Limonin isolated from the seeds of Citrus limetta (Indian sweet lemon)

Bauri, A.K.; Foro, S.; Nhu, Q.N.D.

doi:10.1107/S2414314616001723

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160172

https://doi.org/10.1107/S2414314616001723

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Limonin isolated from the seeds of Citrus limetta (Indian sweet lemon)

A. K. Bauri,^a Sabine Foro ^b and Quynh Nguyen Do Nhu ^c ^*

^aBioorganic Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India, ^bFB Material-und Geowissenschaften, Technische Universität Darmstadt, Alarich-Weiss-Strasse 2, 64287 Darmstadt, Germany, and ^cAccident and Emergency Department, Franco Vietnamese Hospital, 7 Nguyen Luong Bang Street, Ho Chi Minh City, Vietnam
^*Correspondence e-mail: nguyendonhuquynh@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 18 January 2016; accepted 27 January 2016; online 6 February 2016)

The title molecule, C₂₆H₃₀O₈ [systematic name: (4aS,14bR)-12-(furan-3-yl)-6,6,8a,12a-tetramethyldecahydro-1H,3H-oxireno[2,3-d]pyrano[4′,3′:3,3a]isobenzofuro[5,4-f]isochromene-3,8,10(6H,9aH)-trione], commonly known as limonin, is an antiproliferative polyoxgenated bioactive molecule. It comprises a fused cyclic system containing a cyclohexane (D), a cyclohexanone (C), a furan (B), an epoxide and two lactone rings (A and E). In addition to these rings, a second furan ring (F) is present as a substituent. Only the cyclohexane (D) ring has a chair conformation; the other six-membered rings (A, C and E) have twist-boat conformations due to steric hinderance or bonding strain. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming a three-dimensional structure.

Keywords: crystal structure; limonin; tetracyclic terpenoid; polyoxgenated; antiproliferative; C—H⋯O hydrogen bonding.

CCDC reference: 1450293

Structure description

The fruit of Citrus limetta or Indian sweet lemon, is popularly known as Mousombi in Mumbai, India. It was procured from local markets for chemical profiling of the seeds in our search for antiproliferative compounds. The roles of citrous limonoids as functional chemicals in agricultural foods have been reviewed (Berhow et al., 2000 ). The juices of Citrus limetta possess a pleasant aroma and have been used as a natural antioxidant and preservative in various food industries, whereas its seeds are quiet bitter in taste. The seeds have been segregated in two parts such as pericarp (outer coat/peel of the seeds) and seed kernel (inner part of the seeds). The inner part of the seeds is quiet soft and comparatively heavier than the pericarp which was extracted with methanol. The chemical analysis of this extract revealed that the major constituent is a pale-yellow oil, a glycerol ester of different long-chain fatty acid mixtures. Besides this oil, this extract is a rich source of some limonoids and their glycosides. Limonoids are highly oxygenated tetracyclic terpenoids. Herein we report on the extraction and crystal structure of the major constituent, the title compound limonin.

A view of the molecular structure of the title compound is shown in Fig. 1. The molecule is composed of a series of fused rings. It contains a cyclohexane ring (D) with a chair conformation, a cyclohexanone and two lactone rings (D, A and E) with twist-boat conformations, a furan (B) and an epoxide ring. In addition to these rings, a second furan ring (F) with a flat conformation is present as a substituent. In the crystal, a three-dimensional structure is formed by molecules being linked by C—H⋯O hydrogen bonds (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O5ⁱ	0.97	2.35	3.313 (3)	171
C4—H4A⋯O6ⁱⁱ	0.97	2.54	3.442 (3)	156
C21—H21⋯O6ⁱⁱⁱ	0.93	2.52	3.135 (3)	124
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+2, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level

Figure 2
The crystal packing of the title compound, viewed along the a axis. The C—H⋯O hydrogen bonds are shown as dashed lines (see Table 1

Synthesis and crystallization

The source of the title compound is a citrus fruit known as sweet lemon. The crude product has been separated by column chromatography over silica gel by gradient solvent elution. In order to purify the target molecule, it was subjected to preparative thin layer chromtography followed by crystallization. Crystals suitable for X-ray diffraction were obtained by recrystallization of the title compound from hexane–ethylacetate (4:1) at room temperature by slow evaporation.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The final refined Flack x parameter is −0.2 (2), and the Hooft y parameter is −0.02 (10), which despite using Cu Kα radiation does not justify the determination of the absolute structure.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₆H₃₀O₈
M_r	470.50
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	299
a, b, c (Å)	8.877 (1), 14.533 (2), 17.748 (2)
V (Å³)	2289.7 (5)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.84
Crystal size (mm)	0.28 × 0.22 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4
No. of measured, independent and observed [I > 2σ(I)] reflections	5062, 4081, 3659
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.110, 1.10
No. of reflections	4081
No. of parameters	308
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.14
Absolute structure	Flack (1983 ); 1742 Friedel pairs
Absolute structure parameter	−0.2 (2)
Computer programs: CAD-4-PC Software (Enraf–Nonius, 1996 ), REDU4 (Stoe & Cie, 1987 ), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1450293

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616001723/su5274sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001723/su5274Isup2.hkl

checkCIF report

Computing details top

Data collection: CAD-4-PC Software (Enraf–Nonius, 1996); cell refinement: CAD-4-PC Software (Enraf–Nonius, 1996); data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

(4aS,14bR)-12-(Furan-3-yl)-6,6,8a,12a-tetramethyldecahydro-1H,3H-oxireno[2,3-d]pyrano[4',3':3,3a]isobenzofuro[5,4-f]isochromene-3,8,10(6H,9aH)-trione top

Crystal data top

C₂₆H₃₀O₈	D_x = 1.365 Mg m⁻³
M_r = 470.50	Melting point: 320 K
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 8.877 (1) Å	θ = 5.6–20.1°
b = 14.533 (2) Å	µ = 0.84 mm⁻¹
c = 17.748 (2) Å	T = 299 K
V = 2289.7 (5) Å³	Prism, colourless
Z = 4	0.28 × 0.22 × 0.15 mm
F(000) = 1000

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.018
Radiation source: fine-focus sealed tube	θ_max = 67.0°, θ_min = 3.9°
Graphite monochromator	h = −10→10
ω/2θ scans	k = −17→1
5062 measured reflections	l = −21→1
4081 independent reflections	3 standard reflections every 120 min
3659 reflections with I > 2σ(I)	intensity decay: 1.0%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0611P)² + 0.4711P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max = 0.001
S = 1.10	Δρ_max = 0.20 e Å⁻³
4081 reflections	Δρ_min = −0.14 e Å⁻³
308 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0025 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983); 1742 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.2 (2)

Special details top

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 > 2sigma(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	0.6003 (2)	0.80012 (14)	0.33749 (12)	0.0269 (4)
C2	0.5523 (3)	0.73683 (17)	0.40261 (13)	0.0351 (5)
H2A	0.4863	0.7715	0.4357	0.042*
H2B	0.4935	0.6867	0.3817	0.042*
C3	0.7945 (3)	0.66158 (18)	0.41522 (15)	0.0435 (6)
C4	0.8133 (3)	0.68083 (16)	0.33300 (13)	0.0381 (6)
H4A	0.7519	0.6387	0.3038	0.046*
H4B	0.9177	0.6722	0.3185	0.046*
C5	0.7656 (2)	0.77923 (16)	0.31750 (13)	0.0308 (5)
H5	0.7855	0.7952	0.2648	0.037*
C6	0.7664 (3)	0.91464 (17)	0.39612 (14)	0.0380 (6)
C7	0.6193 (2)	0.90414 (15)	0.35240 (13)	0.0301 (5)
H7	0.6422	0.9299	0.3027	0.036*
C8	0.4757 (3)	0.95437 (16)	0.37654 (14)	0.0339 (5)
H8A	0.4382	0.9291	0.4235	0.041*
H8B	0.4961	1.0193	0.3838	0.041*
C9	0.3599 (3)	0.94112 (16)	0.31414 (13)	0.0333 (5)
C10	0.3312 (2)	0.84126 (15)	0.28916 (12)	0.0291 (5)
C11	0.4883 (2)	0.79615 (14)	0.27056 (12)	0.0260 (4)
H11	0.5325	0.8381	0.2334	0.031*
C12	0.4600 (3)	0.70816 (15)	0.22574 (12)	0.0313 (5)
H12A	0.3807	0.6723	0.2493	0.038*
H12B	0.5507	0.6710	0.2241	0.038*
C13	0.4129 (3)	0.73613 (16)	0.14529 (13)	0.0324 (5)
H13A	0.3583	0.6854	0.1226	0.039*
H13B	0.5030	0.7464	0.1156	0.039*
C14	0.3128 (2)	0.82416 (14)	0.14136 (12)	0.0277 (4)
C15	0.2343 (2)	0.83565 (15)	0.21743 (13)	0.0289 (5)
C16	0.0807 (3)	0.87401 (17)	0.21645 (14)	0.0356 (5)
H16	0.0484	0.9054	0.2626	0.043*
C17	0.0162 (3)	0.90980 (17)	0.14487 (15)	0.0392 (5)
C18	0.1886 (2)	0.80715 (16)	0.08166 (13)	0.0317 (5)
H18	0.1360	0.7500	0.0945	0.038*
C19	0.2444 (2)	0.79965 (17)	0.00200 (13)	0.0334 (5)
C20	0.2693 (3)	0.7219 (2)	−0.03703 (14)	0.0429 (6)
H20	0.2550	0.6629	−0.0181	0.051*
C21	0.3232 (3)	0.8340 (2)	−0.11317 (15)	0.0474 (6)
H21	0.3533	0.8663	−0.1558	0.057*
C22	0.2793 (3)	0.87306 (19)	−0.04913 (14)	0.0449 (6)
H22	0.2725	0.9358	−0.0394	0.054*
C23	0.8507 (3)	1.0017 (2)	0.37485 (19)	0.0556 (8)
H23A	0.7888	1.0543	0.3855	0.067*
H23B	0.8744	1.0003	0.3221	0.067*
H23C	0.9421	1.0055	0.4035	0.067*
C24	0.7532 (3)	0.9063 (2)	0.48154 (15)	0.0520 (7)
H24A	0.7134	0.8469	0.4943	0.062*
H24B	0.6871	0.9534	0.5002	0.062*
H24C	0.8510	0.9135	0.5039	0.062*
C25	0.2427 (3)	0.79570 (18)	0.35395 (13)	0.0373 (5)
H25A	0.1498	0.8282	0.3617	0.045*
H25B	0.3017	0.7977	0.3992	0.045*
H25C	0.2214	0.7328	0.3412	0.045*
C26	0.4005 (3)	0.91202 (16)	0.12044 (13)	0.0352 (5)
H26A	0.4466	0.9042	0.0719	0.042*
H26B	0.4771	0.9232	0.1575	0.042*
H26C	0.3325	0.9634	0.1188	0.042*
O1	0.6722 (2)	0.69751 (13)	0.44804 (9)	0.0437 (4)
O2	0.85351 (17)	0.83682 (12)	0.36687 (10)	0.0387 (4)
O3	0.07834 (18)	0.88186 (12)	0.07995 (10)	0.0396 (4)
O4	0.3184 (2)	0.74096 (14)	−0.10816 (10)	0.0492 (5)
O5	0.8815 (3)	0.62005 (18)	0.45340 (13)	0.0760 (8)
O6	0.2971 (2)	1.00559 (12)	0.28523 (11)	0.0510 (5)
O7	0.10294 (17)	0.77602 (11)	0.22248 (9)	0.0362 (4)
O8	−0.0850 (2)	0.96443 (15)	0.14442 (12)	0.0605 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0224 (10)	0.0306 (11)	0.0277 (10)	0.0021 (9)	−0.0003 (8)	−0.0015 (9)
C2	0.0297 (11)	0.0435 (13)	0.0322 (12)	0.0020 (10)	−0.0006 (9)	0.0040 (10)
C3	0.0466 (14)	0.0428 (13)	0.0411 (14)	0.0106 (12)	−0.0133 (12)	−0.0042 (11)
C4	0.0320 (12)	0.0407 (13)	0.0415 (13)	0.0111 (10)	−0.0066 (10)	−0.0083 (11)
C5	0.0252 (10)	0.0383 (12)	0.0290 (11)	0.0011 (9)	−0.0015 (9)	−0.0037 (10)
C6	0.0277 (11)	0.0408 (13)	0.0456 (14)	0.0019 (10)	−0.0039 (10)	−0.0119 (11)
C7	0.0264 (10)	0.0334 (11)	0.0304 (11)	0.0005 (9)	0.0017 (9)	−0.0050 (9)
C8	0.0324 (11)	0.0347 (12)	0.0346 (12)	0.0045 (9)	0.0007 (10)	−0.0097 (9)
C9	0.0286 (11)	0.0347 (12)	0.0367 (12)	0.0059 (9)	0.0052 (10)	−0.0042 (10)
C10	0.0229 (10)	0.0333 (11)	0.0311 (11)	0.0024 (9)	0.0044 (9)	−0.0016 (9)
C11	0.0231 (9)	0.0294 (10)	0.0256 (10)	0.0016 (9)	−0.0002 (8)	0.0033 (9)
C12	0.0307 (11)	0.0291 (11)	0.0340 (11)	0.0024 (9)	−0.0024 (9)	−0.0026 (10)
C13	0.0290 (11)	0.0362 (11)	0.0319 (11)	0.0055 (9)	−0.0026 (9)	−0.0036 (9)
C14	0.0224 (10)	0.0317 (11)	0.0291 (11)	0.0018 (9)	0.0000 (9)	0.0022 (9)
C15	0.0225 (10)	0.0299 (11)	0.0342 (12)	−0.0001 (9)	0.0016 (9)	0.0031 (9)
C16	0.0244 (11)	0.0456 (13)	0.0367 (12)	0.0051 (10)	0.0002 (10)	−0.0022 (11)
C17	0.0260 (11)	0.0446 (13)	0.0470 (14)	0.0032 (10)	−0.0019 (10)	0.0012 (12)
C18	0.0257 (10)	0.0361 (11)	0.0333 (11)	0.0001 (9)	−0.0016 (9)	0.0040 (9)
C19	0.0268 (10)	0.0425 (12)	0.0308 (11)	0.0030 (10)	−0.0062 (9)	0.0044 (10)
C20	0.0473 (14)	0.0503 (15)	0.0311 (12)	0.0024 (12)	−0.0012 (11)	0.0058 (11)
C21	0.0476 (14)	0.0596 (16)	0.0349 (13)	0.0010 (13)	−0.0020 (12)	0.0113 (12)
C22	0.0501 (15)	0.0464 (14)	0.0380 (14)	0.0011 (12)	−0.0050 (12)	0.0090 (12)
C23	0.0387 (14)	0.0449 (15)	0.083 (2)	−0.0059 (12)	−0.0018 (15)	−0.0158 (15)
C24	0.0479 (15)	0.0638 (18)	0.0444 (15)	0.0069 (14)	−0.0124 (12)	−0.0194 (13)
C25	0.0262 (10)	0.0519 (14)	0.0339 (11)	0.0020 (11)	0.0029 (10)	0.0050 (11)
C26	0.0316 (11)	0.0386 (13)	0.0353 (12)	−0.0048 (10)	0.0001 (10)	0.0045 (10)
O1	0.0458 (9)	0.0531 (10)	0.0321 (8)	0.0094 (9)	−0.0067 (8)	0.0054 (8)
O2	0.0231 (7)	0.0424 (9)	0.0505 (10)	0.0022 (7)	−0.0053 (7)	−0.0140 (8)
O3	0.0308 (8)	0.0491 (10)	0.0391 (9)	0.0090 (8)	−0.0037 (7)	0.0060 (8)
O4	0.0526 (11)	0.0624 (12)	0.0326 (9)	0.0133 (10)	0.0019 (8)	−0.0004 (8)
O5	0.0822 (16)	0.0946 (17)	0.0512 (12)	0.0491 (15)	−0.0201 (12)	0.0015 (12)
O6	0.0601 (12)	0.0371 (9)	0.0557 (11)	0.0131 (9)	−0.0180 (10)	−0.0032 (9)
O7	0.0242 (7)	0.0445 (9)	0.0398 (9)	−0.0063 (7)	0.0002 (7)	0.0057 (8)
O8	0.0461 (11)	0.0700 (14)	0.0656 (13)	0.0286 (11)	−0.0029 (10)	0.0012 (11)

Geometric parameters (Å, º) top

C1—C2	1.537 (3)	C13—H13A	0.9700
C1—C5	1.540 (3)	C13—H13B	0.9700
C1—C7	1.544 (3)	C14—C15	1.529 (3)
C1—C11	1.550 (3)	C14—C26	1.541 (3)
C2—O1	1.453 (3)	C14—C18	1.549 (3)
C2—H2A	0.9700	C15—O7	1.455 (3)
C2—H2B	0.9700	C15—C16	1.473 (3)
C3—O5	1.192 (3)	C16—O7	1.442 (3)
C3—O1	1.338 (3)	C16—C17	1.488 (3)
C3—C4	1.495 (4)	C16—H16	0.9800
C4—C5	1.517 (3)	C17—O8	1.199 (3)
C4—H4A	0.9700	C17—O3	1.341 (3)
C4—H4B	0.9700	C18—O3	1.462 (3)
C5—O2	1.441 (3)	C18—C19	1.502 (3)
C5—H5	0.9800	C18—H18	0.9800
C6—O2	1.465 (3)	C19—C20	1.344 (4)
C6—C23	1.517 (4)	C19—C22	1.434 (3)
C6—C24	1.525 (4)	C20—O4	1.364 (3)
C6—C7	1.526 (3)	C20—H20	0.9300
C7—C8	1.531 (3)	C21—C22	1.329 (4)
C7—H7	0.9800	C21—O4	1.356 (3)
C8—C9	1.523 (3)	C21—H21	0.9300
C8—H8A	0.9700	C22—H22	0.9300
C8—H8B	0.9700	C23—H23A	0.9600
C9—O6	1.205 (3)	C23—H23B	0.9600
C9—C10	1.539 (3)	C23—H23C	0.9600
C10—C15	1.539 (3)	C24—H24A	0.9600
C10—C25	1.542 (3)	C24—H24B	0.9600
C10—C11	1.576 (3)	C24—H24C	0.9600
C11—C12	1.527 (3)	C25—H25A	0.9600
C11—H11	0.9800	C25—H25B	0.9600
C12—C13	1.542 (3)	C25—H25C	0.9600
C12—H12A	0.9700	C26—H26A	0.9600
C12—H12B	0.9700	C26—H26B	0.9600
C13—C14	1.559 (3)	C26—H26C	0.9600

C2—C1—C5	108.63 (18)	C14—C13—H13B	108.7
C2—C1—C7	119.16 (18)	H13A—C13—H13B	107.6
C5—C1—C7	97.37 (17)	C15—C14—C26	110.65 (18)
C2—C1—C11	112.09 (17)	C15—C14—C18	107.29 (17)
C5—C1—C11	115.28 (17)	C26—C14—C18	109.09 (17)
C7—C1—C11	103.77 (16)	C15—C14—C13	108.06 (18)
O1—C2—C1	116.69 (18)	C26—C14—C13	113.74 (18)
O1—C2—H2A	108.1	C18—C14—C13	107.77 (17)
C1—C2—H2A	108.1	O7—C15—C16	58.99 (14)
O1—C2—H2B	108.1	O7—C15—C14	110.77 (18)
C1—C2—H2B	108.1	C16—C15—C14	116.94 (19)
H2A—C2—H2B	107.3	O7—C15—C10	115.37 (18)
O5—C3—O1	118.4 (3)	C16—C15—C10	120.47 (19)
O5—C3—C4	125.3 (3)	C14—C15—C10	118.79 (17)
O1—C3—C4	116.3 (2)	O7—C16—C15	59.90 (14)
C3—C4—C5	108.80 (19)	O7—C16—C17	117.5 (2)
C3—C4—H4A	109.9	C15—C16—C17	119.9 (2)
C5—C4—H4A	109.9	O7—C16—H16	116.0
C3—C4—H4B	109.9	C15—C16—H16	116.0
C5—C4—H4B	109.9	C17—C16—H16	116.0
H4A—C4—H4B	108.3	O8—C17—O3	120.2 (2)
O2—C5—C4	106.62 (18)	O8—C17—C16	121.7 (2)
O2—C5—C1	105.16 (17)	O3—C17—C16	118.0 (2)
C4—C5—C1	114.23 (19)	O3—C18—C19	104.78 (17)
O2—C5—H5	110.2	O3—C18—C14	111.85 (18)
C4—C5—H5	110.2	C19—C18—C14	114.90 (18)
C1—C5—H5	110.2	O3—C18—H18	108.4
O2—C6—C23	107.2 (2)	C19—C18—H18	108.4
O2—C6—C24	109.4 (2)	C14—C18—H18	108.4
C23—C6—C24	110.5 (2)	C20—C19—C22	105.3 (2)
O2—C6—C7	101.20 (17)	C20—C19—C18	126.9 (2)
C23—C6—C7	112.2 (2)	C22—C19—C18	127.8 (2)
C24—C6—C7	115.6 (2)	C19—C20—O4	111.0 (2)
C6—C7—C8	121.51 (18)	C19—C20—H20	124.5
C6—C7—C1	106.18 (18)	O4—C20—H20	124.5
C8—C7—C1	115.07 (18)	C22—C21—O4	111.2 (2)
C6—C7—H7	104.0	C22—C21—H21	124.4
C8—C7—H7	104.0	O4—C21—H21	124.4
C1—C7—H7	104.0	C21—C22—C19	106.7 (3)
C9—C8—C7	107.36 (18)	C21—C22—H22	126.7
C9—C8—H8A	110.2	C19—C22—H22	126.7
C7—C8—H8A	110.2	C6—C23—H23A	109.5
C9—C8—H8B	110.2	C6—C23—H23B	109.5
C7—C8—H8B	110.2	H23A—C23—H23B	109.5
H8A—C8—H8B	108.5	C6—C23—H23C	109.5
O6—C9—C8	121.6 (2)	H23A—C23—H23C	109.5
O6—C9—C10	122.3 (2)	H23B—C23—H23C	109.5
C8—C9—C10	116.13 (19)	C6—C24—H24A	109.5
C9—C10—C15	112.40 (18)	C6—C24—H24B	109.5
C9—C10—C25	105.94 (18)	H24A—C24—H24B	109.5
C15—C10—C25	108.01 (18)	C6—C24—H24C	109.5
C9—C10—C11	107.82 (17)	H24A—C24—H24C	109.5
C15—C10—C11	107.42 (17)	H24B—C24—H24C	109.5
C25—C10—C11	115.37 (18)	C10—C25—H25A	109.5
C12—C11—C1	122.43 (17)	C10—C25—H25B	109.5
C12—C11—C10	108.15 (17)	H25A—C25—H25B	109.5
C1—C11—C10	113.04 (16)	C10—C25—H25C	109.5
C12—C11—H11	103.7	H25A—C25—H25C	109.5
C1—C11—H11	103.7	H25B—C25—H25C	109.5
C10—C11—H11	103.7	C14—C26—H26A	109.5
C11—C12—C13	107.83 (17)	C14—C26—H26B	109.5
C11—C12—H12A	110.1	H26A—C26—H26B	109.5
C13—C12—H12A	110.1	C14—C26—H26C	109.5
C11—C12—H12B	110.1	H26A—C26—H26C	109.5
C13—C12—H12B	110.1	H26B—C26—H26C	109.5
H12A—C12—H12B	108.5	C3—O1—C2	120.44 (19)
C12—C13—C14	114.34 (18)	C5—O2—C6	112.20 (16)
C12—C13—H13A	108.7	C17—O3—C18	118.86 (18)
C14—C13—H13A	108.7	C21—O4—C20	105.9 (2)
C12—C13—H13B	108.7	C16—O7—C15	61.11 (14)

C5—C1—C2—O1	20.7 (3)	C26—C14—C15—C16	89.4 (2)
C7—C1—C2—O1	−89.3 (3)	C18—C14—C15—C16	−29.5 (3)
C11—C1—C2—O1	149.30 (19)	C13—C14—C15—C16	−145.5 (2)
O5—C3—C4—C5	−138.2 (3)	C26—C14—C15—C10	−68.8 (2)
O1—C3—C4—C5	39.2 (3)	C18—C14—C15—C10	172.33 (18)
C3—C4—C5—O2	55.3 (2)	C13—C14—C15—C10	56.4 (2)
C3—C4—C5—C1	−60.4 (3)	C9—C10—C15—O7	−127.9 (2)
C2—C1—C5—O2	−87.3 (2)	C25—C10—C15—O7	−11.4 (3)
C7—C1—C5—O2	36.9 (2)	C11—C10—C15—O7	113.65 (19)
C11—C1—C5—O2	145.95 (18)	C9—C10—C15—C16	−60.4 (3)
C2—C1—C5—C4	29.2 (2)	C25—C10—C15—C16	56.1 (3)
C7—C1—C5—C4	153.43 (18)	C11—C10—C15—C16	−178.84 (19)
C11—C1—C5—C4	−97.5 (2)	C9—C10—C15—C14	97.0 (2)
O2—C6—C7—C8	164.4 (2)	C25—C10—C15—C14	−146.51 (19)
C23—C6—C7—C8	−81.6 (3)	C11—C10—C15—C14	−21.5 (3)
C24—C6—C7—C8	46.4 (3)	C14—C15—C16—O7	99.1 (2)
O2—C6—C7—C1	30.4 (2)	C10—C15—C16—O7	−103.1 (2)
C23—C6—C7—C1	144.3 (2)	O7—C15—C16—C17	−106.4 (2)
C24—C6—C7—C1	−87.6 (2)	C14—C15—C16—C17	−7.2 (3)
C2—C1—C7—C6	74.7 (2)	C10—C15—C16—C17	150.5 (2)
C5—C1—C7—C6	−41.4 (2)	O7—C16—C17—O8	133.0 (3)
C11—C1—C7—C6	−159.81 (17)	C15—C16—C17—O8	−157.7 (2)
C2—C1—C7—C8	−62.7 (3)	O7—C16—C17—O3	−49.5 (3)
C5—C1—C7—C8	−178.88 (19)	C15—C16—C17—O3	19.8 (3)
C11—C1—C7—C8	62.8 (2)	C15—C14—C18—O3	57.3 (2)
C6—C7—C8—C9	170.9 (2)	C26—C14—C18—O3	−62.6 (2)
C1—C7—C8—C9	−58.7 (3)	C13—C14—C18—O3	173.45 (17)
C7—C8—C9—O6	−126.2 (2)	C15—C14—C18—C19	176.59 (18)
C7—C8—C9—C10	52.3 (3)	C26—C14—C18—C19	56.7 (2)
O6—C9—C10—C15	8.4 (3)	C13—C14—C18—C19	−67.3 (2)
C8—C9—C10—C15	−170.14 (18)	O3—C18—C19—C20	−137.6 (2)
O6—C9—C10—C25	−109.3 (3)	C14—C18—C19—C20	99.3 (3)
C8—C9—C10—C25	72.1 (2)	O3—C18—C19—C22	41.0 (3)
O6—C9—C10—C11	126.6 (2)	C14—C18—C19—C22	−82.2 (3)
C8—C9—C10—C11	−51.9 (2)	C22—C19—C20—O4	0.6 (3)
C2—C1—C11—C12	−62.9 (2)	C18—C19—C20—O4	179.4 (2)
C5—C1—C11—C12	62.1 (3)	O4—C21—C22—C19	0.6 (3)
C7—C1—C11—C12	167.29 (19)	C20—C19—C22—C21	−0.7 (3)
C2—C1—C11—C10	69.3 (2)	C18—C19—C22—C21	−179.5 (2)
C5—C1—C11—C10	−165.73 (18)	O5—C3—O1—C2	−170.9 (3)
C7—C1—C11—C10	−60.5 (2)	C4—C3—O1—C2	11.6 (3)
C9—C10—C11—C12	−164.55 (17)	C1—C2—O1—C3	−44.8 (3)
C15—C10—C11—C12	−43.2 (2)	C4—C5—O2—C6	−142.4 (2)
C25—C10—C11—C12	77.3 (2)	C1—C5—O2—C6	−20.8 (2)
C9—C10—C11—C1	56.6 (2)	C23—C6—O2—C5	−123.5 (2)
C15—C10—C11—C1	177.98 (17)	C24—C6—O2—C5	116.6 (2)
C25—C10—C11—C1	−61.5 (2)	C7—C6—O2—C5	−5.8 (2)
C1—C11—C12—C13	−151.99 (19)	O8—C17—O3—C18	−172.6 (2)
C10—C11—C12—C13	73.9 (2)	C16—C17—O3—C18	9.8 (3)
C11—C12—C13—C14	−36.6 (2)	C19—C18—O3—C17	−175.0 (2)
C12—C13—C14—C15	−23.7 (2)	C14—C18—O3—C17	−49.9 (3)
C12—C13—C14—C26	99.6 (2)	C22—C21—O4—C20	−0.2 (3)
C12—C13—C14—C18	−139.37 (19)	C19—C20—O4—C21	−0.3 (3)
C26—C14—C15—O7	154.24 (17)	C17—C16—O7—C15	110.4 (2)
C18—C14—C15—O7	35.3 (2)	C14—C15—O7—C16	−109.7 (2)
C13—C14—C15—O7	−80.6 (2)	C10—C15—O7—C16	111.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O5ⁱ	0.97	2.35	3.313 (3)	171
C4—H4A···O6ⁱⁱ	0.97	2.54	3.442 (3)	156
C21—H21···O6ⁱⁱⁱ	0.93	2.52	3.135 (3)	124

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

Acknowledgements

The authors thank Professor Dr Hartmut Fuess, FG Strukturforschung, FB Material-und Geowissenschaften, Technische Universität Darmstadt, Alarich-Weiss-Strasse 2, 64287 Darmstadt, for diffractometer time.

References

Berhow, M. A., Hasegawa, S. & Manners, G. D. (2000). Editors. Citrous limonoids: Functional Chemicals in Agriculture Food. ACS Symposium Series, Vol. 758, Washington, DC: Oxford Press. Google Scholar
Enraf–Nonius (1996). CAD-4-PC Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1987). REDU4. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar

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Volume 1| Part 2| February 2016| x160172

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Limonin isolated from the seeds of Citrus limetta (Indian sweet lemon)

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds