Convenient synthesis of thiolated 2,7-disubstituted tropones <i>via</i> double C-N bond cleavage of tropinone derivatives.
Huang, Lei; Wang, Yan; Liu, Xin; Tian, Shi-Kai; Organic & biomolecular chemistry 21 (2023) 9321–9325; doi:10.1039/d3ob01835k

data_7159683
_publ_section_title
;
 Convenient synthesis of thiolated 2,7-disubstituted tropones <i>via</i>
 double C-N bond cleavage of tropinone derivatives.
;
_journal_issue                   47
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9321
_journal_page_last               9325
_journal_paper_doi               10.1039/d3ob01835k
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C29 H24 O5 S'
_chemical_formula_sum            'C29 H24 O5 S'
_chemical_formula_weight         484.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-02-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-05-02 deposited with the CCDC.	2023-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.5426(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2396(3)
_cell_length_b                   7.38829(13)
_cell_length_c                   27.2180(5)
_cell_measurement_reflns_used    3866
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.7370
_cell_measurement_theta_min      5.9580
_cell_volume                     2458.89(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2169
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.966
_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    -87.00 -61.00   1.00    4.00    --  -41.76 125.00 150.00   26
  2  \w    -65.00  33.00   1.00    4.00    --  -41.76  38.00 -90.00   98
  3  \w    -66.00  26.00   1.00    4.00    --  -41.76  38.00-180.00   92
  4  \w    130.00 162.00   1.00   10.00    --  106.05 125.00 -30.00   32
  5  \w     79.00 176.00   1.00   10.00    --  106.05  30.00 150.00   97
  6  \w     38.00  99.00   1.00   10.00    --  106.05-125.00 -60.00   61
  7  \w     66.00 112.00   1.00   10.00    --  106.05-125.00-150.00   46
  8  \w     87.00 159.00   1.00   10.00    --  106.05  30.00-120.00   72
  9  \w    111.00 148.00   1.00   10.00    --  106.05  77.00-120.00   37
 10  \w     61.00 116.00   1.00   10.00    --  106.05-130.00 170.00   55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0593750000
_diffrn_orient_matrix_UB_12      -0.0212011000
_diffrn_orient_matrix_UB_13      0.0507775000
_diffrn_orient_matrix_UB_21      -0.1044599000
_diffrn_orient_matrix_UB_22      0.0600000000
_diffrn_orient_matrix_UB_23      0.0250506000
_diffrn_orient_matrix_UB_31      -0.0379238000
_diffrn_orient_matrix_UB_32      -0.1985405000
_diffrn_orient_matrix_UB_33      0.0021232000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            8851
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.842
_diffrn_reflns_theta_min         3.898
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.482
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82263
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.309
_exptl_crystal_description       block
_exptl_crystal_F_000             1016
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.00051(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         4740
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0554
_refine_ls_R_factor_gt           0.0436
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0593P)^2^+0.3061P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1144
_refine_ls_wR_factor_ref         0.1250
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3821
_reflns_number_total             4740
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01835k2.cif
_cod_data_source_block           hl-der-m_auto
_cod_depositor_comments
'Adding full bibliography for 7159683--7159684.cif.'
_cod_original_cell_volume        2458.90(8)
_cod_database_code               7159683
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         C20H20O1S1
_shelx_estimated_absorpt_t_max   0.746
_shelx_estimated_absorpt_t_min   0.708
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C15(H15)
1.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
1.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C10(H10), C11(H11), C9(H9), C27(H27), C21(H21), C17(H17), C5(H5),
 C24(H24), C3(H3), C26(H26), C25(H25), C20(H20), C19(H19), C18(H18), C1(H1),
 C2(H2), C6(H6)
1.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C)
;
_shelx_res_checksum              94730
_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 1.281
_oxdiff_exptl_absorpt_empirical_full_min 0.752