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_7711024
_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 O3 Ru S'
_chemical_formula_sum            'C28 H31 Cl N2 O3 Ru S'
_chemical_formula_weight         612.13
_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             2022-02-05
_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                   12.03830(10)
_cell_length_b                   12.88610(10)
_cell_length_c                   18.52100(10)
_cell_measurement_reflns_used    40608
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.4900
_cell_measurement_theta_min      4.1290
_cell_volume                     2873.10(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 1.3-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 1.000
_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    1.50    --  -41.82 125.00 150.00   81
  2  \w    -74.00  34.00   1.00    1.50    --  -41.82  77.00 -60.00  108
  3  \w    -66.00  33.00   1.00    1.50    --  -41.82  37.00 -90.00   99
  4  \w     30.00 101.00   1.00    1.50    --   41.82-131.00  43.00   71
  5  \w     35.00 136.00   1.00    6.00    --  107.00 -61.00 -30.00  101
  6  \w     34.00 133.00   1.00    6.00    --  107.00 -45.00 -30.00   99
  7  \w     97.00 178.00   1.00    6.00    --  107.00 125.00  90.00   81
  8  \w     34.00 112.00   1.00    6.00    --  107.00-125.00-120.00   78
  9  \w     34.00 112.00   1.00    6.00    --  107.00-125.00   0.00   78
 10  \w     34.00 112.00   1.00    6.00    --  107.00-125.00  30.00   78
 11  \w     78.00 178.00   1.00    6.00    --  107.00  61.00 120.00  100
 12  \w    103.00 178.00   1.00    6.00    --  107.00  77.00-120.00   75
 13  \w     81.00 178.00   1.00    6.00    --  107.00  45.00 -30.00   97
 14  \w     31.00 140.00   1.00    6.00    --  107.00 -77.00 -30.00  109
 15  \w     81.00 178.00   1.00    6.00    --  107.00  45.00-120.00   97
 16  \w     34.00 112.00   1.00    6.00    --  107.00-125.00 -60.00   78
 17  \w     34.00 133.00   1.00    6.00    --  107.00 -45.00-180.00   99
 18  \w     35.00 136.00   1.00    6.00    --  107.00 -61.00  90.00  101
 19  \w     31.00 140.00   1.00    6.00    --  107.00 -77.00-150.00  109
 20  \w     31.00 140.00   1.00    6.00    --  107.00 -77.00 -90.00  109
 21  \w    103.00 178.00   1.00    6.00    --  107.00  77.00-150.00   75
 22  \w   -114.00 -14.00   1.00    1.50    --  -41.82 -57.00 -30.00  100
 23  \w    -70.00  31.00   1.00    1.50    --  -41.82  57.00 120.00  101
 24  \w   -114.00 -14.00   1.00    1.50    --  -41.82 -57.00-150.00  100
 25  \w   -114.00 -14.00   1.00    1.50    --  -41.82 -57.00  90.00  100
 26  \w     78.00 178.00   1.00    6.00    --  107.00  61.00 -60.00  100
 27  \w     78.00 178.00   1.00    6.00    --  107.00  61.00 -90.00  100
 28  \w     81.00 178.00   1.00    6.00    --  107.00  45.00-180.00   97
 29  \w     34.00 112.00   1.00    6.00    --  107.00-125.00 150.00   78
 30  \w     81.00 178.00   1.00    6.00    --  107.00  45.00  60.00   97
 31  \w     81.00 178.00   1.00    6.00    --  107.00  45.00-150.00   97
 32  \w     78.00 178.00   1.00    6.00    --  107.00  61.00  90.00  100
 33  \w     78.00 178.00   1.00    6.00    --  107.00  61.00  30.00  100
 34  \w     78.00 178.00   1.00    6.00    --  107.00  61.00 150.00  100
 35  \w     78.00 135.00   1.00    6.00    --  107.00  61.00  60.00   57
 36  \w     78.00 178.00   1.00    6.00    --  107.00  61.00   0.00  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      0.1153383000
_diffrn_orient_matrix_UB_12      0.0464441000
_diffrn_orient_matrix_UB_13      -0.0159593000
_diffrn_orient_matrix_UB_21      -0.0239644000
_diffrn_orient_matrix_UB_22      -0.0059581000
_diffrn_orient_matrix_UB_23      -0.0816165000
_diffrn_orient_matrix_UB_31      -0.0500167000
_diffrn_orient_matrix_UB_32      0.1099694000
_diffrn_orient_matrix_UB_33      0.0022990000
_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  0.0390
_diffrn_reflns_av_unetI/netI     0.0183
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            58813
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.581
_diffrn_reflns_theta_min         4.179
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.196
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (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    1.415
_exptl_crystal_description       block
_exptl_crystal_F_000             1256
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.664
_refine_diff_density_min         -0.515
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 2457 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Flack x: -0.016(2)
Hooft y: -0.026(2)
;
_refine_ls_abs_structure_Flack   -0.016(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         5770
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0202
_refine_ls_R_factor_gt           0.0198
_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^)+(0.0325P)^2^+0.8742P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0514
_refine_ls_wR_factor_ref         0.0517
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5687
_reflns_number_total             5770
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02411j2.cif
_cod_data_source_block           nk7
_cod_database_code               7711024
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 S Ru'
_chemical_oxdiff_usercomment
'C20 H20 N2 O2 S Ru   0.004 0.10 0.16 yellow block ajk287   Wills'
_shelx_estimated_absorpt_t_max   0.790
_shelx_estimated_absorpt_t_min   0.437
_reflns_odcompleteness_completeness 98.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.08
_olex2_refinement_description
;
The NHs on N9 were located in a difference map and placed at calculated 
positions for the refinement.

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.a Ternary CH refined with riding coordinates:
 C9(H9), C8(H8), C29(H29)
2.b Secondary CH2 refined with riding coordinates:
 N9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C23(H23), C17(H17), C26(H26), C22(H22), C11(H11), C21(H21),
 C18(H18), C12(H12), C13(H13), C20(H20), C19(H19), C4(H4), C15(H15), C3(H3),
 C2(H2), C14(H14)
2.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              25159
_shelx_hkl_checksum              74112
_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 1.692
_oxdiff_exptl_absorpt_empirical_full_min 0.816