A new Cryptocarya lactone

The title compound 6-({4-oxo-6-[(1E)-2-phenyl­vinyl]-2H-3,5,6-tri­hydro­pyran-2-yl}methyl)-5H-6-hydro­pyran-2-one, C₁₉H₂₄O₄, is a germination inhibitor isolated from the seeds of Cryptocarya wightiana.

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.057
• wR factor = 0.164
• Data-to-parameter ratio = 5.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



THETM_01  Alert A The value of sine(theta_max)/wavelength is less than 0.550
          Calculated sin(theta_max)/wavelength =    0.5402


 Alert Level B:



REFNR_01  Alert B Ratio of reflections to parameters is < 6 for a
          non-centrosymmetric structure, where ZMAX < 18
          sine(theta)/lambda                0.5402
          Proportion of unique data used    1.0000
          Ratio reflections to parameters   5.9100


 Alert Level C:



PLAT_301  Alert C Main Residue Disorder ........................      15.00 Perc.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           56.40
         From the CIF: _reflns_number_total               2890
         Count of symmetry unique reflns         2417
         Completeness (_total/calc)            119.57%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       473
         Fraction of Friedel pairs measured     0.196
         Are heavy atom types Z>Si present           no
          WARNING: CuKa measured Friedel data can be used to
                   determine absolute structure in a light-atom
                   study only if the Friedel fraction is large.


 1 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

Some extracts of seeds of plants in the genera Cryptocarya have antigermination properties. A study by Spencer et al. (1984) described (-)-cryptocaryalactone {1-[(6-oxo-2H-3-hydropyran-2-yl)methyl]-3-phenylpropyl acetate} and (-)-deacetyl-cryptocaryalactone [6-(2-hydroxy-4-phenylbutyl)-5H-6-hydropyran-2-one], germination inhibitors from Cryptocarya Moschata seeds (i.e. Brazilian nutmeg). Both (-)-cryptocaryalactone and (-)-deacetylcryptocaryalactone inhibit the germination of Abutilon theophrasti (velvetleaf), with the deacetyl compound being more effective. Under conditions that that were lethal to velvetleaf (i.e. 94% inhibition of germination), corn was virtually unaffected, and soybeans were only minimally affected (i.e. 21% inhibition of germination). Based on these results, a project was initiated to identify other natural products that inhibit seed germination of problem weed seeds (such as velvetleaf).

Extracts were prepared from a series of Cryptocarya seeds collected in Sri Lanka. An extract from the seeds of Cryptocarya Wightiana showed antigermination properties. This extract was fractionated further and the active component identified as 6-({4-oxo-6-[(1E)-2-phenylvinyl]-2H-3,5,6-trihydropyran-2-yl}methyl)-5H- 6-hydropyran-2-one, (I).

Two molecules comprise the asymmetric unit of (I) (Fig. 1). Both molecules have disordered phenyl rings with the two alternate positions at approximately 90° to each other and approximately equal occupancy of the two positions.

S2. Experimental

The cryptocarya cightiana seed extract was fractionated by chromatography on silica eluted with mixtures of hexane and ethyl acetate. The ethyl acetate fraction was further separated by preparative HPLC on ODS with CH3CN/H2O/EtOH (1/1/4).

S3. Refinement

Data was collected at three settings of 2θ. With the detector at 95°, 2θ data extend to about 113° [i.e. sin(θ_max)/λ = 0.5402]. Unfortunately, the data crystal for this compound is no longer available so additional data can not be collected. The experimental restriction accounts for, in part, the relatively low data/parameter ratio. H atoms were refined with the riding model.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: XS (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: XP (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Displacement ellipsoid plot (Bruker, 1997) of (I) showing the ellipsoids at the 30% probability level. H atoms are shown as small circles of an arbitrary radii. Atom labels for the alternate conformation of the disordered phenyl rings have been omitted for clarity.

(I)

Crystal data

C19H18O4	F(000) = 656
Mr = 310.33	Dx = 1.275 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
a = 5.2472 (1) Å	Cell parameters from 5137 reflections
b = 5.2528 (1) Å	θ = 3.8–56.4°
c = 58.726 (1) Å	µ = 0.73 mm^−1
β = 92.543 (1)°	T = 153 K
V = 1617.04 (5) Å^3	Prism, colorless
Z = 4	0.84 × 0.35 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer	2890 independent reflections
Radiation source: rotating anode	2868 reflections with I > 2σ(I)
Gobel optics monochromator	Rint = 0.033
ω scans	θmax = 56.4°, θmin = 3.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2000)	h = −5→4
Tmin = 0.712, Tmax = 0.937	k = −4→5
5150 measured reflections	l = −58→62

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.164	w = 1/[σ^2(Fo^2) + (0.1336P)^2 + 0.581P] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.015
2890 reflections	Δρmax = 0.44 e Å^−3
489 parameters	Δρmin = −0.16 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.0 (4)

Special details

Experimental. Final cell refinement and decay correction applied after integration as part of merge process in SAINT v6.02 A.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.2934 (12)	1.2065 (17)	0.76835 (10)	0.091 (2)
H1A	0.3429	1.2671	0.7543	0.109*
C2	0.471 (2)	1.154 (3)	0.7848 (2)	0.085 (4)	0.502 (7)
H2A	0.6421	1.1688	0.7817	0.102*	0.502 (7)
C3	0.4085 (19)	1.080 (2)	0.80548 (17)	0.067 (3)	0.502 (7)
H3A	0.5371	1.0725	0.8169	0.080*	0.502 (7)
C5	−0.0327 (19)	1.088 (2)	0.79383 (14)	0.066 (3)	0.502 (7)
H5A	−0.2026	1.0779	0.7976	0.079*	0.502 (7)
C6	0.0280 (18)	1.170 (2)	0.77219 (14)	0.063 (3)	0.502 (7)
H6A	−0.0973	1.2004	0.7608	0.076*	0.502 (7)
C4	0.1709 (8)	1.0158 (12)	0.81086 (7)	0.0617 (14)
C2'	0.276 (2)	1.349 (3)	0.7861 (2)	0.098 (5)	0.498 (7)
H2'A	0.3026	1.5229	0.7843	0.117*	0.498 (7)
C3'	0.221 (2)	1.263 (3)	0.8076 (2)	0.087 (4)	0.498 (7)
H3'A	0.2178	1.3761	0.8197	0.104*	0.498 (7)
C5'	0.2214 (18)	0.847 (2)	0.79213 (14)	0.063 (3)	0.498 (7)
H5'A	0.2150	0.6715	0.7942	0.075*	0.498 (7)
C6'	0.279 (2)	0.946 (3)	0.77136 (17)	0.075 (3)	0.498 (7)
H6'A	0.3076	0.8374	0.7592	0.090*	0.498 (7)
C7	0.1111 (9)	0.9008 (13)	0.83232 (7)	0.0687 (14)
H7A	0.2060	0.9529	0.8452	0.082*
C8	−0.0663 (13)	0.7288 (17)	0.83506 (8)	0.111 (3)
H8A	−0.1650	0.6826	0.8222	0.133*
C9	−0.1234 (10)	0.6036 (14)	0.85631 (8)	0.0804 (17)
C10	−0.3074 (10)	0.4313 (15)	0.85807 (8)	0.089 (2)
H10A	−0.4289	0.4158	0.8461	0.107*
C11	−0.3270 (9)	0.2685 (11)	0.87749 (8)	0.0680 (14)
O3	−0.4936 (8)	0.1093 (8)	0.87971 (7)	0.0942 (13)
C12	−0.1216 (9)	0.3183 (10)	0.89557 (8)	0.0644 (13)
H12A	−0.1875	0.2798	0.9104	0.077*
H12B	0.0202	0.2041	0.8932	0.077*
C13	−0.0255 (8)	0.5870 (10)	0.89574 (7)	0.0543 (11)
H13A	−0.1624	0.6980	0.9007	0.065*
O2	0.0434 (6)	0.6687 (7)	0.87367 (4)	0.0668 (10)
C14	0.2076 (8)	0.6300 (11)	0.91144 (7)	0.0605 (12)
H14A	0.3290	0.4945	0.9090	0.073*
H14B	0.2871	0.7889	0.9072	0.073*
C15	0.1557 (7)	0.6395 (9)	0.93609 (6)	0.0526 (11)
H15A	0.0410	0.4993	0.9397	0.063*
O1	0.0258 (5)	0.8835 (7)	0.94013 (5)	0.0597 (8)
C16	−0.0078 (10)	0.9599 (12)	0.96170 (8)	0.0670 (14)
O4	−0.1491 (8)	1.1397 (9)	0.96459 (6)	0.0901 (12)
C17	0.1388 (11)	0.8355 (12)	0.97991 (8)	0.0740 (15)
H17A	0.0951	0.8598	0.9949	0.089*
C18	0.3319 (12)	0.6895 (14)	0.97550 (8)	0.0872 (18)
H18A	0.4324	0.6249	0.9876	0.105*
C19	0.3970 (9)	0.6229 (14)	0.95181 (8)	0.0793 (16)
H19A	0.4661	0.4517	0.9515	0.095*
H19B	0.5253	0.7394	0.9466	0.095*
C1A	0.7919 (12)	0.6937 (15)	0.73040 (10)	0.0876 (19)
H1AA	0.8559	0.7464	0.7446	0.105*
C2A	0.738 (2)	0.868 (2)	0.71397 (17)	0.076 (3)	0.515 (7)
H2AA	0.7645	1.0410	0.7168	0.091*	0.515 (7)
C3A	0.6455 (17)	0.786 (2)	0.69322 (19)	0.071 (3)	0.515 (7)
H3AA	0.6261	0.9064	0.6816	0.085*	0.515 (7)
C5A	0.6602 (16)	0.356 (2)	0.70547 (13)	0.062 (3)	0.515 (7)
H5AA	0.6476	0.1842	0.7019	0.074*	0.515 (7)
C6A	0.7507 (18)	0.426 (2)	0.72604 (14)	0.068 (3)	0.515 (7)
H6AA	0.7864	0.3053	0.7373	0.082*	0.515 (7)
C4A	0.5798 (9)	0.5451 (11)	0.68826 (7)	0.0626 (14)
C2A'	0.533 (2)	0.670 (2)	0.72763 (16)	0.077 (3)	0.485 (7)
H2AB	0.4328	0.6968	0.7401	0.092*	0.485 (7)
C3A'	0.4193 (18)	0.610 (2)	0.70721 (14)	0.063 (3)	0.485 (7)
H3AB	0.2425	0.6090	0.7053	0.076*	0.485 (7)
C5A'	0.831 (2)	0.607 (3)	0.6913 (2)	0.086 (4)	0.485 (7)
H5AB	0.9341	0.6121	0.6788	0.103*	0.485 (7)
C6A'	0.935 (2)	0.662 (3)	0.71270 (19)	0.081 (4)	0.485 (7)
H6AB	1.1107	0.6775	0.7147	0.097*	0.485 (7)
C7A	0.4507 (9)	0.4785 (11)	0.66674 (8)	0.0699 (14)
H7AA	0.4939	0.5695	0.6539	0.084*
C8A	0.2766 (12)	0.2988 (16)	0.66401 (9)	0.108 (3)
H8AA	0.2366	0.2053	0.6768	0.129*
C9A	0.1454 (10)	0.2362 (12)	0.64308 (7)	0.0774 (17)
C10A	−0.0310 (11)	0.0469 (13)	0.64090 (8)	0.0870 (18)
H10B	−0.0424	−0.0702	0.6527	0.104*
C11A	−0.1997 (8)	0.0206 (11)	0.62118 (8)	0.0670 (14)
O3A	−0.3607 (7)	−0.1467 (9)	0.61901 (7)	0.0932 (14)
C12A	−0.1626 (8)	0.2154 (11)	0.60358 (8)	0.0661 (14)
H12C	−0.2759	0.3574	0.6062	0.079*
H12D	−0.2096	0.1438	0.5888	0.079*
C13A	0.1093 (8)	0.3134 (10)	0.60331 (7)	0.0565 (12)
H13B	0.2181	0.1753	0.5981	0.068*
O2A	0.2012 (5)	0.3893 (7)	0.62540 (5)	0.0667 (9)
C14A	0.1435 (9)	0.5403 (10)	0.58798 (7)	0.0598 (12)
H14C	0.0066	0.6601	0.5904	0.072*
H14D	0.3027	0.6239	0.5925	0.072*
C15A	0.1463 (7)	0.4796 (9)	0.56311 (7)	0.0534 (11)
H15B	0.0039	0.3650	0.5591	0.064*
O1A	0.3864 (5)	0.3476 (7)	0.55923 (5)	0.0586 (9)
C16A	0.4604 (9)	0.3093 (11)	0.53773 (7)	0.0592 (13)
O4A	0.6348 (7)	0.1650 (9)	0.53516 (6)	0.0844 (12)
C17A	0.3325 (10)	0.4532 (14)	0.51979 (8)	0.0764 (16)
H17B	0.3531	0.4070	0.5047	0.092*
C18A	0.1886 (11)	0.6470 (14)	0.52429 (8)	0.0840 (18)
H18B	0.1233	0.7465	0.5123	0.101*
C19A	0.1249 (10)	0.7145 (12)	0.54802 (8)	0.0753 (15)
H19C	−0.0473	0.7816	0.5481	0.090*
H19D	0.2410	0.8450	0.5539	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.105 (5)	0.110 (7)	0.058 (3)	−0.021 (4)	0.007 (3)	0.001 (4)
C2	0.060 (6)	0.104 (11)	0.092 (9)	−0.016 (6)	0.016 (5)	−0.015 (7)
C3	0.069 (7)	0.066 (8)	0.066 (6)	−0.007 (5)	0.002 (5)	−0.007 (5)
C5	0.078 (6)	0.066 (7)	0.053 (5)	−0.002 (5)	0.004 (4)	0.012 (5)
C6	0.082 (7)	0.061 (7)	0.046 (5)	−0.011 (5)	−0.002 (4)	−0.003 (5)
C4	0.056 (3)	0.072 (5)	0.057 (3)	−0.015 (2)	0.002 (2)	−0.006 (2)
C2'	0.096 (9)	0.085 (11)	0.111 (12)	−0.028 (8)	−0.008 (7)	0.030 (9)
C3'	0.094 (8)	0.075 (11)	0.089 (9)	−0.010 (7)	−0.008 (6)	−0.027 (7)
C5'	0.082 (6)	0.062 (8)	0.044 (5)	−0.019 (5)	0.011 (4)	−0.007 (5)
C6'	0.082 (7)	0.085 (11)	0.058 (6)	−0.015 (6)	0.000 (5)	−0.004 (6)
C7	0.073 (3)	0.084 (4)	0.049 (3)	−0.010 (3)	0.004 (2)	−0.009 (3)
C8	0.127 (5)	0.155 (7)	0.050 (3)	−0.072 (5)	−0.006 (3)	0.012 (3)
C9	0.095 (3)	0.097 (5)	0.049 (3)	−0.029 (4)	−0.002 (2)	0.007 (3)
C10	0.081 (3)	0.120 (6)	0.064 (3)	−0.045 (4)	−0.011 (2)	−0.004 (3)
C11	0.068 (3)	0.070 (4)	0.067 (3)	−0.017 (3)	0.007 (2)	−0.015 (3)
O3	0.105 (3)	0.066 (3)	0.112 (3)	−0.045 (3)	0.001 (2)	0.001 (2)
C12	0.079 (3)	0.051 (4)	0.063 (3)	−0.012 (2)	0.001 (2)	0.002 (2)
C13	0.056 (2)	0.053 (3)	0.054 (2)	−0.009 (2)	0.0008 (18)	0.008 (2)
O2	0.0749 (18)	0.079 (3)	0.0464 (16)	−0.0255 (18)	−0.0003 (13)	0.0043 (16)
C14	0.060 (2)	0.061 (3)	0.061 (3)	−0.007 (2)	0.0043 (19)	0.011 (2)
C15	0.060 (2)	0.045 (3)	0.052 (2)	−0.010 (2)	−0.0067 (17)	0.013 (2)
O1	0.0674 (17)	0.057 (2)	0.0539 (17)	−0.0010 (15)	−0.0022 (12)	0.0102 (15)
C16	0.079 (3)	0.066 (4)	0.056 (3)	−0.018 (3)	−0.004 (2)	0.007 (2)
O4	0.108 (3)	0.072 (3)	0.090 (3)	0.014 (3)	0.008 (2)	−0.006 (2)
C17	0.095 (4)	0.073 (4)	0.052 (3)	−0.008 (3)	−0.010 (2)	0.007 (3)
C18	0.100 (4)	0.095 (5)	0.064 (3)	−0.003 (4)	−0.033 (3)	0.011 (3)
C19	0.069 (3)	0.093 (5)	0.074 (3)	0.003 (3)	−0.017 (2)	0.009 (3)
C1A	0.098 (4)	0.099 (6)	0.065 (3)	−0.027 (4)	−0.006 (3)	−0.005 (3)
C2A	0.110 (8)	0.044 (7)	0.074 (7)	−0.015 (6)	0.009 (5)	−0.020 (6)
C3A	0.053 (6)	0.065 (8)	0.094 (8)	−0.003 (5)	0.010 (5)	0.010 (6)
C5A	0.072 (6)	0.061 (7)	0.052 (5)	−0.017 (5)	−0.002 (4)	0.003 (4)
C6A	0.084 (6)	0.081 (9)	0.040 (5)	−0.011 (5)	0.012 (4)	0.006 (5)
C4A	0.073 (3)	0.063 (4)	0.052 (3)	−0.014 (2)	0.003 (2)	0.007 (2)
C2A'	0.116 (9)	0.066 (9)	0.048 (5)	−0.021 (6)	0.003 (5)	−0.001 (5)
C3A'	0.068 (6)	0.078 (8)	0.044 (5)	−0.027 (5)	0.009 (4)	0.006 (5)
C5A'	0.070 (8)	0.101 (11)	0.091 (8)	−0.003 (7)	0.038 (6)	0.023 (7)
C6A'	0.061 (6)	0.110 (11)	0.070 (8)	−0.011 (7)	−0.009 (6)	0.007 (7)
C7A	0.086 (3)	0.064 (4)	0.060 (3)	−0.009 (3)	0.007 (2)	0.002 (2)
C8A	0.128 (5)	0.141 (7)	0.053 (3)	−0.072 (5)	−0.011 (3)	0.025 (3)
C9A	0.097 (3)	0.094 (5)	0.041 (2)	−0.036 (3)	0.000 (2)	0.004 (3)
C10A	0.115 (4)	0.088 (5)	0.059 (3)	−0.041 (4)	0.007 (3)	0.008 (3)
C11A	0.054 (3)	0.079 (4)	0.068 (3)	−0.016 (3)	0.013 (2)	−0.004 (3)
O3A	0.076 (2)	0.101 (4)	0.103 (3)	−0.045 (2)	0.0073 (17)	0.009 (2)
C12A	0.046 (2)	0.081 (4)	0.071 (3)	−0.014 (2)	0.0007 (19)	−0.009 (3)
C13A	0.062 (2)	0.057 (4)	0.049 (2)	−0.012 (2)	−0.0067 (18)	0.000 (2)
O2A	0.0762 (18)	0.068 (2)	0.0552 (17)	−0.0213 (17)	−0.0065 (13)	0.0002 (17)
C14A	0.069 (3)	0.049 (3)	0.060 (3)	−0.012 (2)	−0.0095 (19)	0.001 (2)
C15A	0.048 (2)	0.050 (3)	0.061 (2)	−0.0081 (19)	−0.0082 (17)	0.007 (2)
O1A	0.0573 (16)	0.065 (2)	0.0531 (17)	0.0003 (14)	−0.0087 (12)	0.0039 (15)
C16A	0.058 (3)	0.070 (4)	0.050 (3)	−0.011 (3)	0.002 (2)	−0.009 (2)
O4A	0.074 (2)	0.098 (3)	0.081 (2)	0.007 (2)	0.0021 (16)	−0.013 (2)
C17A	0.082 (3)	0.100 (5)	0.048 (3)	−0.010 (3)	0.001 (2)	0.006 (3)
C18A	0.098 (4)	0.095 (6)	0.058 (3)	−0.008 (4)	−0.013 (3)	0.027 (3)
C19A	0.086 (3)	0.066 (4)	0.074 (3)	0.007 (3)	−0.004 (2)	0.022 (3)

Geometric parameters (Å, º)

C1—C2'	1.291 (17)	C1A—C6A'	1.318 (13)
C1—C2	1.340 (13)	C1A—C2A	1.352 (13)
C1—C6'	1.382 (15)	C1A—C2A'	1.365 (13)
C1—C6	1.433 (11)	C1A—C6A	1.444 (15)
C2—C3	1.329 (14)	C2A—C3A	1.362 (15)
C3—C4	1.343 (11)	C3A—C4A	1.342 (13)
C5—C6	1.393 (13)	C5A—C6A	1.330 (13)
C5—C4	1.480 (10)	C5A—C4A	1.464 (11)
C4—C3'	1.339 (16)	C4A—C5A'	1.363 (13)
C4—C7	1.444 (7)	C4A—C7A	1.450 (7)
C4—C5'	1.446 (11)	C4A—C3A'	1.465 (12)
C2'—C3'	1.382 (18)	C2A'—C3A'	1.354 (13)
C5'—C6'	1.372 (15)	C5A'—C6A'	1.378 (15)
C7—C8	1.312 (9)	C7A—C8A	1.318 (8)
C8—C9	1.454 (8)	C8A—C9A	1.420 (7)
C9—C10	1.331 (8)	C9A—O2A	1.356 (6)
C9—O2	1.357 (5)	C9A—C10A	1.360 (8)
C10—C11	1.432 (8)	C10A—C11A	1.433 (7)
C11—O3	1.221 (6)	C11A—O3A	1.222 (6)
C11—C12	1.502 (6)	C11A—C12A	1.473 (7)
C12—C13	1.499 (7)	C12A—C13A	1.518 (6)
C13—O2	1.427 (5)	C13A—O2A	1.420 (5)
C13—C14	1.516 (5)	C13A—C14A	1.509 (7)
C14—C15	1.485 (6)	C14A—C15A	1.496 (6)
C15—O1	1.476 (6)	C15A—O1A	1.465 (5)
C15—C19	1.536 (5)	C15A—C19A	1.520 (7)
O1—C16	1.348 (6)	O1A—C16A	1.353 (5)
C16—O4	1.217 (7)	C16A—O4A	1.203 (6)
C16—C17	1.445 (7)	C16A—C17A	1.438 (7)
C17—C18	1.306 (8)	C17A—C18A	1.301 (8)
C18—C19	1.489 (8)	C18A—C19A	1.490 (8)
C2'—C1—C2	67.0 (8)	C6A'—C1A—C2A	68.3 (8)
C2'—C1—C6'	117.7 (10)	C6A'—C1A—C2A'	119.4 (7)
C2—C1—C6'	75.1 (9)	C2A—C1A—C2A'	78.6 (7)
C2'—C1—C6	81.1 (7)	C6A'—C1A—C6A	79.9 (9)
C2—C1—C6	120.5 (8)	C2A—C1A—C6A	120.7 (7)
C6'—C1—C6	77.8 (8)	C2A'—C1A—C6A	75.6 (8)
C3—C2—C1	121.9 (9)	C1A—C2A—C3A	118.5 (11)
C2—C3—C4	123.8 (8)	C4A—C3A—C2A	124.9 (10)
C6—C5—C4	120.6 (8)	C6A—C5A—C4A	121.5 (10)
C5—C6—C1	116.6 (7)	C5A—C6A—C1A	118.2 (9)
C3'—C4—C3	62.2 (8)	C3A—C4A—C5A'	60.6 (9)
C3'—C4—C7	125.7 (7)	C3A—C4A—C7A	121.5 (6)
C3—C4—C7	123.4 (6)	C5A'—C4A—C7A	125.7 (6)
C3'—C4—C5'	116.1 (8)	C3A—C4A—C5A	115.2 (7)
C3—C4—C5'	76.8 (6)	C5A'—C4A—C5A	79.9 (7)
C7—C4—C5'	117.5 (7)	C7A—C4A—C5A	123.2 (6)
C3'—C4—C5	78.1 (8)	C3A—C4A—C3A'	76.5 (7)
C3—C4—C5	115.3 (7)	C5A'—C4A—C3A'	115.6 (8)
C7—C4—C5	121.2 (5)	C7A—C4A—C3A'	117.1 (5)
C5'—C4—C5	78.1 (6)	C5A—C4A—C3A'	77.9 (6)
C1—C2'—C3'	124.8 (14)	C3A'—C2A'—C1A	121.6 (10)
C4—C3'—C2'	120.1 (11)	C2A'—C3A'—C4A	118.8 (9)
C6'—C5'—C4	119.9 (11)	C4A—C5A'—C6A'	120.5 (9)
C5'—C6'—C1	120.3 (10)	C1A—C6A'—C5A'	122.1 (9)
C8—C7—C4	125.3 (4)	C8A—C7A—C4A	125.0 (5)
C7—C8—C9	126.3 (5)	C7A—C8A—C9A	125.3 (5)
C10—C9—O2	124.0 (5)	O2A—C9A—C10A	122.1 (4)
C10—C9—C8	123.5 (4)	O2A—C9A—C8A	114.4 (5)
O2—C9—C8	112.3 (5)	C10A—C9A—C8A	123.5 (5)
C9—C10—C11	123.1 (4)	C9A—C10A—C11A	122.7 (5)
O3—C11—C10	124.8 (4)	O3A—C11A—C10A	123.6 (5)
O3—C11—C12	122.6 (5)	O3A—C11A—C12A	122.6 (4)
C10—C11—C12	112.6 (4)	C10A—C11A—C12A	113.8 (4)
C13—C12—C11	113.5 (4)	C11A—C12A—C13A	113.4 (4)
O2—C13—C12	112.1 (4)	O2A—C13A—C14A	106.2 (4)
O2—C13—C14	106.1 (3)	O2A—C13A—C12A	111.5 (4)
C12—C13—C14	114.0 (4)	C14A—C13A—C12A	114.3 (4)
C9—O2—C13	115.2 (4)	C9A—O2A—C13A	117.2 (4)
C15—C14—C13	114.8 (3)	C15A—C14A—C13A	114.9 (4)
O1—C15—C14	107.0 (4)	O1A—C15A—C14A	107.4 (3)
O1—C15—C19	109.1 (4)	O1A—C15A—C19A	109.6 (4)
C14—C15—C19	113.7 (4)	C14A—C15A—C19A	113.1 (4)
C16—O1—C15	119.4 (4)	C16A—O1A—C15A	120.0 (3)
O4—C16—O1	117.9 (4)	O4A—C16A—O1A	117.5 (4)
O4—C16—C17	123.7 (5)	O4A—C16A—C17A	124.9 (5)
O1—C16—C17	118.2 (5)	O1A—C16A—C17A	117.5 (5)
C18—C17—C16	120.7 (5)	C18A—C17A—C16A	121.2 (5)
C17—C18—C19	122.4 (4)	C17A—C18A—C19A	122.2 (5)
C18—C19—C15	109.3 (4)	C18A—C19A—C15A	109.7 (5)