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_1572165
_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         'C36 H45 Cl2 N O Ru, 2[C6H12]'
_chemical_formula_sum            'C48 H69 Cl2 N O Ru'
_chemical_formula_weight         848.01
_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             2024-05-14
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-15 deposited with the CCDC.	2024-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.441(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.5489(9)
_cell_length_b                   8.9270(4)
_cell_length_c                   27.5267(11)
_cell_measurement_reflns_used    19113
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      74.3700
_cell_measurement_theta_min      2.4920
_cell_volume                     4298.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(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 0.957
_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     26.00  53.00   0.50    4.00    --   20.00  67.00 -29.64   54
  2  \w     50.00  76.00   0.50    4.00    --   36.00  59.00 -33.75   52
  3  \w     43.00  68.00   0.50    4.00    --   40.00  73.00 -79.74   50
  4  \w     60.00  87.00   0.50    4.00    --   56.00  75.00 -87.12   54
  5  \w     11.00  37.00   0.50    4.00    --   59.19 -30.00 120.00   52
  6  \w     11.00  37.00   0.50    4.00    --   59.19 -30.00-180.00   52
  7  \w     10.00  36.00   0.50    4.00    --   59.19 -30.00  90.00   52
  8  \w     10.00  35.00   0.50    4.00    --   59.19 -30.00 -60.00   50
  9  \w   -108.00 -71.00   0.50    4.00    --  -60.00 -39.00 -88.43   74
 10  \w    -89.00 -63.00   0.50    4.00    --  -62.05 -30.00-180.00   52
 11  \w   -109.00 -82.00   0.50    4.00    --  -62.05 -30.00 120.00   54
 12  \w   -105.00 -76.00   0.50    4.00    --  -64.00 -67.00-101.28   58
 13  \w   -101.00 -73.00   0.50    4.00    --  -68.00 -75.00 -30.16   56
 14  \w   -116.00 -85.00   0.50    4.00    --  -71.12 -30.00  30.00   62
 15  \w     34.00 101.00   0.50    4.00    --   71.94   0.00-180.00  134
 16  \w     32.00  64.00   0.50    4.00    --   71.94 -95.00 -60.00   64
 17  \w     34.00  80.00   0.50    4.00    --   71.94 -95.00 120.00   92
 18  \w     74.00  99.00   0.50    4.00    --   71.94  30.00 -90.00   50
 19  \w     32.00  77.00   0.50    4.00    --   71.94 -95.00   0.00   90
 20  \w   -106.00 -75.00   0.50    4.00    --  -72.00 -73.00-108.87   62
 21  \w     51.00  80.00   0.50    4.00    --   73.16 -95.00-150.00   58
 22  \w     33.00  58.00   0.50    4.00    --   73.16 -95.00  90.00   50
 23  \w   -125.00 -81.00   0.50    4.00    --  -75.55 -30.00  30.00   88
 24  \w   -121.00 -78.00   0.50    4.00    --  -75.55-125.00-150.00   86
 25  \w   -119.00 -90.00   0.50    4.00    --  -75.55-125.00 -60.00   58
 26  \w    -55.00 -30.00   0.50    4.00    --  -75.55 125.00  30.00   50
 27  \w   -120.00 -95.00   0.50    4.00    --  -75.55-125.00 -30.00   50
 28  \w   -120.00 -42.00   0.50    4.00    --  -75.55 -15.00 -60.00  156
 29  \w   -106.00 -79.00   0.50    4.00    --  -76.57 -76.00 -36.36   54
 30  \w   -120.00 -85.00   0.50    4.00    --  -76.57 -51.00 -82.01   70
 31  \w     93.00 126.00   0.50    4.00    --   81.20  30.00-150.00   66
 32  \w     45.00 112.00   0.50    4.00    --   81.20-125.00-180.00  134
 33  \w     97.00 127.00   0.50    4.00    --   81.20 125.00-120.00   60
 34  \w     91.00 127.00   0.50    4.00    --   81.20 125.00-180.00   72
 35  \w     79.00 125.00   0.50    4.00    --   81.20 125.00 -30.00   92
 36  \w     82.00 127.00   0.50    4.00    --   81.20 125.00 -90.00   90
 37  \w     39.00 112.00   0.50    4.00    --   81.20-125.00   0.00  146
 38  \w     81.00 109.00   0.50    4.00    --   81.20 125.00-150.00   56
 39  \w     40.00  90.00   0.50    4.00    --   81.20-125.00 120.00  100
 40  \w     88.00 117.00   0.50    4.00    --   81.20 125.00  90.00   58
;
_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      -0.0009277000
_diffrn_orient_matrix_UB_12      -0.0137563000
_diffrn_orient_matrix_UB_13      -0.0559852000
_diffrn_orient_matrix_UB_21      0.0682118000
_diffrn_orient_matrix_UB_22      0.1097144000
_diffrn_orient_matrix_UB_23      0.0119397000
_diffrn_orient_matrix_UB_31      0.0557249000
_diffrn_orient_matrix_UB_32      -0.1324967000
_diffrn_orient_matrix_UB_33      0.0155610000
_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  0.0516
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            46618
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.351
_diffrn_reflns_theta_min         2.526
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.357
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.318
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'clear intense green'
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       needle
_exptl_crystal_F_000             1800
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.188
_refine_diff_density_min         -1.856
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.248(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     678
_refine_ls_number_reflns         16645
_refine_ls_number_restraints     1202
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0966
_refine_ls_R_factor_gt           0.0852
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1092P)^2^+16.8801P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2177
_refine_ls_wR_factor_ref         0.2261
_reflns_Friedel_coverage         0.831
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.910
_reflns_number_gt                13986
_reflns_number_total             16645
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04278f2.cif
_cod_data_source_block           amd-r713
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1572161--1572166.cif.
;
_cod_original_cell_volume        4298.1(3)
_cod_database_code               1572165
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C48 H69 Cl2 N O Ru'
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.365
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.752(18)
 0.248(18)
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
 C36-C34 = C35-C34
 1.54 with sigma of 0.01
 C36-C35
 2.54 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Ternary CH refined with riding coordinates:
 C5(H5), C7(H7), C34(H34), C41(H41), C43(H43), C70(H70)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C39(H39A,H39B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B),
  C47(H47A,H47B), C48(H48A,H48B)
6.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C27(H27), C33(H33), C32(H32), C31(H31), C30(H30),
  C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C62(H62), C61(H61),
 C60(H60), C59(H59), C58(H58), C63(H63), C66(H66), C67(H67), C68(H68), C69(H69)
6.d Fitted hexagon refined as free rotating group:
 C15(C16,C17,C18,C19,C20), C21(C22,C23,C24,C25,C26), C29(C28,C33,C32,C31,C30),
 C51(C52,C53,C54,C55,C56), C57(C62,C61,C60,C59,C58), C65(C66,C67,C68,C69,C64)
6.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C42(H42A,H42B,H42C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 423 electrons were 
found in a volume of 1247\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C6H12] per Asymmetric Unit 
which account for 384 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              27474
_shelx_hkl_checksum              79236
_shelx_fab_checksum              81122
_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 2.505
_oxdiff_exptl_absorpt_empirical_full_min 0.343