Sulfonium cations as versatile strongly π-acidic ligands
Li, Ruiping; Barel, Nitsan; Subramaniyan, Vasudevan; Cohen, Orit; Tibika, Françoise; Tulchinsky, Yuri; Chemical Science  (2022) –; doi:10.1039/D2SC00588C

data_1566712
_publ_section_title
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 Sulfonium cations as versatile strongly \p-acidic ligands
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00588C
_journal_year                    2022
_chemical_formula_moiety         'C42 H32 F P2 S, C F3 O3 S'
_chemical_formula_sum            'C43 H32 F4 O3 P2 S2'
_chemical_formula_weight         798.74
_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     dual
_audit_creation_date             2021-10-25
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2021-11-02 deposited with the CCDC.	2022-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.324(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4956(2)
_cell_length_b                   28.0310(4)
_cell_length_c                   12.6611(2)
_cell_measurement_reflns_used    42465
_cell_measurement_temperature    294(1)
_cell_measurement_theta_max      32.4520
_cell_measurement_theta_min      2.0100
_cell_volume                     3866.48(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      294.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_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      3.00  49.00   0.50   49.00    --    8.37-112.00  51.00   92
  2  \w    -84.00   3.00   0.50   49.00    --   -9.62 -30.00 -13.00  174
  3  \w    -22.00  65.00   0.50   49.00    --   -9.62  30.00 147.00  174
  4  \w     -6.00  81.00   0.50   49.00    --    8.37  57.00 -90.00  174
  5  \w    -23.00  42.00   0.50   49.00    --    8.37 -99.00  90.00  130
  6  \w     -4.00  82.00   0.50   49.00    --    8.37  37.00   0.00  172
  7  \w    -66.00   5.00   0.50   49.00    --    8.37 -19.00 -60.00  142
  8  \w    -23.00  24.00   0.50   49.00    --   -9.62 -99.00 120.00   94
  9  \w    -85.00   3.00   0.50   49.00    --   -9.62 -19.00  60.00  176
 10  \w    -23.00  11.00   0.50   49.00    --   -9.62 -99.00-180.00   68
 11  \w    -32.00  63.00   0.50   49.00    --   -9.62  77.00-150.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0628
_diffrn_reflns_av_unetI/netI     0.0219
_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       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            84590
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.006
_exptl_absorpt_coefficient_mu    0.280
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41963
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.372
_exptl_crystal_description       block
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.287
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.085
_refine_diff_density_max         1.069
_refine_diff_density_min         -1.342
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.987
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     458
_refine_ls_number_reflns         6794
_refine_ls_number_restraints     186
_refine_ls_restrained_S_all      2.002
_refine_ls_R_factor_all          0.1156
_refine_ls_R_factor_gt           0.1103
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3948
_refine_ls_wR_factor_ref         0.4059
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6192
_reflns_number_total             6794
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9544\% 
around [1.00 0.00 -0.00] (reciprocal) or [0.90 0.00 0.43] (direct)
;
_cod_data_source_file            d2sc00588c2.cif
_cod_data_source_block           4b_OTf
_cod_original_cell_volume        3866.48(12)
_cod_database_code               1566712
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C43-F2 \\sim C43-F3 \\sim C43-F4
 with sigma of 0.02
 F2-F3 \\sim F3-F4 \\sim F4-F2
 with sigma of 0.04
 C43-O2 \\sim C43-O3 \\sim C43-O1
 with sigma of 0.04
 S2-F2 \\sim S2-F3 \\sim S2-F4
 with sigma of 0.04
 S2-O2 \\sim S2-O3 \\sim S2-O1
 with sigma of 0.02
 O2-O3 \\sim O3-O1 \\sim O2-O1
 with sigma of 0.04
 F3-F4 \\sim F3A-F1A
 with sigma of 0.04
 C43-F4 \\sim C43A-F1A
 with sigma of 0.02
 C43-S2 \\sim C43A-S2A
 with sigma of 0.02
 C43-F2 \\sim C43A-F2A
 with sigma of 0.02
 C43-F3 \\sim C43A-F3A
 with sigma of 0.02
 F2-S2 \\sim F2A-S2A
 with sigma of 0.04
 O2-O3 \\sim O2A-O3A
 with sigma of 0.04
 S2-O2 \\sim S2A-O2A
 with sigma of 0.02
 S2-O3 \\sim S2A-O3A
 with sigma of 0.02
 S2-O1 \\sim S2A-O1A
 with sigma of 0.02
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F2-F4 \\sim F2A-F1A
 with sigma of 0.04
 F3-S2 \\sim F3A-S2A
 with sigma of 0.04
 F4-S2 \\sim F1A-S2A
 with sigma of 0.04
 O2-O1 \\sim O2A-O1A
 with sigma of 0.04
 C43-O2 \\sim C43A-O2A
 with sigma of 0.04
 C43-O3 \\sim C43A-O3A
 with sigma of 0.04
 C43-O1 \\sim C43A-O1A
 with sigma of 0.04
 O3-O1 \\sim O3A-O1A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C43 \\sim F2 \\sim F3 \\sim F4 \\sim S2 \\sim O2 \\sim O3 \\sim O1: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F2A) = Uanis(F3A) = Uanis(C43A) = Uanis(F1A) = Uanis(O1A) = Uanis(O2A) =
Uanis(O3A) = Uanis(F4) = Uanis(C43) = Uanis(F2) = Uanis(F3) = Uanis(O2) =
Uanis(O3) = Uanis(O1)
Uanis(S2A) = Uanis(S2)
4. Rigid body (RIGU) restrains
 C43, F2, F3, F4, S2, O2, O3, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F3A)=Sof(C43A)=Sof(F1A)=Sof(S2A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(F2A)=1-
 FVAR(1)
 Sof(C43)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(S2)=Sof(O2)=Sof(O3)=Sof(O1)=FVAR(1)
6.a Free rotating group:
 C43(F2,F3,F4,S2,O2,O3,O1)
6.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C14(H14), C16(H16), C17(H17), C29(H29), C28(H28), C26(H26),
 C42(H42), C20(H20), C2(H2), C38(H38), C8(H8), C27(H27), C6(H6), C32(H32),
 C41(H41), C40(H40), C12(H12), C36(H36), C10(H10), C35(H35), C39(H39), C9(H9),
 C4(H4), C34(H34), C33(H33), C5(H5), C11(H11), C3(H3), C21(H21), C23(H23),
 C22(H22)
;
_shelx_res_checksum              24280
_shelx_hkl_checksum              10853
_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
;