19-nor-, 20-nor-, and tetranor-Halimane-Type Furanoditerpenoids from Croton crassifolius
Wang, Rong; Fan, Run-Zhu; Ni, Fu-Qiang; Sang, Jun; Xie, Xing-Lin; Luo, Si-Yuan; Tang, Gui-Hua; Yin, Sheng; Journal of Natural Products  (2020) –; doi:10.1021/acs.jnatprod.9b00634

data_1557202
_publ_section_title
;
 19-nor-, 20-nor-, and tetranor-Halimane-Type Furanoditerpenoids from
 Croton crassifolius
;
_journal_name_full               'Journal of Natural Products'
_journal_paper_doi               10.1021/acs.jnatprod.9b00634
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H26 O5'
_chemical_formula_sum            'C21 H26 O5'
_chemical_formula_weight         358.42
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                87.9040(10)
_cell_angle_beta                 80.1980(10)
_cell_angle_gamma                87.6940(10)
_cell_formula_units_Z            1
_cell_length_a                   6.30620(10)
_cell_length_b                   7.68480(10)
_cell_length_c                   9.7183(2)
_cell_measurement_reflns_used    17322
_cell_measurement_temperature    99.99(11)
_cell_measurement_theta_max      76.9890
_cell_measurement_theta_min      4.5930
_cell_volume                     463.505(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -75.00  26.00   0.50    0.05    --  -46.62  87.00 -67.00  202
  2  \w    -25.00  75.00   0.50    0.05    --   46.62 -87.00 174.00  200
  3  \w   -128.00 -27.00   0.50    0.05    -- -100.00  87.00 -67.00  202
  4  \w   -173.00 -77.00   0.50    0.05    -- -100.00 -87.00 174.00  192
  5  \w     34.00 136.00   0.50    0.05    --  107.00 -87.00 174.00  204
  6  \w     81.00 178.00   0.50    0.05    --  107.00  87.00 -67.00  194
  7  \w    -54.00 -28.00   0.50    0.05    --   16.00 160.00 -43.33   52
  8  \w   -119.00 -23.00   0.50    0.05    --  -46.62 -77.00  90.00  192
  9  \w   -119.00 -23.00   0.50    0.05    --  -46.62 -77.00   0.00  192
 10  \w   -119.00 -23.00   0.50    0.05    --  -46.62 -77.00 150.00  192
 11  \w   -119.00 -23.00   0.50    0.05    --  -46.62 -77.00-150.00  192
 12  \w   -119.00 -30.00   0.50    0.05    --  -46.62 -57.00-150.00  178
 13  \w   -120.00 -32.00   0.50    0.05    --  -46.62 -38.00-120.00  176
 14  \w     15.00  95.00   0.50    0.05    --   46.62-125.00-120.00  160
 15  \w     32.00 120.00   0.50    0.05    --   46.62  38.00  60.00  176
 16  \w     31.00 122.00   0.50    0.05    --   46.62  19.00   0.00  182
 17  \w     25.00 121.00   0.50    0.05    --   48.00  76.00 -95.60  192
 18  \w   -124.00 -27.00   0.50    0.05    --  -52.00 -80.00  84.51  194
 19  \w     27.00 125.00   0.50    0.05    --   52.00  79.00-140.31  196
 20  \w     30.00 125.00   0.50    0.05    --   52.00  72.00 -56.11  190
 21  \w     32.00 129.00   0.50    0.05    --   56.00  77.00   0.70  194
 22  \w     34.00 129.00   0.50    0.05    --   56.00  72.00  92.37  190
 23  \w   -132.00 -36.00   0.50    0.05    --  -60.00 -77.00 130.37  192
 24  \w     35.00 132.00   0.50    0.05    --   60.00  81.00 -51.42  194
 25  \w     41.00 137.00   0.50    0.05    --   64.00  75.00-119.59  192
 26  \w   -140.00 -49.00   0.50    0.05    --  -68.00 -66.00 125.55  182
 27  \w   -140.00 -47.00   0.50    0.05    --  -68.00 -71.00-142.34  186
 28  \w   -140.00 -46.00   0.50    0.05    --  -68.00 -72.00  -2.35  188
 29  \w   -145.00 -51.00   0.50    0.05    --  -72.00 -69.00 -93.17  188
 30  \w   -145.00 -45.00   0.50    0.05    --  -72.00 -83.00 112.66  200
 31  \w   -145.00 -45.00   0.50    0.05    --  -72.00 -83.00  68.33  200
 32  \w     49.00 145.00   0.50    0.05    --   72.00  75.00-169.16  192
 33  \w   -149.00 -52.00   0.50    0.05    --  -76.00 -77.00  -3.10  194
 34  \w   -153.00 -58.00   0.50    0.05    --  -80.00 -73.00 -45.43  190
 35  \w    -82.00 -56.00   0.50    0.05    --  -80.00 -76.00 -99.17   52
 36  \w   -100.00 -66.00   0.50    0.05    --  -84.00 -66.00 148.05   68
 37  \w    -95.00 -70.00   0.50    0.05    --  -84.00 -52.00 -93.19   50
 38  \w   -102.00 -63.00   0.50    0.05    --  -84.00 -74.00  70.04   78
 39  \w   -156.00-130.00   0.50    0.05    --  -84.00 -74.00  70.04   52
 40  \w    -93.00 -67.00   0.50    0.05    --  -84.00 -60.00 -48.83   52
 41  \w    -91.00 -65.00   0.50    0.05    --  -84.00 -67.00-167.61   52
 42  \w    -91.00 -65.00   0.50    0.05    --  -84.00 -64.00  27.86   52
 43  \w    -96.00 -70.00   0.50    0.05    --  -88.00 -65.00-145.55   52
 44  \w   -103.00 -70.00   0.50    0.05    --  -88.00 -63.00 127.00   66
 45  \w   -100.00 -71.00   0.50    0.05    --  -88.00 -54.00-107.15   58
 46  \w    -91.00 -65.00   0.50    0.05    --  -92.00 -83.00 111.96   52
 47  \w   -109.00 -72.00   0.50    0.05    --  -96.00 -76.00-165.39   74
 48  \w   -168.00 -80.00   0.50    0.05    --  -96.00 -51.00 -42.36  176
 49  \w   -113.00 -73.00   0.50    0.05    --  -96.00 -76.00  46.79   80
 50  \w   -168.00-127.00   0.50    0.05    -- -100.00 -73.00 102.57   82
 51  \w   -103.00 -78.00   0.50    0.05    -- -100.00 -77.00-180.00   50
 52  \w   -161.00-130.00   0.50    0.05    -- -100.00 -77.00-180.00   62
 53  \w   -141.00 -78.00   0.50    0.05    -- -100.00 -76.00  15.25  126
 54  \w   -126.00 -82.00   0.50    0.05    -- -100.00 -61.00 108.81   88
 55  \w   -118.00 -82.00   0.50    0.05    -- -100.00 -77.00   0.00   72
 56  \w   -123.00 -76.00   0.50    0.05    -- -100.00 -77.00 -90.00   94
 57  \w   -136.00 -77.00   0.50    0.05    -- -100.00 -76.00 140.93  118
 58  \w   -114.00 -88.00   0.50    0.05    -- -100.00 -61.00-150.00   52
 59  \w   -104.00 -78.00   0.50    0.05    -- -100.00 -77.00  60.00   52
 60  \w   -121.00 -75.00   0.50    0.05    -- -100.00 -79.00 -72.23   92
 61  \w   -158.00 -81.00   0.50    0.05    -- -100.00 -71.00  29.34  154
 62  \w   -113.00 -81.00   0.50    0.05    -- -100.00 -67.00-118.67   64
 63  \w   -167.00-125.00   0.50    0.05    -- -100.00 -79.00 -72.23   84
 64  \w   -150.00-120.00   0.50    0.05    -- -100.00 -67.00-118.67   60
 65  \w   -134.00 -83.00   0.50    0.05    -- -100.00 -61.00  60.00  102
 66  \w   -121.00 -76.00   0.50    0.05    -- -100.00 -77.00 -35.29   90
 67  \w   -173.00-148.00   0.50    0.05    -- -100.00 -61.00  60.00   50
 68  \w   -123.00 -79.00   0.50    0.05    -- -100.00 -73.00 102.57   88
 69  \w   -173.00-132.00   0.50    0.05    -- -100.00 -77.00 -35.29   82
 70  \w     86.00 163.00   0.50    0.05    --  107.00  77.00 150.00  154
 71  \w     35.00 124.00   0.50    0.05    --  107.00 -61.00 -90.00  178
 72  \w     85.00 169.00   0.50    0.05    --  107.00 125.00 150.00  168
 73  \w    129.00 177.00   0.50    0.05    --  107.00  30.00 -60.00   96
 74  \w     35.00 124.00   0.50    0.05    --  107.00 -61.00 120.00  178
 75  \w     34.00 123.00   0.50    0.05    --  107.00 -30.00 150.00  178
 76  \w     63.00 109.00   0.50    0.05    --  107.00 -94.00 -90.00   92
 77  \w     96.00 176.00   0.50    0.05    --  107.00  61.00  90.00  160
 78  \w     92.00 144.00   0.50    0.05    --  107.00  61.00-120.00  104
 79  \w     88.00 113.00   0.50    0.05    --  107.00-125.00  30.00   50
 80  \w    152.00 178.00   0.50    0.05    --  107.00  61.00-150.00   52
 81  \w     98.00 124.00   0.50    0.05    --  107.00  61.00-150.00   52
 82  \w     82.00 117.00   0.50    0.05    --  107.00-125.00-120.00   70
 83  \w     78.00 104.00   0.50    0.05    --  107.00 -94.00  90.00   52
 84  \w     45.00  73.00   0.50    0.05    --  107.00 -94.00  90.00   56
 85  \w     41.00  74.00   0.50    0.05    --  107.00-125.00  30.00   66
 86  \w     68.00 102.00   0.50    0.05    --  107.00 -94.00  60.00   68
 87  \w     34.00  60.00   0.50    0.05    --  107.00 -94.00  60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1112149000
_diffrn_orient_matrix_UB_12      -0.1532160000
_diffrn_orient_matrix_UB_13      0.0861297000
_diffrn_orient_matrix_UB_21      0.1307928000
_diffrn_orient_matrix_UB_22      0.0294478000
_diffrn_orient_matrix_UB_23      0.1168321000
_diffrn_orient_matrix_UB_31      -0.1790506000
_diffrn_orient_matrix_UB_32      0.1262835000
_diffrn_orient_matrix_UB_33      0.0695323000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0235
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            18427
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.124
_diffrn_reflns_theta_min         4.620
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.739
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81820
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       block
_exptl_crystal_F_000             192
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0
_refine_diff_density_max         0.151
_refine_diff_density_min         -0.174
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1663 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3525
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0271
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0422P)^2^+0.0853P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0699
_refine_ls_wR_factor_ref         0.0725
_reflns_Friedel_coverage         0.939
_reflns_Friedel_fraction_full    0.951
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                3492
_reflns_number_total             3525
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np9b00634_si_002.cif
_cod_data_source_block           wangr_39_190419
_cod_database_code               1557202
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   1.000
_shelx_estimated_absorpt_t_min   0.809
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C10(H10), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C5(H5A,H5B), C12(H12A,H12B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C25(H25), C23(H23)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C18(H18A,H18B,
 H18C)
;
_shelx_res_checksum              62488
_shelx_hkl_checksum              9039
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.777
_oxdiff_exptl_absorpt_empirical_full_min 0.725