K<sub>2</sub>CO<sub>3</sub>/TFAA-activated diarylation of α-sulfonyl <i>o</i>-hydroxyacetophenones with <i>o</i>-nitroaryl disulfides to construct sulfonyl bis-<i>o</i>-nitroaryl acetophenones.
Chang, Meng-Yang; Hsueh, Nai-Chen; Organic & biomolecular chemistry 23 (2025) 4751–4757; doi:10.1039/d5ob00380f

data_7160501
_publ_section_title
;
 K<sub>2</sub>CO<sub>3</sub>/TFAA-activated diarylation of
 &#x3b1;-sulfonyl <i>o</i>-hydroxyacetophenones with <i>o</i>-nitroaryl
 disulfides to construct sulfonyl bis-<i>o</i>-nitroaryl acetophenones.
;
_journal_issue                   19
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4751
_journal_page_last               4757
_journal_paper_doi               10.1039/d5ob00380f
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         '0.333(C27 H18 Cl2 N2 O8 S)'
_chemical_formula_sum            'C9 H6 Cl0.67 N0.67 O2.67 S0.33'
_chemical_formula_weight         200.46
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-08-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-25 deposited with the CCDC.	2025-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                80.891(2)
_cell_angle_beta                 88.429(2)
_cell_angle_gamma                81.563(2)
_cell_formula_units_Z            6
_cell_length_a                   9.5100(2)
_cell_length_b                   10.9393(3)
_cell_length_c                   14.4361(2)
_cell_measurement_reflns_used    18881
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      26.9120
_cell_measurement_theta_min      1.9040
_cell_volume                     1466.83(6)
_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 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -17.00 100.00   0.50    1.76    --   10.60  82.00  30.00  234
  2  \w    -17.00 100.00   0.50    1.76    --   10.60  82.00 -60.00  234
  3  \w    -20.00 100.00   0.50    1.76    --   10.60  57.00 -90.00  240
  4  \w    -79.00  36.00   0.50    1.76    --   10.60 -77.00 150.00  230
  5  \w    -17.00 100.00   0.50    1.76    --   10.60  82.00 120.00  234
  6  \w    -27.00 100.00   0.50    1.76    --   10.60  37.00  90.00  254
  7  \w    -15.00 100.00   0.50    1.76    --   10.60  77.00 -90.00  230
  8  \w    -17.00 100.00   0.50    1.76    --   10.60  82.00   0.00  234
  9  \w    -79.00  26.00   0.50    1.76    --   10.60 -77.00 120.00  210
 10  \w     -7.00  33.00   0.50    1.76    --   10.60  82.00-180.00   80
 11  \w     47.00  84.00   0.50    1.76    --   10.60  82.00-180.00   74
 12  \w    -13.00  48.00   0.50    1.76    --   10.60  82.00-120.00  122
 13  \w    -31.00  59.00   0.50    1.76    --  -10.90  57.00-180.00  180
 14  \w    -56.00 -30.00   0.50    1.76    --  -10.90 -82.00  90.00   52
;
_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      -0.0159909000
_diffrn_orient_matrix_UB_12      -0.0256183000
_diffrn_orient_matrix_UB_13      0.0466936000
_diffrn_orient_matrix_UB_21      0.0043727000
_diffrn_orient_matrix_UB_22      0.0582451000
_diffrn_orient_matrix_UB_23      0.0146227000
_diffrn_orient_matrix_UB_31      -0.0735564000
_diffrn_orient_matrix_UB_32      0.0188454000
_diffrn_orient_matrix_UB_33      -0.0090628000
_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  0.0281
_diffrn_reflns_av_unetI/netI     0.0215
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            30871
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.165
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.342
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72095
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       block
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.511
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     448
_refine_ls_number_reflns         5122
_refine_ls_number_restraints     215
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0402
_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^)+(0.0503P)^2^+1.2755P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1051
_refine_ls_wR_factor_ref         0.1076
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4601
_reflns_number_total             5122
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00380f2.cif
_cod_data_source_block           k11108-myc-d(lyf808)_auto
_cod_depositor_comments
'Adding full bibliography for 7160498--7160503.cif.'
_cod_database_code               7160501
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.848
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C27 \\sim Cl-C30
 with sigma of 0.02
 C23-C25 \\sim C31-C28
 with sigma of 0.04
 C22-C23 \\sim C22-C31
 with sigma of 0.02
 C22-C27 \\sim C22-C30
 with sigma of 0.02
 C26-C25 \\sim C29-C28
 with sigma of 0.02
 C22-N2 \\sim C22-N1A
 with sigma of 0.04
 C23-O8 \\sim C31-O0
 with sigma of 0.04
 C23-C24 \\sim C31-C32
 with sigma of 0.02
 C25-C27 \\sim C28-C30
 with sigma of 0.04
 C23-N2 \\sim C31-N1A
 with sigma of 0.02
 C24-N2 \\sim C32-N1A
 with sigma of 0.04
 O7-O8 \\sim O00U-O0
 with sigma of 0.04
 C26-C27 \\sim C29-C30
 with sigma of 0.02
 C25-C24 \\sim C28-C32
 with sigma of 0.02
 C26-C24 \\sim C29-C32
 with sigma of 0.04
 C23-O7 \\sim C31-O00U
 with sigma of 0.04
 O7-N2 \\sim O00U-N1A
 with sigma of 0.02
 O8-N2 \\sim O0-N1A
 with sigma of 0.02
 Cl2-C22 \\sim Cl-C22
 with sigma of 0.04
 Cl2-C26 \\sim Cl-C29
 with sigma of 0.04
 C22-C26 \\sim C22-C29
 with sigma of 0.04
 C22-C24 \\sim C22-C32
 with sigma of 0.04
3. Rigid bond restraints
 O3, N1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
4. Uiso/Uaniso restraints and constraints
Uanis(C16) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C9) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C31) \\sim Ueq,
Uanis(C32) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
5. Others
 Sof(O00U)=Sof(N1A)=Sof(O0)=Sof(C31)=Sof(C32)=Sof(H32)=Sof(C28)=Sof(H28)=
 Sof(C29)=Sof(H29)=Sof(C30)=Sof(Cl)=1-FVAR(1)
 Sof(Cl2)=Sof(C26)=Sof(H26)=Sof(C23)=Sof(C25)=Sof(H25)=Sof(C27)=Sof(C24)=
 Sof(H24)=Sof(O7)=Sof(O8)=Sof(N2)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C26(H26), C25(H25), C20(H20), C24(H24), C17(H17), C6(H6), C19(H19), C18(H18),
 C5(H5), C11(H11), C13(H13), C12(H12), C2(H2), C3(H3), C32(H32), C28(H28),
 C29(H29)
6.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              59838
_shelx_fab_checksum              29656
_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 1.347
_oxdiff_exptl_absorpt_empirical_full_min 0.803