Electrophilic and Nucleophilic Displacement Reactions at the Bridgehead Borons of Tris(pyridyl)borate Scorpionate Complexes
Goura, Joydeb; McQuade, James; Shimoyama, Daisuke; Lalancette, Roger A.; Sheridan, John B.; Jaekle, Frieder; Chemical Communications  (2022) –; doi:10.1039/D1CC06181J

data_7129473
_publ_section_title
;
 Electrophilic and Nucleophilic Displacement Reactions at the Bridgehead
 Borons of Tris(pyridyl)borate Scorpionate Complexes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06181J
_journal_year                    2022
_chemical_formula_moiety         'C32 H24 B2 F5.999 N6 O5.999 Ru1 S2'
_chemical_formula_sum            'C32 H24 B2 F6 N6 O6 Ru S2'
_chemical_formula_weight         889.38
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-08-17
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2021-10-25 deposited with the CCDC.	2021-12-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   12.67330(10)
_cell_length_b                   12.67330(10)
_cell_length_c                   17.5398(2)
_cell_measurement_reflns_used    15571
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.1480
_cell_measurement_theta_min      4.7360
_cell_volume                     2439.69(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.962
_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     23.00 119.00   0.50    0.10    --   46.34  77.00 -90.00  192
  2  \w     23.00 119.00   0.50    0.10    --   46.34  77.00 -60.00  192
  3  \w     31.00 122.00   0.50    0.10    --   46.34  19.00 -90.00  182
  4  \w     23.00 119.00   0.50    0.10    --   46.34  77.00 -30.00  192
  5  \w     23.00 119.00   0.50    0.10    --   46.34  77.00  30.00  192
  6  \w     23.00 119.00   0.50    0.10    --   46.34  77.00  90.00  192
  7  \w     23.00  48.00   0.50    0.10    --   46.34  77.00 150.00   50
  8  \w    -28.00  32.00   0.50    0.10    --   46.34 -10.00 -15.00  120
  9  \w     43.00 104.00   0.50    0.10    --   46.34-141.00 115.00  122
 10  \w     34.00  95.00   0.50    0.10    --   46.34-125.00 -30.00  122
 11  \w     34.00 112.00   0.50    0.30    --  106.22-125.00 -93.00  156
 12  \w    -29.00  30.00   0.50    0.10    --   46.34 -19.00-120.00  118
 13  \w   -167.00 -70.00   0.50    0.30    --  -91.75 -10.00 -15.00  194
 14  \w   -164.00 -71.00   0.50    0.30    --  -91.75 -68.00 -59.56  186
 15  \w   -164.00 -68.00   0.50    0.30    --  -91.75 -77.00 -60.00  192
 16  \w   -164.00 -68.00   0.50    0.30    --  -91.75 -77.00 -90.00  192
 17  \w   -164.00 -71.00   0.50    0.30    --  -91.75 -69.00-118.49  186
 18  \w   -164.00 -70.00   0.50    0.30    --  -91.75 -71.00-149.70  188
 19  \w   -164.00 -73.00   0.50    0.30    --  -91.75 -65.00-149.82  182
 20  \w   -164.00 -73.00   0.50    0.30    --  -91.75 -65.00-141.50  182
 21  \w   -164.00 -73.00   0.50    0.30    --  -91.75 -64.00-133.24  182
 22  \w   -164.00 -76.00   0.50    0.30    --  -91.75 -55.00-124.97  176
 23  \w   -164.00 -74.00   0.50    0.30    --  -91.75 -61.00-120.00  180
 24  \w   -164.00 -73.00   0.50    0.30    --  -91.75 -63.00-101.99  182
 25  \w   -164.00 -74.00   0.50    0.30    --  -91.75 -61.00 -90.00  180
 26  \w   -164.00 -76.00   0.50    0.30    --  -91.75-121.00-117.00  176
 27  \w   -164.00 -73.00   0.50    0.30    --  -91.75-125.00 -93.00  182
 28  \w   -164.00 -70.00   0.50    0.30    --  -91.75-130.00 -71.00  188
 29  \w   -149.00 -56.00   0.50    0.30    --  -91.75-150.00   1.00  186
 30  \w   -118.00 -53.00   0.50    0.10    --  -46.34-155.00  84.00  130
 31  \w   -118.00 -56.00   0.50    0.10    --  -46.34-150.00   1.00  124
 32  \w   -121.00 -25.00   0.50    0.10    --  -46.34 -10.00 -15.00  192
 33  \w   -120.00 -32.00   0.50    0.10    --  -46.34 -38.00-150.00  176
 34  \w   -118.00 -23.00   0.50    0.10    --  -46.34 -77.00-180.00  190
 35  \w   -118.00 -30.00   0.50    0.10    --  -46.34 -56.00-143.17  176
 36  \w   -118.00 -30.00   0.50    0.10    --  -46.34 -57.00 120.00  176
 37  \w    -32.00  30.00   0.50    0.10    --  -46.34  10.00 157.00  124
 38  \w   -102.00 -25.00   0.50    0.30    --  -91.75 148.00 149.00  154
 39  \w     84.00 178.00   0.50    0.30    --  106.22  10.00 157.00  188
 40  \w     72.00 158.00   0.50    0.30    --  106.22 159.00 100.00  172
 41  \w     99.00 178.00   0.50    0.30    --  106.22 119.00 -52.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1139968000
_diffrn_orient_matrix_UB_12      -0.0137262000
_diffrn_orient_matrix_UB_13      0.0038997000
_diffrn_orient_matrix_UB_21      -0.0816864000
_diffrn_orient_matrix_UB_22      -0.1383989000
_diffrn_orient_matrix_UB_23      0.0115000000
_diffrn_orient_matrix_UB_31      -0.0056943000
_diffrn_orient_matrix_UB_32      -0.0190307000
_diffrn_orient_matrix_UB_33      -0.0869809000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_av_unetI/netI     0.0138
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            19624
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.979
_diffrn_reflns_theta_min         4.753
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.935
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.631
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (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_density_diffrn    1.816
_exptl_crystal_description       block
_exptl_crystal_F_000             1338
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.458
_refine_diff_density_min         -0.690
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.131
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     132
_refine_ls_number_reflns         1095
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0335
_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^)+(0.0514P)^2^+7.2015P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0938
_refine_ls_wR_factor_ref         0.0939
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1091
_reflns_number_total             1095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06181j2.cif
_cod_data_source_block           210601ral_jmcq_140_6_100ka
_cod_original_cell_volume        2439.69(5)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7129473
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C24H24B2F6N6O6RuS2
_shelx_estimated_absorpt_t_max   0.648
_shelx_estimated_absorpt_t_min   0.513
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Others
 Fixed Sof: C6(0.3333) F1(0.3333) F2(0.3333) F3(0.3333) S1(0.3333) O2(0.3333)
 O3(0.3333) O1(0.3333)
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C3(H3), C4(H4)
;
_shelx_res_checksum              7129
_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 1.440
_oxdiff_exptl_absorpt_empirical_full_min 0.728