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_4034572
_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
'0.33(C46 H64 O8), 0.33(C46 H63 O8), 0.33(C46 H62 O8)'
_chemical_formula_sum            'C46 H63 O8'
_chemical_formula_weight         743.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.374(4)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   28.4549(14)
_cell_length_b                   6.8073(3)
_cell_length_c                   70.292(3)
_cell_measurement_reflns_used    8296
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.9200
_cell_measurement_theta_min      3.0930
_cell_volume                     13531.5(11)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_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    -64.00  32.00   1.00    3.00    --  -41.11  57.00   0.00   96
  2  \w    -65.00  33.00   1.00    3.00    --  -41.11  38.00 150.00   98
  3  \w     26.00  63.00   1.00    3.00    --   41.11-125.00  60.00   37
  4  \w     32.00 119.00   1.00    2.00    --  106.95 -77.00 -30.00   87
  5  \w     71.00 119.00   1.00    2.00    --  106.95-125.00   0.00   48
  6  \w     35.00 132.00   1.00    2.00    --  106.95 -45.00  60.00   97
  7  \w    110.00 163.00   1.00    2.00    --  106.95  45.00 150.00   53
  8  \w    142.00 171.00   1.00    2.00    --  106.95  77.00  30.00   29
  9  \w    132.00 158.00   1.00    2.00    --  106.95  77.00   0.00   26
 10  \w    100.00 126.00   1.00    2.00    --  106.95 125.00-150.00   26
 11  \w     79.00 104.00   1.00    2.00    --  106.95  77.00   0.00   25
 12  \w     74.00 106.00   1.00    2.00    --  106.95  77.00  30.00   32
 13  \w     40.00 177.00   1.00    1.50    --  106.95   0.00 120.00  137
 14  \w     38.00  64.00   1.00    1.50    --  106.95-125.00   0.00   26
 15  \w     28.00 107.00   1.00    1.50    --  106.95 -95.00  90.00   79
 16  \w     23.00  92.00   1.00    3.00    --   41.11-125.00-180.00   69
 17  \w     35.00 134.00   1.00    1.50    --  106.95 -61.00-180.00   99
 18  \w     58.00 104.00   1.00    5.00    --  106.95 -95.00-180.00   46
 19  \w   -107.00 -48.00   1.00    3.00    --  -41.11 -57.00-150.00   59
;
_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      0.0004913000
_diffrn_orient_matrix_UB_12      -0.0366428000
_diffrn_orient_matrix_UB_13      0.0216608000
_diffrn_orient_matrix_UB_21      -0.0537270000
_diffrn_orient_matrix_UB_22      0.0360226000
_diffrn_orient_matrix_UB_23      -0.0016622000
_diffrn_orient_matrix_UB_31      -0.0088242000
_diffrn_orient_matrix_UB_32      -0.2204097000
_diffrn_orient_matrix_UB_33      -0.0038605000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0627
_diffrn_reflns_av_unetI/netI     0.0591
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       85
_diffrn_reflns_limit_l_min       -86
_diffrn_reflns_number            47504
_diffrn_reflns_point_group_measured_fraction_full 0.729
_diffrn_reflns_point_group_measured_fraction_max 0.705
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.845
_diffrn_reflns_theta_min         2.320
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.586
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47114
_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    1.096
_exptl_crystal_description       block
_exptl_crystal_F_000             4836
_refine_diff_density_max         0.908
_refine_diff_density_min         -0.683
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 2512 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1508
_refine_ls_number_reflns         19369
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.500
_refine_ls_R_factor_all          0.0939
_refine_ls_R_factor_gt           0.0786
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1255P)^2^+9.7535P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2114
_refine_ls_wR_factor_ref         0.2289
_reflns_Friedel_coverage         0.323
_reflns_Friedel_fraction_full    0.403
_reflns_Friedel_fraction_max     0.377
_reflns_number_gt                15244
_reflns_number_total             19369
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01864_si_004.cif
_cod_data_source_block           baa-4
_cod_original_cell_volume        13531.4(11)
_cod_database_code               4034572
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.98
_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. Rigid bond restraints
 C1AA, C045
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8AA, C6AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C0BA, O1AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C1AA \\sim C045: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
C8AA \\sim C6AA: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
C0BA \\sim O1AA: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
4.a Ternary CH refined with riding coordinates:
 C00M(H00M), C00P(H00P), C23(H23), C013(H013), C24(H24), C1(H1), C34(H34),
 C01G(H01G), C01H(H01H), C40(H40), C30(H30), C020(H020), C9(H9), C023(H023),
 C025(H025), C5(H5), C02L(H02L), C02V(H02V), C02Z(H02Z), C03J(H03U), C040(H040),
  C046(H046), C1BA(H1BA)
4.b Secondary CH2 refined with riding coordinates:
 C00T(H00D,H00E), C29(H29A,H29B), C00Y(H00F,H00G), C00Z(H00H,H00I), C011(H01A,
 H01B), C01C(H01C,H01D), C01J(H01E,H01F), C01V(H01M,H01N), C01X(H01O,H01P),
 C38(H38A,H38B), C39(H39A,H39B), C33(H33A,H33B), C43(H43A,H43B), C8(H8A,H8B),
 C11(H11A,H11B), C02Q(H02O,H02P), C7(H7A,H7B), C32(H32A,H32B), C02W(H02J,H02K),
 C031(H03N,H03O), C4(H4A,H4B), C033(H03P,H03Q), C03C(H03D,H03E), C03D(H03F,
 H03G), C03F(H03H,H03I), C27(H27A,H27B), C3(H3A,H3B), C03I(H03R,H03T),
 C03L(H03V,H03W), C03M(H03J,H03K), C045(H04G,H04H), C8AA(H8AA,H8AB), C1AA(H1AA,
 H1AB)
4.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C016(H016), C21(H21), C01B(H01L), C19(H19), C01K(H01K), C01S(H01S),
 C28(H28), C029(H029), C02U(H02U), C030(H030), C03S(H03S), C03U(H03Z),
 C03X(H03), C6AA(H6AA)
4.d X=CH2 refined with riding coordinates:
 C03N(H03L,H03M), C17(H17A,H17B)
4.e Idealised Me refined as rotating group:
 C00J(H00A,H00B,H00C), C36(H36A,H36B,H36C), C01Y(H01Q,H01R,H01T), C02E(H02A,
 H02B,H02C), C02I(H02D,H02E,H02F), C16(H16A,H16B,H16C), C02T(H02G,H02H,H02I),
 C45(H45A,H45B,H45C), C034(H03A,H03B,H03C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C13(H13A,H13B,H13C), C42(H42A,H42B,H42C), C46(H46A,H46B,H46C),
 C03P(H03X,H03Y,H), C03Z(H0AA,HA,HB), C042(H04A,H04B,H04C), C043(H04D,H04E,
 H04F), C3BA(H3BA,H3BB,H3BC), C2AA(H2AA,H2AB,H2AC), C4AA(H4AA,H4AB,H4AC),
 C5AA(H5AA,H5AB,H5AC), C9AA(H9AA,H9AB,H9AC), C7AA(H7AA,H7AB,H7AC), C2BA(H2BA,
 H2BB,H2BC)
;
_olex2_date_sample_data_collection 2018-10-29
_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 3.348
_oxdiff_exptl_absorpt_empirical_full_min 0.543