Streamlined synthetic assembly of α-chiral CAAC ligands and catalytic performance of their copper and ruthenium complexes.
Madron du Vigné, Adrien; Cramer, Nicolai; Chemical science 15 (2024) 13864–13871; doi:10.1039/d4sc04278f

data_1572164
_publ_section_title
;
 Streamlined synthetic assembly of &#x3b1;-chiral CAAC ligands and
 catalytic performance of their copper and ruthenium complexes.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              13864
_journal_page_last               13871
_journal_paper_doi               10.1039/d4sc04278f
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H35 Cl Cu N S'
_chemical_formula_sum            'C23 H35 Cl Cu N S'
_chemical_formula_weight         456.57
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-11-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-06-27 deposited with the CCDC.	2024-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.104(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.5182(2)
_cell_length_b                   15.3074(5)
_cell_length_c                   9.1646(3)
_cell_measurement_reflns_used    6828
_cell_measurement_temperature    140.0(3)
_cell_measurement_theta_max      72.7060
_cell_measurement_theta_min      4.9370
_cell_volume                     1163.87(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_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    -87.00 -54.00   1.00    6.50    --  -40.29 -26.00 -11.00   33
  2  \w     10.00 117.00   1.00    6.50    --   40.29  26.00 152.00  107
  3  \w     14.00  40.00   1.00    6.50    --   40.29 -26.00 -11.00   26
  4  \w     62.00 108.00   1.00   26.00    --  105.78 -26.00 -11.00   46
  5  \w    102.00 127.00   1.00   26.00    --  105.78  26.00 152.00   25
  6  \w     33.00  60.00   1.00   26.00    --  105.78 -26.00 -11.00   27
  7  \w   -110.00 -13.00   1.00    6.50    --  -40.29 -57.00 150.00   97
  8  \w    -51.00 -17.00   1.00    6.50    --  -40.29 -38.00-120.00   34
  9  \w    -42.00 -17.00   1.00    6.50    --  -40.29  26.00 152.00   25
 10  \w   -112.00 -12.00   1.00    6.50    --  -40.29 -57.00-120.00  100
 11  \w     14.00  41.00   1.00    6.50    --   40.29  57.00 -30.00   27
 12  \w     29.00  89.00   1.00    6.50    --   40.29-125.00-150.00   60
 13  \w     21.00  46.00   1.00    6.50    --   40.29  57.00 -90.00   25
 14  \w      6.00  78.00   1.00    6.50    --   40.29 -99.00   0.00   72
 15  \w     78.00 105.00   1.00   26.00    --  105.78  61.00-120.00   27
 16  \w     61.00  91.00   1.00   26.00    --  105.78 178.00   0.00   30
 17  \w     77.00 103.00   1.00   26.00    --  105.78  61.00 -60.00   26
 18  \w    109.00 141.00   1.00   26.00    --  105.78 178.00   0.00   32
 19  \w    121.00 158.00   1.00   26.00    --  105.78  61.00 -30.00   37
 20  \w     85.00 147.00   1.00   26.00    --  105.78  45.00-180.00   62
 21  \w     72.00 105.00   1.00   26.00    --  105.78 -94.00 -60.00   33
 22  \w     78.00 109.00   1.00   26.00    --  105.78  61.00-180.00   31
 23  \w     82.00 107.00   1.00   26.00    --  105.78  45.00 -60.00   25
 24  \w    113.00 174.00   1.00   26.00    --  105.78  61.00 -90.00   61
 25  \w     77.00 112.00   1.00   26.00    --  105.78  30.00-120.00   35
 26  \w     81.00 108.00   1.00   26.00    --  105.78  45.00 -30.00   27
 27  \w    105.00 167.00   1.00   26.00    --  105.78 111.00-180.00   62
 28  \w     82.00 109.00   1.00   26.00    --  105.78  45.00-120.00   27
 29  \w     80.00 122.00   1.00   26.00    --  105.78  45.00 -90.00   42
 30  \w     83.00 110.00   1.00   26.00    --  105.78  45.00-150.00   27
 31  \w     81.00 108.00   1.00   26.00    --  105.78  38.00 -69.63   27
 32  \w     78.00 106.00   1.00   26.00    --  105.78  61.00 -30.00   28
 33  \w     77.00 104.00   1.00   26.00    --  105.78  61.00 -90.00   27
 34  \w     78.00 103.00   1.00   26.00    --  105.78  61.00-150.00   25
 35  \w     83.00 110.00   1.00   26.00    --  105.78  30.00 -30.00   27
 36  \w     86.00 126.00   1.00   26.00    --  105.78  30.00 -90.00   40
 37  \w    112.00 170.00   1.00   26.00    --  105.78 111.00  90.00   58
 38  \w     26.00 106.00   1.00   26.00    --  105.78 -94.00  30.00   80
 39  \w     31.00  71.00   1.00   26.00    --  105.78 -94.00 -60.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0366484000
_diffrn_orient_matrix_UB_12      -0.0111847000
_diffrn_orient_matrix_UB_13      0.1714515000
_diffrn_orient_matrix_UB_21      0.1709877000
_diffrn_orient_matrix_UB_22      -0.0320690000
_diffrn_orient_matrix_UB_23      -0.0014574000
_diffrn_orient_matrix_UB_31      0.0621914000
_diffrn_orient_matrix_UB_32      0.0947931000
_diffrn_orient_matrix_UB_33      0.0196493000
_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  0.0465
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            10462
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.322
_diffrn_reflns_theta_min         4.955
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.255
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.309
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
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            'clear pale colourless'
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_description       plate
_exptl_crystal_F_000             484
_exptl_crystal_size_max          0.398
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.087
_refine_diff_density_max         1.344
_refine_diff_density_min         -0.555
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 1729 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     248
_refine_ls_number_reflns         4323
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0892P)^2^+0.0102P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1217
_refine_ls_wR_factor_ref         0.1234
_reflns_Friedel_coverage         0.810
_reflns_Friedel_fraction_full    0.910
_reflns_Friedel_fraction_max     0.859
_reflns_number_gt                4127
_reflns_number_total             4323
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04278f2.cif
_cod_data_source_block           amd-r1398-dia2
_cod_depositor_comments
'Adding full bibliography for 1572161--1572166.cif.'
_cod_database_code               1572164
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C23 H35 N1 S1 Cl1 Cu1'
_shelx_estimated_absorpt_t_max   0.765
_shelx_estimated_absorpt_t_min   0.357
_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.a Ternary CH refined with riding coordinates:
 C16(H16), C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C6(H6A,H6B), C7(H7A,H7B), C19(H19A,H19B), C20(H20A,H20B),
 C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13)
2.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              73349
_shelx_hkl_checksum              21911
_olex2_date_sample_data_collection 2023-09-19
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 6.570
_oxdiff_exptl_absorpt_empirical_full_min 0.400