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_7711025
_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         'C29 H34 Cl N3 O2 Ru S2, O'
_chemical_formula_sum            'C29 H34 Cl N3 O3 Ru S2'
_chemical_formula_weight         673.23
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-15
_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                120
_cell_formula_units_Z            6
_cell_length_a                   16.90780(10)
_cell_length_b                   16.90780(10)
_cell_length_c                   19.27870(10)
_cell_measurement_reflns_used    72679
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.5640
_cell_measurement_theta_min      2.9580
_cell_volume                     4772.90(5)
_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 0.999
_diffrn_measured_fraction_theta_max 0.997
_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    4.00    --  -41.82 125.00 120.00   81
  2  \w   -114.00 -14.00   1.00    4.00    --  -41.82 -57.00 120.00  100
  3  \w    -87.00  -6.00   1.00    4.00    --  -41.82 125.00   0.00   81
  4  \w    -87.00  -6.00   1.00    4.00    --  -41.82 125.00  60.00   81
  5  \w    -33.00  66.00   1.00    4.00    --   41.82 -37.00-150.00   99
  6  \w    -21.00  74.00   1.00    4.00    --   41.82 -77.00  30.00   95
  7  \w     97.00 178.00   1.00   16.00    --  107.00 125.00  90.00   81
  8  \w    103.00 178.00   1.00   16.00    --  107.00  77.00 -30.00   75
  9  \w     78.00 178.00   1.00   16.00    --  107.00  61.00 -30.00  100
 10  \w    103.00 178.00   1.00   16.00    --  107.00  77.00-120.00   75
 11  \w     97.00 178.00   1.00   16.00    --  107.00 125.00   0.00   81
 12  \w     97.00 178.00   1.00   16.00    --  107.00 125.00 -30.00   81
 13  \w     81.00 178.00   1.00   16.00    --  107.00  45.00  30.00   97
 14  \w     81.00 178.00   1.00   16.00    --  107.00  45.00  60.00   97
 15  \w     97.00 178.00   1.00   16.00    --  107.00 125.00 120.00   81
 16  \w     97.00 178.00   1.00   16.00    --  107.00 125.00 -90.00   81
 17  \w     35.00 136.00   1.00   16.00    --  107.00 -61.00   0.00  101
 18  \w     97.00 178.00   1.00   16.00    --  107.00 125.00-120.00   81
 19  \w    103.00 178.00   1.00   16.00    --  107.00  77.00-180.00   75
 20  \w    103.00 178.00   1.00   16.00    --  107.00  77.00 120.00   75
 21  \w     81.00 178.00   1.00   16.00    --  107.00  45.00  90.00   97
 22  \w     78.00 178.00   1.00   16.00    --  107.00  61.00 150.00  100
 23  \w     24.00 107.00   1.00   16.00    --  107.00 -94.00 120.00   83
 24  \w     81.00 178.00   1.00   16.00    --  107.00  45.00-120.00   97
 25  \w     97.00 178.00   1.00   16.00    --  107.00 125.00 -60.00   81
 26  \w     81.00 178.00   1.00   16.00    --  107.00  45.00   0.00   97
 27  \w     34.00 133.00   1.00   16.00    --  107.00 -45.00-150.00   99
 28  \w     24.00 107.00   1.00   16.00    --  107.00 -94.00  30.00   83
 29  \w   -114.00 -14.00   1.00    4.00    --  -41.82 -57.00-150.00  100
 30  \w   -114.00 -14.00   1.00    4.00    --  -41.82 -57.00  30.00  100
 31  \w   -114.00 -14.00   1.00    4.00    --  -41.82 -57.00 -60.00  100
 32  \w   -114.00 -14.00   1.00    4.00    --  -41.82 -57.00   0.00  100
 33  \w   -114.00 -14.00   1.00    4.00    --  -41.82 -57.00 -90.00  100
 34  \w   -114.00 -14.00   1.00    4.00    --  -41.82 -57.00 150.00  100
 35  \w    -70.00  31.00   1.00    4.00    --  -41.82  57.00   0.00  101
 36  \w     78.00 127.00   1.00   16.00    --  107.00  61.00 120.00   49
 37  \w     78.00 178.00   1.00   16.00    --  107.00  61.00-180.00  100
 38  \w     78.00 178.00   1.00   16.00    --  107.00  61.00 -90.00  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      -0.0704208000
_diffrn_orient_matrix_UB_12      0.0280935000
_diffrn_orient_matrix_UB_13      0.0210372000
_diffrn_orient_matrix_UB_21      0.0031343000
_diffrn_orient_matrix_UB_22      -0.0284210000
_diffrn_orient_matrix_UB_23      0.0754422000
_diffrn_orient_matrix_UB_31      0.0780648000
_diffrn_orient_matrix_UB_32      0.0973013000
_diffrn_orient_matrix_UB_33      0.0159790000
_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  0.0416
_diffrn_reflns_av_unetI/netI     0.0134
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            96080
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.674
_diffrn_reflns_theta_min         3.791
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.253
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16968
_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    1.405
_exptl_crystal_description       block
_exptl_crystal_F_000             2076
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.010
_refine_diff_density_min         -0.745
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.

Flack x: -0.027(11)  Shelx 2018
Hooft y: -0.0278(16) Olex2

Additionally, the complex is synthesised from a stating material of known configuration
;
_refine_ls_abs_structure_Flack   -0.027(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     356
_refine_ls_number_reflns         6407
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0424
_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^)+(0.0910P)^2^+2.0772P] 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         0.939
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                6357
_reflns_number_total             6407
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02411j2.cif
_cod_data_source_block           nk5
_cod_original_cell_volume        4772.90(6)
_cod_database_code               7711025
_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 0.1 0.16  nk226 Wills'
_shelx_estimated_absorpt_t_max   0.705
_shelx_estimated_absorpt_t_min   0.434
_reflns_odcompleteness_completeness 99.14
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.08
_olex2_refinement_description
;
The water was modelled as disordered over two closely related positions. 
The occupancy of the two positions was fixed at 50% each. 
No hydrogens were located on these disordered solvents and they were refined isotropically.
The hydrogens were located on the amine but refined 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
2. Others
 Fixed Sof: O33(0.5) O34(0.5)
3.a Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C30(H30)
3.b Secondary CH2 refined with riding coordinates:
 N10(H10A,H10B)
3.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27)
3.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C)
;
_shelx_res_checksum              94137
_shelx_hkl_checksum              78746
_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 3.834
_oxdiff_exptl_absorpt_empirical_full_min 0.653