<i>A priori</i> Design of [Mn(i)-Cinchona] catalyst for Asymmetric Hydrogenation of Ketones and β-Keto carbonyl Derivatives.
Paira, Soumen; Jain, Nupur; Adhikari, Debarsee; Sunoj, Raghavan B.; Sundararaju, Basker; Chemical science 16 (2025) 13826–13837; doi:10.1039/d5sc02606g

data_1574873
_publ_section_title
;
 <i>A priori</i> Design of [Mn(i)-Cinchona] catalyst for Asymmetric
 Hydrogenation of Ketones and &#x3b2;-Keto carbonyl Derivatives.
;
_journal_issue                   30
_journal_name_full               'Chemical science'
_journal_page_first              13826
_journal_page_last               13837
_journal_paper_doi               10.1039/d5sc02606g
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration co
_chemical_formula_moiety         '2(C29 H26 Br2 Mn N4 O5)'
_chemical_formula_sum            'C58 H52 Br4 Mn2 N8 O10'
_chemical_formula_weight         1450.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           3
_space_group_name_Hall           'P 2y'
_space_group_name_H-M_alt        'P 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-03-10
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-12-27 deposited with the CCDC.	2025-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.215(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.471(5)
_cell_length_b                   8.507(3)
_cell_length_c                   23.459(7)
_cell_measurement_reflns_used    6593
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      27.80
_cell_measurement_theta_min      2.55
_cell_volume                     2887.9(17)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0655
_diffrn_reflns_av_unetI/netI     0.1281
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            15719
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        24.405
_diffrn_reflns_theta_max         24.405
_diffrn_reflns_theta_min         2.231
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.270
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.668
_exptl_crystal_description       block
_exptl_crystal_F_000             1452
_exptl_crystal_size_max          0.56
_exptl_crystal_size_mid          0.42
_exptl_crystal_size_min          0.22
_refine_diff_density_max         1.190
_refine_diff_density_min         -1.147
_refine_diff_density_rms         0.155
_refine_ls_abs_structure_details
;
 Flack x determined using 2382 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.066(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     735
_refine_ls_number_reflns         9457
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.1088
_refine_ls_R_factor_gt           0.0809
_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^)+(0.0521P)^2^+32.2138P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1865
_refine_ls_wR_factor_ref         0.2002
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                7285
_reflns_number_total             9457
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02606g2.cif
_cod_data_source_block           mnjan
_cod_depositor_comments
'Adding full bibliography for 1574873--1574875.cif.'
_cod_original_cell_volume        2887.9(15)
_cod_database_code               1574873
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.533
_shelx_estimated_absorpt_t_min   0.262
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(N3) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C10) \\sim
Ueq, Uanis(C18) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C106) \\sim Ueq,
Uanis(N102) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C126) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
Uanis(C121) \\sim Ueq, Uanis(N104) \\sim Ueq, Uanis(C115) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
Uanis(C102) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C129) = Uanis(C128)
3.a Ternary CH refined with riding coordinates:
 C101(H101), C121(H121), C1(H1), C18(H18), C20(H20), C124(H124), C123(H123),
 C24(H24)
3.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C125(H12A,H12B), C127(H12C,H12D), C22(H22A,H22B), C126(H12E,
 H12F), C23(H23A,H23B), C122(H12G,H12H), C19(H19A,H19B)
3.c Aromatic/amide H refined with riding coordinates:
 C104(H104), C110(H110), C111(H111), C9(H9), C10(H10), C3(H3), C4(H4),
 C103(H103), C17(H17), C114(H114), C116(H116), C107(H107), C7(H7), C115(H115),
 C25(H25), C128(H128), C16(H16), C15(H15)
3.d X=CH2 refined with riding coordinates:
 C129(H12I,H12J), C26(H26A,H26B)
3.e Idealised Me refined as rotating group:
 C109(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              22641
_olex2_submission_special_instructions 'No special instructions were received'