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A new iridoid glycoside, methyl (3R,4R,4aS,7S,7aR)-3-hy­droxy-7-methyl-5-oxo­octa­hydro­cyclo­penta­[c]pyran-4-carboxyl­ate-3-O-β-D-(1′S,2′R,3′S,4′S,5′R)-gluco­pyran­oside, named loniceroside A, C17H26O10, (1), was obtained from the aerial parts of Lonicera saccata. Its structure was established based on an analysis of spectroscopic data, including 1D NMR, 2D NMR and HRESIMS, and the configurations of the chiral C atoms were determined by X-ray crystallographic analysis. The single-crystal structure reveals that the cyclo­penta­[c]pyran scaffold is formed from a five-membered ring and a chair-like six-membered ring connected through two bridgehead chiral C atoms. In the solid state, the glucose group of (1) plays an important role in constructing an unusual supra­molecular motif. The structure analysis revealed adjacent mol­ecules linked together through inter­molecular O—H...O hydrogen bonds to generate a banded structure. Furthermore, the banded structures are linked into a three-dimensional network by inter­esting hydrogen bonds. Biogenetically, com­pound (1) carries a gluco­pyranos­yloxy moiety at the C-3 position, representing a rare structural feature for naturally occurring iridoid glycosides. The growth inhibitory effects against human cervical carcinoma cells (Hela), human lung adenocarcinoma cells (A549), human acute mononuclear granulocyte leukaemia (THP-1) and the human liver hepatocellular carcinoma cell line (HepG2) were evaluated by the MTT method.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620001977/zo3001sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229620001977/zo3001Isup2.hkl
Contains datablock I

CCDC reference: 1945812

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2017 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(3R,4R,4aS,7S,7aR)-3-Hydroxy-7-methyl-5-oxooctahydrocyclopenta[c]pyran-4-carboxylate-3-O-β-D-(1'S,2'R,3'S,4'S,5'R)-glucopyranoside top
Crystal data top
C17H26O10Dx = 1.469 Mg m3
Mr = 390.38Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121Cell parameters from 6911 reflections
a = 8.1545 (1) Åθ = 2.8–73.4°
b = 13.8326 (1) ŵ = 1.04 mm1
c = 15.6478 (2) ÅT = 100 K
V = 1765.04 (3) Å3Block, colourless
Z = 40.14 × 0.12 × 0.11 mm
F(000) = 832
Data collection top
Rigaku OD SuperNova Dual source
diffractometer with an AtlasS2 detector
3265 independent reflections
Radiation source: micro-focus sealed X-ray tube3220 reflections with I > 2σ(I)
Detector resolution: 5.2684 pixels mm-1Rint = 0.017
CCD plate scansθmax = 73.5°, θmin = 4.3°
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2015)
h = 69
Tmin = 0.772, Tmax = 1.000k = 1117
7835 measured reflectionsl = 1919
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027 w = 1/[σ2(Fo2) + (0.0408P)2 + 0.3089P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.070(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.14 e Å3
3265 reflectionsΔρmin = 0.23 e Å3
250 parametersAbsolute structure: Flack x determined using 1242 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraintsAbsolute structure parameter: 0.03 (6)
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8825 (2)0.33241 (13)0.09344 (11)0.0154 (4)
H1A0.8759440.2680860.1178940.018*
H1B0.9924690.3411040.0711460.018*
C20.6965 (2)0.39603 (12)0.19570 (11)0.0128 (3)
H20.6866870.4443640.2412070.015*
C30.5620 (2)0.41489 (12)0.12919 (10)0.0117 (3)
H30.5718770.4820420.1099180.014*
C40.5804 (2)0.34860 (12)0.05068 (10)0.0113 (3)
H40.5333100.2846190.0616970.014*
C50.4938 (2)0.39817 (12)0.02397 (11)0.0130 (3)
C60.6211 (2)0.43206 (14)0.08765 (11)0.0179 (4)
H6A0.5982670.4977010.1059360.022*
H6B0.6224100.3903520.1374760.022*
C70.7854 (2)0.42707 (13)0.04023 (11)0.0150 (4)
H70.7985790.4858910.0060030.018*
C80.7604 (2)0.34036 (13)0.02049 (11)0.0126 (3)
H80.7695090.2813050.0137700.015*
C90.9327 (2)0.41669 (14)0.09931 (11)0.0184 (4)
H9A0.9177010.3613970.1355560.028*
H9B1.0302700.4084110.0657820.028*
H9C0.9429820.4737280.1338550.028*
C100.3951 (2)0.40290 (13)0.17150 (11)0.0136 (4)
C110.2243 (3)0.46925 (15)0.27950 (12)0.0218 (4)
H11A0.1327970.4517720.2441510.033*
H11B0.2038740.5309220.3055470.033*
H11C0.2390320.4213020.3231860.033*
C1'0.7413 (2)0.28047 (12)0.30756 (10)0.0123 (3)
H1'0.7689560.3395800.3389270.015*
C2'0.6231 (2)0.21843 (13)0.35974 (11)0.0136 (3)
H2'0.5856000.1638320.3249410.016*
C3'0.7077 (2)0.18070 (13)0.43929 (11)0.0143 (4)
H3'0.7332670.2353910.4767990.017*
C4'0.8668 (2)0.12993 (13)0.41514 (11)0.0145 (4)
H4'0.8387250.0746790.3787760.017*
C5'0.9738 (2)0.19821 (13)0.36269 (11)0.0139 (4)
H5'1.0037010.2548420.3969520.017*
C6'1.1266 (2)0.14760 (13)0.33143 (12)0.0171 (4)
H6'11.1802560.1167030.3795460.021*
H6'21.0953810.0973880.2913340.021*
O10.85326 (15)0.40307 (9)0.15992 (8)0.0143 (3)
O20.66240 (15)0.30343 (8)0.23077 (8)0.0132 (3)
O30.37105 (16)0.47493 (9)0.22765 (8)0.0170 (3)
O40.29929 (16)0.33827 (9)0.15891 (8)0.0173 (3)
O50.34744 (16)0.41156 (10)0.02954 (8)0.0186 (3)
O60.88595 (15)0.22801 (9)0.28735 (8)0.0143 (3)
O70.48610 (16)0.27566 (10)0.38412 (8)0.0189 (3)
H7A0.4070970.2617640.3541130.028*
O80.59971 (17)0.11647 (10)0.48326 (9)0.0205 (3)
H8A0.6534230.0742410.5071180.031*
O90.94861 (17)0.09380 (10)0.48831 (8)0.0185 (3)
H90.9570930.1369300.5239850.028*
O101.23965 (17)0.21100 (10)0.29105 (9)0.0223 (3)
H101.1932440.2402750.2524270.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0124 (8)0.0195 (9)0.0143 (8)0.0031 (7)0.0002 (7)0.0020 (7)
C20.0113 (8)0.0135 (8)0.0135 (7)0.0004 (7)0.0001 (7)0.0010 (6)
C30.0102 (8)0.0122 (7)0.0128 (7)0.0007 (7)0.0001 (7)0.0001 (6)
C40.0101 (8)0.0123 (7)0.0115 (7)0.0009 (7)0.0004 (7)0.0002 (6)
C50.0140 (8)0.0116 (8)0.0135 (8)0.0006 (7)0.0021 (7)0.0029 (6)
C60.0159 (9)0.0222 (9)0.0156 (8)0.0001 (8)0.0009 (8)0.0040 (7)
C70.0130 (9)0.0163 (8)0.0156 (8)0.0009 (7)0.0005 (7)0.0003 (7)
C80.0105 (8)0.0146 (8)0.0129 (8)0.0008 (7)0.0003 (7)0.0014 (7)
C90.0153 (9)0.0229 (9)0.0172 (8)0.0022 (8)0.0026 (8)0.0015 (7)
C100.0127 (8)0.0165 (8)0.0116 (7)0.0034 (8)0.0009 (7)0.0016 (6)
C110.0173 (10)0.0293 (10)0.0187 (9)0.0056 (9)0.0062 (8)0.0020 (8)
C1'0.0101 (8)0.0153 (8)0.0116 (7)0.0016 (7)0.0022 (6)0.0001 (6)
C2'0.0096 (8)0.0165 (8)0.0147 (8)0.0012 (7)0.0002 (7)0.0008 (6)
C3'0.0139 (8)0.0157 (8)0.0132 (8)0.0020 (7)0.0017 (7)0.0010 (7)
C4'0.0141 (8)0.0156 (8)0.0137 (7)0.0008 (7)0.0026 (7)0.0009 (6)
C5'0.0119 (8)0.0154 (8)0.0145 (7)0.0005 (7)0.0033 (7)0.0014 (7)
C6'0.0127 (8)0.0183 (8)0.0204 (8)0.0006 (7)0.0007 (7)0.0032 (7)
O10.0104 (6)0.0174 (6)0.0149 (5)0.0007 (5)0.0005 (5)0.0019 (5)
O20.0135 (6)0.0144 (6)0.0117 (5)0.0002 (5)0.0035 (5)0.0015 (5)
O30.0137 (6)0.0211 (6)0.0161 (6)0.0029 (6)0.0023 (5)0.0042 (5)
O40.0132 (6)0.0215 (6)0.0174 (6)0.0033 (6)0.0012 (5)0.0008 (5)
O50.0119 (6)0.0251 (7)0.0188 (6)0.0012 (6)0.0029 (5)0.0013 (5)
O60.0112 (6)0.0190 (6)0.0127 (5)0.0026 (5)0.0006 (5)0.0024 (5)
O70.0116 (6)0.0268 (7)0.0184 (6)0.0046 (6)0.0001 (5)0.0016 (5)
O80.0176 (7)0.0227 (7)0.0211 (6)0.0021 (6)0.0042 (6)0.0078 (5)
O90.0210 (7)0.0192 (6)0.0153 (6)0.0033 (6)0.0037 (6)0.0028 (5)
O100.0123 (6)0.0295 (7)0.0251 (7)0.0017 (6)0.0006 (6)0.0076 (6)
Geometric parameters (Å, º) top
C1—O11.447 (2)C11—O31.448 (2)
C1—C81.519 (2)C11—H11A0.9600
C1—H1A0.9700C11—H11B0.9600
C1—H1B0.9700C11—H11C0.9600
C2—O11.399 (2)C1'—O21.399 (2)
C2—O21.421 (2)C1'—O61.421 (2)
C2—C31.535 (2)C1'—C2'1.527 (2)
C2—H20.9800C1'—H1'0.9800
C3—C101.522 (2)C2'—O71.421 (2)
C3—C41.540 (2)C2'—C3'1.516 (2)
C3—H30.9800C2'—H2'0.9800
C4—C51.527 (2)C3'—O81.428 (2)
C4—C81.546 (2)C3'—C4'1.523 (3)
C4—H40.9800C3'—H3'0.9800
C5—O51.211 (2)C4'—O91.416 (2)
C5—C61.513 (3)C4'—C5'1.525 (2)
C6—C71.533 (3)C4'—H4'0.9800
C6—H6A0.9700C5'—O61.440 (2)
C6—H6B0.9700C5'—C6'1.510 (3)
C7—C91.523 (3)C5'—H5'0.9800
C7—C81.544 (2)C6'—O101.420 (2)
C7—H70.9800C6'—H6'10.9700
C8—H80.9800C6'—H6'20.9700
C9—H9A0.9600O7—H7A0.8200
C9—H9B0.9600O8—H8A0.8200
C9—H9C0.9600O9—H90.8200
C10—O41.204 (2)O10—H100.8200
C10—O31.343 (2)
O1—C1—C8112.55 (14)O4—C10—C3126.16 (16)
O1—C1—H1A109.1O3—C10—C3109.54 (15)
C8—C1—H1A109.1O3—C11—H11A109.5
O1—C1—H1B109.1O3—C11—H11B109.5
C8—C1—H1B109.1H11A—C11—H11B109.5
H1A—C1—H1B107.8O3—C11—H11C109.5
O1—C2—O2113.34 (14)H11A—C11—H11C109.5
O1—C2—C3111.72 (14)H11B—C11—H11C109.5
O2—C2—C3105.96 (14)O2—C1'—O6107.85 (13)
O1—C2—H2108.6O2—C1'—C2'107.25 (13)
O2—C2—H2108.6O6—C1'—C2'110.86 (14)
C3—C2—H2108.6O2—C1'—H1'110.3
C10—C3—C2109.01 (13)O6—C1'—H1'110.3
C10—C3—C4111.67 (14)C2'—C1'—H1'110.3
C2—C3—C4111.72 (14)O7—C2'—C3'109.21 (14)
C10—C3—H3108.1O7—C2'—C1'109.06 (14)
C2—C3—H3108.1C3'—C2'—C1'110.21 (14)
C4—C3—H3108.1O7—C2'—H2'109.4
C5—C4—C3107.32 (13)C3'—C2'—H2'109.4
C5—C4—C8103.77 (13)C1'—C2'—H2'109.4
C3—C4—C8112.34 (14)O8—C3'—C2'109.24 (15)
C5—C4—H4111.0O8—C3'—C4'110.98 (14)
C3—C4—H4111.0C2'—C3'—C4'110.04 (14)
C8—C4—H4111.0O8—C3'—H3'108.8
O5—C5—C6125.53 (17)C2'—C3'—H3'108.8
O5—C5—C4125.39 (16)C4'—C3'—H3'108.8
C6—C5—C4109.02 (15)O9—C4'—C3'111.31 (14)
C5—C6—C7105.45 (14)O9—C4'—C5'112.59 (15)
C5—C6—H6A110.7C3'—C4'—C5'109.59 (14)
C7—C6—H6A110.7O9—C4'—H4'107.7
C5—C6—H6B110.7C3'—C4'—H4'107.7
C7—C6—H6B110.7C5'—C4'—H4'107.7
H6A—C6—H6B108.8O6—C5'—C6'106.15 (14)
C9—C7—C6113.56 (15)O6—C5'—C4'109.45 (14)
C9—C7—C8113.87 (15)C6'—C5'—C4'111.04 (15)
C6—C7—C8102.57 (14)O6—C5'—H5'110.0
C9—C7—H7108.9C6'—C5'—H5'110.0
C6—C7—H7108.9C4'—C5'—H5'110.0
C8—C7—H7108.9O10—C6'—C5'113.15 (15)
C1—C8—C7115.61 (15)O10—C6'—H6'1108.9
C1—C8—C4113.46 (14)C5'—C6'—H6'1108.9
C7—C8—C4104.84 (14)O10—C6'—H6'2108.9
C1—C8—H8107.5C5'—C6'—H6'2108.9
C7—C8—H8107.5H6'1—C6'—H6'2107.8
C4—C8—H8107.5C2—O1—C1113.02 (13)
C7—C9—H9A109.5C1'—O2—C2116.50 (13)
C7—C9—H9B109.5C10—O3—C11116.57 (15)
H9A—C9—H9B109.5C1'—O6—C5'112.17 (13)
C7—C9—H9C109.5C2'—O7—H7A109.5
H9A—C9—H9C109.5C3'—O8—H8A109.5
H9B—C9—H9C109.5C4'—O9—H9109.5
O4—C10—O3124.28 (16)C6'—O10—H10109.5
O1—C2—C3—C10178.17 (14)O6—C1'—C2'—O7175.60 (13)
O2—C2—C3—C1054.28 (17)O2—C1'—C2'—C3'173.23 (13)
O1—C2—C3—C454.28 (18)O6—C1'—C2'—C3'55.72 (18)
O2—C2—C3—C469.61 (17)O7—C2'—C3'—O865.07 (18)
C10—C3—C4—C580.83 (17)C1'—C2'—C3'—O8175.15 (14)
C2—C3—C4—C5156.80 (14)O7—C2'—C3'—C4'172.86 (14)
C10—C3—C4—C8165.73 (14)C1'—C2'—C3'—C4'53.08 (19)
C2—C3—C4—C843.36 (18)O8—C3'—C4'—O958.92 (19)
C3—C4—C5—O567.2 (2)C2'—C3'—C4'—O9179.96 (14)
C8—C4—C5—O5173.73 (17)O8—C3'—C4'—C5'175.88 (14)
C3—C4—C5—C6110.14 (16)C2'—C3'—C4'—C5'54.84 (18)
C8—C4—C5—C68.97 (18)O9—C4'—C5'—O6177.08 (13)
O5—C5—C6—C7162.52 (17)C3'—C4'—C5'—O658.46 (18)
C4—C5—C6—C714.77 (19)O9—C4'—C5'—C6'60.21 (19)
C5—C6—C7—C9155.70 (15)C3'—C4'—C5'—C6'175.32 (14)
C5—C6—C7—C832.36 (18)O6—C5'—C6'—O1068.25 (18)
O1—C1—C8—C774.23 (19)C4'—C5'—C6'—O10172.88 (14)
O1—C1—C8—C447.0 (2)O2—C2—O1—C157.51 (18)
C9—C7—C8—C172.9 (2)C3—C2—O1—C162.12 (17)
C6—C7—C8—C1163.99 (14)C8—C1—O1—C258.58 (18)
C9—C7—C8—C4161.40 (14)O6—C1'—O2—C295.05 (16)
C6—C7—C8—C438.27 (17)C2'—C1'—O2—C2145.50 (14)
C5—C4—C8—C1156.25 (15)O1—C2—O2—C1'73.21 (18)
C3—C4—C8—C140.65 (19)C3—C2—O2—C1'163.92 (14)
C5—C4—C8—C729.20 (17)O4—C10—O3—C114.2 (2)
C3—C4—C8—C786.40 (16)C3—C10—O3—C11174.33 (14)
C2—C3—C10—O4109.65 (19)O2—C1'—O6—C5'178.19 (13)
C4—C3—C10—O414.3 (2)C2'—C1'—O6—C5'61.05 (17)
C2—C3—C10—O368.81 (17)C6'—C5'—O6—C1'177.66 (14)
C4—C3—C10—O3167.28 (13)C4'—C5'—O6—C1'62.43 (18)
O2—C1'—C2'—O766.90 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O10—H10···O4i0.822.172.7588 (19)128
O9—H9···O7ii0.821.892.7091 (19)173
O8—H8A···O90.822.442.8635 (19)113
O8—H8A···O5iii0.822.282.9571 (19)141
O7—H7A···O10iv0.821.832.638 (2)171
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1/2, z+1; (iii) x+1, y1/2, z+1/2; (iv) x1, y, z.
1H and 13C NMR data for compound (1) in pyridine-d6 [δ in ppm (J in Hz)] top
Positionδ(H)δ(C)COSYHMBCNOESY
13.64 dd (12.6, 1.8);56.9H-7aH-1/C-3,4a,7,7a
4.57 dd (12.6, 4.2)
35.82 d (3.6)97.4H-4H-3/C-1,4,4a,9,1'H-4, H-1'
43.09 dd (11.4, 4.2)42.3H-4a,3H-4/C-3,4a,5,9H-3, H-7
4a3.54 dd (11.4, 7.8)42.5H-7a,4H-4a/C-3,4,5,6,7,7a,9H-7a
5216.4
61.85 ddd (18.6, 10.8, 1.2);46.0H-7H-6/C-4a,5,7,7a,8
2.49 dd (18.6, 7.8)
72.26 m30.2H-6,7a,8H-7/C-1,6,7a,8H-4
7a1.68 m41.3H-1,4a,7H-7a/C-4,4a,7,8H-4a, H-8
80.87 d (6.6)18.0H-7H-8/C-6,7,7aH-7a
9169.9
OCH33.76 s51.8C-9
1'5.07 d (7.8)103.8H-2'H-1'/C-3,2',5'H-3', H-5', H-3
2'3.94 t (9.0)75.1H-1',3'H-2'/C-3',4'
3'4.13 t (9.0)78.6H-2',4'H-3'/C-1',5'H-1', H-5'
4'4.21 t (9.0)70.9H-3',5'H-4'/C-2',6'
5'3.89 m78.7H-4',6'H-5'/C-4',6'H-1', H-3'
6'4.37 dd (12.0, 4.8);62.4H-5'H-6'/C-4',5'
4.48 dd (12.0, 2.4)
Cytotoxic activity of (1) presented as IC50M). top
CompoundIC50
HelaA549THP-1HepG2
(1)5.5±0.4810.2±0.97>50>50
Doxorubicin1.34±0.060.88±0.090.51±0.021.01±0.14
 

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