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_1566715
_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         'C31 H36 P2 Pt S, 2(B F4), C H3 N O2'
_chemical_formula_sum            'C32 H39 B2 F8 N O2 P2 Pt S'
_chemical_formula_weight         932.35
_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             2021-09-01
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6392)
;
_audit_update_record
;
2021-11-02 deposited with the CCDC.	2022-03-14 downloaded from the CCDC.
;
_cell_angle_alpha                65.687(2)
_cell_angle_beta                 75.1110(10)
_cell_angle_gamma                75.5460(10)
_cell_formula_units_Z            2
_cell_length_a                   10.7270(2)
_cell_length_b                   13.1882(2)
_cell_length_c                   15.1430(2)
_cell_measurement_reflns_used    20593
_cell_measurement_temperature    293.6(6)
_cell_measurement_theta_max      31.7230
_cell_measurement_theta_min      1.9890
_cell_volume                     1861.41(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.6(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     -8.00  80.00   0.50    5.00    --   11.54  57.00  90.00  176
  2  \w     35.00  60.00   0.50    5.00    --  -12.64  57.00 150.00   50
  3  \w    -31.00  17.00   0.50    5.00    --  -12.64  57.00 150.00   96
  4  \w    -52.00 -27.00   0.50    5.00    --  -12.64 108.00  86.00   50
  5  \w    -64.00  -8.00   0.50    5.00    --   11.54 -19.00 -30.00  112
  6  \w    -23.00  49.00   0.50    5.00    --   11.54 -99.00 -30.00  144
  7  \w      0.00  26.00   0.50    5.00    --   11.54-108.00 -11.00   52
  8  \w    -23.00   9.00   0.50    5.00    --  -12.64 -99.00 150.00   64
  9  \w     -1.00  24.00   0.50    5.00    --  -12.64 -99.00   0.00   50
 10  \w    -23.00  23.00   0.50    5.00    --  -12.64 -99.00 -30.00   92
 11  \w    -54.00  39.00   0.50    5.00    --   11.54 -77.00 -90.00  186
 12  \w    -87.00 -51.00   0.50    5.00    --  -12.64-178.00   0.00   72
;
_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      -0.0207904000
_diffrn_orient_matrix_UB_12      0.0477467000
_diffrn_orient_matrix_UB_13      -0.0403825000
_diffrn_orient_matrix_UB_21      0.0233437000
_diffrn_orient_matrix_UB_22      -0.0317418000
_diffrn_orient_matrix_UB_23      -0.0307542000
_diffrn_orient_matrix_UB_31      -0.0619065000
_diffrn_orient_matrix_UB_32      -0.0170620000
_diffrn_orient_matrix_UB_33      0.0121829000
_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     0.0264
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            25834
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.991
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.981
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.601
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
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    1.663
_exptl_crystal_description       plate
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.203
_exptl_crystal_size_mid          0.136
_exptl_crystal_size_min          0.074
_refine_diff_density_max         1.513
_refine_diff_density_min         -0.832
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     393
_refine_ls_number_reflns         6546
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0286
_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^)+(0.0416P)^2^+2.1257P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0722
_refine_ls_wR_factor_ref         0.0738
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5985
_reflns_number_total             6546
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00588c2.cif
_cod_data_source_block           7a_BF4_2
_cod_database_code               1566715
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C32 H39 B2 F8 N O2 P2 Pt S'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Restrained distances
 C15-C16 \\sim C15-C16A
 with sigma of 0.02
 F1-B2 \\sim F1A-B2
 with sigma of 0.02
 F2-B2 \\sim F2A-B2
 with sigma of 0.02
 F4-B2 \\sim F4A-B2
 with sigma of 0.02
 F3-B2 \\sim F3A-B2
 with sigma of 0.02
 N1-O1 \\sim N1-O1A
 with sigma of 0.02
 N1-O2 \\sim N1-O2A
 with sigma of 0.02
 C7-C8 \\sim C7-C8A
 with sigma of 0.02
 C7-C11 \\sim C7-C11A
 with sigma of 0.04
 C12-C11 \\sim C12A-C11A
 with sigma of 0.02
 C8-C10 \\sim C8A-C10
 with sigma of 0.04
 C12-C10 \\sim C12A-C10
 with sigma of 0.04
 C9-C10 \\sim C9A-C10
 with sigma of 0.02
 C8-C9 \\sim C8A-C9A
 with sigma of 0.02
 C10-C11 \\sim C10-C11A
 with sigma of 0.02
 C7-C12 \\sim C7-C12A
 with sigma of 0.02
 C7-C9 \\sim C7-C9A
 with sigma of 0.04
 C9-C9A \\sim C11A-C11 \\sim C12A-C12 \\sim C8-C8A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
Uanis(F1A) = Uanis(F1) = Uanis(F3A) = Uanis(F3) = Uanis(F4A) = Uanis(F4) =
Uanis(F2) = Uanis(F2A)
Uanis(C16) = Uanis(C16A)
Uanis(O1) = Uanis(O1A) = Uanis(O2) = Uanis(O2A) = Uanis(C31)
Uanis(C21) = Uanis(C20) = Uanis(C22) = Uanis(C23) = Uanis(C24)
Uanis(C8A) = Uanis(C8) = Uanis(C9) = Uanis(C9A) = Uanis(C11) = Uanis(C11A) =
Uanis(C12) = Uanis(C12A)
Uanis(C19) = Uanis(C20) = Uanis(C24) = Uanis(C23) = Uanis(C22) = Uanis(C21)
3. Others
 Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
 Sof(F1A)=Sof(F3A)=Sof(F4A)=Sof(F2A)=1-FVAR(2)
 Sof(F2)=Sof(F4)=Sof(F1)=Sof(F3)=FVAR(2)
 Sof(O1A)=Sof(O2A)=1-FVAR(3)
 Sof(O1)=Sof(O2)=FVAR(3)
 Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=
 Sof(H12A)=1-FVAR(4)
 Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(H10)=
 FVAR(4)
4.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C18(H18A,H18B), C17(H17A,H17B), C14(H14A,H14B), C15(H15A,
 H15B), C15(H15C,H15D)
4.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C5(H5), C2(H2), C26(H26), C4(H4), C30(H30), C8(H8), C9(H9), C11(H11),
 C12(H12), C3(H3), C20(H20), C24(H24), C29(H29), C27(H27), C21(H21), C28(H28),
 C23(H23), C22(H22), C8A(H8A), C9A(H9A), C10(H10), C10(H10A), C11A(H11A),
 C12A(H12A)
4.c Fitted hexagon refined as free rotating group:
 C8A(C9A,C10,C11A,C12A,C7)
4.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F), C31(H31A,H31B,
 H31C)
;
_shelx_res_checksum              26993
_shelx_hkl_checksum              19556
_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 1.361
_oxdiff_exptl_absorpt_empirical_full_min 0.756