One-pot synthesis of symmetrical bis-sulfonyl 2,6-diarylpyridines <i>via</i> BiCl<sub>3</sub>-catalyzed and K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-mediated domino annulation of β-ketosulfones and <i>N</i>,<i>N</i>-dimethylacetamide.
Chang, Meng-Yang; Lin, Chun-Yi; Organic & biomolecular chemistry 23 (2025) 844–853; doi:10.1039/d4ob01681e

data_7160262
_publ_section_title
;
 One-pot synthesis of symmetrical bis-sulfonyl 2,6-diarylpyridines
 <i>via</i> BiCl<sub>3</sub>-catalyzed and
 K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-mediated domino annulation of
 &#x3b2;-ketosulfones and <i>N</i>,<i>N</i>-dimethylacetamide.
;
_journal_issue                   4
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              844
_journal_page_last               853
_journal_paper_doi               10.1039/d4ob01681e
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C33 H32 O8 S2'
_chemical_formula_sum            'C33 H32 O8 S2'
_chemical_formula_weight         620.70
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-10-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-09-09 deposited with the CCDC.	2024-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.735(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3904(6)
_cell_length_b                   21.7691(7)
_cell_length_c                   12.4795(6)
_cell_measurement_reflns_used    24562
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      26.7620
_cell_measurement_theta_min      1.8670
_cell_volume                     2979.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      130(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -79.00  35.00   0.50   26.42    --   10.60 -69.00-117.00  228
  2  \w     31.00  57.00   0.50   26.42    --   10.60  69.00  14.00   52
  3  \w     11.00  37.00   0.50   26.42    --  -10.90  69.00  14.00   52
  4  \w    -60.00   5.00   0.50   26.42    --  -10.90 -69.00-117.00  130
  5  \w     -2.00  44.00   0.50   26.42    --   10.60  82.00  90.00   92
  6  \w     -6.00  28.00   0.50   26.42    --   10.60  82.00   0.00   68
  7  \w    -15.00 100.00   0.50   26.42    --   10.60  77.00-120.00  230
  8  \w    -44.00  37.00   0.50   26.42    --   10.60 -80.00 131.08  162
  9  \w    -17.00  69.00   0.50   26.42    --   10.60  82.00  60.00  172
 10  \w     18.00  84.00   0.50   26.42    --   10.60  82.00  30.00  132
 11  \w     28.00 100.00   0.50   26.42    --   10.60  82.00 150.00  144
 12  \w    -78.00 -48.00   0.50   26.42    --   10.60 -80.00 131.08   60
 13  \w    -17.00  55.00   0.50   26.42    --   10.60  82.00 -90.00  144
 14  \w     49.00  95.00   0.50   26.42    --   10.60  77.00 120.00   92
 15  \w     65.00  99.00   0.50   26.42    --   10.60  82.00 -90.00   68
 16  \w    -17.00  30.00   0.50   26.42    --   10.60  82.00-180.00   94
 17  \w     44.00  70.00   0.50   26.42    --   10.60  82.00-180.00   52
 18  \w     -4.00 100.00   0.50   26.42    --   10.60  82.00 -60.00  208
 19  \w      1.00  27.00   0.50   26.42    --   10.60  77.00  60.00   52
 20  \w     51.00  77.00   0.50   26.42    --   10.60  77.00  60.00   52
 21  \w     -9.00  17.00   0.50   26.42    --  -10.90 -82.00   0.00   52
 22  \w    -58.00 -32.00   0.50   26.42    --  -10.90 -82.00   0.00   52
 23  \w    -24.00   2.00   0.50   26.42    --  -10.90 -82.00-150.00   52
 24  \w    -27.00  76.00   0.50   26.42    --  -10.90  57.00   0.00  206
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0445079000
_diffrn_orient_matrix_UB_12      0.0159091000
_diffrn_orient_matrix_UB_13      0.0511211000
_diffrn_orient_matrix_UB_21      -0.0111342000
_diffrn_orient_matrix_UB_22      -0.0198567000
_diffrn_orient_matrix_UB_23      0.0388476000
_diffrn_orient_matrix_UB_31      0.0455614000
_diffrn_orient_matrix_UB_32      -0.0203488000
_diffrn_orient_matrix_UB_33      0.0019743000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0810
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            59375
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.997
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         1.871
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.231
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39160
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
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    1.384
_exptl_crystal_description       plate
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.477
_refine_diff_density_min         -0.650
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         5233
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0830
_refine_ls_R_factor_gt           0.0717
_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^)+(0.0682P)^2^+9.1389P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1724
_refine_ls_wR_factor_ref         0.1793
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4378
_reflns_number_total             5233
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob01681e2.cif
_cod_data_source_block           K11110-MYC-A(YCM5285)
_cod_depositor_comments
'Adding full bibliography for 7160261--7160263.cif.'
_cod_database_code               7160262
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.913
_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
 C20, C25, C24, C23, C22, C21
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
3. Uiso/Uaniso restraints and constraints
C22 \\sim C21 \\sim C20 \\sim C25 \\sim C24 \\sim C23: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
4.a Ternary CH refined with riding coordinates:
 C8(H8), C18(H18)
4.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B)
4.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C2(H2), C6(H6), C14(H14), C15(H15), C3(H3), C5(H5),
 C28(H28), C32(H32), C29(H29), C21(H21), C25(H25), C31(H31), C24(H24), C22(H22)
4.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C33(H33A,H33B,H33C), C7(H7A,H7B,H7C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              52688
_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 1.535
_oxdiff_exptl_absorpt_empirical_full_min 0.426