#_______________________________________________________________________
#
# Crystallography by:  Douglas M. Ho
#                      Harvard University
#                      Department of Chemistry and Chemical Biology
#                      12 Oxford Street, B05-B06
#                      Cambridge, MA   02138
#                      Email: doug32009@gmail.com
#
# Comments:            bmc08002 = 7TM42E = C26H35NO8 . 0.25C2H6O
#                               = 16-(Dimethylaminomethyl)salvinorin A
#                               = (2S,4aR,6aR,7R,9S,10aS,10bR)-Methyl
#                                 9-Acetoxy-2-[2-(dimethylaminomethyl)-
#                                 3-furyl]-6a,10b-dimethyl-4,10-dioxo-
#                                 2,4a,5,6,7,8,9,10a-octahydro-1H-
#                                 benzo[f]isochromene-7-carboxylate
#                                 at 193(2) K
#
#                      The title compound crystallizes from ethanol /
#                      hexanes as colorless prisms in the chiral
#                      monoclinic space group P2(1) (No. 4) with 2
#                      formula units per cell, i.e., Z = 2.
#
#                      The final Flack parameter x = -0.1(9) indicates
#                      that the absolute structure of the compound
#                      cannot be determined based on anomalous-dispersion
#                      effects alone (due to the lack of a heavy atom).
#                      Fortunately, the compound belongs to a family
#                      of natural products for which the chiral centers
#                      are known from previous crystallographic studies.
#                      The absolute structure is therefore completely
#                      assignable by reference to those known centers
#                      of chirality.  The hand of the compound in this
#                      study is thus unequivocally (2S,4aR,6aR,7R,9S,
#                      10aS,10bR).
#
#                      The following translation is provided between the
#                      terpenoid numbering used in the CIF, and the IUPAC
#                      numbers in the systematic name: (CIF atom numbers,
#                      IUPAC atom numbers):
#
#                      CIF:    (12S,  8R,   5R,  4R,  2S,  10S,   9R)
#                      IUPAC:  (2S,  4aR,  6aR,  7R,  9S, 10aS, 10bR)
#
#                      Hence, the resorted CIF / X-ray numbers are:
#                              (2S,4R,5R,8R,9R,10S,12S) 
#
# CheckCIF:            PLAT220_ALERT_2_A Large Non-Solvent             C
#                      PLAT222_ALERT_3_A Large Non-Solvent             H
#                      DIFMX01_ALERT_2_B Max diff density > 0.1*ZMAX*1.00
#                      PLAT097_ALERT_2_B Large Reported  Max Res Density
#                      DIFMX02_ALERT_1_C Max diff density > 0.1*ZMAX*0.75
#                      PLAT094_ALERT_2_C Ratio of  Max / Min Res Density
#                      PLAT215_ALERT_3_C Disordered C25' ADP max/min Ratio
#                      PLAT230_ALERT_2_C Hirshfeld Test Diff for C4--C18
#                      PLAT242_ALERT_2_C Check Low Ueq for           N24
#                      PLAT242_ALERT_2_C Check Low Ueq for           C24
#                      PLAT242_ALERT_2_C Check Low Ueq for           C24'
#                      PLAT313_ALERT_2_C three covalent bonds        O27'
#                      PLAT077_ALERT_4_C non-integer number of atoms
#                      PLAT301_ALERT_3_G Main Residue Disorder 11.00 Perc
#                      PLAT860_ALERT_3_G Least-Squares Restraints     67
#                      PLAT811_ALERT_5_G No ADDSYM...Too Many Excl Atoms
#
#                         The above alerts are due to severe disorder as
#                         described in the _refine_special_details
#                         section.  The researchers have made a best
#                         effort to treat the disorder, but as may be
#                         the case from time to time, "perfect" results
#                         cannot be obtained.
#
#
#                      PLAT024_ALERT_4_C Merging of Friedel Pairs
#                      STRVA01_ALERT_4_C Flack results are meaningless
#                      PLAT032_ALERT_4_C Std. Uncertainty in Flack
#                      REFLT03_ALERT_4_G MoKa measured Friedel data
#                      PLAT066_ALERT_1_C Transmissions Identical
#                      PLAT041_ALERT_1_C Calc/Rep SumFormula Differ
#                      PLAT042_ALERT_1_C Calc/Rep MoietyFormula Differ
#                      PLAT045_ALERT_1_C Calc/Rep Z Differ
#                      PLAT153_ALERT_1_C su's on the Cell Axes are Equal
#
#                         Merging of Friedel Pairs is a "recommendation"
#                         only.  Merging is theoretically and technically
#                         wrong.  We are within our rights to not follow
#                         this recommendation.  The high standard
#                         uncertainty in the Flack parameter is normal
#                         for light-atom data, and similarly, meaningless
#                         Flack results in such cases are also normal
#                         with MoKa Friedel data.  The transmissions are
#                         not identical.  This alert is due to a rounding
#                         error in Platon/CheckCIF.  The transmissions
#                         are normal for light-atom data, and are not a
#                         problem.  The calculated and reported values
#                         for SumFormula, MoietyFormula and Z differ
#                         because the CheckCIF calculated values are
#                         wrong.  The reported values in our CIF are the
#                         right values.  And yes, the su's on the Cell
#                         Axes are Equal.
#
#
#                      PLAT366_ALERT_2_C Short C13-C16         1.35 Ang.
#
#                         The C(13)-C(16) double bond is 1.353(3) Ang.
#                         The C(14)-C(15) double bond in the same furyl
#                         ring is 1.334(4) Ang, and is even shorter.
#                         Both bonds are not short.  They are normal.
#                         This alert was probably generated by an error
#                         in Platon/CheckCIF to correctly assign the
#                         carbon atoms as sp2 due to the disorder
#                         attached to C(16).
#
#
#                      PLAT791_ALERT_4_G Chirality at C10
#
#                         Platon/CheckCIF suggests 10R.  Symyx Draw
#                         gives 10S.  Presumably, Platon/CheckCIF is
#                         in error.  No correction to the CIF file is
#                         needed.
#
# Version date:        June 19, 2009
#_______________________________________________________________________

data_bmc08002

_audit_creation_method            SHELXL-97
_chemical_name_systematic
;
(2S,4aR,6aR,7R,9S,10aS,10bR)-
Methyl 9-Acetoxy-2-[2-(dimethylaminomethyl)-3-furyl]-6a,10b-dimethyl-
4,10-dioxo-2,4a,5,6,7,8,9,10a-octahydro-1H-benzo[f]isochromene-
7-carboxylate
;
_chemical_name_common             '16-(Dimethylaminomethyl)salvinorin A'
_chemical_formula_iupac           'C26 H35 N O8 . 0.25(C2 H6 O)'
_chemical_formula_moiety          'C26 H35 N O8, 0.25(C2 H6 O)'
_chemical_formula_structural      '(C26 H35 N O8) 0.25(C2 H6 O)'
_chemical_formula_analytical      ?
_chemical_formula_sum             'C26.50 H36.50 N O8.25'
_chemical_formula_weight          501.07
_chemical_melting_point_gt        429
_chemical_melting_point_lt        431
_chemical_compound_source         'chemical synthesis'

loop_
 _atom_type_symbol
 _atom_type_description
 _atom_type_scat_dispersion_real
 _atom_type_scat_dispersion_imag
 _atom_type_scat_source
 'C'  'C'   0.0033   0.0016
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'H'  'H'   0.0000   0.0000
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'N'  'N'   0.0061   0.0033
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'O'  'O'   0.0106   0.0060
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting            monoclinic
_symmetry_space_group_name_Hall   'P 2yb'
_symmetry_space_group_name_H-M    'P 21'
_symmetry_Int_Tables_number       4

loop_
 _symmetry_equiv_pos_as_xyz
 'x, y, z'
 '-x, y+1/2, -z'

_cell_length_a                    10.9397(2)
_cell_length_b                    10.1557(2)
_cell_length_c                    12.7466(2)
_cell_angle_alpha                 90.00
_cell_angle_beta                  109.839(1)
_cell_angle_gamma                 90.00
_cell_volume                      1332.10(4)
_cell_formula_units_Z             2
_cell_measurement_temperature     193(2)
_cell_measurement_reflns_used     5859
_cell_measurement_theta_min       2.63
_cell_measurement_theta_max       28.86

_exptl_crystal_description        prism
_exptl_crystal_colour             colourless
_exptl_crystal_size_max           0.267
_exptl_crystal_size_mid           0.222
_exptl_crystal_size_min           0.207
_exptl_crystal_recrystallization_method 
;
dissolved in minimal hot ethanol, diluted to approximately 10% in 
hexanes, warmed until clear, then left to evaporate in a fumehood.
;
_exptl_crystal_density_diffrn     1.249
_exptl_crystal_density_method     'not measured'
_exptl_crystal_density_meas       ?
_exptl_crystal_F_000              537
_exptl_absorpt_coefficient_mu     0.092
_exptl_absorpt_correction_type    'multi-scan'
_exptl_absorpt_correction_T_min   0.9758
_exptl_absorpt_correction_T_max   0.9811
_exptl_absorpt_process_details    'SADABS (Bruker AXS, 2004)'

_exptl_special_details
;
The compound was provided as colorless prisms from an ethanol / hexanes
solution.  A prism cut to 0.207 mm x 0.222 mm x 0.267 mm in size was
mounted on a nylon loop with Paratone-N oil, and transferred to a
Bruker SMART APEX II diffractometer equipped with an Oxford Cryosystems
700 Series Cryostream Cooler and Mo Kα radiation (λ = 0.71073 Å).
A total of 1228 frames were collected at 193(2) K to θₘₐₓ = 30.00°
with an oscillation range of 0.5°/frame, and an exposure time of 20
s/frame using the APEX2 suite of software. (Bruker AXS, 2006a)  Unit
cell refinement on all observed reflections, and data reduction with
corrections for Lp and decay were performed using SAINT. (Bruker AXS,
2006b)  Scaling and a multi-scan absorption correction were done using
SADABS. (Bruker AXS, 2004)  The minimum and maximum transmission
factors were 0.9758 and 0.9811, respectively.  A total of 17282
reflections were collected, 7755 were unique (Rint = 0.0210), and
6232 had I > 2σ(I).  Systematic absences were consistent
with the compound having crystallized in the monoclinic space group
P2₁ or P2₁/m.  The chiral space group P2₁ (No. 4) was selected
based on an observed mean |E²-1| value of 0.766 (versus the
expectation values of 0.968 and 0.736 for centric and noncentric data,
respectively).

________________________________________________________________________

Bruker AXS (2004).  SADABS.  Bruker AXS Inc., Madison, Wisconsin,
USA.

Bruker AXS (2006a).  APEX2 v2.1-0.  Bruker AXS Inc.,
Madison, Wisconsin, USA.

Bruker AXS (2006b).  SAINT V7.34A.  Bruker AXS Inc.,
Madison, Wisconsin, USA.
________________________________________________________________________
;

_diffrn_ambient_temperature       193(2)
_diffrn_radiation_wavelength      0.71073
_diffrn_radiation_type            'Mo K\a'
_diffrn_radiation_source          'fine-focus sealed tube'
_diffrn_radiation_monochromator   'graphite'
_diffrn_measurement_device_type   'Bruker APEX II CCD'
_diffrn_measurement_method        'ω scans, 1228 0.5° rotations'
_diffrn_detector_area_resol_mean  836.6
_diffrn_standards_number          0
_diffrn_standards_interval_count  ?
_diffrn_standards_interval_time   ?
_diffrn_standards_decay_%         0
_diffrn_reflns_number             17282
_diffrn_reflns_av_R_equivalents   0.0210
_diffrn_reflns_av_sigmaI/netI     0.0305
_diffrn_reflns_limit_h_min        -12
_diffrn_reflns_limit_h_max        15
_diffrn_reflns_limit_k_min        -14
_diffrn_reflns_limit_k_max        14
_diffrn_reflns_limit_l_min        -17
_diffrn_reflns_limit_l_max        17
_diffrn_reflns_theta_min          1.70
_diffrn_reflns_theta_max          30.00

_diffrn_measured_fraction_theta_max    1.000
_diffrn_reflns_theta_full              30.00
_diffrn_measured_fraction_theta_full   1.000

_reflns_number_total              7755
_reflns_number_gt                 6232
_reflns_threshold_expression      'I>2σ(I)'

_computing_data_collection        'APEX2 v2.1-0 (Bruker AXS, 2006a)'
_computing_cell_refinement        'SAINT V7.34A (Bruker AXS, 2006b)'
_computing_data_reduction         'SAINT V7.34A (Bruker AXS, 2006b)'
_computing_structure_solution     'SHELXTL v2008/4 (Bruker AXS, 2008)'
_computing_structure_refinement   'SHELXTL v2008/4 (Bruker AXS, 2008)'
_computing_molecular_graphics     'SHELXTL v2008/4 (Bruker AXS, 2008)'
_computing_publication_material   'SHELXTL v2008/4 (Bruker AXS, 2008)'

_refine_special_details
;
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 > 2σ(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.

The structure was solved by direct methods and refined by full-matrix
least-squares on F² using SHELXTL. (Bruker AXS, 2008)
The asymmetric unit was found to contain one molecule of
(2S,4aR,6aR,7R,9S,10aS,10bR)-
Methyl 9-Acetoxy-2-[2-(dimethylaminomethyl)-3-furyl]-6a,10b-dimethyl-
4,10-dioxo-2,4a,5,6,7,8,9,10a-octahydro-1H-benzo[f]isochromene-
7-carboxylate, and a partially occupied ethanol solvent site.  The
dimethylaminomethyl moiety was severely disordered and was treated
with a two-site model [C(24), N(24), C(25), C(26)] and [C(24'), N(24'),
C(25'), C(26')].  These eight partial atoms were assigned fixed site
occupancy factors of 0.5, and included in the refinements with rigid
bond, Uij similarity, and 1,2- and 1,3-distance restraints.  The C(24)
and C(24') atoms were also restrained to be coplanar with the furyl
ring.  The ethanol appears to be associated with only the primed
component of the disorder.  Hence, its atoms were designated O(27'),
C(28') and C(29'), and were included in the refinements with fixed
site occupancy factors of 0.25.  The reason for this grouping is that
the ethanol hydroxy hydrogen H(27') can hydrogen bond to N(24') but
not to N(24).  Also, there are bad contacts between C(26) and O(27'),
suggesting that in the unprimed conformation, ethanol cannot be
comfortably accommodated in the lattice.  Therefore, the structure
was treated as suffering from both rotational and compositional
disorder.

All of the nonhydrogen atoms were refined with anisotropic displacement
coefficients.  The hydrogen atoms were assigned isotropic displacement
coefficients U(H) = 1.2U(C), 1.5U(Cmethyl) or 1.5U(O), and their
coordinates were allowed to ride on their respective carbons or oxygen.
The refinement converged to R(F) = 0.0584,
wR(F²) = 0.1661, and S = 1.040 for 6232
reflections with I > 2σ(I), and R(F) =
0.0727, wR(F²) = 0.1820, and S = 1.040 for 7755
unique reflections, 388 parameters, and 67 restraints.  The maximum
|Δ/σ| in the final cycle of least-squares was less than 0.001, and the
residual peaks on the final difference-Fourier map ranged from -0.354
to 0.990 eÅ⁻³.  Scattering factors were taken from the International
Tables for Crystallography, Volume C. (Maslen et al., 1992, and Creagh
& McAuley, 1992)

The Flack absolute structure parameter refined to x = -0.1(9) [versus
the expectation values of 0 (within 3 esd's) for the correct and +1 for
the inverted absolute structure] indicating that the absolute structure
cannot be established in this study by anomalous-dispersion effects.
(Flack, 1983)  Fortunately, the compound belongs to a family of natural
products for which the chiral centers are known from previous
crystallographic studies.  The absolute structure is therefore
completely assignable by reference to those known centers of chirality.
The hand of the compound in this study is thus unequivocally
(2S,4aR,6aR,7R,9S,10aS,10bR).
________________________________________________________________________

R(F ) = R1 =
Σ ||Fₒ|-|Fc|| / Σ|Fₒ|,
wR(F ²) = wR2 =
[ Σ w (Fₒ²-Fc²)² / 
Σ w (Fₒ²)² ]^1/2^, and
S = Goodness-of-fit on F ² =
[ Σ w (Fₒ²-Fc²)² / 
(n-p) ]^1/2^, where n is the number of reflections
and p is the number of parameters refined.

________________________________________________________________________

Bruker AXS (2008). SHELXTL v2008/4.  Bruker AXS Inc.,
Madison, Wisconsin, USA.

Creagh, D. C. & McAuley, W. J. (1992). International Tables for
Crystallography: Mathematical, Physical and Chemical Tables, Vol C,
edited by A. J. C. Wilson, pp. 206-222. Dordrecht, The Netherlands:
Kluwer.

Flack, H. D. (1983). Acta Crystallographica, Section A, 39,
876-881.

Maslen, E. N., Fox, A. G. & O'Keefe, M. A. (1992). International
Tables for Crystallography: Mathematical, Physical and Chemical
Tables, Vol C, edited by A. J. C. Wilson, pp. 476-516. Dordrecht,
The Netherlands: Kluwer.
________________________________________________________________________
;

_refine_ls_structure_factor_coef  Fsqd
_refine_ls_matrix_type            full
_refine_ls_weighting_scheme       calc
_refine_ls_weighting_details
 'w=1/[σ²(Fo²)+(0.1211P)²+0.0446P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary      direct
_atom_sites_solution_secondary    difmap
_atom_sites_solution_hydrogens    geom
_refine_ls_hydrogen_treatment     constr
_refine_ls_extinction_method      none
_refine_ls_extinction_coef        ?
_refine_ls_abs_structure_details
 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack    -0.1(9)
_chemical_absolute_configuration syn
_refine_ls_number_reflns          7755
_refine_ls_number_parameters      388
_refine_ls_number_restraints      67
_refine_ls_R_factor_all           0.0727
_refine_ls_R_factor_gt            0.0584
_refine_ls_wR_factor_ref          0.1820
_refine_ls_wR_factor_gt           0.1661
_refine_ls_goodness_of_fit_ref    1.040
_refine_ls_restrained_S_all       1.045
_refine_ls_shift/su_max           0.000
_refine_ls_shift/su_mean          0.000
_refine_diff_density_max          0.990
_refine_diff_density_min          -0.354
_refine_diff_density_rms          0.054

loop_ 
 _atom_site_label 
 _atom_site_type_symbol 
 _atom_site_fract_x 
 _atom_site_fract_y 
 _atom_site_fract_z 
 _atom_site_U_iso_or_equiv 
 _atom_site_adp_type 
 _atom_site_occupancy 
 _atom_site_symmetry_multiplicity 
 _atom_site_calc_flag 
 _atom_site_refinement_flags 
 _atom_site_disorder_assembly 
 _atom_site_disorder_group 
C1 C 0.2664(2) 0.1432(2) 0.78291(16) 0.0383(4) Uani 1 1 d . . . 
O1 O 0.37855(15) 0.16297(19) 0.79773(15) 0.0514(4) Uani 1 1 d . . . 
C2 C 0.2182(2) 0.0141(2) 0.81584(19) 0.0441(5) Uani 1 1 d . . . 
H2 H 0.1696 -0.0356 0.7465 0.053 Uiso 1 1 calc R . . 
O2 O 0.33187(18) -0.06059(18) 0.87787(15) 0.0571(5) Uani 1 1 d . . . 
C3 C 0.1294(2) 0.0343(2) 0.88372(19) 0.0473(5) Uani 1 1 d . . . 
H3A H 0.1805 0.0684 0.9585 0.057 Uiso 1 1 calc R . . 
H3B H 0.0909 -0.0511 0.8935 0.057 Uiso 1 1 calc R . . 
C4 C 0.02125(19) 0.1314(2) 0.82525(16) 0.0395(4) Uani 1 1 d . . . 
H4 H -0.0292 0.0943 0.7504 0.047 Uiso 1 1 calc R . . 
C5 C 0.07674(18) 0.2681(2) 0.80674(16) 0.0347(4) Uani 1 1 d . . . 
C6 C -0.03680(19) 0.3606(2) 0.74666(18) 0.0397(4) Uani 1 1 d . . . 
H6A H -0.1018 0.3112 0.6861 0.048 Uiso 1 1 calc R . . 
H6B H -0.0793 0.3890 0.8002 0.048 Uiso 1 1 calc R . . 
C7 C 0.0044(2) 0.4820(2) 0.69728(19) 0.0414(4) Uani 1 1 d . . . 
H7A H 0.0643 0.5360 0.7577 0.050 Uiso 1 1 calc R . . 
H7B H -0.0728 0.5361 0.6578 0.050 Uiso 1 1 calc R . . 
C8 C 0.07213(18) 0.4399(2) 0.61612(16) 0.0343(4) Uani 1 1 d . . . 
H8 H 0.0107 0.3791 0.5615 0.041 Uiso 1 1 calc R . . 
C9 C 0.19728(16) 0.36029(18) 0.67189(15) 0.0322(3) Uani 1 1 d . . . 
C10 C 0.15642(17) 0.23994(18) 0.72708(15) 0.0313(3) Uani 1 1 d . . . 
H10 H 0.0953 0.1895 0.6634 0.038 Uiso 1 1 calc R . . 
C11 C 0.23884(18) 0.31158(19) 0.57411(16) 0.0348(4) Uani 1 1 d . . . 
H11A H 0.3201 0.2601 0.6046 0.042 Uiso 1 1 calc R . . 
H11B H 0.1709 0.2520 0.5266 0.042 Uiso 1 1 calc R . . 
C12 C 0.26072(19) 0.4225(2) 0.50229(17) 0.0373(4) Uani 1 1 d . . . 
H12 H 0.3511 0.4563 0.5385 0.045 Uiso 1 1 calc R . . 
O12 O 0.17044(16) 0.53422(16) 0.48697(14) 0.0452(4) Uani 1 1 d . . . 
C13 C 0.24795(19) 0.37622(18) 0.38827(16) 0.0386(4) Uani 1 1 d D A . 
C14 C 0.1372(2) 0.3096(2) 0.31107(18) 0.0464(5) Uani 1 1 d D . . 
H14 H 0.0585 0.2877 0.3230 0.056 Uiso 1 1 calc R . . 
C15 C 0.1669(3) 0.2848(2) 0.2198(2) 0.0547(6) Uani 1 1 d D . . 
H15 H 0.1114 0.2411 0.1553 0.066 Uiso 1 1 calc R . . 
O15 O 0.28902(18) 0.33144(16) 0.23205(13) 0.0543(4) Uani 1 1 d D A . 
C16 C 0.33639(19) 0.38679(16) 0.33596(17) 0.0414(4) Uani 1 1 d D . . 
C17 C 0.09536(19) 0.5533(2) 0.54885(18) 0.0381(4) Uani 1 1 d . . . 
O17 O 0.04333(17) 0.65991(17) 0.54276(15) 0.0527(4) Uani 1 1 d . . . 
C18 C -0.0700(2) 0.1420(3) 0.89210(19) 0.0488(5) Uani 1 1 d . . . 
O18 O -0.03758(19) 0.1418(3) 0.99149(15) 0.0726(7) Uani 1 1 d . . . 
C19 C 0.1601(2) 0.3293(3) 0.91886(17) 0.0459(5) Uani 1 1 d . . . 
H19A H 0.1164 0.3173 0.9737 0.069 Uiso 1 1 calc R . . 
H19B H 0.1718 0.4235 0.9086 0.069 Uiso 1 1 calc R . . 
H19C H 0.2452 0.2860 0.9455 0.069 Uiso 1 1 calc R . . 
C20 C 0.30514(19) 0.4477(2) 0.75020(17) 0.0399(4) Uani 1 1 d . . . 
H20A H 0.3212 0.5226 0.7082 0.060 Uiso 1 1 calc R . . 
H20B H 0.3850 0.3960 0.7809 0.060 Uiso 1 1 calc R . . 
H20C H 0.2777 0.4800 0.8112 0.060 Uiso 1 1 calc R . . 
O21 O -0.19323(16) 0.1513(2) 0.82504(14) 0.0558(4) Uani 1 1 d . . . 
C21 C -0.2875(3) 0.1642(5) 0.8812(3) 0.0749(9) Uani 1 1 d . . . 
H21A H -0.3629 0.2138 0.8338 0.112 Uiso 1 1 calc R . . 
H21B H -0.2481 0.2109 0.9519 0.112 Uiso 1 1 calc R . . 
H21C H -0.3155 0.0765 0.8959 0.112 Uiso 1 1 calc R . . 
C22 C 0.3304(3) -0.1875(3) 0.8616(3) 0.0643(8) Uani 1 1 d . . . 
O22 O 0.2309(3) -0.2466(2) 0.8144(3) 0.0924(8) Uani 1 1 d . . . 
C23 C 0.4605(3) -0.2478(3) 0.9237(3) 0.0713(8) Uani 1 1 d . . . 
H23A H 0.4479 -0.3353 0.9508 0.107 Uiso 1 1 calc R . . 
H23B H 0.5073 -0.1916 0.9871 0.107 Uiso 1 1 calc R . . 
H23C H 0.5111 -0.2558 0.8736 0.107 Uiso 1 1 calc R . . 
C24 C 0.4698(3) 0.4486(3) 0.3790(7) 0.0440(19) Uani 0.50 1 d PDU A 1 
H24A H 0.4833 0.5040 0.3200 0.053 Uiso 0.50 1 calc PR A 1 
H24B H 0.4764 0.5058 0.4436 0.053 Uiso 0.50 1 calc PR A 1 
N24 N 0.5709(4) 0.3460(4) 0.4130(4) 0.0679(14) Uani 0.50 1 d PDU A 1 
C25 C 0.6985(4) 0.4049(8) 0.4325(6) 0.079(2) Uani 0.50 1 d PDU A 1 
H25A H 0.6991 0.4497 0.3645 0.119 Uiso 0.50 1 calc PR A 1 
H25B H 0.7650 0.3359 0.4524 0.119 Uiso 0.50 1 calc PR A 1 
H25C H 0.7169 0.4688 0.4935 0.119 Uiso 0.50 1 calc PR A 1 
C26 C 0.5687(6) 0.2797(9) 0.5138(7) 0.097(3) Uani 0.50 1 d PDU A 1 
H26A H 0.5087 0.2049 0.4933 0.145 Uiso 0.50 1 calc PR A 1 
H26B H 0.5397 0.3416 0.5595 0.145 Uiso 0.50 1 calc PR A 1 
H26C H 0.6562 0.2481 0.5563 0.145 Uiso 0.50 1 calc PR A 1 
C24' C 0.4708(3) 0.4421(4) 0.3597(6) 0.043(2) Uani 0.50 1 d PDU A 2 
H24C H 0.5061 0.4130 0.3016 0.051 Uiso 0.50 1 calc PR A 2 
H24D H 0.4674 0.5395 0.3591 0.051 Uiso 0.50 1 calc PR A 2 
N24' N 0.5545(4) 0.3955(5) 0.4692(5) 0.087(2) Uani 0.50 1 d PDU A 2 
C25' C 0.5879(7) 0.2574(5) 0.4605(10) 0.164(7) Uani 0.50 1 d PDU A 2 
H25D H 0.5099 0.2029 0.4453 0.245 Uiso 0.50 1 calc PR A 2 
H25E H 0.6534 0.2293 0.5307 0.245 Uiso 0.50 1 calc PR A 2 
H25F H 0.6229 0.2475 0.3995 0.245 Uiso 0.50 1 calc PR A 2 
C26' C 0.6717(6) 0.4757(8) 0.5099(8) 0.119(4) Uani 0.50 1 d PDU A 2 
H26D H 0.6531 0.5645 0.4784 0.179 Uiso 0.50 1 calc PR A 2 
H26E H 0.7404 0.4357 0.4872 0.179 Uiso 0.50 1 calc PR A 2 
H26F H 0.7003 0.4808 0.5915 0.179 Uiso 0.50 1 calc PR A 2 
O27' O 0.5825(10) 0.3708(11) 0.6668(8) 0.084(3) Uani 0.25 1 d P B 2 
H27' H 0.5585 0.3691 0.5968 0.126 Uiso 0.25 1 calc PR B 2 
C28' C 0.6268(16) 0.506(2) 0.7071(12) 0.088(5) Uani 0.25 1 d P B 2 
H28A H 0.5554 0.5699 0.6765 0.105 Uiso 0.25 1 calc PR B 2 
H28B H 0.7008 0.5321 0.6837 0.105 Uiso 0.25 1 calc PR B 2 
C29' C 0.6678(14) 0.501(2) 0.8329(9) 0.092(6) Uani 0.25 1 d P B 2 
H29A H 0.6939 0.5891 0.8635 0.138 Uiso 0.25 1 calc PR B 2 
H29B H 0.7412 0.4402 0.8621 0.138 Uiso 0.25 1 calc PR B 2 
H29C H 0.5949 0.4702 0.8546 0.138 Uiso 0.25 1 calc PR B 2 
 
 
_geom_special_details 
; 
 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. 
; 
 
loop_ 
 _geom_bond_atom_site_label_1 
 _geom_bond_atom_site_label_2 
 _geom_bond_distance 
 _geom_bond_site_symmetry_2 
 _geom_bond_publ_flag 
C1 O1 1.193(3) . ? 
C1 C2 1.524(3) . ? 
C1 C10 1.530(3) . ? 
C2 O2 1.442(3) . ? 
C2 C3 1.518(4) . ? 
C2 H2 1.0000 . ? 
O2 C22 1.305(3) . ? 
C3 C4 1.526(3) . ? 
C3 H3A 0.9900 . ? 
C3 H3B 0.9900 . ? 
C4 C18 1.521(3) . ? 
C4 C5 1.564(3) . ? 
C4 H4 1.0000 . ? 
C5 C6 1.538(3) . ? 
C5 C19 1.541(3) . ? 
C5 C10 1.573(3) . ? 
C6 C7 1.521(3) . ? 
C6 H6A 0.9900 . ? 
C6 H6B 0.9900 . ? 
C7 C8 1.524(3) . ? 
C7 H7A 0.9900 . ? 
C7 H7B 0.9900 . ? 
C8 C17 1.508(3) . ? 
C8 C9 1.541(2) . ? 
C8 H8 1.0000 . ? 
C9 C20 1.542(3) . ? 
C9 C11 1.546(3) . ? 
C9 C10 1.550(3) . ? 
C10 H10 1.0000 . ? 
C11 C12 1.521(3) . ? 
C11 H11A 0.9900 . ? 
C11 H11B 0.9900 . ? 
C12 O12 1.473(3) . ? 
C12 C13 1.488(3) . ? 
C12 H12 1.0000 . ? 
O12 C17 1.332(3) . ? 
C13 C16 1.353(3) . ? 
C13 C14 1.444(3) . ? 
C14 C15 1.334(4) . ? 
C14 H14 0.9500 . ? 
C15 O15 1.376(3) . ? 
C15 H15 0.9500 . ? 
O15 C16 1.369(3) . ? 
C16 C24' 1.505(3) . ? 
C16 C24 1.511(3) . ? 
C17 O17 1.213(3) . ? 
C18 O18 1.194(3) . ? 
C18 O21 1.332(3) . ? 
C19 H19A 0.9800 . ? 
C19 H19B 0.9800 . ? 
C19 H19C 0.9800 . ? 
C20 H20A 0.9800 . ? 
C20 H20B 0.9800 . ? 
C20 H20C 0.9800 . ? 
O21 C21 1.448(3) . ? 
C21 H21A 0.9800 . ? 
C21 H21B 0.9800 . ? 
C21 H21C 0.9800 . ? 
C22 O22 1.209(4) . ? 
C22 C23 1.504(4) . ? 
C23 H23A 0.9800 . ? 
C23 H23B 0.9800 . ? 
C23 H23C 0.9800 . ? 
C24 N24 1.474(3) . ? 
C24 H24A 0.9900 . ? 
C24 H24B 0.9900 . ? 
N24 C26 1.457(3) . ? 
N24 C25 1.460(3) . ? 
C25 H25A 0.9800 . ? 
C25 H25B 0.9800 . ? 
C25 H25C 0.9800 . ? 
C26 H26A 0.9800 . ? 
C26 H26B 0.9800 . ? 
C26 H26C 0.9800 . ? 
C24' N24' 1.464(3) . ? 
C24' H24C 0.9900 . ? 
C24' H24D 0.9900 . ? 
N24' C26' 1.457(3) . ? 
N24' C25' 1.463(3) . ? 
C25' H25D 0.9800 . ? 
C25' H25E 0.9800 . ? 
C25' H25F 0.9800 . ? 
C26' H26D 0.9800 . ? 
C26' H26E 0.9800 . ? 
C26' H26F 0.9800 . ? 
O27' C28' 1.49(2) . ? 
O27' H27' 0.8400 . ? 
C28' C29' 1.512(18) . ? 
C28' H28A 0.9900 . ? 
C28' H28B 0.9900 . ? 
C29' H29A 0.9800 . ? 
C29' H29B 0.9800 . ? 
C29' H29C 0.9800 . ? 
 
loop_ 
 _geom_angle_atom_site_label_1 
 _geom_angle_atom_site_label_2 
 _geom_angle_atom_site_label_3 
 _geom_angle 
 _geom_angle_site_symmetry_1 
 _geom_angle_site_symmetry_3 
 _geom_angle_publ_flag 
O1 C1 C2 122.32(19) . . ? 
O1 C1 C10 124.7(2) . . ? 
C2 C1 C10 112.92(17) . . ? 
O2 C2 C3 110.98(18) . . ? 
O2 C2 C1 106.79(18) . . ? 
C3 C2 C1 112.89(19) . . ? 
O2 C2 H2 108.7 . . ? 
C3 C2 H2 108.7 . . ? 
C1 C2 H2 108.7 . . ? 
C22 O2 C2 118.1(2) . . ? 
C2 C3 C4 110.43(18) . . ? 
C2 C3 H3A 109.6 . . ? 
C4 C3 H3A 109.6 . . ? 
C2 C3 H3B 109.6 . . ? 
C4 C3 H3B 109.6 . . ? 
H3A C3 H3B 108.1 . . ? 
C18 C4 C3 108.65(18) . . ? 
C18 C4 C5 112.57(18) . . ? 
C3 C4 C5 111.76(17) . . ? 
C18 C4 H4 107.9 . . ? 
C3 C4 H4 107.9 . . ? 
C5 C4 H4 107.9 . . ? 
C6 C5 C19 109.80(17) . . ? 
C6 C5 C4 109.14(16) . . ? 
C19 C5 C4 110.84(17) . . ? 
C6 C5 C10 108.67(15) . . ? 
C19 C5 C10 112.88(16) . . ? 
C4 C5 C10 105.35(15) . . ? 
C7 C6 C5 113.49(16) . . ? 
C7 C6 H6A 108.9 . . ? 
C5 C6 H6A 108.9 . . ? 
C7 C6 H6B 108.9 . . ? 
C5 C6 H6B 108.9 . . ? 
H6A C6 H6B 107.7 . . ? 
C6 C7 C8 109.54(17) . . ? 
C6 C7 H7A 109.8 . . ? 
C8 C7 H7A 109.8 . . ? 
C6 C7 H7B 109.8 . . ? 
C8 C7 H7B 109.8 . . ? 
H7A C7 H7B 108.2 . . ? 
C17 C8 C7 112.73(16) . . ? 
C17 C8 C9 111.62(15) . . ? 
C7 C8 C9 113.23(16) . . ? 
C17 C8 H8 106.2 . . ? 
C7 C8 H8 106.2 . . ? 
C9 C8 H8 106.2 . . ? 
C8 C9 C20 111.19(15) . . ? 
C8 C9 C11 104.74(14) . . ? 
C20 C9 C11 109.66(15) . . ? 
C8 C9 C10 105.98(14) . . ? 
C20 C9 C10 115.82(15) . . ? 
C11 C9 C10 108.82(15) . . ? 
C1 C10 C9 114.53(15) . . ? 
C1 C10 C5 109.71(15) . . ? 
C9 C10 C5 117.28(15) . . ? 
C1 C10 H10 104.6 . . ? 
C9 C10 H10 104.6 . . ? 
C5 C10 H10 104.6 . . ? 
C12 C11 C9 113.45(16) . . ? 
C12 C11 H11A 108.9 . . ? 
C9 C11 H11A 108.9 . . ? 
C12 C11 H11B 108.9 . . ? 
C9 C11 H11B 108.9 . . ? 
H11A C11 H11B 107.7 . . ? 
O12 C12 C13 106.09(16) . . ? 
O12 C12 C11 114.51(16) . . ? 
C13 C12 C11 111.87(17) . . ? 
O12 C12 H12 108.0 . . ? 
C13 C12 H12 108.0 . . ? 
C11 C12 H12 108.0 . . ? 
C17 O12 C12 123.65(16) . . ? 
C16 C13 C14 106.04(19) . . ? 
C16 C13 C12 127.63(19) . . ? 
C14 C13 C12 126.33(19) . . ? 
C15 C14 C13 106.7(2) . . ? 
C15 C14 H14 126.7 . . ? 
C13 C14 H14 126.7 . . ? 
C14 C15 O15 110.5(2) . . ? 
C14 C15 H15 124.7 . . ? 
O15 C15 H15 124.7 . . ? 
C16 O15 C15 106.58(18) . . ? 
C13 C16 O15 110.20(18) . . ? 
C13 C16 C24' 138.0(4) . . ? 
O15 C16 C24' 111.8(3) . . ? 
C13 C16 C24 128.2(4) . . ? 
O15 C16 C24 121.6(4) . . ? 
O17 C17 O12 117.5(2) . . ? 
O17 C17 C8 123.5(2) . . ? 
O12 C17 C8 118.82(17) . . ? 
O18 C18 O21 123.6(2) . . ? 
O18 C18 C4 125.4(2) . . ? 
O21 C18 C4 111.05(18) . . ? 
C5 C19 H19A 109.5 . . ? 
C5 C19 H19B 109.5 . . ? 
H19A C19 H19B 109.5 . . ? 
C5 C19 H19C 109.5 . . ? 
H19A C19 H19C 109.5 . . ? 
H19B C19 H19C 109.5 . . ? 
C9 C20 H20A 109.5 . . ? 
C9 C20 H20B 109.5 . . ? 
H20A C20 H20B 109.5 . . ? 
C9 C20 H20C 109.5 . . ? 
H20A C20 H20C 109.5 . . ? 
H20B C20 H20C 109.5 . . ? 
C18 O21 C21 115.1(2) . . ? 
O21 C21 H21A 109.5 . . ? 
O21 C21 H21B 109.5 . . ? 
H21A C21 H21B 109.5 . . ? 
O21 C21 H21C 109.5 . . ? 
H21A C21 H21C 109.5 . . ? 
H21B C21 H21C 109.5 . . ? 
O22 C22 O2 122.0(3) . . ? 
O22 C22 C23 126.2(3) . . ? 
O2 C22 C23 111.1(3) . . ? 
C22 C23 H23A 109.5 . . ? 
C22 C23 H23B 109.5 . . ? 
H23A C23 H23B 109.5 . . ? 
C22 C23 H23C 109.5 . . ? 
H23A C23 H23C 109.5 . . ? 
H23B C23 H23C 109.5 . . ? 
N24 C24 C16 110.4(3) . . ? 
N24 C24 H24A 109.6 . . ? 
C16 C24 H24A 109.6 . . ? 
N24 C24 H24B 109.6 . . ? 
C16 C24 H24B 109.6 . . ? 
H24A C24 H24B 108.1 . . ? 
C26 N24 C25 109.9(3) . . ? 
C26 N24 C24 110.5(4) . . ? 
C25 N24 C24 109.8(3) . . ? 
N24' C24' C16 108.9(4) . . ? 
N24' C24' H24C 109.9 . . ? 
C16 C24' H24C 109.9 . . ? 
N24' C24' H24D 109.9 . . ? 
C16 C24' H24D 109.9 . . ? 
H24C C24' H24D 108.3 . . ? 
C26' N24' C25' 110.5(4) . . ? 
C26' N24' C24' 110.4(3) . . ? 
C25' N24' C24' 109.2(4) . . ? 
N24' C25' H25D 109.5 . . ? 
N24' C25' H25E 109.5 . . ? 
H25D C25' H25E 109.5 . . ? 
N24' C25' H25F 109.5 . . ? 
H25D C25' H25F 109.5 . . ? 
H25E C25' H25F 109.5 . . ? 
N24' C26' H26D 109.5 . . ? 
N24' C26' H26E 109.5 . . ? 
H26D C26' H26E 109.5 . . ? 
N24' C26' H26F 109.5 . . ? 
H26D C26' H26F 109.5 . . ? 
H26E C26' H26F 109.5 . . ? 
C28' O27' H27' 109.5 . . ? 
O27' C28' C29' 106.3(16) . . ? 
O27' C28' H28A 110.5 . . ? 
C29' C28' H28A 110.5 . . ? 
O27' C28' H28B 110.5 . . ? 
C29' C28' H28B 110.5 . . ? 
H28A C28' H28B 108.7 . . ? 
C28' C29' H29A 109.5 . . ? 
C28' C29' H29B 109.5 . . ? 
H29A C29' H29B 109.5 . . ? 
C28' C29' H29C 109.5 . . ? 
H29A C29' H29C 109.5 . . ? 
H29B C29' H29C 109.5 . . ? 
 
loop_ 
 _geom_torsion_atom_site_label_1 
 _geom_torsion_atom_site_label_2 
 _geom_torsion_atom_site_label_3 
 _geom_torsion_atom_site_label_4 
 _geom_torsion 
 _geom_torsion_site_symmetry_1 
 _geom_torsion_site_symmetry_2 
 _geom_torsion_site_symmetry_3 
 _geom_torsion_site_symmetry_4 
 _geom_torsion_publ_flag 
O1 C1 C2 O2 7.9(3) . . . . ? 
C10 C1 C2 O2 -173.75(16) . . . . ? 
O1 C1 C2 C3 130.1(2) . . . . ? 
C10 C1 C2 C3 -51.5(2) . . . . ? 
C3 C2 O2 C22 95.6(3) . . . . ? 
C1 C2 O2 C22 -141.0(3) . . . . ? 
O2 C2 C3 C4 170.90(18) . . . . ? 
C1 C2 C3 C4 51.1(2) . . . . ? 
C2 C3 C4 C18 176.44(18) . . . . ? 
C2 C3 C4 C5 -58.7(2) . . . . ? 
C18 C4 C5 C6 -58.0(2) . . . . ? 
C3 C4 C5 C6 179.45(17) . . . . ? 
C18 C4 C5 C19 63.1(2) . . . . ? 
C3 C4 C5 C19 -59.5(2) . . . . ? 
C18 C4 C5 C10 -174.49(16) . . . . ? 
C3 C4 C5 C10 62.9(2) . . . . ? 
C19 C5 C6 C7 73.6(2) . . . . ? 
C4 C5 C6 C7 -164.71(17) . . . . ? 
C10 C5 C6 C7 -50.3(2) . . . . ? 
C5 C6 C7 C8 57.6(2) . . . . ? 
C6 C7 C8 C17 170.08(16) . . . . ? 
C6 C7 C8 C9 -62.0(2) . . . . ? 
C17 C8 C9 C20 59.2(2) . . . . ? 
C7 C8 C9 C20 -69.4(2) . . . . ? 
C17 C8 C9 C11 -59.21(19) . . . . ? 
C7 C8 C9 C11 172.29(16) . . . . ? 
C17 C8 C9 C10 -174.20(16) . . . . ? 
C7 C8 C9 C10 57.3(2) . . . . ? 
O1 C1 C10 C9 9.6(3) . . . . ? 
C2 C1 C10 C9 -168.70(16) . . . . ? 
O1 C1 C10 C5 -124.7(2) . . . . ? 
C2 C1 C10 C5 57.0(2) . . . . ? 
C8 C9 C10 C1 177.10(15) . . . . ? 
C20 C9 C10 C1 -59.1(2) . . . . ? 
C11 C9 C10 C1 64.93(19) . . . . ? 
C8 C9 C10 C5 -52.17(19) . . . . ? 
C20 C9 C10 C5 71.6(2) . . . . ? 
C11 C9 C10 C5 -164.33(14) . . . . ? 
C6 C5 C10 C1 -177.49(15) . . . . ? 
C19 C5 C10 C1 60.4(2) . . . . ? 
C4 C5 C10 C1 -60.64(18) . . . . ? 
C6 C5 C10 C9 49.6(2) . . . . ? 
C19 C5 C10 C9 -72.5(2) . . . . ? 
C4 C5 C10 C9 166.44(14) . . . . ? 
C8 C9 C11 C12 57.94(19) . . . . ? 
C20 C9 C11 C12 -61.5(2) . . . . ? 
C10 C9 C11 C12 170.92(15) . . . . ? 
C9 C11 C12 O12 -36.4(2) . . . . ? 
C9 C11 C12 C13 -157.12(16) . . . . ? 
C13 C12 O12 C17 138.43(19) . . . . ? 
C11 C12 O12 C17 14.5(3) . . . . ? 
O12 C12 C13 C16 110.28(19) . . . . ? 
C11 C12 C13 C16 -124.20(18) . . . . ? 
O12 C12 C13 C14 -70.1(2) . . . . ? 
C11 C12 C13 C14 55.4(2) . . . . ? 
C16 C13 C14 C15 0.30(15) . . . . ? 
C12 C13 C14 C15 -179.37(19) . . . . ? 
C13 C14 C15 O15 -0.35(17) . . . . ? 
C14 C15 O15 C16 0.27(16) . . . . ? 
C14 C13 C16 O15 -0.14(13) . . . . ? 
C12 C13 C16 O15 179.53(19) . . . . ? 
C14 C13 C16 C24' 179.70(19) . . . . ? 
C12 C13 C16 C24' -0.6(3) . . . . ? 
C14 C13 C16 C24 179.91(13) . . . . ? 
C12 C13 C16 C24 -0.4(3) . . . . ? 
C15 O15 C16 C13 -0.07(14) . . . . ? 
C15 O15 C16 C24' -179.95(13) . . . . ? 
C15 O15 C16 C24 179.89(12) . . . . ? 
C12 O12 C17 O17 166.75(19) . . . . ? 
C12 O12 C17 C8 -17.3(3) . . . . ? 
C7 C8 C17 O17 -14.2(3) . . . . ? 
C9 C8 C17 O17 -143.0(2) . . . . ? 
C7 C8 C17 O12 170.16(18) . . . . ? 
C9 C8 C17 O12 41.4(2) . . . . ? 
C3 C4 C18 O18 38.3(3) . . . . ? 
C5 C4 C18 O18 -86.1(3) . . . . ? 
C3 C4 C18 O21 -141.5(2) . . . . ? 
C5 C4 C18 O21 94.2(2) . . . . ? 
O18 C18 O21 C21 1.2(4) . . . . ? 
C4 C18 O21 C21 -179.0(3) . . . . ? 
C2 O2 C22 O22 -14.7(5) . . . . ? 
C2 O2 C22 C23 174.3(2) . . . . ? 
C13 C16 C24 N24 103.6(6) . . . . ? 
O15 C16 C24 N24 -76.3(6) . . . . ? 
C16 C24 N24 C26 -70.2(7) . . . . ? 
C16 C24 N24 C25 168.4(6) . . . . ? 
C13 C16 C24' N24' 49.0(5) . . . . ? 
O15 C16 C24' N24' -131.2(4) . . . . ? 
C16 C24' N24' C26' -163.0(6) . . . . ? 
C16 C24' N24' C25' 75.3(6) . . . . ? 
