Heterocycle-containing Noyori-Ikariya Catalysts for Asymmetric Transfer Hydrogenation of Ketones
Khamis, Noha; Clarkson, Guy James; Wills, Martin; Dalton Transactions  (2022) –; doi:10.1039/D2DT02411J

data_7711023
_publ_section_title
;
 Heterocycle-containing Noyori-Ikariya Catalysts for Asymmetric Transfer
 Hydrogenation of Ketones
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02411J
_journal_year                    2022
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C32 H33 Cl N2 O2 Ru S2, 0.5(C H4 O), 0.25(O)'
_chemical_formula_sum            'C32.5 H35 Cl N2 O2.75 Ru S2'
_chemical_formula_weight         698.26
_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
_audit_creation_date             2021-11-14
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2022-06-28 deposited with the CCDC.	2022-08-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.3866(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.78513(4)
_cell_length_b                   11.79817(5)
_cell_length_c                   14.04533(5)
_cell_measurement_reflns_used    68389
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.5030
_cell_measurement_theta_min      3.6900
_cell_volume                     1599.775(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (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)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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    -32.00  42.00   1.00    1.00    --    2.00  81.00  13.20   74
  2  \w     -4.00  22.00   1.00    1.00    --   34.00  93.00-161.46   26
  3  \w    -66.00  33.00   1.00    1.00    --  -41.82  37.00 -60.00   99
  4  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-180.00  108
  5  \w      7.00  33.00   1.00    1.00    --   41.82  84.00 -49.40   26
  6  \w     34.00 105.00   1.00    1.00    --   41.82-137.00  20.00   71
  7  \w    -33.00  66.00   1.00    1.00    --   41.82 -37.00   0.00   99
  8  \w      8.00  34.00   1.00    1.00    --   42.00  83.00 126.62   26
  9  \w     13.00  42.00   1.00    1.00    --   46.00  80.00  62.42   29
 10  \w     16.00  42.00   1.00    1.00    --   50.00  81.00-124.77   26
 11  \w     16.00  42.00   1.00    1.00    --   50.00  81.00 133.82   26
 12  \w     16.00  42.00   1.00    1.00    --   50.00  82.00 -92.70   26
 13  \w     23.00 128.00   1.00    1.00    --   54.00  70.00 163.59  105
 14  \w     27.00 132.00   1.00    1.00    --   58.00  71.00   5.60  105
 15  \w     32.00 135.00   1.00    1.00    --   62.00  64.00 102.42  103
 16  \w     31.00 136.00   1.00    1.00    --   62.00  71.00-165.16  105
 17  \w     31.00 136.00   1.00    1.00    --   62.00  71.00-112.00  105
 18  \w     36.00 139.00   1.00    1.00    --   66.00  68.00 115.11  103
 19  \w     35.00 140.00   1.00    1.00    --   66.00  71.00  28.14  105
 20  \w     35.00 140.00   1.00    1.00    --   66.00  71.00 -69.31  105
 21  \w     39.00 144.00   1.00    1.00    --   70.00  70.00  60.44  105
 22  \w     40.00 143.00   1.00    1.00    --   70.00  68.00 -33.65  103
 23  \w     44.00 147.00   1.00    1.00    --   74.00  66.00 156.95  103
 24  \w     50.00 150.00   1.00    2.00    --   78.00  55.00-146.17  100
 25  \w     52.00 155.00   1.00    2.00    --   82.00  65.00 -13.32  103
 26  \w     56.00 159.00   1.00    2.00    --   86.00  68.00 -88.40  103
 27  \w     61.00 163.00   1.00    2.00    --   90.00  63.00  60.93  102
 28  \w     69.00 170.00   1.00    2.00    --   98.00  61.00 173.77  101
 29  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 -30.00  100
 30  \w     34.00 133.00   1.00    2.00    --  107.00 -45.00  90.00   99
 31  \w     35.00 136.00   1.00    2.00    --  107.00 -61.00   0.00  101
 32  \w     81.00 178.00   1.00    2.00    --  107.00  45.00 150.00   97
 33  \w     34.00 112.00   1.00    2.00    --  107.00-125.00 -30.00   78
 34  \w     78.00 178.00   1.00    2.00    --  107.00  61.00   0.00  100
 35  \w     34.00 112.00   1.00    2.00    --  107.00-125.00-180.00   78
 36  \w     34.00 112.00   1.00    2.00    --  107.00-125.00  90.00   78
 37  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 -60.00  100
 38  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 120.00  100
 39  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 150.00  100
 40  \w     78.00 178.00   1.00    2.00    --  107.00  61.00-120.00  100
 41  \w     78.00 178.00   1.00    2.00    --  107.00  61.00-150.00  100
 42  \w     78.00 178.00   1.00    2.00    --  107.00  61.00  60.00  100
 43  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00  90.00   83
 44  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00 -30.00   83
 45  \w     97.00 178.00   1.00    2.00    --  107.00 125.00 120.00   81
 46  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00  30.00   83
 47  \w     78.00 178.00   1.00    2.00    --  107.00  61.00  30.00  100
 48  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 -90.00  100
 49  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00   0.00   83
 50  \w     81.00 178.00   1.00    2.00    --  107.00  45.00   0.00   97
 51  \w     78.00 178.00   1.00    2.00    --  107.00  61.00-180.00  100
 52  \w     77.00 178.00   1.00    2.00    --  107.00  64.00  10.14  101
 53  \w     81.00 178.00   1.00    2.00    --  107.00  45.00-150.00   97
 54  \w    103.00 178.00   1.00    2.00    --  107.00  77.00 -60.00   75
 55  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00 -60.00   83
 56  \w     78.00 178.00   1.00    2.00    --  107.00  61.00  90.00  100
 57  \w     34.00 112.00   1.00    2.00    --  107.00-125.00 -90.00   78
 58  \w     34.00 112.00   1.00    2.00    --  107.00-125.00 -60.00   78
 59  \w     97.00 178.00   1.00    2.00    --  107.00 125.00 -90.00   81
 60  \w     31.00 140.00   1.00    2.00    --  107.00 -77.00  90.00  109
 61  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00-180.00   83
 62  \w     -4.00  24.00   1.00    1.00    --   34.00  91.00 -82.33   28
 63  \w      3.00  31.00   1.00    1.00    --   38.00  86.00  76.77   28
 64  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 -60.00  108
 65  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 -30.00  108
 66  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-180.00  108
 67  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00 -90.00  108
 68  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-150.00  108
 69  \w    -74.00  34.00   1.00    1.00    --  -41.82  77.00-120.00  108
 70  \w     30.00 101.00   1.00    1.00    --   41.82-132.00-162.00   71
 71  \w      9.00  42.00   1.00    1.00    --   42.00  80.00 -12.19   33
 72  \w      7.00  33.00   1.00    1.00    --   42.00  84.00 156.13   26
 73  \w     16.00  42.00   1.00    1.00    --   50.00  81.00 -25.64   26
 74  \w     16.00  42.00   1.00    1.00    --   50.00  82.00 176.26   26
 75  \w     16.00  42.00   1.00    1.00    --   50.00  81.00  32.57   26
 76  \w     23.00 127.00   1.00    1.00    --   54.00  69.00-165.49  104
 77  \w     24.00 127.00   1.00    1.00    --   54.00  66.00 134.28  103
 78  \w     23.00 128.00   1.00    1.00    --   54.00  70.00-111.27  105
 79  \w     31.00 135.00   1.00    1.00    --   62.00  69.00 138.96  104
 80  \w     34.00 135.00   1.00    1.00    --   62.00  58.00  42.14  101
 81  \w     31.00 136.00   1.00    1.00    --   62.00  71.00 -38.75  105
 82  \w     38.00 139.00   1.00    1.00    --   66.00  57.00 -68.18  101
 83  \w     48.00 151.00   1.00    2.00    --   78.00  68.00  -6.36  103
 84  \w     34.00 112.00   1.00    2.00    --  107.00-125.00  60.00   78
 85  \w     34.00 133.00   1.00    2.00    --  107.00 -45.00 -90.00   99
 86  \w     81.00 178.00   1.00    2.00    --  107.00  45.00  60.00   97
 87  \w     81.00 178.00   1.00    2.00    --  107.00  45.00 -60.00   97
 88  \w     81.00 178.00   1.00    2.00    --  107.00  45.00-120.00   97
 89  \w     81.00 178.00   1.00    2.00    --  107.00  45.00-180.00   97
 90  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00-120.00   83
 91  \w     81.00 178.00   1.00    2.00    --  107.00  45.00  90.00   97
 92  \w     97.00 178.00   1.00    2.00    --  107.00 125.00  30.00   81
 93  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00 150.00   83
;
_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      -0.1394844000
_diffrn_orient_matrix_UB_12      -0.0112210000
_diffrn_orient_matrix_UB_13      -0.0682788000
_diffrn_orient_matrix_UB_21      0.0751595000
_diffrn_orient_matrix_UB_22      0.0118487000
_diffrn_orient_matrix_UB_23      -0.0877063000
_diffrn_orient_matrix_UB_31      0.0189604000
_diffrn_orient_matrix_UB_32      -0.1295535000
_diffrn_orient_matrix_UB_33      -0.0021378000
_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  0.0891
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            76379
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.684
_diffrn_reflns_theta_min         3.189
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.227
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.14149
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.450
_exptl_crystal_description       block
_exptl_crystal_F_000             718
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.285
_refine_diff_density_min         -0.788
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 2790 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).

Flack x: -0.017(9) Shelx 2018
Hooft y: -0.038(2) Olex2

Compound is synthesised from a starting material of known chirality
;
_refine_ls_abs_structure_Flack   -0.017(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     378
_refine_ls_number_reflns         6201
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0373
_refine_ls_R_factor_gt           0.0373
_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^)+(0.0812P)^2^+1.2898P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1064
_refine_ls_wR_factor_ref         0.1065
_reflns_Friedel_coverage         0.828
_reflns_Friedel_fraction_full    0.938
_reflns_Friedel_fraction_max     0.916
_reflns_number_gt                6195
_reflns_number_total             6201
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02411j2.cif
_cod_data_source_block           nk4
_cod_original_cell_volume        1599.776(11)
_cod_original_formula_sum        'C32.50 H35 Cl N2 O2.75 Ru S2'
_cod_database_code               7711023
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 S Cl Ru'
_chemical_oxdiff_usercomment
'C20 H20 N2 O2 S Cl Ru  yellow block 0.06 0.22 0.30  nk227 Wills'
_shelx_estimated_absorpt_t_max   0.706
_shelx_estimated_absorpt_t_min   0.257
_reflns_odcompleteness_completeness 98.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.08
_olex2_refinement_description
;
The asymmetric unit contains the complex and some partially occupied methanol (O36-C37)
and water (O38). 
The minor component solvents were refined isotropically.
The hydrogens were placed at calculated positions on the methanol but no hydrogens were 
located on the partially occupied water O31. The hydrogens were located on the amine and 
refined with restraints.

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 Cl1-H36
 2.45 with sigma of 0.015
3. Others
 Fixed Sof: O36(0.5) H36(0.5) C37(0.5) H37A(0.5) H37B(0.5) H37C(0.5) O38(0.25)
4.a Ternary CH refined with riding coordinates:
 C12(H12), C33(H33), C13(H13)
4.b Secondary CH2 refined with riding coordinates:
 N13(H13A,H13B)
4.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C15(H15), C8(H8), C3(H3), C30(H30), C19(H19), C21(H21), C29(H29),
 C16(H16), C26(H26), C22(H22), C25(H25), C18(H18), C17(H17), C24(H24), C4(H4),
 C23(H23), C6(H6), C5(H5)
4.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C34(H34A,H34B,H34C), C32(H32A,H32B,H32C), C37(H37A,H37B,
 H37C)
4.e Idealised tetrahedral OH refined as rotating group:
 O36(H36)
;
_shelx_res_checksum              23076
_shelx_hkl_checksum              9610
_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 6.393
_oxdiff_exptl_absorpt_empirical_full_min 0.532