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_7711022
_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         'C33 H38 Cl N3 O2 Ru S, C H4 O'
_chemical_formula_sum            'C34 H42 Cl N3 O3 Ru S'
_chemical_formula_weight         709.28
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-19
_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                 102.9107(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.40940(6)
_cell_length_b                   14.51707(10)
_cell_length_c                   12.09559(8)
_cell_measurement_reflns_used    30883
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.4860
_cell_measurement_theta_min      3.7030
_cell_volume                     1610.451(19)
_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  (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    -87.00  -6.00   1.00    1.00    --  -41.82 125.00-120.00   81
  2  \w   -116.00 -17.00   1.00    1.00    --  -41.82 -37.00-180.00   99
  3  \w    -87.00  -6.00   1.00    1.00    --  -41.82 125.00  30.00   81
  4  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00 120.00  100
  5  \w    -66.00  33.00   1.00    1.00    --  -41.82  37.00  60.00   99
  6  \w     27.00  98.00   1.00    1.00    --   41.82-125.00-150.00   71
  7  \w     78.00 178.00   1.00    2.00    --  107.00  61.00-120.00  100
  8  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 -90.00  100
  9  \w     81.00 178.00   1.00    2.00    --  107.00  45.00 150.00   97
 10  \w     34.00 112.00   1.00    2.00    --  107.00-125.00-150.00   78
 11  \w     97.00 178.00   1.00    2.00    --  107.00 125.00  90.00   81
 12  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 150.00  100
 13  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00  30.00   83
 14  \w     34.00 112.00   1.00    2.00    --  107.00-125.00  30.00   78
 15  \w    103.00 178.00   1.00    2.00    --  107.00  77.00   0.00   75
 16  \w     78.00 178.00   1.00    2.00    --  107.00  61.00-180.00  100
 17  \w     81.00 178.00   1.00    2.00    --  107.00  45.00-180.00   97
 18  \w     35.00 136.00   1.00    2.00    --  107.00 -61.00  60.00  101
 19  \w     81.00 178.00   1.00    2.00    --  107.00  45.00-150.00   97
 20  \w     31.00 140.00   1.00    2.00    --  107.00 -77.00   0.00  109
 21  \w     34.00 133.00   1.00    2.00    --  107.00 -45.00   0.00   99
 22  \w     34.00 112.00   1.00    2.00    --  107.00-125.00 120.00   78
 23  \w    103.00 178.00   1.00    2.00    --  107.00  77.00 -90.00   75
 24  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00-150.00   83
 25  \w    103.00 178.00   1.00    2.00    --  107.00  77.00 -30.00   75
 26  \w     81.00 178.00   1.00    2.00    --  107.00  45.00   0.00   97
 27  \w     81.00 178.00   1.00    2.00    --  107.00  45.00 120.00   97
 28  \w     35.00 136.00   1.00    2.00    --  107.00 -61.00-150.00  101
 29  \w    103.00 178.00   1.00    2.00    --  107.00  77.00 150.00   75
 30  \w    103.00 178.00   1.00    2.00    --  107.00  77.00  60.00   75
 31  \w     24.00 107.00   1.00    2.00    --  107.00 -94.00 -30.00   83
 32  \w     78.00 178.00   1.00    2.00    --  107.00  61.00-150.00  100
 33  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00 -90.00  100
 34  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00   0.00  100
 35  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00  60.00  100
 36  \w   -114.00 -13.00   1.00    1.00    --  -41.82 -61.00 -56.00  101
 37  \w   -114.00 -14.00   1.00    1.00    --  -41.82 -57.00-180.00  100
 38  \w    -33.00  66.00   1.00    1.00    --   41.82 -37.00 120.00   99
 39  \w     81.00 178.00   1.00    2.00    --  107.00  45.00  60.00   97
 40  \w     78.00 178.00   1.00    2.00    --  107.00  61.00  30.00  100
 41  \w     78.00 178.00   1.00    2.00    --  107.00  61.00  60.00  100
 42  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 -30.00  100
 43  \w     78.00 178.00   1.00    2.00    --  107.00  61.00  81.00  100
 44  \w     81.00 178.00   1.00    2.00    --  107.00  45.00  30.00   97
 45  \w     78.00 178.00   1.00    2.00    --  107.00  61.00   0.00  100
 46  \w     78.00 178.00   1.00    2.00    --  107.00  61.00 -60.00  100
;
_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      -0.1130780000
_diffrn_orient_matrix_UB_12      0.0744168000
_diffrn_orient_matrix_UB_13      0.0103306000
_diffrn_orient_matrix_UB_21      -0.0296568000
_diffrn_orient_matrix_UB_22      0.0165891000
_diffrn_orient_matrix_UB_23      -0.1289320000
_diffrn_orient_matrix_UB_31      -0.1205936000
_diffrn_orient_matrix_UB_32      -0.0738145000
_diffrn_orient_matrix_UB_33      -0.0186477000
_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  0.0384
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            41114
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.615
_diffrn_reflns_theta_min         3.749
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.616
_exptl_absorpt_correction_T_max  0.12964
_exptl_absorpt_correction_T_min  0.03703
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (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    1.463
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_exptl_crystal_size_rad          0.105
_refine_diff_density_max         2.201
_refine_diff_density_min         -0.922
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Flack x determined using 2999 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Flack x: -0.011(10) Shelx2018
Hooft y: -0.028(3)  Olex2
Additionally, the complex is made from a starting material of known handedness
;
_refine_ls_abs_structure_Flack   -0.011(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     396
_refine_ls_number_reflns         6469
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0764P)^2^+1.8032P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1132
_reflns_Friedel_coverage         0.912
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                6432
_reflns_number_total             6469
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02411j2.cif
_cod_data_source_block           nk6
_cod_original_cell_volume        1610.45(2)
_cod_database_code               7711022
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 S Ru'
_chemical_oxdiff_usercomment     'C20 H20 N2 O2 S Ru yellow  block'
_shelx_estimated_absorpt_t_max   0.767
_shelx_estimated_absorpt_t_min   0.507
_reflns_odcompleteness_completeness 99.18
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.08
_olex2_refinement_description
;
The NHs and the OH on the methanol were located in a difference map and refined with distance restraints

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H) groups, All O(H) groups
2. Restrained distances
 N2-H2
 0.9 with sigma of 0.02
 H2-N12
 2.3 with sigma of 0.02
 Cl1-H2
 2.7 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C13(H13), C14(H14), C34(H34)
3.b Secondary CH2 refined with riding coordinates:
 N14(H14A,H14B), C3(H3A,H3B), C5(H5A,H5B), C4(H4A,H4B)
3.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C26(H26), C22(H22), C31(H31), C27(H27), C20(H20), C28(H28), C7(H7),
 C23(H23), C16(H16), C25(H25), C9(H9), C24(H24), C19(H19), C8(H8), C17(H17),
 C18(H18)
3.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C35(H35A,H35B,H35C), C38(H38A,H38B,H38C), C33(H33A,H33B,
 H33C)
3.e Idealised tetrahedral OH refined as rotating group:
 O37(H37)
;
_shelx_res_checksum              48257
_shelx_hkl_checksum              66703
_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 2.496
_oxdiff_exptl_absorpt_empirical_full_min 0.746