Regiodivergent C-H alkynylation of 2-arylthiazoles switched by Ru<sup>II</sup> and Pd<sup>II</sup> catalysis.
Zhou, Pengfei; Liang, Xinyao; Xu, Zekun; Chen, Honggu; Wei, Zongwu; Liang, Taoyuan; Jiang, Jun; Zhang, Zhuan; Chemical communications (Cambridge, England) 60 (2024) 6679–6682; doi:10.1039/d4cc02254h

data_7133152
_publ_section_title
;
 Regiodivergent C-H alkynylation of 2-arylthiazoles switched by
 Ru<sup>II</sup> and Pd<sup>II</sup> catalysis.
;
_journal_issue                   52
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6679
_journal_page_last               6682
_journal_paper_doi               10.1039/d4cc02254h
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C31 H46 F N S Si2'
_chemical_formula_sum            'C31 H46 F N S Si2'
_chemical_formula_weight         539.93
_chemical_name_systematic        LXY
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-19
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-19 deposited with the CCDC.	2024-06-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.946(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.1462(4)
_cell_length_b                   13.1951(5)
_cell_length_c                   15.8775(7)
_cell_measurement_reflns_used    3828
_cell_measurement_temperature    298.15
_cell_measurement_theta_max      23.7030
_cell_measurement_theta_min      2.5140
_cell_volume                     1694.15(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.99a (Rigaku OD, 2023)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1213
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.878
_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    -52.00  24.00   1.00    4.00    --   16.88 -57.00 -90.00   76
  2  \w    -39.00   4.00   1.00    4.00    --   16.88 -19.00 120.00   43
  3  \w    -34.00  50.00   1.00    4.00    --   16.88 -19.00 -30.00   84
  4  \w    -44.00  17.00   1.00    4.00    --  -17.43  77.00 150.00   61
  5  \w    -37.00   9.00   1.00    4.00    --  -17.43 -77.00 -60.00   46
  6  \w    -33.00   2.00   1.00    4.00    --  -17.43 -77.00-180.00   35
  7  \w    -36.00  10.00   1.00    4.00    --  -17.43 -77.00  30.00   46
  8  \w    -39.00 -14.00   1.00    4.00    --  -17.43 -77.00-120.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0479328000
_diffrn_orient_matrix_UB_12      -0.0300430000
_diffrn_orient_matrix_UB_13      0.0308554000
_diffrn_orient_matrix_UB_21      0.0517916000
_diffrn_orient_matrix_UB_22      -0.0145754000
_diffrn_orient_matrix_UB_23      -0.0307427000
_diffrn_orient_matrix_UB_31      0.0520783000
_diffrn_orient_matrix_UB_32      0.0421190000
_diffrn_orient_matrix_UB_33      0.0113655000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.878
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            15050
_diffrn_reflns_point_group_measured_fraction_full 0.907
_diffrn_reflns_point_group_measured_fraction_max 0.755
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.205
_diffrn_reflns_theta_min         2.519
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.190
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89704
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.99a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.058
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.710
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1486 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.65(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     348
_refine_ls_number_reflns         6943
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0993
_refine_ls_R_factor_gt           0.0659
_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^)+(0.1002P)^2^+0.2582P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1685
_refine_ls_wR_factor_ref         0.1946
_reflns_Friedel_coverage         0.652
_reflns_Friedel_fraction_full    0.806
_reflns_Friedel_fraction_max     0.622
_reflns_number_gt                4700
_reflns_number_total             6943
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02254h2.cif
_cod_data_source_block           exp_14225_auto
_cod_depositor_comments
'Adding full bibliography for 7133152--7133153.cif.'
_cod_database_code               7133152
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.963
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C30-C29 = C31-C29 = C28-C26 = C27-C26 = C24-C23 = C20-C18 = C19-C18 = C16-C15
 = C17-C15 = C13-C12 = C14-C12
 1.54 with sigma of 0.01
3. Rigid bond restraints
 F1, C6
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Others
 Sof(H23A)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=1-FVAR(1)
 Sof(H23)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C26(H26), C18(H18), C29(H29), C23(H23A), C23(H23), C12(H12), C15(H15)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C9(H9), C8(H8)
5.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C31(H31A,H31B,H31C), C24(H24A,H24B,H24C), C27(H27A,H27B,
 H27C), C30(H30A,H30B,H30C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C14(H14A,
 H14B,H14C), C16(H16A,H16B,H16C), C13(H13A,H13B,H13C), C17(H17A,H17B,H17C),
 C32(H32A,H32B,H32C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              19628
_shelx_hkl_checksum              42199
_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 1.189
_oxdiff_exptl_absorpt_empirical_full_min 0.797