organic compounds
(2S,3R,4S,4aR)-2,3,4,7-Tetrahydroxy-3,4,4a,5-tetrahydro[1,3]dioxolo[4,5-j]phenanthridin-6(2H)-one hemihydrate
aInstitute of Applied Physics of the Academy of Sciences of Moldova, 5 Academy Street, MD-2028, Chisinau, Republic of Moldova, bDepartment of Chemistry and Biochemistry, Texas State University, 601 University Drive, San Marcos, TX 78666, USA, cDipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, Via Cinthia 4, Napoli 80126, Italy, and dDepartment of Chemistry & Biology, New Mexico Highlands University, 803 University Avenue, Las Vegas, NM 87701, USA
*Correspondence e-mail: evgheny.jukov@gmail.com
The title natural compound, isolated from Narcissus pseudonarcissus var. King Alfred crystallizes as a hemihydrate, C14H13NO7·0.5H2O, with four crystallographically independent dioxolophenanthridinone molecules and two crystallographically independent solvent water molecules in the All four crystallographically independent dioxolophenanthridinone molecules are geometrically very similar and differ only in the orientations of the three hydroxy groups at the terminal cyclohexene rings. The five-membered dioxolane ring has a planar conformation (the r.m.s. deviations are 0.010, 0.019, 0.025 and 0.004 Å, for the four crystallographically independent molecules), and the six-membered dihydropyridone and cyclohexene rings adopt sofa conformations in each molecule. The flattened structure of each dioxolophenanthridinone molecule is supported by a strong intramolecular O—H⋯O hydrogen bond. The N atom has a slightly pyramidalized configuration. In the crystal, the dioxolophenanthridinone molecules form layers parallel to (101) with O—H⋯O and N—H⋯O hydrogen bonds linking the dioxolophenanthridinone molecules both within and between the layers and the water molecules, forming a three-dimensional framework. The absolute configurations of the chiral centers are 2S, 3R, 4S and 4aR.
Related literature
For general background to narciclasine, see: Ceriotti (1967a,b); Ceriotti et al. (1967); Kornienko & Evidente (2008). For the crystal structures of related compounds, see: Savona et al. (1970); Immirzi & Fuganti (1972); Bi et al. (1998); McNulty et al. (2011).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis PRO; 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
https://doi.org/10.1107/S1600536812048763/rk2387sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048763/rk2387Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812048763/rk2387Isup3.cml
Narciclasine, I, was isolated from the dried and minced bulbs of Narcissus pseudonarcissus var. King Alfred using an alternative method compared to those reported previously (Kornienko & Evidente, 2008). The methanol organic extract obtained using a Soxhlet was purified with two steps of column flash
and 1 g of I was collected as amorphous solid. White single crystals of I suitable for an X-ray analysis were obtained by a slow dissolution of water in narciclasine-containing DMSO.The hydrogen atoms of the hydroxy- and amino-groups were localized in the difference Fourier map and refined isotropically. The other hydrogen atoms were placed in calculated positions with C–H = 0.95-1.00Å and refined in the riding model with fixed isotropic displacement parameters with Uiso(H) = 1.2Ueq(C).
The
of I was objectively determined by the of which has become equal to 0.05 (8).Since his first isolation from Narcissus bulbs by Ceriotti in 1967 (Ceriotti, 1967a; Ceriotti, 1967b; Ceriotti et al., 1967), narciclasine has been extensively studied from chemical and biological standpoints (Kornienko & Evidente, 2008). It exhibits a broad range of biological activities and thus has various potential practical applications, for example, in the treatment of brain cancers, such as glioblastoma multiforme. The structure and absolute stereochemistry of this isocarbostyril related to the Amaryllidaceae
was unambiguously elucidated by an X-ray analysis of the corresponding tetraacetate (Savona et al., 1970; Immirzi & Fuganti, 1972). In 1998, narciclasine isolated from the mucilage of Narcissustazetta L. bulbs was studied by an X-ray but the crystallographic data and structure details were not presented and deposited (Bi et al., 1998). Furthermore, the X-ray data of cis-dihydronarciclasine were reported very recently (McNulty et al., 2011). Because of its biological importance, narciclasine is studied in complexes with the target proteins. To assist in these investigations we prepared crystalline natural product and performed an X-ray single-crystal analysis.The title compound, I, crystallizes as hemihydrate, i.e., C14H13NO7.0.5H2O, with the four crystallographically independent molecules of I and the two crystallographically independent water solvate molecules in the
(Fig. 1). All the four crystallographically independent molecules of I are geometrically very similar and differ only by the orientations of the three hydroxy groups at the terminal cyclohexene rings.The molecule of I comprises a fused tetracyclic system containing one five-membered ring (dioxolane) and three six-membered rings (benzene, dihydropyridone and cyclohexene) (Fig. 1). The five-membered dioxolane ring has the planar conformation, and the six-membered dihydropyridone and cyclohexene rings adopt the sofa conformations. In the case of dihydropyridone ring, the bridged carbon atom adjacent to the nitrogen atom deviates from the plane passed through the other atoms of the ring, and, in the case of cyclohexene ring, the carbon atom bearing the hydroxy group and adjacent to the bridged carbon atom is out of the plane passed through the other atoms of the ring. The flattened structure of molecule of I is supported by the strong intramolecular O–H···O hydrogen bond (Table 1). The nitrogen atom has a slightly pyramidalized configuration.
The different disposition of the hydrogen atoms of the hydroxy groups in the four crystallographically independent molecules of I as well as the observed configurations of the nitrogen atoms is explained by developed hydrogen bonding system in the crystal of I (Table 1). In the crystal, the molecules of I form the layers parallel to (101) (Fig. 2). The intermolecular O–H···O and N–H···O hydrogen bonds link the molecules of I both within and between the layers and water solvate molecules into three-dimensional framework (Fig. 2).
The molecule of I possesses four asymmetric centers at the quaternary carbon atoms of the terminal cyclohexene ring. The α radiation and the of The absolute configurations of the chiral centers are 2S,3R,4S,4aR.
of I was objectively determined by use of Cu KFor general background to narciclasine, see: Ceriotti (1967a,b); Ceriotti et al. (1967); Kornienko & Evidente (2008). For the crystal structures of related compounds, see: Savona et al. (1970); Immirzi & Fuganti (1972); Bi et al. (1998); McNulty et al. (2011).
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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).Fig. 1. Molecular structure with the atom numbering scheme of I (four crystallographically independent molecules and two water solvate molecules are presented). Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as small spheres of arbitrary radius. Dashed lines indicate the O–H···O and N–H···O hydrogen bonds. | |
Fig. 2. Crystal packing of I. Dashed lines indicate the O–H···O and N–H···O hydrogen bonds. |
C14H13NO7·0.5H2O | F(000) = 1320 |
Mr = 316.26 | Dx = 1.643 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.5418 Å |
Hall symbol: P 2yb | Cell parameters from 36580 reflections |
a = 10.90063 (8) Å | θ = 3.8–73.8° |
b = 20.37357 (17) Å | µ = 1.16 mm−1 |
c = 11.88385 (9) Å | T = 100 K |
β = 104.3549 (8)° | Plate, colourless |
V = 2556.82 (4) Å3 | 0.25 × 0.23 × 0.06 mm |
Z = 8 |
Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer | 10051 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 9997 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.028 |
Detector resolution: 10.3756 pixels mm-1 | θmax = 74.0°, θmin = 3.8° |
ω–scans | h = −13→13 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −25→23 |
Tmin = 0.738, Tmax = 1.000 | l = −14→14 |
57161 measured reflections |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.1041P)2 + 0.4322P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.122 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.27 e Å−3 |
10051 reflections | Δρmin = −0.21 e Å−3 |
908 parameters | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.00102 (16) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 4707 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.05 (8) |
C14H13NO7·0.5H2O | V = 2556.82 (4) Å3 |
Mr = 316.26 | Z = 8 |
Monoclinic, P21 | Cu Kα radiation |
a = 10.90063 (8) Å | µ = 1.16 mm−1 |
b = 20.37357 (17) Å | T = 100 K |
c = 11.88385 (9) Å | 0.25 × 0.23 × 0.06 mm |
β = 104.3549 (8)° |
Agilent SuperNova (Dual, Cu at zero, Atlas CCD) diffractometer | 10051 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 9997 reflections with I > 2σ(I) |
Tmin = 0.738, Tmax = 1.000 | Rint = 0.028 |
57161 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | Δρmax = 0.27 e Å−3 |
S = 1.05 | Δρmin = −0.21 e Å−3 |
10051 reflections | Absolute structure: Flack (1983), 4707 Friedel pairs |
908 parameters | Absolute structure parameter: 0.05 (8) |
1 restraint |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.10128 (16) | 0.58845 (7) | 0.40287 (15) | 0.0248 (3) | |
O2 | −0.16470 (17) | 0.49383 (8) | 0.48170 (15) | 0.0280 (4) | |
O3 | 0.05191 (14) | 0.58470 (7) | 0.23220 (13) | 0.0186 (3) | |
H3 | 0.103 (3) | 0.5663 (17) | 0.185 (3) | 0.033 (8)* | |
O4 | 0.17583 (14) | 0.51247 (7) | 0.13295 (12) | 0.0173 (3) | |
O5 | 0.24849 (13) | 0.27851 (7) | 0.07456 (12) | 0.0153 (3) | |
H5 | 0.203 (4) | 0.253 (2) | 0.027 (4) | 0.056 (11)* | |
O6 | 0.03231 (13) | 0.21287 (7) | 0.12059 (12) | 0.0161 (3) | |
H6 | 0.013 (3) | 0.1724 (16) | 0.118 (2) | 0.022 (7)* | |
O7 | 0.22117 (13) | 0.21004 (7) | 0.42339 (12) | 0.0173 (3) | |
H7 | 0.292 (3) | 0.2276 (16) | 0.413 (3) | 0.032 (8)* | |
N1 | 0.17149 (15) | 0.40217 (8) | 0.14336 (14) | 0.0133 (3) | |
H1 | 0.222 (3) | 0.3984 (16) | 0.094 (3) | 0.032 (8)* | |
C1 | −0.1697 (2) | 0.56383 (10) | 0.48424 (18) | 0.0187 (4) | |
H1A | −0.1304 | 0.5801 | 0.5635 | 0.022* | |
H1B | −0.2588 | 0.5789 | 0.4618 | 0.022* | |
C2 | −0.05465 (18) | 0.53344 (10) | 0.36023 (17) | 0.0150 (4) | |
C3 | 0.01784 (18) | 0.52988 (10) | 0.28006 (17) | 0.0143 (4) | |
C4 | 0.05381 (17) | 0.46632 (10) | 0.25195 (16) | 0.0123 (4) | |
C5 | 0.01637 (17) | 0.40965 (10) | 0.30334 (15) | 0.0124 (4) | |
C6 | −0.06126 (18) | 0.41495 (10) | 0.38108 (17) | 0.0150 (4) | |
H6A | −0.0907 | 0.3773 | 0.4137 | 0.018* | |
C7 | −0.09250 (18) | 0.47744 (11) | 0.40765 (17) | 0.0167 (4) | |
C8 | 0.13693 (17) | 0.46133 (9) | 0.17180 (15) | 0.0123 (4) | |
C9 | 0.11265 (16) | 0.34097 (9) | 0.16808 (15) | 0.0109 (3) | |
H9 | 0.0386 | 0.3315 | 0.1014 | 0.013* | |
C10 | 0.06533 (16) | 0.34561 (10) | 0.27760 (15) | 0.0113 (3) | |
C11 | 0.20704 (16) | 0.28453 (9) | 0.17845 (15) | 0.0115 (3) | |
H11 | 0.2824 | 0.2949 | 0.2434 | 0.014* | |
C12 | 0.14720 (17) | 0.22178 (9) | 0.20911 (15) | 0.0128 (3) | |
H12 | 0.2054 | 0.1838 | 0.2089 | 0.015* | |
C13 | 0.11638 (17) | 0.22692 (10) | 0.32783 (15) | 0.0129 (3) | |
H13 | 0.0470 | 0.1948 | 0.3280 | 0.015* | |
C14 | 0.06725 (16) | 0.29371 (10) | 0.34676 (15) | 0.0128 (3) | |
H14 | 0.0349 | 0.2996 | 0.4133 | 0.015* | |
O1A | −0.17618 (14) | 0.57428 (7) | 0.96267 (13) | 0.0192 (3) | |
O2A | −0.24300 (15) | 0.47333 (8) | 1.01724 (14) | 0.0212 (3) | |
O3A | −0.01378 (14) | 0.58673 (7) | 0.80411 (13) | 0.0173 (3) | |
H3A | 0.049 (3) | 0.5769 (19) | 0.758 (3) | 0.048 (10)* | |
O4A | 0.11829 (13) | 0.52761 (7) | 0.69631 (12) | 0.0161 (3) | |
O5A | 0.24668 (12) | 0.30645 (7) | 0.62426 (12) | 0.0153 (3) | |
H5A | 0.217 (3) | 0.2783 (17) | 0.569 (3) | 0.030 (8)* | |
O6A | 0.02956 (12) | 0.22587 (8) | 0.59640 (11) | 0.0151 (3) | |
H6AA | 0.028 (3) | 0.1870 (18) | 0.578 (3) | 0.037 (9)* | |
O7A | 0.13673 (14) | 0.19497 (8) | 0.90368 (12) | 0.0185 (3) | |
H7A | 0.100 (4) | 0.163 (2) | 0.923 (3) | 0.051 (10)* | |
N1A | 0.12678 (15) | 0.41726 (8) | 0.68905 (14) | 0.0134 (3) | |
H1AA | 0.175 (3) | 0.4229 (17) | 0.640 (3) | 0.031 (8)* | |
C1A | −0.24805 (18) | 0.54300 (10) | 1.03442 (17) | 0.0157 (4) | |
H1AB | −0.2116 | 0.5540 | 1.1171 | 0.019* | |
H1AC | −0.3370 | 0.5584 | 1.0124 | 0.019* | |
C2A | −0.12403 (18) | 0.52349 (10) | 0.91416 (17) | 0.0143 (4) | |
C3A | −0.04642 (17) | 0.52784 (10) | 0.83915 (16) | 0.0128 (4) | |
C4A | −0.00376 (17) | 0.46811 (10) | 0.80138 (15) | 0.0117 (4) | |
C5A | −0.04178 (17) | 0.40713 (10) | 0.83707 (15) | 0.0115 (4) | |
C6A | −0.12623 (18) | 0.40417 (10) | 0.90945 (16) | 0.0134 (4) | |
H6AB | −0.1564 | 0.3636 | 0.9313 | 0.016* | |
C7A | −0.16278 (17) | 0.46344 (10) | 0.94683 (16) | 0.0145 (4) | |
C8A | 0.08361 (17) | 0.47205 (10) | 0.72538 (16) | 0.0124 (4) | |
C9A | 0.07358 (17) | 0.35238 (10) | 0.69731 (15) | 0.0120 (3) | |
H9A | 0.0084 | 0.3436 | 0.6233 | 0.014* | |
C10A | 0.01006 (16) | 0.34682 (10) | 0.79716 (15) | 0.0118 (3) | |
C11A | 0.17709 (16) | 0.30016 (10) | 0.71063 (15) | 0.0125 (3) | |
H11A | 0.2374 | 0.3062 | 0.7884 | 0.015* | |
C12A | 0.11766 (17) | 0.23275 (9) | 0.70834 (15) | 0.0125 (4) | |
H12A | 0.1851 | 0.1985 | 0.7169 | 0.015* | |
C13A | 0.04951 (17) | 0.22481 (10) | 0.80618 (16) | 0.0140 (4) | |
H13A | −0.0242 | 0.1946 | 0.7788 | 0.017* | |
C14A | 0.00246 (17) | 0.28815 (10) | 0.84499 (15) | 0.0128 (4) | |
H14A | −0.0357 | 0.2863 | 0.9086 | 0.015* | |
O1B | 0.60207 (15) | 0.38711 (8) | 0.67445 (14) | 0.0224 (3) | |
O2B | 0.66136 (15) | 0.48840 (8) | 0.61543 (13) | 0.0215 (3) | |
O3B | 0.45297 (15) | 0.37256 (7) | 0.84392 (13) | 0.0207 (3) | |
H3B | 0.405 (4) | 0.386 (2) | 0.902 (4) | 0.055 (11)* | |
O4B | 0.34387 (14) | 0.43363 (7) | 0.97790 (13) | 0.0185 (3) | |
O5B | 0.19712 (12) | 0.65451 (7) | 1.02628 (12) | 0.0160 (3) | |
H5B | 0.212 (4) | 0.679 (2) | 1.095 (4) | 0.058 (11)* | |
O6B | 0.20914 (13) | 0.73271 (7) | 0.82583 (11) | 0.0161 (3) | |
H6B | 0.137 (3) | 0.7348 (18) | 0.847 (3) | 0.043 (9)* | |
O7B | 0.52571 (13) | 0.76627 (7) | 0.98119 (12) | 0.0184 (3) | |
H7B | 0.596 (4) | 0.768 (2) | 0.962 (3) | 0.050 (10)* | |
N1B | 0.31833 (16) | 0.54343 (9) | 0.96672 (14) | 0.0155 (3) | |
H1BA | 0.277 (3) | 0.5380 (17) | 1.022 (3) | 0.037 (8)* | |
C1B | 0.67792 (18) | 0.41867 (10) | 0.60769 (17) | 0.0171 (4) | |
H1BB | 0.6512 | 0.4043 | 0.5256 | 0.021* | |
H1BC | 0.7682 | 0.4069 | 0.6385 | 0.021* | |
C2B | 0.55542 (18) | 0.43707 (10) | 0.72953 (17) | 0.0143 (4) | |
C3B | 0.48186 (18) | 0.43187 (10) | 0.80840 (16) | 0.0150 (4) | |
C4B | 0.44111 (17) | 0.49147 (10) | 0.84873 (15) | 0.0131 (4) | |
C5B | 0.47705 (17) | 0.55285 (10) | 0.81149 (15) | 0.0125 (4) | |
C6B | 0.55311 (18) | 0.55598 (10) | 0.73210 (17) | 0.0144 (4) | |
H6BA | 0.5780 | 0.5968 | 0.7059 | 0.017* | |
C7B | 0.58981 (18) | 0.49713 (11) | 0.69404 (16) | 0.0151 (4) | |
C8B | 0.36408 (17) | 0.48781 (10) | 0.93492 (16) | 0.0142 (4) | |
C9B | 0.31785 (17) | 0.60607 (10) | 0.90653 (16) | 0.0126 (4) | |
H9B | 0.2407 | 0.6077 | 0.8403 | 0.015* | |
C10B | 0.43332 (17) | 0.61301 (10) | 0.85803 (15) | 0.0125 (4) | |
C11B | 0.31061 (17) | 0.66210 (10) | 0.98879 (15) | 0.0131 (4) | |
H11B | 0.3849 | 0.6597 | 1.0577 | 0.016* | |
C12B | 0.31304 (17) | 0.72767 (10) | 0.92712 (16) | 0.0134 (4) | |
H12B | 0.3067 | 0.7641 | 0.9818 | 0.016* | |
C13B | 0.43532 (17) | 0.73580 (9) | 0.88773 (15) | 0.0134 (4) | |
H13B | 0.4183 | 0.7662 | 0.8195 | 0.016* | |
C14B | 0.48536 (17) | 0.67210 (10) | 0.85247 (15) | 0.0134 (4) | |
H14B | 0.5595 | 0.6740 | 0.8241 | 0.016* | |
O1C | 0.53886 (17) | 0.38983 (8) | 0.24948 (15) | 0.0276 (4) | |
O2C | 0.60370 (18) | 0.48792 (8) | 0.18242 (15) | 0.0289 (4) | |
O3C | 0.38164 (13) | 0.38340 (7) | 0.41199 (12) | 0.0158 (3) | |
H3C | 0.332 (5) | 0.396 (2) | 0.464 (4) | 0.074 (14)* | |
O4C | 0.27433 (14) | 0.44915 (7) | 0.53502 (12) | 0.0167 (3) | |
O5C | 0.17104 (12) | 0.67618 (7) | 0.60239 (12) | 0.0147 (3) | |
H5C | 0.182 (3) | 0.6905 (17) | 0.669 (3) | 0.034 (8)* | |
O6C | 0.22150 (12) | 0.76137 (7) | 0.42056 (11) | 0.0149 (3) | |
H6C | 0.146 (3) | 0.7503 (17) | 0.429 (3) | 0.038 (8)* | |
O7C | 0.54366 (12) | 0.75389 (7) | 0.59326 (12) | 0.0159 (3) | |
H7C | 0.553 (3) | 0.7959 (18) | 0.598 (2) | 0.026 (7)* | |
N1C | 0.26085 (15) | 0.55955 (8) | 0.52635 (14) | 0.0136 (3) | |
H1C | 0.211 (3) | 0.5576 (18) | 0.577 (3) | 0.039 (9)* | |
C1C | 0.6107 (2) | 0.41765 (11) | 0.17460 (18) | 0.0188 (4) | |
H1CA | 0.7000 | 0.4030 | 0.1992 | 0.023* | |
H1CB | 0.5753 | 0.4032 | 0.0935 | 0.023* | |
C2C | 0.49214 (19) | 0.44261 (10) | 0.29700 (16) | 0.0149 (4) | |
C3C | 0.41672 (17) | 0.44140 (10) | 0.37436 (16) | 0.0127 (4) | |
C4C | 0.38239 (17) | 0.50309 (10) | 0.41249 (15) | 0.0116 (4) | |
C5C | 0.42654 (17) | 0.56230 (10) | 0.37607 (16) | 0.0128 (4) | |
C6C | 0.50168 (18) | 0.56195 (10) | 0.29527 (16) | 0.0147 (4) | |
H6CA | 0.5302 | 0.6014 | 0.2675 | 0.018* | |
C7C | 0.53138 (19) | 0.50111 (11) | 0.25880 (17) | 0.0169 (4) | |
C8C | 0.30235 (17) | 0.50300 (10) | 0.49545 (15) | 0.0126 (4) | |
C9C | 0.27952 (17) | 0.62357 (9) | 0.47638 (15) | 0.0122 (3) | |
H9C | 0.2044 | 0.6331 | 0.4107 | 0.015* | |
C10C | 0.39702 (17) | 0.62355 (10) | 0.43001 (16) | 0.0121 (3) | |
C11C | 0.28799 (16) | 0.67616 (10) | 0.56871 (15) | 0.0122 (3) | |
H11C | 0.3581 | 0.6647 | 0.6377 | 0.015* | |
C12C | 0.31542 (17) | 0.74292 (9) | 0.52269 (15) | 0.0128 (3) | |
H12C | 0.3185 | 0.7768 | 0.5843 | 0.015* | |
C13C | 0.44355 (16) | 0.74143 (9) | 0.49068 (15) | 0.0127 (3) | |
H13C | 0.4444 | 0.7770 | 0.4328 | 0.015* | |
C14C | 0.47034 (16) | 0.67711 (9) | 0.43991 (15) | 0.0131 (3) | |
H14C | 0.5451 | 0.6741 | 0.4127 | 0.016* | |
O1W | 0.53702 (14) | 0.73287 (8) | 0.21514 (14) | 0.0222 (3) | |
H1WA | 0.533 (3) | 0.7470 (19) | 0.142 (3) | 0.046 (9)* | |
H1WB | 0.578 (4) | 0.762 (2) | 0.265 (4) | 0.070 (13)* | |
O2W | 0.27386 (15) | 0.74364 (9) | 0.19752 (13) | 0.0257 (3) | |
H2WA | 0.359 (3) | 0.7453 (15) | 0.212 (2) | 0.024 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0383 (9) | 0.0097 (8) | 0.0359 (8) | 0.0010 (6) | 0.0274 (7) | −0.0011 (6) |
O2 | 0.0433 (9) | 0.0121 (8) | 0.0414 (9) | 0.0030 (7) | 0.0345 (8) | −0.0008 (7) |
O3 | 0.0263 (7) | 0.0084 (7) | 0.0260 (7) | 0.0003 (5) | 0.0156 (6) | 0.0021 (5) |
O4 | 0.0246 (7) | 0.0108 (7) | 0.0206 (7) | −0.0009 (5) | 0.0137 (5) | 0.0024 (5) |
O5 | 0.0172 (6) | 0.0158 (7) | 0.0158 (6) | 0.0015 (5) | 0.0096 (5) | −0.0016 (5) |
O6 | 0.0183 (7) | 0.0112 (7) | 0.0184 (6) | −0.0048 (5) | 0.0041 (5) | −0.0021 (5) |
O7 | 0.0161 (6) | 0.0192 (8) | 0.0173 (6) | 0.0032 (5) | 0.0054 (5) | 0.0079 (5) |
N1 | 0.0163 (7) | 0.0103 (8) | 0.0157 (7) | −0.0007 (6) | 0.0084 (6) | 0.0002 (6) |
C1 | 0.0254 (10) | 0.0116 (10) | 0.0239 (9) | 0.0021 (8) | 0.0149 (8) | 0.0002 (8) |
C2 | 0.0186 (9) | 0.0087 (10) | 0.0194 (9) | 0.0014 (7) | 0.0082 (7) | −0.0018 (7) |
C3 | 0.0167 (8) | 0.0097 (9) | 0.0166 (8) | −0.0003 (7) | 0.0046 (7) | 0.0000 (7) |
C4 | 0.0140 (8) | 0.0099 (9) | 0.0135 (8) | 0.0009 (7) | 0.0047 (6) | −0.0002 (7) |
C5 | 0.0134 (8) | 0.0122 (10) | 0.0119 (8) | −0.0004 (7) | 0.0037 (6) | 0.0000 (7) |
C6 | 0.0179 (8) | 0.0104 (9) | 0.0198 (9) | 0.0004 (7) | 0.0105 (7) | 0.0009 (7) |
C7 | 0.0205 (9) | 0.0154 (10) | 0.0177 (9) | −0.0004 (7) | 0.0114 (7) | −0.0001 (7) |
C8 | 0.0146 (8) | 0.0101 (9) | 0.0118 (8) | −0.0006 (7) | 0.0029 (6) | 0.0000 (7) |
C9 | 0.0134 (8) | 0.0076 (9) | 0.0129 (8) | −0.0009 (6) | 0.0055 (6) | 0.0005 (6) |
C10 | 0.0106 (7) | 0.0106 (9) | 0.0136 (8) | −0.0014 (6) | 0.0047 (6) | −0.0014 (7) |
C11 | 0.0117 (8) | 0.0118 (9) | 0.0123 (8) | 0.0005 (6) | 0.0054 (6) | 0.0007 (6) |
C12 | 0.0135 (8) | 0.0104 (9) | 0.0155 (8) | 0.0018 (7) | 0.0059 (6) | 0.0017 (7) |
C13 | 0.0130 (8) | 0.0123 (9) | 0.0144 (8) | 0.0000 (7) | 0.0055 (6) | 0.0033 (7) |
C14 | 0.0137 (8) | 0.0122 (9) | 0.0137 (8) | −0.0007 (7) | 0.0057 (6) | 0.0002 (7) |
O1A | 0.0249 (7) | 0.0109 (7) | 0.0281 (7) | −0.0004 (6) | 0.0182 (6) | −0.0047 (6) |
O2A | 0.0290 (7) | 0.0135 (8) | 0.0289 (8) | 0.0005 (6) | 0.0221 (6) | −0.0028 (6) |
O3A | 0.0228 (7) | 0.0075 (7) | 0.0257 (7) | −0.0006 (5) | 0.0139 (6) | −0.0013 (5) |
O4A | 0.0215 (7) | 0.0085 (7) | 0.0220 (6) | −0.0015 (5) | 0.0127 (5) | −0.0005 (5) |
O5A | 0.0166 (6) | 0.0151 (7) | 0.0177 (6) | −0.0017 (5) | 0.0106 (5) | −0.0017 (5) |
O6A | 0.0177 (6) | 0.0129 (7) | 0.0150 (6) | −0.0016 (5) | 0.0043 (5) | −0.0034 (5) |
O7A | 0.0279 (7) | 0.0112 (7) | 0.0169 (7) | 0.0050 (6) | 0.0066 (5) | 0.0047 (5) |
N1A | 0.0182 (7) | 0.0087 (8) | 0.0171 (7) | −0.0006 (6) | 0.0115 (6) | 0.0002 (6) |
C1A | 0.0192 (9) | 0.0135 (10) | 0.0176 (8) | 0.0011 (7) | 0.0105 (7) | −0.0012 (7) |
C2A | 0.0153 (8) | 0.0116 (10) | 0.0173 (8) | 0.0008 (7) | 0.0063 (7) | −0.0036 (7) |
C3A | 0.0139 (8) | 0.0084 (9) | 0.0161 (8) | −0.0004 (7) | 0.0036 (6) | −0.0011 (7) |
C4A | 0.0125 (8) | 0.0109 (9) | 0.0123 (8) | 0.0000 (7) | 0.0042 (6) | −0.0007 (7) |
C5A | 0.0118 (8) | 0.0109 (10) | 0.0119 (8) | −0.0002 (6) | 0.0031 (6) | 0.0004 (7) |
C6A | 0.0150 (8) | 0.0106 (9) | 0.0161 (8) | −0.0002 (7) | 0.0068 (7) | 0.0014 (7) |
C7A | 0.0140 (8) | 0.0158 (10) | 0.0155 (9) | 0.0004 (7) | 0.0071 (7) | 0.0002 (7) |
C8A | 0.0134 (8) | 0.0105 (9) | 0.0136 (8) | −0.0010 (7) | 0.0038 (6) | 0.0000 (7) |
C9A | 0.0142 (8) | 0.0086 (9) | 0.0139 (8) | −0.0007 (7) | 0.0050 (6) | 0.0006 (7) |
C10A | 0.0111 (8) | 0.0115 (9) | 0.0133 (8) | −0.0014 (6) | 0.0039 (6) | −0.0003 (7) |
C11A | 0.0149 (8) | 0.0105 (9) | 0.0135 (8) | 0.0002 (7) | 0.0064 (6) | 0.0011 (7) |
C12A | 0.0145 (8) | 0.0100 (9) | 0.0140 (8) | 0.0006 (7) | 0.0052 (6) | −0.0012 (6) |
C13A | 0.0173 (8) | 0.0102 (9) | 0.0152 (8) | 0.0000 (7) | 0.0052 (7) | 0.0009 (7) |
C14A | 0.0138 (8) | 0.0120 (9) | 0.0135 (8) | 0.0006 (7) | 0.0051 (6) | −0.0006 (7) |
O1B | 0.0318 (8) | 0.0134 (7) | 0.0282 (8) | 0.0006 (6) | 0.0189 (6) | −0.0040 (6) |
O2B | 0.0281 (7) | 0.0150 (7) | 0.0287 (7) | 0.0007 (6) | 0.0208 (6) | −0.0029 (6) |
O3B | 0.0303 (8) | 0.0104 (7) | 0.0251 (7) | −0.0025 (6) | 0.0141 (6) | 0.0002 (6) |
O4B | 0.0251 (7) | 0.0129 (8) | 0.0212 (7) | −0.0015 (6) | 0.0130 (5) | 0.0017 (5) |
O5B | 0.0155 (6) | 0.0168 (7) | 0.0193 (7) | −0.0002 (5) | 0.0113 (5) | 0.0010 (5) |
O6B | 0.0154 (6) | 0.0186 (7) | 0.0153 (6) | 0.0031 (5) | 0.0055 (5) | 0.0023 (5) |
O7B | 0.0190 (7) | 0.0203 (8) | 0.0191 (7) | −0.0068 (5) | 0.0108 (5) | −0.0068 (5) |
N1B | 0.0187 (8) | 0.0137 (9) | 0.0176 (7) | −0.0009 (6) | 0.0112 (6) | 0.0028 (6) |
C1B | 0.0177 (8) | 0.0162 (10) | 0.0194 (9) | 0.0012 (7) | 0.0082 (7) | −0.0028 (8) |
C2B | 0.0167 (8) | 0.0112 (9) | 0.0158 (8) | 0.0012 (7) | 0.0051 (7) | −0.0032 (7) |
C3B | 0.0178 (8) | 0.0121 (10) | 0.0157 (8) | −0.0024 (7) | 0.0050 (7) | 0.0013 (7) |
C4B | 0.0131 (8) | 0.0145 (10) | 0.0120 (8) | −0.0004 (7) | 0.0039 (6) | −0.0005 (7) |
C5B | 0.0120 (8) | 0.0132 (10) | 0.0125 (8) | −0.0005 (7) | 0.0032 (6) | 0.0007 (7) |
C6B | 0.0160 (8) | 0.0126 (10) | 0.0165 (8) | 0.0013 (7) | 0.0078 (7) | 0.0009 (7) |
C7B | 0.0152 (8) | 0.0174 (10) | 0.0145 (8) | 0.0001 (7) | 0.0070 (7) | 0.0001 (7) |
C8B | 0.0144 (8) | 0.0142 (10) | 0.0147 (8) | −0.0023 (7) | 0.0048 (6) | 0.0014 (7) |
C9B | 0.0141 (8) | 0.0113 (9) | 0.0141 (8) | 0.0002 (6) | 0.0068 (6) | 0.0022 (7) |
C10B | 0.0116 (8) | 0.0159 (10) | 0.0109 (8) | 0.0019 (7) | 0.0046 (6) | 0.0022 (7) |
C11B | 0.0125 (8) | 0.0145 (9) | 0.0148 (8) | −0.0001 (7) | 0.0080 (6) | 0.0011 (7) |
C12B | 0.0145 (8) | 0.0134 (9) | 0.0135 (8) | 0.0011 (7) | 0.0057 (6) | 0.0003 (7) |
C13B | 0.0155 (8) | 0.0125 (9) | 0.0142 (8) | −0.0021 (7) | 0.0075 (6) | −0.0013 (7) |
C14B | 0.0139 (8) | 0.0157 (10) | 0.0121 (8) | 0.0011 (7) | 0.0061 (6) | 0.0005 (7) |
O1C | 0.0464 (10) | 0.0102 (8) | 0.0385 (9) | 0.0022 (7) | 0.0336 (8) | −0.0022 (6) |
O2C | 0.0463 (9) | 0.0135 (8) | 0.0405 (9) | −0.0004 (7) | 0.0364 (8) | −0.0034 (7) |
O3C | 0.0235 (7) | 0.0074 (7) | 0.0200 (7) | 0.0002 (5) | 0.0121 (5) | 0.0015 (5) |
O4C | 0.0234 (7) | 0.0110 (7) | 0.0199 (6) | −0.0007 (5) | 0.0132 (5) | 0.0015 (5) |
O5C | 0.0161 (6) | 0.0156 (7) | 0.0152 (6) | 0.0014 (5) | 0.0089 (5) | −0.0011 (5) |
O6C | 0.0140 (6) | 0.0144 (7) | 0.0169 (6) | 0.0020 (5) | 0.0048 (5) | 0.0038 (5) |
O7C | 0.0153 (6) | 0.0124 (7) | 0.0189 (7) | −0.0009 (5) | 0.0020 (5) | −0.0031 (5) |
N1C | 0.0167 (7) | 0.0108 (8) | 0.0160 (7) | −0.0014 (6) | 0.0093 (6) | 0.0006 (6) |
C1C | 0.0251 (9) | 0.0130 (10) | 0.0233 (9) | 0.0010 (8) | 0.0153 (8) | −0.0015 (8) |
C2C | 0.0193 (8) | 0.0096 (10) | 0.0180 (9) | 0.0022 (7) | 0.0090 (7) | −0.0025 (7) |
C3C | 0.0154 (8) | 0.0104 (9) | 0.0127 (8) | −0.0013 (7) | 0.0043 (7) | 0.0002 (7) |
C4C | 0.0130 (8) | 0.0106 (10) | 0.0116 (8) | 0.0009 (7) | 0.0038 (6) | −0.0005 (7) |
C5C | 0.0133 (8) | 0.0126 (10) | 0.0128 (8) | −0.0002 (7) | 0.0036 (6) | 0.0004 (7) |
C6C | 0.0190 (9) | 0.0104 (10) | 0.0169 (8) | −0.0016 (7) | 0.0090 (7) | −0.0007 (7) |
C7C | 0.0203 (9) | 0.0167 (11) | 0.0175 (9) | −0.0009 (7) | 0.0117 (7) | −0.0020 (7) |
C8C | 0.0131 (8) | 0.0130 (9) | 0.0119 (8) | −0.0015 (7) | 0.0034 (6) | 0.0007 (7) |
C9C | 0.0138 (8) | 0.0108 (9) | 0.0131 (8) | 0.0000 (7) | 0.0053 (6) | −0.0002 (7) |
C10C | 0.0149 (8) | 0.0111 (9) | 0.0113 (8) | 0.0005 (7) | 0.0049 (6) | 0.0009 (7) |
C11C | 0.0118 (8) | 0.0128 (9) | 0.0131 (8) | 0.0012 (6) | 0.0053 (6) | 0.0000 (7) |
C12C | 0.0143 (8) | 0.0118 (9) | 0.0131 (8) | 0.0006 (6) | 0.0048 (6) | −0.0003 (7) |
C13C | 0.0141 (8) | 0.0101 (9) | 0.0142 (8) | −0.0008 (7) | 0.0043 (6) | −0.0002 (7) |
C14C | 0.0137 (8) | 0.0134 (9) | 0.0136 (8) | 0.0006 (7) | 0.0062 (6) | 0.0000 (7) |
O1W | 0.0246 (7) | 0.0219 (8) | 0.0212 (7) | −0.0058 (6) | 0.0078 (6) | 0.0013 (6) |
O2W | 0.0200 (7) | 0.0395 (10) | 0.0184 (7) | 0.0018 (6) | 0.0062 (5) | −0.0084 (6) |
O1—C1 | 1.450 (2) | O2B—C1B | 1.438 (3) |
O1—C2 | 1.378 (2) | O2B—C7B | 1.369 (2) |
O2—C1 | 1.428 (3) | O3B—H3B | 1.01 (4) |
O2—C7 | 1.360 (2) | O3B—C3B | 1.343 (3) |
O3—H3 | 0.96 (3) | O4B—C8B | 1.258 (3) |
O3—C3 | 1.347 (2) | O5B—H5B | 0.94 (4) |
O4—C8 | 1.255 (2) | O5B—C11B | 1.424 (2) |
O5—H5 | 0.84 (4) | O6B—H6B | 0.89 (4) |
O5—C11 | 1.421 (2) | O6B—C12B | 1.437 (2) |
O6—H6 | 0.85 (3) | O7B—H7B | 0.86 (4) |
O6—C12 | 1.433 (2) | O7B—C13B | 1.431 (2) |
O7—H7 | 0.89 (3) | N1B—H1BA | 0.89 (4) |
O7—C13 | 1.439 (2) | N1B—C8B | 1.330 (3) |
N1—H1 | 0.91 (4) | N1B—C9B | 1.462 (2) |
N1—C8 | 1.331 (3) | C1B—H1BB | 0.9900 |
N1—C9 | 1.465 (2) | C1B—H1BC | 0.9900 |
C1—H1A | 0.9900 | C2B—C3B | 1.380 (3) |
C1—H1B | 0.9900 | C2B—C7B | 1.376 (3) |
C2—C3 | 1.382 (3) | C3B—C4B | 1.417 (3) |
C2—C7 | 1.380 (3) | C4B—C5B | 1.414 (3) |
C3—C4 | 1.417 (3) | C4B—C8B | 1.479 (2) |
C4—C5 | 1.413 (3) | C5B—C6B | 1.403 (3) |
C4—C8 | 1.472 (2) | C5B—C10B | 1.472 (3) |
C5—C6 | 1.403 (3) | C6B—H6BA | 0.9500 |
C5—C10 | 1.470 (3) | C6B—C7B | 1.375 (3) |
C6—H6A | 0.9500 | C9B—H9B | 1.0000 |
C6—C7 | 1.375 (3) | C9B—C10B | 1.515 (2) |
C9—H9 | 1.0000 | C9B—C11B | 1.518 (3) |
C9—C10 | 1.517 (2) | C10B—C14B | 1.339 (3) |
C9—C11 | 1.528 (2) | C11B—H11B | 1.0000 |
C10—C14 | 1.336 (3) | C11B—C12B | 1.527 (3) |
C11—H11 | 1.0000 | C12B—H12B | 1.0000 |
C11—C12 | 1.520 (2) | C12B—C13B | 1.527 (2) |
C12—H12 | 1.0000 | C13B—H13B | 1.0000 |
C12—C13 | 1.533 (2) | C13B—C14B | 1.507 (3) |
C13—H13 | 1.0000 | C14B—H14B | 0.9500 |
C13—C14 | 1.500 (3) | O1C—C1C | 1.439 (2) |
C14—H14 | 0.9500 | O1C—C2C | 1.370 (2) |
O1A—C1A | 1.441 (2) | O2C—C1C | 1.438 (3) |
O1A—C2A | 1.374 (2) | O2C—C7C | 1.368 (2) |
O2A—C1A | 1.437 (3) | O3C—H3C | 0.95 (5) |
O2A—C7A | 1.367 (2) | O3C—C3C | 1.352 (2) |
O3A—H3A | 1.00 (4) | O4C—C8C | 1.261 (2) |
O3A—C3A | 1.346 (2) | O5C—H5C | 0.82 (3) |
O4A—C8A | 1.268 (2) | O5C—C11C | 1.428 (2) |
O5A—H5A | 0.87 (3) | O6C—H6C | 0.88 (4) |
O5A—C11A | 1.425 (2) | O6C—C12C | 1.430 (2) |
O6A—H6AA | 0.82 (4) | O7C—H7C | 0.86 (4) |
O6A—C12A | 1.442 (2) | O7C—C13C | 1.443 (2) |
O7A—H7A | 0.83 (4) | N1C—H1C | 0.91 (4) |
O7A—C13A | 1.439 (2) | N1C—C8C | 1.323 (3) |
N1A—H1AA | 0.89 (3) | N1C—C9C | 1.468 (2) |
N1A—C8A | 1.325 (3) | C1C—H1CA | 0.9900 |
N1A—C9A | 1.456 (2) | C1C—H1CB | 0.9900 |
C1A—H1AB | 0.9900 | C2C—C3C | 1.377 (3) |
C1A—H1AC | 0.9900 | C2C—C7C | 1.380 (3) |
C2A—C3A | 1.376 (3) | C3C—C4C | 1.417 (3) |
C2A—C7A | 1.381 (3) | C4C—C5C | 1.406 (3) |
C3A—C4A | 1.415 (3) | C4C—C8C | 1.470 (2) |
C4A—C5A | 1.408 (3) | C5C—C6C | 1.408 (3) |
C4A—C8A | 1.468 (2) | C5C—C10C | 1.475 (3) |
C5A—C6A | 1.408 (3) | C6C—H6CA | 0.9500 |
C5A—C10A | 1.479 (3) | C6C—C7C | 1.378 (3) |
C6A—H6AB | 0.9500 | C9C—H9C | 1.0000 |
C6A—C7A | 1.379 (3) | C9C—C10C | 1.515 (2) |
C9A—H9A | 1.0000 | C9C—C11C | 1.520 (3) |
C9A—C10A | 1.519 (2) | C10C—C14C | 1.340 (3) |
C9A—C11A | 1.530 (3) | C11C—H11C | 1.0000 |
C10A—C14A | 1.335 (3) | C11C—C12C | 1.523 (3) |
C11A—H11A | 1.0000 | C12C—H12C | 1.0000 |
C11A—C12A | 1.516 (3) | C12C—C13C | 1.536 (2) |
C12A—H12A | 1.0000 | C13C—H13C | 1.0000 |
C12A—C13A | 1.536 (2) | C13C—C14C | 1.501 (3) |
C13A—H13A | 1.0000 | C14C—H14C | 0.9500 |
C13A—C14A | 1.503 (3) | O1W—H1WA | 0.90 (4) |
C14A—H14A | 0.9500 | O1W—H1WB | 0.89 (5) |
O1B—C1B | 1.432 (2) | O2W—H2WA | 0.90 (3) |
O1B—C2B | 1.374 (2) | O2W—H2WB | 0.87 (4) |
C2—O1—C1 | 105.17 (15) | C7B—O2B—C1B | 105.90 (15) |
C7—O2—C1 | 106.90 (16) | C3B—O3B—H3B | 100 (2) |
C3—O3—H3 | 101 (2) | C11B—O5B—H5B | 104 (3) |
C11—O5—H5 | 113 (3) | C12B—O6B—H6B | 109 (2) |
C12—O6—H6 | 108.5 (18) | C13B—O7B—H7B | 108 (3) |
C13—O7—H7 | 110 (2) | C8B—N1B—H1BA | 113 (2) |
C8—N1—H1 | 120 (2) | C8B—N1B—C9B | 124.11 (16) |
C8—N1—C9 | 123.65 (15) | C9B—N1B—H1BA | 122 (2) |
C9—N1—H1 | 115 (2) | O1B—C1B—O2B | 108.01 (15) |
O1—C1—H1A | 110.2 | O1B—C1B—H1BB | 110.1 |
O1—C1—H1B | 110.2 | O1B—C1B—H1BC | 110.1 |
O2—C1—O1 | 107.61 (16) | O2B—C1B—H1BB | 110.1 |
O2—C1—H1A | 110.2 | O2B—C1B—H1BC | 110.1 |
O2—C1—H1B | 110.2 | H1BB—C1B—H1BC | 108.4 |
H1A—C1—H1B | 108.5 | O1B—C2B—C3B | 127.77 (19) |
O1—C2—C3 | 128.47 (19) | O1B—C2B—C7B | 110.58 (17) |
O1—C2—C7 | 110.32 (17) | C7B—C2B—C3B | 121.64 (19) |
C7—C2—C3 | 121.20 (19) | O3B—C3B—C2B | 120.24 (19) |
O3—C3—C2 | 120.81 (18) | O3B—C3B—C4B | 123.17 (17) |
O3—C3—C4 | 122.49 (17) | C2B—C3B—C4B | 116.59 (19) |
C2—C3—C4 | 116.70 (18) | C3B—C4B—C8B | 118.08 (18) |
C3—C4—C8 | 117.80 (17) | C5B—C4B—C3B | 121.18 (16) |
C5—C4—C3 | 121.24 (17) | C5B—C4B—C8B | 120.70 (18) |
C5—C4—C8 | 120.89 (17) | C4B—C5B—C10B | 118.57 (16) |
C4—C5—C10 | 118.47 (16) | C6B—C5B—C4B | 120.42 (18) |
C6—C5—C4 | 120.51 (18) | C6B—C5B—C10B | 121.00 (18) |
C6—C5—C10 | 120.97 (17) | C5B—C6B—H6BA | 121.6 |
C5—C6—H6A | 121.7 | C7B—C6B—C5B | 116.74 (18) |
C7—C6—C5 | 116.53 (18) | C7B—C6B—H6BA | 121.6 |
C7—C6—H6A | 121.7 | O2B—C7B—C2B | 109.76 (18) |
O2—C7—C2 | 109.92 (18) | O2B—C7B—C6B | 126.81 (19) |
O2—C7—C6 | 126.32 (18) | C6B—C7B—C2B | 123.42 (17) |
C6—C7—C2 | 123.75 (18) | O4B—C8B—N1B | 121.09 (16) |
O4—C8—N1 | 121.03 (17) | O4B—C8B—C4B | 120.80 (18) |
O4—C8—C4 | 119.94 (17) | N1B—C8B—C4B | 118.10 (18) |
N1—C8—C4 | 119.02 (17) | N1B—C9B—H9B | 108.3 |
N1—C9—H9 | 108.2 | N1B—C9B—C10B | 111.40 (16) |
N1—C9—C10 | 112.21 (15) | N1B—C9B—C11B | 109.63 (15) |
N1—C9—C11 | 109.71 (14) | C10B—C9B—H9B | 108.3 |
C10—C9—H9 | 108.2 | C10B—C9B—C11B | 110.82 (16) |
C10—C9—C11 | 110.07 (15) | C11B—C9B—H9B | 108.3 |
C11—C9—H9 | 108.2 | C5B—C10B—C9B | 116.24 (17) |
C5—C10—C9 | 116.86 (16) | C14B—C10B—C5B | 123.32 (17) |
C14—C10—C5 | 121.70 (16) | C14B—C10B—C9B | 120.31 (17) |
C14—C10—C9 | 121.44 (18) | O5B—C11B—C9B | 107.93 (15) |
O5—C11—C9 | 110.35 (14) | O5B—C11B—H11B | 109.2 |
O5—C11—H11 | 108.1 | O5B—C11B—C12B | 111.42 (15) |
O5—C11—C12 | 112.55 (15) | C9B—C11B—H11B | 109.2 |
C9—C11—H11 | 108.1 | C9B—C11B—C12B | 109.82 (15) |
C12—C11—C9 | 109.39 (14) | C12B—C11B—H11B | 109.2 |
C12—C11—H11 | 108.1 | O6B—C12B—C11B | 111.14 (15) |
O6—C12—C11 | 106.22 (14) | O6B—C12B—H12B | 108.9 |
O6—C12—H12 | 109.8 | O6B—C12B—C13B | 107.57 (14) |
O6—C12—C13 | 109.46 (14) | C11B—C12B—H12B | 108.9 |
C11—C12—H12 | 109.8 | C11B—C12B—C13B | 111.24 (15) |
C11—C12—C13 | 111.60 (15) | C13B—C12B—H12B | 108.9 |
C13—C12—H12 | 109.8 | O7B—C13B—C12B | 107.13 (14) |
O7—C13—C12 | 113.45 (14) | O7B—C13B—H13B | 108.3 |
O7—C13—H13 | 107.2 | O7B—C13B—C14B | 111.25 (15) |
O7—C13—C14 | 109.98 (15) | C12B—C13B—H13B | 108.3 |
C12—C13—H13 | 107.2 | C14B—C13B—C12B | 113.29 (16) |
C14—C13—C12 | 111.60 (15) | C14B—C13B—H13B | 108.3 |
C14—C13—H13 | 107.2 | C10B—C14B—C13B | 124.99 (16) |
C10—C14—C13 | 125.27 (16) | C10B—C14B—H14B | 117.5 |
C10—C14—H14 | 117.4 | C13B—C14B—H14B | 117.5 |
C13—C14—H14 | 117.4 | C2C—O1C—C1C | 105.10 (16) |
C2A—O1A—C1A | 104.91 (15) | C7C—O2C—C1C | 106.67 (16) |
C7A—O2A—C1A | 106.58 (15) | C3C—O3C—H3C | 103 (3) |
C3A—O3A—H3A | 105 (2) | C11C—O5C—H5C | 110 (2) |
C11A—O5A—H5A | 109 (2) | C12C—O6C—H6C | 109 (2) |
C12A—O6A—H6AA | 108 (2) | C13C—O7C—H7C | 106.1 (19) |
C13A—O7A—H7A | 107 (3) | C8C—N1C—H1C | 117 (2) |
C8A—N1A—H1AA | 115 (2) | C8C—N1C—C9C | 124.78 (15) |
C8A—N1A—C9A | 124.28 (15) | C9C—N1C—H1C | 118 (2) |
C9A—N1A—H1AA | 118 (2) | O1C—C1C—H1CA | 110.1 |
O1A—C1A—H1AB | 110.1 | O1C—C1C—H1CB | 110.1 |
O1A—C1A—H1AC | 110.1 | O2C—C1C—O1C | 107.84 (16) |
O2A—C1A—O1A | 107.88 (15) | O2C—C1C—H1CA | 110.1 |
O2A—C1A—H1AB | 110.1 | O2C—C1C—H1CB | 110.1 |
O2A—C1A—H1AC | 110.1 | H1CA—C1C—H1CB | 108.5 |
H1AB—C1A—H1AC | 108.4 | O1C—C2C—C3C | 127.27 (19) |
O1A—C2A—C3A | 127.45 (19) | O1C—C2C—C7C | 111.40 (17) |
O1A—C2A—C7A | 111.22 (16) | C3C—C2C—C7C | 121.32 (18) |
C3A—C2A—C7A | 121.30 (18) | O3C—C3C—C2C | 120.07 (18) |
O3A—C3A—C2A | 120.67 (18) | O3C—C3C—C4C | 123.41 (16) |
O3A—C3A—C4A | 122.38 (16) | C2C—C3C—C4C | 116.50 (18) |
C2A—C3A—C4A | 116.96 (18) | C3C—C4C—C8C | 117.46 (17) |
C3A—C4A—C8A | 117.54 (17) | C5C—C4C—C3C | 121.64 (16) |
C5A—C4A—C3A | 121.26 (17) | C5C—C4C—C8C | 120.86 (18) |
C5A—C4A—C8A | 121.18 (17) | C4C—C5C—C6C | 120.46 (18) |
C4A—C5A—C6A | 120.50 (18) | C4C—C5C—C10C | 117.64 (16) |
C4A—C5A—C10A | 118.17 (16) | C6C—C5C—C10C | 121.82 (18) |
C6A—C5A—C10A | 121.32 (18) | C5C—C6C—H6CA | 121.9 |
C5A—C6A—H6AB | 121.8 | C7C—C6C—C5C | 116.15 (18) |
C7A—C6A—C5A | 116.35 (18) | C7C—C6C—H6CA | 121.9 |
C7A—C6A—H6AB | 121.8 | O2C—C7C—C2C | 108.97 (18) |
O2A—C7A—C2A | 109.16 (17) | O2C—C7C—C6C | 127.17 (19) |
O2A—C7A—C6A | 127.30 (18) | C6C—C7C—C2C | 123.85 (17) |
C6A—C7A—C2A | 123.52 (17) | O4C—C8C—N1C | 121.55 (17) |
O4A—C8A—N1A | 120.63 (17) | O4C—C8C—C4C | 119.37 (18) |
O4A—C8A—C4A | 119.93 (17) | N1C—C8C—C4C | 119.08 (17) |
N1A—C8A—C4A | 119.44 (17) | N1C—C9C—H9C | 108.6 |
N1A—C9A—H9A | 108.1 | N1C—C9C—C10C | 111.19 (15) |
N1A—C9A—C10A | 112.74 (15) | N1C—C9C—C11C | 108.90 (15) |
N1A—C9A—C11A | 110.01 (15) | C10C—C9C—H9C | 108.6 |
C10A—C9A—H9A | 108.1 | C10C—C9C—C11C | 110.94 (15) |
C10A—C9A—C11A | 109.54 (15) | C11C—C9C—H9C | 108.6 |
C11A—C9A—H9A | 108.1 | C5C—C10C—C9C | 116.99 (16) |
C5A—C10A—C9A | 118.22 (16) | C14C—C10C—C5C | 122.51 (17) |
C14A—C10A—C5A | 122.58 (16) | C14C—C10C—C9C | 120.49 (17) |
C14A—C10A—C9A | 119.20 (17) | O5C—C11C—C9C | 107.69 (14) |
O5A—C11A—C9A | 111.93 (15) | O5C—C11C—H11C | 108.9 |
O5A—C11A—H11A | 108.0 | O5C—C11C—C12C | 111.65 (15) |
O5A—C11A—C12A | 111.71 (15) | C9C—C11C—H11C | 108.9 |
C9A—C11A—H11A | 108.0 | C9C—C11C—C12C | 110.64 (14) |
C12A—C11A—C9A | 109.10 (14) | C12C—C11C—H11C | 108.9 |
C12A—C11A—H11A | 108.0 | O6C—C12C—C11C | 112.11 (14) |
O6A—C12A—C11A | 106.78 (15) | O6C—C12C—H12C | 109.1 |
O6A—C12A—H12A | 109.3 | O6C—C12C—C13C | 107.37 (14) |
O6A—C12A—C13A | 110.60 (14) | C11C—C12C—H12C | 109.1 |
C11A—C12A—H12A | 109.3 | C11C—C12C—C13C | 110.04 (15) |
C11A—C12A—C13A | 111.51 (15) | C13C—C12C—H12C | 109.1 |
C13A—C12A—H12A | 109.3 | O7C—C13C—C12C | 109.32 (14) |
O7A—C13A—C12A | 107.89 (15) | O7C—C13C—H13C | 108.6 |
O7A—C13A—H13A | 108.6 | O7C—C13C—C14C | 108.14 (14) |
O7A—C13A—C14A | 108.86 (15) | C12C—C13C—H13C | 108.6 |
C12A—C13A—H13A | 108.6 | C14C—C13C—C12C | 113.34 (15) |
C14A—C13A—C12A | 114.07 (16) | C14C—C13C—H13C | 108.6 |
C14A—C13A—H13A | 108.6 | C10C—C14C—C13C | 125.07 (16) |
C10A—C14A—C13A | 125.19 (16) | C10C—C14C—H14C | 117.5 |
C10A—C14A—H14A | 117.4 | C13C—C14C—H14C | 117.5 |
C13A—C14A—H14A | 117.4 | H1WA—O1W—H1WB | 109 (4) |
C2B—O1B—C1B | 105.30 (16) | H2WA—O2W—H2WB | 107 (3) |
O1—C2—C3—O3 | −0.2 (3) | O1B—C2B—C3B—O3B | 3.3 (3) |
O1—C2—C3—C4 | 179.64 (18) | O1B—C2B—C3B—C4B | −177.19 (17) |
O1—C2—C7—O2 | 0.2 (2) | O1B—C2B—C7B—O2B | −0.7 (2) |
O1—C2—C7—C6 | 179.57 (19) | O1B—C2B—C7B—C6B | 177.95 (18) |
O3—C3—C4—C5 | −179.83 (17) | O3B—C3B—C4B—C5B | 178.08 (17) |
O3—C3—C4—C8 | 3.2 (3) | O3B—C3B—C4B—C8B | 0.6 (3) |
O5—C11—C12—O6 | −66.93 (18) | O5B—C11B—C12B—O6B | −60.52 (19) |
O5—C11—C12—C13 | 173.83 (14) | O5B—C11B—C12B—C13B | 179.64 (14) |
O6—C12—C13—O7 | 156.75 (15) | O6B—C12B—C13B—O7B | 148.66 (15) |
O6—C12—C13—C14 | −78.34 (18) | O6B—C12B—C13B—C14B | −88.28 (18) |
O7—C13—C14—C10 | 118.47 (19) | O7B—C13B—C14B—C10B | 118.34 (19) |
N1—C9—C10—C5 | 34.0 (2) | N1B—C9B—C10B—C5B | 37.0 (2) |
N1—C9—C10—C14 | −146.53 (17) | N1B—C9B—C10B—C14B | −147.00 (17) |
N1—C9—C11—O5 | −58.02 (19) | N1B—C9B—C11B—O5B | −59.61 (19) |
N1—C9—C11—C12 | 177.64 (14) | N1B—C9B—C11B—C12B | 178.75 (15) |
C1—O1—C2—C3 | −179.75 (19) | C1B—O1B—C2B—C3B | −176.65 (19) |
C1—O1—C2—C7 | 1.5 (2) | C1B—O1B—C2B—C7B | 4.6 (2) |
C1—O2—C7—C2 | −1.9 (2) | C1B—O2B—C7B—C2B | −3.5 (2) |
C1—O2—C7—C6 | 178.8 (2) | C1B—O2B—C7B—C6B | 177.91 (19) |
C2—O1—C1—O2 | −2.6 (2) | C2B—O1B—C1B—O2B | −6.6 (2) |
C2—C3—C4—C5 | 0.3 (3) | C2B—C3B—C4B—C5B | −1.4 (3) |
C2—C3—C4—C8 | −176.66 (16) | C2B—C3B—C4B—C8B | −178.91 (16) |
C3—C2—C7—O2 | −178.66 (17) | C3B—C2B—C7B—O2B | −179.54 (17) |
C3—C2—C7—C6 | 0.7 (3) | C3B—C2B—C7B—C6B | −0.9 (3) |
C3—C4—C5—C6 | 2.1 (3) | C3B—C4B—C5B—C6B | 0.8 (3) |
C3—C4—C5—C10 | −175.14 (16) | C3B—C4B—C5B—C10B | −179.02 (16) |
C3—C4—C8—O4 | 1.6 (3) | C3B—C4B—C8B—O4B | 5.5 (3) |
C3—C4—C8—N1 | −179.57 (16) | C3B—C4B—C8B—N1B | −175.36 (16) |
C4—C5—C6—C7 | −3.0 (3) | C4B—C5B—C6B—C7B | −0.2 (3) |
C4—C5—C10—C9 | −21.2 (2) | C4B—C5B—C10B—C9B | −21.3 (2) |
C4—C5—C10—C14 | 159.35 (18) | C4B—C5B—C10B—C14B | 162.86 (18) |
C5—C4—C8—O4 | −175.36 (16) | C5B—C4B—C8B—O4B | −172.00 (16) |
C5—C4—C8—N1 | 3.4 (3) | C5B—C4B—C8B—N1B | 7.1 (3) |
C5—C6—C7—O2 | −179.04 (19) | C5B—C6B—C7B—O2B | 178.59 (18) |
C5—C6—C7—C2 | 1.7 (3) | C5B—C6B—C7B—C2B | 0.2 (3) |
C5—C10—C14—C13 | −179.43 (16) | C5B—C10B—C14B—C13B | 173.39 (16) |
C6—C5—C10—C9 | 161.62 (17) | C6B—C5B—C10B—C9B | 158.87 (17) |
C6—C5—C10—C14 | −17.9 (3) | C6B—C5B—C10B—C14B | −17.0 (3) |
C7—O2—C1—O1 | 2.7 (2) | C7B—O2B—C1B—O1B | 6.3 (2) |
C7—C2—C3—O3 | 178.45 (17) | C7B—C2B—C3B—O3B | −178.04 (17) |
C7—C2—C3—C4 | −1.7 (3) | C7B—C2B—C3B—C4B | 1.5 (3) |
C8—N1—C9—C10 | −30.9 (2) | C8B—N1B—C9B—C10B | −34.1 (3) |
C8—N1—C9—C11 | −153.55 (16) | C8B—N1B—C9B—C11B | −157.12 (17) |
C8—C4—C5—C6 | 178.98 (16) | C8B—C4B—C5B—C6B | 178.22 (16) |
C8—C4—C5—C10 | 1.8 (3) | C8B—C4B—C5B—C10B | −1.6 (3) |
C9—N1—C8—O4 | −168.63 (16) | C9B—N1B—C8B—O4B | −168.45 (17) |
C9—N1—C8—C4 | 12.6 (3) | C9B—N1B—C8B—C4B | 12.4 (3) |
C9—C10—C14—C13 | 1.1 (3) | C9B—C10B—C14B—C13B | −2.3 (3) |
C9—C11—C12—O6 | 56.11 (18) | C9B—C11B—C12B—O6B | 59.00 (19) |
C9—C11—C12—C13 | −63.13 (18) | C9B—C11B—C12B—C13B | −60.84 (19) |
C10—C5—C6—C7 | 174.14 (16) | C10B—C5B—C6B—C7B | 179.65 (16) |
C10—C9—C11—O5 | 178.03 (14) | C10B—C9B—C11B—O5B | 177.02 (14) |
C10—C9—C11—C12 | 53.69 (19) | C10B—C9B—C11B—C12B | 55.38 (19) |
C11—C9—C10—C5 | 156.46 (15) | C11B—C9B—C10B—C5B | 159.39 (15) |
C11—C9—C10—C14 | −24.0 (2) | C11B—C9B—C10B—C14B | −24.7 (2) |
C11—C12—C13—O7 | −85.96 (19) | C11B—C12B—C13B—O7B | −89.41 (18) |
C11—C12—C13—C14 | 38.95 (19) | C11B—C12B—C13B—C14B | 33.7 (2) |
C12—C13—C14—C10 | −8.4 (2) | C12B—C13B—C14B—C10B | −2.4 (2) |
O1A—C2A—C3A—O3A | −0.5 (3) | O1C—C2C—C3C—O3C | 0.4 (3) |
O1A—C2A—C3A—C4A | 179.59 (17) | O1C—C2C—C3C—C4C | 178.95 (18) |
O1A—C2A—C7A—O2A | 0.6 (2) | O1C—C2C—C7C—O2C | 1.2 (2) |
O1A—C2A—C7A—C6A | 179.06 (17) | O1C—C2C—C7C—C6C | −177.97 (19) |
O3A—C3A—C4A—C5A | −178.42 (16) | O3C—C3C—C4C—C5C | 176.47 (16) |
O3A—C3A—C4A—C8A | 2.7 (3) | O3C—C3C—C4C—C8C | −1.3 (3) |
O5A—C11A—C12A—O6A | −62.49 (18) | O5C—C11C—C12C—O6C | −62.17 (19) |
O5A—C11A—C12A—C13A | 176.59 (14) | O5C—C11C—C12C—C13C | 178.41 (14) |
O6A—C12A—C13A—O7A | 147.36 (15) | O6C—C12C—C13C—O7C | 153.23 (15) |
O6A—C12A—C13A—C14A | −91.56 (19) | O6C—C12C—C13C—C14C | −86.06 (18) |
O7A—C13A—C14A—C10A | 124.37 (19) | O7C—C13C—C14C—C10C | 116.59 (19) |
N1A—C9A—C10A—C5A | 26.8 (2) | N1C—C9C—C10C—C5C | 35.9 (2) |
N1A—C9A—C10A—C14A | −153.50 (17) | N1C—C9C—C10C—C14C | −143.25 (17) |
N1A—C9A—C11A—O5A | −50.89 (19) | N1C—C9C—C11C—O5C | −61.17 (18) |
N1A—C9A—C11A—C12A | −175.04 (14) | N1C—C9C—C11C—C12C | 176.56 (14) |
C1A—O1A—C2A—C3A | −179.61 (19) | C1C—O1C—C2C—C3C | 179.72 (19) |
C1A—O1A—C2A—C7A | 2.5 (2) | C1C—O1C—C2C—C7C | −1.0 (2) |
C1A—O2A—C7A—C2A | −3.5 (2) | C1C—O2C—C7C—C2C | −0.8 (2) |
C1A—O2A—C7A—C6A | 178.11 (18) | C1C—O2C—C7C—C6C | 178.3 (2) |
C2A—O1A—C1A—O2A | −4.62 (19) | C2C—O1C—C1C—O2C | 0.5 (2) |
C2A—C3A—C4A—C5A | 1.5 (3) | C2C—C3C—C4C—C5C | −2.0 (3) |
C2A—C3A—C4A—C8A | −177.38 (16) | C2C—C3C—C4C—C8C | −179.76 (16) |
C3A—C2A—C7A—O2A | −177.39 (17) | C3C—C2C—C7C—O2C | −179.49 (18) |
C3A—C2A—C7A—C6A | 1.1 (3) | C3C—C2C—C7C—C6C | 1.3 (3) |
C3A—C4A—C5A—C6A | 1.6 (3) | C3C—C4C—C5C—C6C | 3.2 (3) |
C3A—C4A—C5A—C10A | −178.01 (16) | C3C—C4C—C5C—C10C | −173.58 (16) |
C3A—C4A—C8A—O4A | 0.2 (3) | C3C—C4C—C8C—O4C | 4.6 (3) |
C3A—C4A—C8A—N1A | 179.32 (16) | C3C—C4C—C8C—N1C | −175.10 (15) |
C4A—C5A—C6A—C7A | −3.2 (3) | C4C—C5C—C6C—C7C | −2.1 (3) |
C4A—C5A—C10A—C9A | −15.2 (2) | C4C—C5C—C10C—C9C | −26.4 (2) |
C4A—C5A—C10A—C14A | 165.18 (17) | C4C—C5C—C10C—C14C | 152.74 (18) |
C5A—C4A—C8A—O4A | −178.64 (16) | C5C—C4C—C8C—O4C | −173.22 (16) |
C5A—C4A—C8A—N1A | 0.5 (3) | C5C—C4C—C8C—N1C | 7.1 (3) |
C5A—C6A—C7A—O2A | −179.85 (18) | C5C—C6C—C7C—O2C | −179.17 (19) |
C5A—C6A—C7A—C2A | 2.0 (3) | C5C—C6C—C7C—C2C | −0.1 (3) |
C5A—C10A—C14A—C13A | 178.01 (16) | C5C—C10C—C14C—C13C | 178.13 (17) |
C6A—C5A—C10A—C9A | 165.26 (16) | C6C—C5C—C10C—C9C | 156.83 (17) |
C6A—C5A—C10A—C14A | −14.4 (3) | C6C—C5C—C10C—C14C | −24.0 (3) |
C7A—O2A—C1A—O1A | 5.1 (2) | C7C—O2C—C1C—O1C | 0.2 (2) |
C7A—C2A—C3A—O3A | 177.13 (16) | C7C—C2C—C3C—O3C | −178.76 (16) |
C7A—C2A—C3A—C4A | −2.8 (3) | C7C—C2C—C3C—C4C | −0.2 (3) |
C8A—N1A—C9A—C10A | −27.3 (2) | C8C—N1C—C9C—C10C | −26.4 (2) |
C8A—N1A—C9A—C11A | −149.93 (17) | C8C—N1C—C9C—C11C | −148.98 (17) |
C8A—C4A—C5A—C6A | −179.63 (16) | C8C—C4C—C5C—C6C | −179.08 (16) |
C8A—C4A—C5A—C10A | 0.8 (3) | C8C—C4C—C5C—C10C | 4.1 (2) |
C9A—N1A—C8A—O4A | −166.72 (17) | C9C—N1C—C8C—O4C | −174.15 (17) |
C9A—N1A—C8A—C4A | 14.2 (3) | C9C—N1C—C8C—C4C | 5.5 (3) |
C9A—C10A—C14A—C13A | −1.6 (3) | C9C—C10C—C14C—C13C | −2.8 (3) |
C9A—C11A—C12A—O6A | 61.79 (17) | C9C—C11C—C12C—O6C | 57.75 (19) |
C9A—C11A—C12A—C13A | −59.13 (19) | C9C—C11C—C12C—C13C | −61.66 (18) |
C10A—C5A—C6A—C7A | 176.34 (16) | C10C—C5C—C6C—C7C | 174.59 (16) |
C10A—C9A—C11A—O5A | −175.35 (15) | C10C—C9C—C11C—O5C | 176.14 (14) |
C10A—C9A—C11A—C12A | 60.50 (19) | C10C—C9C—C11C—C12C | 53.87 (19) |
C11A—C9A—C10A—C5A | 149.70 (16) | C11C—C9C—C10C—C5C | 157.25 (15) |
C11A—C9A—C10A—C14A | −30.6 (2) | C11C—C9C—C10C—C14C | −21.9 (2) |
C11A—C12A—C13A—O7A | −93.98 (18) | C11C—C12C—C13C—O7C | −84.50 (18) |
C11A—C12A—C13A—C14A | 27.1 (2) | C11C—C12C—C13C—C14C | 36.21 (19) |
C12A—C13A—C14A—C10A | 3.8 (3) | C12C—C13C—C14C—C10C | −4.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4 | 0.96 (3) | 1.57 (4) | 2.4842 (19) | 158 (3) |
O5—H5···O7Ai | 0.84 (4) | 1.88 (4) | 2.698 (2) | 166 (4) |
O6—H6···O3Aii | 0.85 (3) | 1.98 (3) | 2.745 (2) | 150 (3) |
O7—H7···O7Ciii | 0.89 (3) | 1.89 (3) | 2.768 (2) | 170 (3) |
N1—H1···O4Bi | 0.91 (4) | 2.25 (4) | 3.105 (2) | 157 (3) |
O3A—H3A···O4A | 1.00 (4) | 1.55 (4) | 2.4656 (19) | 151 (4) |
O5A—H5A···O7 | 0.87 (3) | 2.23 (3) | 3.050 (2) | 157 (3) |
O6A—H6AA···O1ii | 0.82 (4) | 2.15 (4) | 2.906 (2) | 153 (3) |
O7A—H7A···O1Aiv | 0.83 (4) | 2.29 (4) | 2.901 (2) | 131 (3) |
N1A—H1AA···O4C | 0.89 (3) | 1.91 (3) | 2.796 (2) | 171 (3) |
O3B—H3B···O4B | 1.01 (4) | 1.57 (4) | 2.537 (2) | 159 (4) |
O5B—H5B···O2Wv | 0.94 (4) | 1.80 (4) | 2.701 (2) | 159 (4) |
O6B—H6B···O6vi | 0.89 (4) | 2.03 (4) | 2.8857 (19) | 163 (3) |
O7B—H7B···O5vii | 0.86 (4) | 1.86 (4) | 2.714 (2) | 175 (4) |
N1B—H1BA···O4v | 0.89 (4) | 1.99 (4) | 2.870 (2) | 171 (3) |
O3C—H3C···O4C | 0.95 (5) | 1.59 (5) | 2.4797 (18) | 154 (5) |
O5C—H5C···O6B | 0.82 (3) | 2.01 (4) | 2.829 (2) | 175 (3) |
O6C—H6C···O6Avi | 0.88 (4) | 1.93 (3) | 2.7893 (19) | 165 (3) |
O7C—H7C···O3Cvii | 0.86 (4) | 1.93 (4) | 2.767 (2) | 162 (3) |
N1C—H1C···O4A | 0.91 (4) | 2.03 (4) | 2.911 (2) | 164 (3) |
O1W—H1WA···O7Bi | 0.90 (4) | 1.94 (4) | 2.835 (2) | 173 (4) |
O1W—H1WB···O5Avii | 0.89 (5) | 2.22 (5) | 3.036 (2) | 153 (4) |
O2W—H2WA···O1W | 0.90 (3) | 1.94 (3) | 2.833 (2) | 167 (3) |
O2W—H2WB···O6C | 0.87 (4) | 2.00 (4) | 2.869 (2) | 172 (3) |
Symmetry codes: (i) x, y, z−1; (ii) −x, y−1/2, −z+1; (iii) −x+1, y−1/2, −z+1; (iv) −x, y−1/2, −z+2; (v) x, y, z+1; (vi) −x, y+1/2, −z+1; (vii) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H13NO7·0.5H2O |
Mr | 316.26 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 100 |
a, b, c (Å) | 10.90063 (8), 20.37357 (17), 11.88385 (9) |
β (°) | 104.3549 (8) |
V (Å3) | 2556.82 (4) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 1.16 |
Crystal size (mm) | 0.25 × 0.23 × 0.06 |
Data collection | |
Diffractometer | Agilent SuperNova (Dual, Cu at zero, Atlas CCD) |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.738, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 57161, 10051, 9997 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.122, 1.05 |
No. of reflections | 10051 |
No. of parameters | 908 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 |
Absolute structure | Flack (1983), 4707 Friedel pairs |
Absolute structure parameter | 0.05 (8) |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4 | 0.96 (3) | 1.57 (4) | 2.4842 (19) | 158 (3) |
O5—H5···O7Ai | 0.84 (4) | 1.88 (4) | 2.698 (2) | 166 (4) |
O6—H6···O3Aii | 0.85 (3) | 1.98 (3) | 2.745 (2) | 150 (3) |
O7—H7···O7Ciii | 0.89 (3) | 1.89 (3) | 2.768 (2) | 170 (3) |
N1—H1···O4Bi | 0.91 (4) | 2.25 (4) | 3.105 (2) | 157 (3) |
O3A—H3A···O4A | 1.00 (4) | 1.55 (4) | 2.4656 (19) | 151 (4) |
O5A—H5A···O7 | 0.87 (3) | 2.23 (3) | 3.050 (2) | 157 (3) |
O6A—H6AA···O1ii | 0.82 (4) | 2.15 (4) | 2.906 (2) | 153 (3) |
O7A—H7A···O1Aiv | 0.83 (4) | 2.29 (4) | 2.901 (2) | 131 (3) |
N1A—H1AA···O4C | 0.89 (3) | 1.91 (3) | 2.796 (2) | 171 (3) |
O3B—H3B···O4B | 1.01 (4) | 1.57 (4) | 2.537 (2) | 159 (4) |
O5B—H5B···O2Wv | 0.94 (4) | 1.80 (4) | 2.701 (2) | 159 (4) |
O6B—H6B···O6vi | 0.89 (4) | 2.03 (4) | 2.8857 (19) | 163 (3) |
O7B—H7B···O5vii | 0.86 (4) | 1.86 (4) | 2.714 (2) | 175 (4) |
N1B—H1BA···O4v | 0.89 (4) | 1.99 (4) | 2.870 (2) | 171 (3) |
O3C—H3C···O4C | 0.95 (5) | 1.59 (5) | 2.4797 (18) | 154 (5) |
O5C—H5C···O6B | 0.82 (3) | 2.01 (4) | 2.829 (2) | 175 (3) |
O6C—H6C···O6Avi | 0.88 (4) | 1.93 (3) | 2.7893 (19) | 165 (3) |
O7C—H7C···O3Cvii | 0.86 (4) | 1.93 (4) | 2.767 (2) | 162 (3) |
N1C—H1C···O4A | 0.91 (4) | 2.03 (4) | 2.911 (2) | 164 (3) |
O1W—H1WA···O7Bi | 0.90 (4) | 1.94 (4) | 2.835 (2) | 173 (4) |
O1W—H1WB···O5Avii | 0.89 (5) | 2.22 (5) | 3.036 (2) | 153 (4) |
O2W—H2WA···O1W | 0.90 (3) | 1.94 (3) | 2.833 (2) | 167 (3) |
O2W—H2WB···O6C | 0.87 (4) | 2.00 (4) | 2.869 (2) | 172 (3) |
Symmetry codes: (i) x, y, z−1; (ii) −x, y−1/2, −z+1; (iii) −x+1, y−1/2, −z+1; (iv) −x, y−1/2, −z+2; (v) x, y, z+1; (vi) −x, y+1/2, −z+1; (vii) −x+1, y+1/2, −z+1. |
Acknowledgements
The authors are grateful to Dr Sergey Lindeman for help with this work and to the NSF for support via DMR grant 0934212 (PREM) and CHE 0832622.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Since his first isolation from Narcissus bulbs by Ceriotti in 1967 (Ceriotti, 1967a; Ceriotti, 1967b; Ceriotti et al., 1967), narciclasine has been extensively studied from chemical and biological standpoints (Kornienko & Evidente, 2008). It exhibits a broad range of biological activities and thus has various potential practical applications, for example, in the treatment of brain cancers, such as glioblastoma multiforme. The structure and absolute stereochemistry of this isocarbostyril related to the Amaryllidaceae alkaloids was unambiguously elucidated by an X-ray analysis of the corresponding tetraacetate (Savona et al., 1970; Immirzi & Fuganti, 1972). In 1998, narciclasine isolated from the mucilage of Narcissustazetta L. bulbs was studied by an X-ray diffraction analysis, but the crystallographic data and structure refinement details were not presented and deposited (Bi et al., 1998). Furthermore, the X-ray data of cis-dihydronarciclasine were reported very recently (McNulty et al., 2011). Because of its biological importance, narciclasine is studied in complexes with the target proteins. To assist in these investigations we prepared crystalline natural product and performed an X-ray single-crystal analysis.
The title compound, I, crystallizes as hemihydrate, i.e., C14H13NO7.0.5H2O, with the four crystallographically independent molecules of I and the two crystallographically independent water solvate molecules in the unit cell (Fig. 1). All the four crystallographically independent molecules of I are geometrically very similar and differ only by the orientations of the three hydroxy groups at the terminal cyclohexene rings.
The molecule of I comprises a fused tetracyclic system containing one five-membered ring (dioxolane) and three six-membered rings (benzene, dihydropyridone and cyclohexene) (Fig. 1). The five-membered dioxolane ring has the planar conformation, and the six-membered dihydropyridone and cyclohexene rings adopt the sofa conformations. In the case of dihydropyridone ring, the bridged carbon atom adjacent to the nitrogen atom deviates from the plane passed through the other atoms of the ring, and, in the case of cyclohexene ring, the carbon atom bearing the hydroxy group and adjacent to the bridged carbon atom is out of the plane passed through the other atoms of the ring. The flattened structure of molecule of I is supported by the strong intramolecular O–H···O hydrogen bond (Table 1). The nitrogen atom has a slightly pyramidalized configuration.
The different disposition of the hydrogen atoms of the hydroxy groups in the four crystallographically independent molecules of I as well as the observed configurations of the nitrogen atoms is explained by developed hydrogen bonding system in the crystal of I (Table 1). In the crystal, the molecules of I form the layers parallel to (101) (Fig. 2). The intermolecular O–H···O and N–H···O hydrogen bonds link the molecules of I both within and between the layers and water solvate molecules into three-dimensional framework (Fig. 2).
The molecule of I possesses four asymmetric centers at the quaternary carbon atoms of the terminal cyclohexene ring. The absolute structure of I was objectively determined by use of Cu Kα radiation and the refinement of Flack parameter. The absolute configurations of the chiral centers are 2S,3R,4S,4aR.