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_1566711
_publ_section_title
;
 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 Cl F P2 Rh S, F6 P, 0.5(C7 H8)'
_chemical_formula_sum            'C45.5 H36 Cl F7 P3 Rh S'
_chemical_formula_weight         979.07
_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             2021-09-13
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2021-11-02 deposited with the CCDC.	2022-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                102.063(2)
_cell_angle_beta                 92.077(2)
_cell_angle_gamma                103.656(2)
_cell_formula_units_Z            2
_cell_length_a                   9.1404(2)
_cell_length_b                   12.3384(3)
_cell_length_c                   19.4965(5)
_cell_measurement_reflns_used    19128
_cell_measurement_temperature    149.98(10)
_cell_measurement_theta_max      31.2760
_cell_measurement_theta_min      2.1440
_cell_volume                     2080.95(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.111a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.111a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.111a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.98(10)
_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 0.999
_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      0.00  27.00   0.50   90.00    --    2.69  97.00  86.00   54
  2  \w    -26.00  18.00   0.50   90.00    --    2.69 -97.00 -22.00   88
  3  \w    -32.00   0.00   0.50   90.00    --   -3.94  97.00  86.00   64
  4  \w    -13.00  13.00   0.50   90.00    --   -3.94 -97.00 -22.00   52
  5  \w    -22.00  31.00   0.50   90.00    --    2.69 -99.00-150.00  106
  6  \w     -4.00  76.00   0.50   90.00    --    2.69  19.00  60.00  160
  7  \w    -23.00  18.00   0.50   90.00    --    2.69 -99.00 120.00   82
  8  \w    -18.00  32.00   0.50   90.00    --    2.69 -99.00  60.00  100
  9  \w    -22.00  34.00   0.50   90.00    --    2.69 -99.00 -90.00  112
 10  \w    -22.00  23.00   0.50   90.00    --   -3.94 -99.00-120.00   90
 11  \w    -23.00   9.00   0.50   90.00    --   -3.94 -99.00-180.00   64
;
_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      0.0064923000
_diffrn_orient_matrix_UB_12      0.0252277000
_diffrn_orient_matrix_UB_13      -0.0296325000
_diffrn_orient_matrix_UB_21      -0.0607360000
_diffrn_orient_matrix_UB_22      -0.0448383000
_diffrn_orient_matrix_UB_23      -0.0186912000
_diffrn_orient_matrix_UB_31      -0.0519464000
_diffrn_orient_matrix_UB_32      0.0322162000
_diffrn_orient_matrix_UB_33      0.0129575000
_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  0.0347
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            31769
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.145
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.705
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.852
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.111a (Rigaku Oxford Diffraction, 2021)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.563
_exptl_crystal_description       needle
_exptl_crystal_F_000             990
_exptl_crystal_size_max          0.106
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.047
_refine_diff_density_max         1.118
_refine_diff_density_min         -0.496
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     580
_refine_ls_number_reflns         7313
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0308
_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^)+(0.0384P)^2^+1.9623P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0739
_refine_ls_wR_factor_ref         0.0764
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6469
_reflns_number_total             7313
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00588c2.cif
_cod_data_source_block           5b_PF6
_cod_original_cell_volume        2080.94(9)
_cod_original_formula_sum        'C45.50 H36 Cl F7 P3 Rh S'
_cod_database_code               1566711
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C66H52 B Cl F7 S P3 Rh'
_chemical_oxdiff_usercomment     'NB-219 TOL'
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.929
_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
 C45-C46 = C47-C48 = C48-C49
 1.38 with sigma of 0.02
 C43-C44
 1.51 with sigma of 0.02
 C44-C45 = C44-C49 = C46-C47
 1.39 with sigma of 0.02
 C46-C48 = C47-C49
 2.4 with sigma of 0.04
 C44-C48
 2.41 with sigma of 0.04
 C44-C46
 2.42 with sigma of 0.04
 C45-C47
 2.39 with sigma of 0.04
 C43-C45 = C43-C49
 2.52 with sigma of 0.04
 F1-C20 \\sim F1A-C20A
 with sigma of 0.02
 C19-C20 \\sim C19-C20A
 with sigma of 0.02
 C19-C23 \\sim C19-C23A
 with sigma of 0.04
 C19-C24 \\sim C19-C24A
 with sigma of 0.02
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 F1-C21 \\sim F1A-C21A
 with sigma of 0.04
 C19-C21 \\sim C19-C21A
 with sigma of 0.04
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C20-C22 \\sim C20A-C22A
 with sigma of 0.04
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 F1-C19 \\sim F1A-C19
 with sigma of 0.04
 P3-F2A \\sim P3-F2
 with sigma of 0.02
 P3-F5A \\sim P3-F5
 with sigma of 0.02
 P3-F3A \\sim P3-F3
 with sigma of 0.02
 P3-F4A \\sim P3-F4
 with sigma of 0.02
 C44-C45 \\sim C45-C46 \\sim C46-C47 \\sim C47-C48 \\sim C48-C49 \\sim C49-C44
 with sigma of 0.02
 C44-C48 \\sim C44-C46 \\sim C49-C47 \\sim C45-C49 \\sim C46-C48 \\sim C45-C47
 with sigma of 0.04
 C43-C49 \\sim C43-C45
 with sigma of 0.04
3. Restrained planarity
 C43, C44, C45, C46, C47, C48, C49
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C24A) = Uanis(C20) = Uanis(C21) = Uanis(C23A) = Uanis(C22) = Uanis(C22A)
= Uanis(C21A) = Uanis(C23) = Uanis(C24) = Uanis(C20A)
Uanis(F1A) = Uanis(F1)
5. Rigid body (RIGU) restrains
 C43, C44, C45, C46, C47, C48, C49
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F1A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=Sof(C24A)=
 Sof(H24A)=Sof(C23A)=Sof(H23A)=1-FVAR(1)
 Sof(F1)=Sof(C20)=Sof(C22)=Sof(H22)=Sof(C21)=Sof(H21)=Sof(C23)=Sof(H23)=
 Sof(C24)=Sof(H24)=FVAR(1)
 Sof(F4)=Sof(F3)=Sof(F5)=Sof(F2)=1-FVAR(2)
 Sof(F3A)=Sof(F4A)=Sof(F2A)=Sof(F5A)=FVAR(2)
 Fixed Sof: C43(0.5) H43A(0.5) H43B(0.5) H43C(0.5) C44(0.5) C45(0.5) H45(0.5)
 C46(0.5) H46(0.5) C47(0.5) H47(0.5) C48(0.5) H48(0.5) C49(0.5) H49(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C27(H27), C2(H2), C17(H17), C22(H22), C36(H36), C42(H42), C14(H14),
 C35(H35), C26(H26), C21(H21), C12(H12), C28(H28), C11(H11), C6(H6), C23(H23),
 C24(H24), C16(H16), C32(H32), C29(H29), C4(H4), C9(H9), C3(H3), C34(H34),
 C33(H33), C10(H10), C5(H5), C15(H15), C41(H41), C38(H38), C40(H40), C39(H39),
 C22A(H22A), C21A(H21A), C24A(H24A), C23A(H23A), C45(H45), C46(H46), C47(H47),
 C48(H48), C49(H49)
7.b Fitted hexagon refined as free rotating group:
 C22A(C21A,C20A,C19,C24A,C23A)
7.c Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C)
;
_shelx_res_checksum              81956
_shelx_hkl_checksum              88932
_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 1.307
_oxdiff_exptl_absorpt_empirical_full_min 0.753