4)	C19—H19B	0.97
O3—C7	1.383 (4)	C20—C21	1.541 (4)
O4—C18	1.228 (4)	C20—H20	0.98
C2—C3	1.537 (5)	C21—C23	1.531 (5)
C3—C9	1.513 (4)	C21—C22	1.541 (5)
C3—C10	1.550 (4)	C22—H22A	0.96
C3—C21	1.585 (4)	C22—H22B	0.96
C4—C9	1.382 (5)	C22—H22C	0.96
C4—C5	1.388 (4)	C23—H23A	0.96
C4—H4	0.93	C23—H23B	0.96
C5—C6	1.385 (5)	C23—H23C	0.96
C5—H5	0.93	C24—C25	1.313 (5)
C6—C7	1.382 (5)	C24—H24	0.93
C7—C8	1.378 (4)	C25—C26	1.489 (5)
C8—C9	1.395 (5)	C25—H25	0.93
C10—C11	1.529 (5)	C26—C28	1.522 (5)
C10—H10A	0.97	C26—C27	1.522 (5)
C10—H10B	0.97	C27—H27A	0.96
C11—C12	1.532 (5)	C27—H27B	0.96
C11—C20	1.533 (4)	C27—H27C	0.96
C12—H12A	0.97	C28—H28A	0.96
C12—H12B	0.97	C28—H28B	0.96
C13—C14	1.525 (5)	C28—H28C	0.96
C13—C19	1.528 (5)	C29—H29A	0.96
C13—C18	1.546 (5)	C29—H29B	0.96
C14—C17	1.516 (6)	C29—H29C	0.96

C2—N1—C8	110.8 (3)	N2—C16—H16A	111.0
C2—N1—H1	124.6	C15—C16—H16A	111.0
C8—N1—H1	124.6	N2—C16—H16B	111.0
C16—N2—C12	117.0 (3)	C15—C16—H16B	111.0
C16—N2—C13	106.3 (3)	H16A—C16—H16B	109.0
C12—N2—C13	112.7 (3)	C14—C17—H17A	109.5
C18—N3—C29	122.1 (3)	C14—C17—H17B	109.5
C18—N3—C11	114.2 (3)	H17A—C17—H17B	109.5
C29—N3—C11	123.7 (3)	C14—C17—H17C	109.5
C6—O2—C26	115.2 (3)	H17A—C17—H17C	109.5
C24—O3—C7	121.8 (3)	H17B—C17—H17C	109.5
O1—C2—N1	124.4 (3)	O4—C18—N3	123.5 (3)
O1—C2—C3	126.5 (3)	O4—C18—C13	125.3 (3)
N1—C2—C3	109.1 (3)	N3—C18—C13	111.1 (3)
C9—C3—C2	100.8 (3)	C13—C19—C20	107.6 (3)
C9—C3—C10	116.5 (3)	C13—C19—H19A	110.2
C2—C3—C10	109.4 (3)	C20—C19—H19A	110.2
C9—C3—C21	114.7 (2)	C13—C19—H19B	110.2
C2—C3—C21	110.2 (3)	C20—C19—H19B	110.2
C10—C3—C21	105.2 (2)	H19A—C19—H19B	108.5
C9—C4—C5	118.9 (3)	C19—C20—C11	108.8 (3)
C9—C4—H4	120.6	C19—C20—C21	124.0 (3)
C5—C4—H4	120.6	C11—C20—C21	107.1 (2)
C6—C5—C4	121.4 (3)	C19—C20—H20	105.2
C6—C5—H5	119.3	C11—C20—H20	105.2
C4—C5—H5	119.3	C21—C20—H20	105.2
O2—C6—C7	121.5 (3)	C23—C21—C20	112.2 (3)
O2—C6—C5	118.3 (3)	C23—C21—C22	107.2 (3)
C7—C6—C5	120.1 (3)	C20—C21—C22	113.4 (3)
C8—C7—C6	118.3 (3)	C23—C21—C3	112.2 (3)
C8—C7—O3	116.6 (3)	C20—C21—C3	99.7 (2)
C6—C7—O3	125.1 (3)	C22—C21—C3	112.3 (3)
C7—C8—C9	122.3 (3)	C21—C22—H22A	109.5
C7—C8—N1	128.2 (3)	C21—C22—H22B	109.5
C9—C8—N1	109.5 (3)	H22A—C22—H22B	109.5
C4—C9—C8	119.0 (3)	C21—C22—H22C	109.5
C4—C9—C3	131.7 (3)	H22A—C22—H22C	109.5
C8—C9—C3	109.3 (3)	H22B—C22—H22C	109.5
C11—C10—C3	107.6 (3)	C21—C23—H23A	109.5
C11—C10—H10A	110.2	C21—C23—H23B	109.5
C3—C10—H10A	110.2	H23A—C23—H23B	109.5
C11—C10—H10B	110.2	C21—C23—H23C	109.5
C3—C10—H10B	110.2	H23A—C23—H23C	109.5
H10A—C10—H10B	108.5	H23B—C23—H23C	109.5
N3—C11—C10	117.5 (3)	C25—C24—O3	129.5 (4)
N3—C11—C12	103.8 (3)	C25—C24—H24	115.2
C10—C11—C12	111.5 (3)	O3—C24—H24	115.2
N3—C11—C20	104.5 (2)	C24—C25—C26	130.5 (4)
C10—C11—C20	104.6 (3)	C24—C25—H25	114.8
C12—C11—C20	115.0 (3)	C26—C25—H25	114.8
N2—C12—C11	108.9 (3)	O2—C26—C25	110.5 (3)
N2—C12—H12A	109.9	O2—C26—C28	109.7 (3)
C11—C12—H12A	109.9	C25—C26—C28	110.9 (3)
N2—C12—H12B	109.9	O2—C26—C27	103.4 (3)
C11—C12—H12B	109.9	C25—C26—C27	110.7 (3)
H12A—C12—H12B	108.3	C28—C26—C27	111.5 (3)
N2—C13—C14	100.2 (3)	C26—C27—H27A	109.5
N2—C13—C19	106.9 (3)	C26—C27—H27B	109.5
C14—C13—C19	116.1 (3)	H27A—C27—H27B	109.5
N2—C13—C18	106.9 (3)	C26—C27—H27C	109.5
C14—C13—C18	115.3 (3)	H27A—C27—H27C	109.5
C19—C13—C18	110.2 (3)	H27B—C27—H27C	109.5
C17—C14—C13	119.7 (3)	C26—C28—H28A	109.5
C17—C14—C15	114.2 (3)	C26—C28—H28B	109.5
C13—C14—C15	102.1 (4)	H28A—C28—H28B	109.5
C17—C14—H14	106.7	C26—C28—H28C	109.5
C13—C14—H14	106.7	H28A—C28—H28C	109.5
C15—C14—H14	106.7	H28B—C28—H28C	109.5
C16—C15—C14	106.0 (3)	N3—C29—H29A	109.5
C16—C15—H15A	110.5	N3—C29—H29B	109.5
C14—C15—H15A	110.5	H29A—C29—H29B	109.5
C16—C15—H15B	110.5	N3—C29—H29C	109.5
C14—C15—H15B	110.5	H29A—C29—H29C	109.5
H15A—C15—H15B	108.7	H29B—C29—H29C	109.5
N2—C16—C15	103.8 (4)

C8—N1—C2—O1	174.9 (3)	C16—N2—C13—C18	73.7 (4)
C8—N1—C2—C3	−5.3 (4)	C12—N2—C13—C18	−55.7 (3)
O1—C2—C3—C9	−173.3 (3)	N2—C13—C14—C17	167.8 (4)
N1—C2—C3—C9	7.0 (3)	C19—C13—C14—C17	−77.6 (5)
O1—C2—C3—C10	−50.0 (4)	C18—C13—C14—C17	53.5 (5)
N1—C2—C3—C10	130.2 (3)	N2—C13—C14—C15	40.5 (4)
O1—C2—C3—C21	65.1 (4)	C19—C13—C14—C15	155.1 (3)
N1—C2—C3—C21	−114.6 (3)	C18—C13—C14—C15	−73.7 (4)
C9—C4—C5—C6	0.3 (5)	C17—C14—C15—C16	−152.3 (4)
C26—O2—C6—C7	−66.8 (4)	C13—C14—C15—C16	−21.5 (5)
C26—O2—C6—C5	116.4 (3)	C12—N2—C16—C15	160.1 (3)
C4—C5—C6—O2	178.3 (3)	C13—N2—C16—C15	33.2 (4)
C4—C5—C6—C7	1.4 (5)	C14—C15—C16—N2	−6.0 (5)
O2—C6—C7—C8	−177.3 (3)	C29—N3—C18—O4	1.6 (5)
C5—C6—C7—C8	−0.5 (5)	C11—N3—C18—O4	−177.4 (3)
O2—C6—C7—O3	−0.9 (5)	C29—N3—C18—C13	−174.5 (3)
C5—C6—C7—O3	175.9 (3)	C11—N3—C18—C13	6.5 (4)
C24—O3—C7—C8	−141.1 (3)	N2—C13—C18—O4	−121.8 (4)
C24—O3—C7—C6	42.5 (5)	C14—C13—C18—O4	−11.4 (5)
C6—C7—C8—C9	−2.2 (5)	C19—C13—C18—O4	122.4 (4)
O3—C7—C8—C9	−178.8 (3)	N2—C13—C18—N3	54.3 (3)
C6—C7—C8—N1	178.3 (3)	C14—C13—C18—N3	164.6 (3)
O3—C7—C8—N1	1.6 (5)	C19—C13—C18—N3	−61.5 (4)
C2—N1—C8—C7	−179.3 (3)	N2—C13—C19—C20	−70.9 (3)
C2—N1—C8—C9	1.1 (4)	C14—C13—C19—C20	178.3 (3)
C5—C4—C9—C8	−2.9 (5)	C18—C13—C19—C20	44.8 (4)
C5—C4—C9—C3	176.9 (3)	C13—C19—C20—C11	17.3 (4)
C7—C8—C9—C4	3.9 (5)	C13—C19—C20—C21	144.4 (3)
N1—C8—C9—C4	−176.5 (3)	N3—C11—C20—C19	−69.8 (3)
C7—C8—C9—C3	−175.9 (3)	C10—C11—C20—C19	166.1 (3)
N1—C8—C9—C3	3.7 (4)	C12—C11—C20—C19	43.4 (4)
C2—C3—C9—C4	173.8 (3)	N3—C11—C20—C21	154.0 (3)
C10—C3—C9—C4	55.7 (5)	C10—C11—C20—C21	29.8 (3)
C21—C3—C9—C4	−67.8 (5)	C12—C11—C20—C21	−92.8 (3)
C2—C3—C9—C8	−6.3 (3)	C19—C20—C21—C23	73.5 (4)
C10—C3—C9—C8	−124.5 (3)	C11—C20—C21—C23	−158.6 (3)
C21—C3—C9—C8	112.1 (3)	C19—C20—C21—C22	−48.1 (4)
C9—C3—C10—C11	−146.2 (3)	C11—C20—C21—C22	79.8 (3)
C2—C3—C10—C11	100.4 (3)	C19—C20—C21—C3	−167.6 (3)
C21—C3—C10—C11	−18.0 (3)	C11—C20—C21—C3	−39.7 (3)
C18—N3—C11—C10	172.4 (3)	C9—C3—C21—C23	−77.2 (4)
C29—N3—C11—C10	−6.6 (5)	C2—C3—C21—C23	35.6 (4)
C18—N3—C11—C12	−64.0 (3)	C10—C3—C21—C23	153.4 (3)
C29—N3—C11—C12	117.0 (4)	C9—C3—C21—C20	163.9 (3)
C18—N3—C11—C20	57.0 (3)	C2—C3—C21—C20	−83.2 (3)
C29—N3—C11—C20	−122.0 (4)	C10—C3—C21—C20	34.5 (3)
C3—C10—C11—N3	−121.9 (3)	C9—C3—C21—C22	43.6 (4)
C3—C10—C11—C12	118.4 (3)	C2—C3—C21—C22	156.5 (3)
C3—C10—C11—C20	−6.5 (3)	C10—C3—C21—C22	−85.8 (3)
C16—N2—C12—C11	−124.8 (3)	C7—O3—C24—C25	−20.7 (6)
C13—N2—C12—C11	−1.1 (4)	O3—C24—C25—C26	−3.5 (7)
N3—C11—C12—N2	59.7 (3)	C6—O2—C26—C25	71.2 (4)
C10—C11—C12—N2	−172.8 (3)	C6—O2—C26—C28	−51.3 (4)
C20—C11—C12—N2	−53.9 (4)	C6—O2—C26—C27	−170.3 (3)
C16—N2—C13—C14	−46.9 (4)	C24—C25—C26—O2	−23.2 (6)
C12—N2—C13—C14	−176.3 (3)	C24—C25—C26—C28	98.6 (5)
C16—N2—C13—C19	−168.3 (3)	C24—C25—C26—C27	−137.2 (5)
C12—N2—C13—C19	62.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.86	2.21	2.968 (4)	147
C17—H17A···O4	0.96	2.39	3.016 (5)	123
C20—H20···O1	0.98	2.44	3.126 (4)	126

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₈H₃₅N₃O₄
M_r	477.59
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	6.5069 (2), 16.0351 (8), 23.9713 (11)
V (Å³)	2501.14 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.946, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	8444, 2889, 1746
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.102, 0.98
No. of reflections	2889
No. of parameters	322
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al. 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.86	2.21	2.968 (4)	147
C17—H17A···O4	0.96	2.39	3.016 (5)	123
C20—H20···O1	0.98	2.44	3.126 (4)	126

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

This work wass supported by the Thai Government Stimulus Package 2 (TKK2555), under the Project for the Establishment of a Comprehensive Center for Innovative Food, Health Products and Agriculture (PERFECTA), the Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University (to TA), the Thailand Research Fund (TRF) and the Center for Environmental Health, Toxicology and Management of Chemicals (ETM) (to PK).

References

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