Bicyclic sulfonium pincer ligand with a thiatriptycenium backbone-synthesis and applications in π-acid catalysis.
Zafar, Mohammad; Shamali, Donia; Barel, Nitsan; Danovich, David; Tulchinsky, Yuri; Chemical communications (Cambridge, England) 61 (2025) 4559–4562; doi:10.1039/d5cc00310e

data_7134256
_publ_section_title
;
 Bicyclic sulfonium pincer ligand with a thiatriptycenium
 backbone-synthesis and applications in &#x3c0;-acid catalysis.
;
_journal_issue                   23
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4559
_journal_page_last               4562
_journal_paper_doi               10.1039/d5cc00310e
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C52 H49 O P2 S, C F3 O3 S, 0.5(C7)'
_chemical_formula_sum            'C56.5 H49 F3 O4 P2 S2'
_chemical_formula_weight         975.01
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-20
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-01-11 deposited with the CCDC.	2025-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                80.179(2)
_cell_angle_beta                 80.228(2)
_cell_angle_gamma                67.613(3)
_cell_formula_units_Z            2
_cell_length_a                   10.0296(3)
_cell_length_b                   12.2752(3)
_cell_length_c                   22.7212(6)
_cell_measurement_reflns_used    12975
_cell_measurement_temperature    200.0(1)
_cell_measurement_theta_max      31.1080
_cell_measurement_theta_min      2.2700
_cell_volume                     2531.69(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.141a 64-bit (release 04-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.0(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.778
_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     -9.00  33.00   0.50  105.00    --    2.63 -99.00-120.00   84
  2  \w    -62.00  10.00   0.50  105.00    --    2.63 -37.00 120.00  144
  3  \w    -70.00   5.00   0.50  105.00    --    2.63 -19.00   0.00  150
  4  \w    -66.00   1.00   0.50  105.00    --    2.63 -19.00-120.00  134
  5  \w    -23.00   4.00   0.50  105.00    --    2.63 -99.00   0.00   54
  6  \w    -55.00 -28.00   0.50  105.00    --    2.63 -57.00-120.00   54
  7  \w    -20.00  20.00   0.50  105.00    --   -4.03 -99.00  60.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0416468000
_diffrn_orient_matrix_UB_12      -0.0359139000
_diffrn_orient_matrix_UB_13      0.0009742000
_diffrn_orient_matrix_UB_21      -0.0089965000
_diffrn_orient_matrix_UB_22      -0.0050918000
_diffrn_orient_matrix_UB_23      0.0318708000
_diffrn_orient_matrix_UB_31      -0.0641326000
_diffrn_orient_matrix_UB_32      0.0514116000
_diffrn_orient_matrix_UB_33      -0.0007007000
_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  0.0360
_diffrn_reflns_av_unetI/netI     0.0426
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.778
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            34010
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.778
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.017
_diffrn_reflns_theta_min         2.211
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.225
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.606
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.141a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.279
_exptl_crystal_description       plate
_exptl_crystal_F_000             1018
_exptl_crystal_size_max          0.287
_exptl_crystal_size_mid          0.132
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.329
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     678
_refine_ls_number_reflns         12574
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0657
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0701P)^2^+0.6391P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1240
_refine_ls_wR_factor_ref         0.1322
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9615
_reflns_number_total             12574
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00310e3.cif
_cod_data_source_block           yuri18
_cod_depositor_comments          'Adding full bibliography for 7134256.cif.'
_cod_original_cell_volume        2531.68(13)
_cod_original_formula_sum        'C56.50 H49 F3 O4 P2 S2'
_cod_database_code               7134256
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C56H3F3O4P2S2
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.938
_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
 C7T-C1T
 1.51 with sigma of 0.02
 C1T-C6T = C1T-C2T = C5T-C4T
 1.39 with sigma of 0.02
 C6T-C5T = C4T-C3T = C3T-C2T
 1.38 with sigma of 0.02
 C7T-C6T = C7T-C2T
 2.52 with sigma of 0.04
 C1T-C5T
 2.42 with sigma of 0.04
 C1T-C3T
 2.41 with sigma of 0.04
 C6T-C4T
 2.39 with sigma of 0.04
 C5T-C3T = C4T-C2T
 2.4 with sigma of 0.04
 C1T-C6T \\sim C6T-C5T \\sim C5T-C4T \\sim C4T-C3T \\sim C3T-C2T \\sim C2T-C1T
 with sigma of 0.02
 C1T-C3T \\sim C1T-C5T \\sim C2T-C4T \\sim C6T-C2T \\sim C5T-C3T \\sim C6T-C4T
 with sigma of 0.04
 C7T-C2T \\sim C7T-C6T
 with sigma of 0.04
3. Restrained planarity
 C1T, C2T, C3T, C4T, C5T, C6T, C7T
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C1T \\sim C2T \\sim C3T \\sim C4T \\sim C5T \\sim C6T \\sim C7T: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C1T, C2T, C3T, C4T, C5T, C6T, C7T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=Sof(C23B)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Fixed Sof: C1T(0.5) C2T(0.5) C3T(0.5) C4T(0.5) C5T(0.5) C6T(0.5) C7T(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C15(H15), C16(H16), C17(H17), C18(H18),
 C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37), C38(H38),
  C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
 C48(H48), C49(H49), C50(H50), C51(H51), C52(H52)
7.b Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C21A(H21A,H21B,H21C), C22A(H22A,H22B,H22C), C23A(H23A,H23B,H23C),
 C21B(H21D,H21E,H21F), C22B(H22D,H22E,H22F), C23B(H23D,H23E,H23F)
;
_shelx_res_checksum              53698
_shelx_hkl_checksum              88240
_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 0.820