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_7711021
_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         'C28 H31 Cl N2 O2 Ru S2, 0.5(O)'
_chemical_formula_sum            'C28 H31 Cl N2 O2.5 Ru S2'
_chemical_formula_weight         636.19
_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             2021-10-21
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.94996(8)
_cell_length_b                   12.97812(10)
_cell_length_c                   19.21709(12)
_cell_measurement_reflns_used    60216
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.4970
_cell_measurement_theta_min      3.7220
_cell_volume                     2980.34(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.116a (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  (Sheldrick, 2015)'
_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   -114.00 -14.00   1.00    1.43    --  -41.82 -57.00-180.00  100
  2  \w    -87.00  -6.00   1.00    1.43    --  -41.82 125.00  90.00   81
  3  \w      6.00  83.00   1.00    1.43    --   41.82 -99.00  60.00   77
  4  \w      8.00  34.00   1.00    1.43    --   41.82  83.00   8.57   26
  5  \w    -33.00  66.00   1.00    1.43    --   41.82 -37.00 -90.00   99
  6  \w      8.00  34.00   1.00    1.43    --   41.82  83.00-163.07   26
  7  \w    -33.00  66.00   1.00    1.43    --   41.82 -37.00   0.00   99
  8  \w      7.00  33.00   1.00    1.43    --   41.82  84.00 -97.52   26
  9  \w     10.00  36.00   1.00    1.43    --   41.82  75.00 -55.91   26
 10  \w     81.00 178.00   1.00    5.70    --  107.00  45.00 150.00   97
 11  \w     97.00 178.00   1.00    5.70    --  107.00 125.00 120.00   81
 12  \w     97.00 178.00   1.00    5.70    --  107.00 125.00 -60.00   81
 13  \w     24.00 107.00   1.00    5.70    --  107.00 -94.00   0.00   83
 14  \w     77.00 178.00   1.00    5.70    --  107.00  64.00 -37.85  101
 15  \w     35.00 136.00   1.00    5.70    --  107.00 -61.00-180.00  101
 16  \w     78.00 178.00   1.00    5.70    --  107.00  61.00 -60.00  100
 17  \w     97.00 178.00   1.00    5.70    --  107.00 125.00  30.00   81
 18  \w     81.00 178.00   1.00    5.70    --  107.00  45.00  90.00   97
 19  \w     77.00 178.00   1.00    5.70    --  107.00  66.00 -15.63  101
 20  \w     35.00 136.00   1.00    5.70    --  107.00 -61.00-120.00  101
 21  \w     78.00 178.00   1.00    5.70    --  107.00  61.00-180.00  100
 22  \w     79.00 178.00   1.00    5.70    --  107.00  56.00 123.46   99
 23  \w     97.00 178.00   1.00    5.70    --  107.00 125.00 -30.00   81
 24  \w     24.00 107.00   1.00    5.70    --  107.00 -94.00 -90.00   83
 25  \w     24.00 107.00   1.00    5.70    --  107.00 -94.00 120.00   83
 26  \w     34.00 112.00   1.00    5.70    --  107.00-125.00-120.00   78
 27  \w     34.00 112.00   1.00    5.70    --  107.00-125.00  60.00   78
 28  \w     76.00 178.00   1.00    5.70    --  107.00  70.00 -39.14  102
 29  \w     79.00 178.00   1.00    5.70    --  107.00  58.00  -2.55   99
 30  \w     34.00 112.00   1.00    5.70    --  107.00-125.00   0.00   78
 31  \w     34.00 133.00   1.00    5.70    --  107.00 -45.00-180.00   99
 32  \w     97.00 178.00   1.00    5.70    --  107.00 125.00  60.00   81
 33  \w     34.00 112.00   1.00    5.70    --  107.00-125.00 -60.00   78
 34  \w     24.00 107.00   1.00    5.70    --  107.00 -94.00  90.00   83
 35  \w     34.00 133.00   1.00    5.70    --  107.00 -45.00-120.00   99
 36  \w     82.00 178.00   1.00    5.70    --  107.00  39.00 -99.53   96
 37  \w     81.00 178.00   1.00    5.70    --  107.00  45.00-180.00   97
 38  \w    103.00 178.00   1.00    5.70    --  107.00  77.00  90.00   75
 39  \w     34.00 112.00   1.00    5.70    --  107.00-125.00  30.00   78
 40  \w    103.00 178.00   1.00    5.70    --  107.00  77.00-180.00   75
 41  \w     32.00 109.00   1.00    5.70    --  107.00-115.00  -2.74   77
 42  \w    103.00 178.00   1.00    5.70    --  107.00  77.00 -90.00   75
 43  \w     97.00 178.00   1.00    5.70    --  107.00 125.00-150.00   81
 44  \w     24.00 107.00   1.00    5.70    --  107.00 -94.00-180.00   83
 45  \w     24.00 107.00   1.00    5.70    --  107.00 -94.00 150.00   83
 46  \w     78.00 178.00   1.00    5.70    --  107.00  61.00 -90.00  100
 47  \w     78.00 178.00   1.00    5.70    --  107.00  61.00  90.00  100
 48  \w     78.00 178.00   1.00    5.70    --  107.00  59.00 173.53  100
 49  \w     35.00 136.00   1.00    5.70    --  107.00 -61.00 -60.00  101
 50  \w     31.00 140.00   1.00    5.70    --  107.00 -77.00 -90.00  109
 51  \w     26.00 107.00   1.00    5.70    --  107.00 -99.00 151.38   81
 52  \w   -114.00 -14.00   1.00    1.43    --  -41.82 -57.00 120.00  100
 53  \w   -116.00 -17.00   1.00    1.43    --  -41.82 -37.00-150.00   99
 54  \w    -87.00  -6.00   1.00    1.43    --  -41.82 125.00-180.00   81
 55  \w   -114.00 -14.00   1.00    1.43    --  -41.82 -57.00  60.00  100
 56  \w   -116.00 -17.00   1.00    1.43    --  -41.82 -37.00 -60.00   99
 57  \w    -66.00  33.00   1.00    1.43    --  -41.82  37.00 -90.00   99
 58  \w      7.00  33.00   1.00    1.43    --   41.82  84.00  34.34   26
 59  \w     10.00  36.00   1.00    1.43    --   41.82  75.00 166.40   26
 60  \w      7.00  33.00   1.00    1.43    --   41.82  84.00 -33.04   26
 61  \w      9.00  42.00   1.00    1.43    --   41.82  77.00  87.71   33
 62  \w     78.00 135.00   1.00    5.70    --  107.00  61.00  30.00   57
;
_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      -0.0465571000
_diffrn_orient_matrix_UB_12      -0.0496758000
_diffrn_orient_matrix_UB_13      -0.0668057000
_diffrn_orient_matrix_UB_21      -0.0630592000
_diffrn_orient_matrix_UB_22      0.1004211000
_diffrn_orient_matrix_UB_23      -0.0170566000
_diffrn_orient_matrix_UB_31      0.1023149000
_diffrn_orient_matrix_UB_32      0.0392617000
_diffrn_orient_matrix_UB_33      -0.0409182000
_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  0.0515
_diffrn_reflns_av_unetI/netI     0.0176
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            91422
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.599
_diffrn_reflns_theta_min         4.110
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.620
_exptl_absorpt_correction_T_max  0.45054
_exptl_absorpt_correction_T_min  0.39570
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.116a (Rigaku Oxford Diffraction, 2021)
Spherical absorption correction
using equivalent radius and absorption coefficient.
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    1.418
_exptl_crystal_description       block
_exptl_crystal_F_000             1304
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_exptl_crystal_size_rad          0.083
_refine_diff_density_max         0.803
_refine_diff_density_min         -0.892
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Flack x determined using 2574 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Flack x: -0.018(3)  Shelx 2018
Hooft y: -0.027(2)  Olex2

synthesis from a known chiral diamine
;
_refine_ls_abs_structure_Flack   -0.018(3)
_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     336
_refine_ls_number_reflns         5988
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0293
_refine_ls_R_factor_gt           0.0291
_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^)+(0.0498P)^2^+1.6809P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0789
_refine_ls_wR_factor_ref         0.0791
_reflns_Friedel_coverage         0.779
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                5938
_reflns_number_total             5988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02411j2.cif
_cod_data_source_block           nk3
_cod_original_formula_sum        'C28 H31 Cl N2 O2.50 Ru S2'
_cod_database_code               7711021
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 S2 Ru'
_chemical_oxdiff_usercomment
'C20 H20 N2 O2 S Ru   yellow block 0.06 0.12  0.2   nk218   Wills'
_shelx_estimated_absorpt_t_max   0.692
_shelx_estimated_absorpt_t_min   0.351
_reflns_odcompleteness_completeness 98.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.08
_olex2_refinement_description
;
The NHs on the amine were located in a difference map and refined with restrains.
There a was some electron density between molecules and this was modelled as partially 
occupied molecules of water. O100 and O101 were both refined at 25% occupancy.  
No hydrogens were located for these partially occupied solvents

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
2. Others
 Fixed Sof: O101(0.25) O100(0.25)
3.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C29(H29)
3.b Secondary CH2 refined with riding coordinates:
 N9(H9A,H9B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25),
  C26(H26)
3.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              1195
_shelx_hkl_checksum              23097
_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 2.387
_oxdiff_exptl_absorpt_empirical_full_min 0.620