Unusual <i>ent</i>-Labdane Diterpenoid Dimers and their Selective Activation of TRPV Channels.
Gao, Suyu; Wang, Dun; Chai, Hao; Xu, Jiamin; Li, Tianyu; Niu, Yingxue; Chen, Xinxin; Qiu, Feng; Li, Yang; Li, Hua; Chen, Lixia; The Journal of organic chemistry 84 (2019) 13595–13603; doi:10.1021/acs.joc.9b01864

data_4034573
_publ_section_title
;
 Unusual <i>ent</i>-Labdane Diterpenoid Dimers and their Selective
 Activation of TRPV Channels.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13595
_journal_page_last               13603
_journal_paper_doi               10.1021/acs.joc.9b01864
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C46 H64 O8'
_chemical_formula_sum            'C46 H64 O8'
_chemical_formula_weight         744.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-11-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.3181(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.14826(9)
_cell_length_b                   21.3979(3)
_cell_length_c                   26.9591(4)
_cell_measurement_reflns_used    29147
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.5140
_cell_measurement_theta_min      2.0870
_cell_volume                     4122.51(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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   -117.00  -8.00   1.00    1.00    --  -40.98 -77.00 150.00  109
  2  \w   -113.00 -13.00   1.00    1.00    --  -40.98 -57.00  30.00  100
  3  \w    -74.00  35.00   1.00    1.00    --  -40.98  77.00 -60.00  109
  4  \w   -115.00 -16.00   1.00    1.00    --  -40.98 -38.00  90.00   99
  5  \w    -96.00  -2.00   1.00    1.00    --  -40.98 125.00-180.00   94
  6  \w   -113.00 -13.00   1.00    1.00    --  -40.98 -57.00  90.00  100
  7  \w     16.00 115.00   1.00    1.00    --   40.98  38.00 150.00   99
  8  \w     13.00 113.00   1.00    1.00    --   40.98  57.00 -90.00  100
  9  \w      1.00  82.00   1.00    1.00    --   40.98 -99.00  30.00   81
 10  \w      8.00 117.00   1.00    1.00    --   40.98  77.00-180.00  109
 11  \w     78.00 178.00   1.00    1.26    --  106.95  61.00  60.00  100
 12  \w     81.00 178.00   1.00    1.26    --  106.95  45.00  90.00   97
 13  \w     74.00 178.00   1.00    1.26    --  106.95  77.00 150.00  104
 14  \w     78.00 178.00   1.00    1.26    --  106.95  61.00  90.00  100
 15  \w     94.00 178.00   1.00    1.26    --  106.95 125.00-150.00   84
 16  \w     79.00 178.00   1.00    1.26    --  106.95  30.00-180.00   99
 17  \w     78.00 178.00   1.00    1.26    --  106.95  61.00 150.00  100
 18  \w     74.00 178.00   1.00    1.26    --  106.95  77.00  90.00  104
 19  \w     25.00 109.00   1.00    1.26    --  106.95 -95.00 120.00   84
 20  \w     74.00 178.00   1.00    1.26    --  106.95  77.00  30.00  104
 21  \w     81.00 178.00   1.00    1.26    --  106.95  45.00-180.00   97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.2029070000
_diffrn_orient_matrix_UB_12      -0.0086049000
_diffrn_orient_matrix_UB_13      0.0168450000
_diffrn_orient_matrix_UB_21      0.0577398000
_diffrn_orient_matrix_UB_22      0.0220823000
_diffrn_orient_matrix_UB_23      0.0525700000
_diffrn_orient_matrix_UB_31      -0.0443632000
_diffrn_orient_matrix_UB_32      0.0679445000
_diffrn_orient_matrix_UB_33      -0.0149429000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            48267
_diffrn_reflns_point_group_measured_fraction_full 0.923
_diffrn_reflns_point_group_measured_fraction_max 0.890
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.704
_diffrn_reflns_theta_min         2.637
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.641
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77450
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.200
_exptl_crystal_description       block
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.284
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 5810 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.10(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1021
_refine_ls_number_reflns         14799
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0564P)^2^+2.6794P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1186
_refine_ls_wR_factor_ref         0.1201
_reflns_Friedel_coverage         0.757
_reflns_Friedel_fraction_full    0.843
_reflns_Friedel_fraction_max     0.789
_reflns_number_gt                14280
_reflns_number_total             14799
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01864_si_003.cif
_cod_data_source_block           ba-e6-2
_cod_original_cell_volume        4122.50(10)
_cod_database_code               4034573
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.921
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C3(H3), C00P(H00P), C00V(H00V), C4'(H4'), C013(H013), C019(H019), C01C(H01M),
 C15(H15), C11'(H11'), C01K(H01R), C01O(H01W), C8'(H8'), C5(H5), C9(H9),
 C028(H028), C3'(H3')
2.b Secondary CH2 refined with riding coordinates:
 C18'(H18A,H18B), C014(H01A,H01B), C015(H01C,H01D), C016(H01E,H01F), C018(H01G,
 H01H), C01J(H01P,H01Q), C01L(H01S,H01T), C01M(H01U,H01V), C18(H18C,H18D),
 C1'(H1'A,H1'B), C5'(H5'A,H5'B), C2(H2A,H2B), C020(H02A,H02B), C023(H02C,H02D),
 C024(H02E,H02F), C6'(H6'A,H6'B), C10'(H10A,H10B), C2'(H2'A,H2'B), C14'(H14A,
 H14B), C1(H1A,H1B), C02G(H02H,H02I), C7(H7A,H7B), C6(H6A,H6B), C02R(H02S,H02T)
2.c Aromatic/amide H refined with riding coordinates:
 C00O(H00O), C14(H14), C12(H12), C11(H11), C012(H012), C01B(H01L), C13'(H13'),
 C02B(H02G)
2.d Idealised Me refined as rotating group:
 C01A(H01I,H01J,H01K), C01T(H01X,H01Y,H), C19'(H19A,H19B,H19C), C025(H02,HA,
 HB), C20(H20A,H20B,H20C), C23(H23A,H23B,H23C), C02K(H02J,H02K,H02L), C19(H19D,
 H19E,H19F), C02O(H02M,H02N,H02O), C02P(H02P,H02Q,H02R), C21'(H21A,H21B,H21C),
 C22'(H22A,H22B,H22C), C02X(H02W,H02X,H02Y), C02Y(H02Z,HC,HD), C22(H22D,H22E,
 H22F), C030(H03A,H03B,H03C)
;
_shelx_res_checksum              8875
_shelx_hkl_checksum              82828
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.504
_oxdiff_exptl_absorpt_empirical_full_min 0.737