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_1572163
_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'
_chemical_formula_sum            'C23 H35 Cl Cu N'
_chemical_formula_weight         424.51
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-01-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_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                   10.5297(5)
_cell_length_b                   13.2008(7)
_cell_length_c                   16.3003(7)
_cell_measurement_reflns_used    5635
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      72.4760
_cell_measurement_theta_min      4.2570
_cell_volume                     2265.75(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.78a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.78a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.78a (Rigaku OD, 2022)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -96.00  33.00   1.00    2.50    --  -42.88  -9.00-139.00  129
  2  \w    137.00 164.00   1.00   10.00    --  103.18 126.00 106.00   27
  3  \w     35.00 101.00   1.00   10.00    --  103.18   9.00  33.00   66
  4  \w    105.00 134.00   1.00   10.00    --  103.18 122.00-160.00   29
  5  \w    -86.00 -28.00   1.00    2.50    --  -42.88 126.00 106.00   58
  6  \w     30.00 127.00   1.00   10.00    --  103.18 -45.00 -90.00   97
  7  \w     34.00  66.00   1.00   10.00    --  103.18-111.00  90.00   32
  8  \w     67.00 106.00   1.00   10.00    --  103.18-111.00  90.00   39
  9  \w    110.00 158.00   1.00   10.00    --  103.18  77.00-120.00   48
 10  \w     34.00 133.00   1.00   10.00    --  103.18 -77.00  90.00   99
 11  \w    138.00 176.00   1.00   10.00    --  103.18   9.00  33.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0544436000
_diffrn_orient_matrix_UB_12      -0.0082787000
_diffrn_orient_matrix_UB_13      0.0874434000
_diffrn_orient_matrix_UB_21      0.1356657000
_diffrn_orient_matrix_UB_22      0.0110439000
_diffrn_orient_matrix_UB_23      -0.0343119000
_diffrn_orient_matrix_UB_31      -0.0088817000
_diffrn_orient_matrix_UB_32      0.1158228000
_diffrn_orient_matrix_UB_33      0.0100201000
_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  0.0688
_diffrn_reflns_av_unetI/netI     0.0559
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9478
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.975
_diffrn_reflns_theta_min         4.310
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.467
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.490
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.78a (Rigaku Oxford Diffraction, 2022)
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    1.244
_exptl_crystal_description       irregular
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.368
_exptl_crystal_size_mid          0.247
_exptl_crystal_size_min          0.213
_refine_diff_density_max         0.840
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.12(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         4349
_refine_ls_number_restraints     250
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0905
_refine_ls_R_factor_gt           0.0855
_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^)+(0.1671P)^2^+0.7776P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2395
_refine_ls_wR_factor_ref         0.2470
_reflns_Friedel_coverage         0.746
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                3876
_reflns_number_total             4349
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04278f2.cif
_cod_data_source_block           amd-r1097-dia1
_cod_depositor_comments
'Adding full bibliography for 1572161--1572166.cif.'
_cod_database_code               1572163
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H35 N1 Cl1 Cu1'
_shelx_estimated_absorpt_t_max   0.622
_shelx_estimated_absorpt_t_min   0.464
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.88(7)
 0.12(7)
2. 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
3. Restrained distances
 C22-C21 \\sim C24-C21 \\sim C23-C21
 with sigma of 0.02
 C22-C23 \\sim C23-C24
 with sigma of 0.02
 C27-C26 \\sim C28-C27 \\sim C29-C28 \\sim C30-C29 \\sim C30-C25 \\sim C26-C25
\\sim C7-C6 \\sim C8-C7 ~
 C9-C8 \\sim C9-C10 \\sim C11-C10 \\sim C6-C11
 with sigma of 0.02
 C5-C25 \\sim C6-C5
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C25 \\sim C26 \\sim C27
\\sim C28 \\sim C29 \\sim C30: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
5. Others
 Sof(H21A)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=1-FVAR(1)
 Sof(H21)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(H5B)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=
 Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=
 Sof(H30A)=Sof(H30B)=1-FVAR(2)
 Sof(H5A)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C5(H5A), C5(H5B), C6(H6), C21(H21), C21(H21A), C25(H25)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,
 H11B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B),
 C30(H30A,H30B)
6.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              61226
_shelx_hkl_checksum              33012
_olex2_date_sample_data_collection 2022-12-19
_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 2.021
_oxdiff_exptl_absorpt_empirical_full_min 0.595