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_1572166
_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         'C35 H45 Cl2 N O Ru'
_chemical_formula_sum            'C35 H45 Cl2 N O Ru'
_chemical_formula_weight         667.69
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-01
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-27 deposited with the CCDC.	2024-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5043(3)
_cell_length_b                   16.0340(4)
_cell_length_c                   17.8672(5)
_cell_measurement_reflns_used    16254
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      73.3690
_cell_measurement_theta_min      3.6770
_cell_volume                     3295.78(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.120a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.120a 64-bit (release 16-04-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.120a (Rigaku OD, 2024)'
_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      139.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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     50.00  75.00   0.50    2.00    --   63.42-167.00  34.00   50
  2  \w     45.00  70.00   0.50    2.00    --   63.42-116.00-179.00   50
  3  \w    -76.00 -51.00   0.50    2.00    --  -64.25-167.00  34.00   50
  4  \w    -96.00 -71.00   0.50    2.00    --  -64.25 167.00  54.00   50
  5  \w    -79.00 -54.00   0.50    2.00    --  -64.25 116.00 -91.00   50
  6  \w    -90.00 -58.00   0.50    2.00    --  -70.98 116.00 -91.00   64
  7  \w    -83.00 -43.00   0.50    2.00    --  -70.98 167.00  54.00   80
  8  \w     56.00  81.00   0.50    2.00    --   75.74-116.00-179.00   50
  9  \w     87.00 113.00   0.50    2.00    --   76.22-167.00  34.00   52
 10  \w     43.00  68.00   0.50    2.00    --   76.22-116.00-179.00   50
 11  \w     58.00  83.00   0.50    2.00    --   76.22 167.00  54.00   50
 12  \w     28.00  53.00   0.50    2.00    --   63.42 -95.00-120.00   50
 13  \w     44.00  69.00   0.50    2.00    --   63.42 -95.00 -90.00   50
 14  \w     33.00  72.00   0.50    2.00    --   63.42 -95.00  30.00   78
 15  \w     22.00  62.00   0.50    2.00    --   63.42-125.00 120.00   80
 16  \w    -63.00 -37.00   0.50    2.00    --  -70.98   0.00   0.00   52
 17  \w    -72.00 -42.00   0.50    2.00    --  -70.98   0.00 150.00   60
 18  \w    -69.00 -35.00   0.50    2.00    --  -70.98   0.00-180.00   68
 19  \w    -68.00 -35.00   0.50    2.00    --  -70.98   0.00-120.00   66
 20  \w     39.00  82.00   0.50    2.00    --   75.74 -95.00  30.00   86
 21  \w     38.00  63.00   0.50    2.00    --   75.74 -95.00-180.00   50
 22  \w     43.00  68.00   0.50    2.00    --   75.74 -95.00 150.00   50
 23  \w     98.00 123.00   0.50    2.00    --   76.00  23.00  43.15   50
 24  \w     38.00  63.00   0.50    2.00    --   76.22 -95.00  90.00   50
 25  \w     66.00  91.00   0.50    2.00    --   76.22-125.00 150.00   50
 26  \w     38.00  63.00   0.50    2.00    --   76.22 -95.00 -60.00   50
 27  \w     48.00  79.00   0.50    2.00    --   76.22 -95.00 -90.00   62
 28  \w     74.00  99.00   0.50    2.00    --   76.22-125.00  30.00   50
 29  \w     73.00  98.00   0.50    2.00    --   76.22-125.00  60.00   50
 30  \w   -108.00 -80.00   0.50    2.00    --  -76.25 -86.00 -73.87   56
 31  \w    -97.00 -71.00   0.50    2.00    --  -76.25 118.00-131.70   52
 32  \w    -70.00 -45.00   0.50    2.00    --  -76.25  78.00 -64.87   50
 33  \w   -109.00 -82.00   0.50    2.00    --  -76.25 -82.00 -26.89   54
 34  \w     46.00  78.00   0.50    2.00    --   79.75   6.00  90.86   64
 35  \w     62.00  87.00   0.50    2.00    --   79.75  21.00  61.24   50
 36  \w     66.00  93.00   0.50    2.00    --   79.75  21.00 -90.79   54
 37  \w     83.00 109.00   0.50    2.00    --   79.75   1.00 -67.96   52
 38  \w     73.00 125.00   0.50    2.00    --   79.75  22.00-139.63  104
 39  \w     43.00  74.00   0.50    2.00    --   79.75   1.00 -67.96   62
 40  \w     68.00  94.00   0.50    2.00    --   79.75  16.00 176.08   52
 41  \w     88.00 114.00   0.50    2.00    --   79.75   4.00-136.35   52
 42  \w    101.00 126.00   0.50    2.00    --   79.75  19.00   5.04   50
 43  \w     85.00 119.00   0.50    2.00    --   79.75   2.00 -41.19   68
 44  \w     53.00  79.00   0.50    2.00    --   79.75  19.00   5.04   52
 45  \w     88.00 116.00   0.50    2.00    --   79.75   4.00  21.81   56
 46  \w     89.00 121.00   0.50    2.00    --   79.75  20.00 -74.32   64
 47  \w     83.00 120.00   0.50    2.00    --   79.75  22.00 179.32   74
 48  \w     72.00 110.00   0.50    2.00    --   79.75  22.00  -2.27   76
 49  \w     87.00 116.00   0.50    2.00    --   79.75   6.00  90.86   58
 50  \w     59.00  86.00   0.50    2.00    --   79.75   4.00  21.81   54
 51  \w     95.00 123.00   0.50    2.00    --   79.75  54.00-115.13   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0939025000
_diffrn_orient_matrix_UB_12      -0.0325142000
_diffrn_orient_matrix_UB_13      0.0543017000
_diffrn_orient_matrix_UB_21      -0.0930516000
_diffrn_orient_matrix_UB_22      0.0499257000
_diffrn_orient_matrix_UB_23      -0.0426431000
_diffrn_orient_matrix_UB_31      -0.0211053000
_diffrn_orient_matrix_UB_32      -0.0754221000
_diffrn_orient_matrix_UB_33      -0.0516376000
_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  0.0565
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            38532
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.776
_diffrn_reflns_theta_min         3.704
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.538
_exptl_absorpt_correction_T_max  0.910
_exptl_absorpt_correction_T_min  0.574
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.120a (Rigaku Oxford Diffraction, 2024)
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 intense green'
_exptl_crystal_density_diffrn    1.346
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1392
_exptl_crystal_size_max          0.166
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.458
_refine_diff_density_min         -1.661
_refine_diff_density_rms         0.107
_refine_ls_abs_structure_details
;
 Flack x determined using 2227 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.037(7)
_refine_ls_extinction_coef       0.00039(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         6742
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0550
_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^)+(0.0802P)^2^+4.6774P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1370
_refine_ls_wR_factor_ref         0.1448
_reflns_Friedel_coverage         0.777
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                5827
_reflns_number_total             6742
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04278f2.cif
_cod_data_source_block           amd-r1392
_cod_depositor_comments
'Adding full bibliography for 1572161--1572166.cif.'
_cod_database_code               1572166
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C35 H45 N1 O1 Cl2 Ru1'
_shelx_estimated_absorpt_t_max   0.747
_shelx_estimated_absorpt_t_min   0.460
_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:
 C18(H18), C19(H19), C33(H33)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,
 H23B), C24(H24A,H24B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C25(H25), C28(H28),
 C29(H29), C30(H30), C31(H31)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C32(H32A,H32B,
 H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              2973
_shelx_hkl_checksum              16286
_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 1.648
_oxdiff_exptl_absorpt_empirical_full_min 0.644