1,2-Diaminocyclohexane-derived chiral tetradentate ligands for Mn(i)-catalyzed asymmetric hydrogenation of ketones
Su, Yi; Zhu, Dongzhi; Ma, Zhifeng; Wang, Yizhou; Wang, Zechen; Wang, Zheng; Ma, Yanping; Sun, Wen-Hua; RSC Advances 15 (2025) 23097–23102; doi:10.1039/D5RA03062E

data_7250660
_publ_section_title
;
 1,2-Diaminocyclohexane-derived chiral tetradentate ligands for
 Mn(i)-catalyzed asymmetric hydrogenation of ketones
;
_journal_issue                   28
_journal_name_full               'RSC Advances'
_journal_page_first              23097
_journal_page_last               23102
_journal_paper_doi               10.1039/D5RA03062E
_journal_volume                  15
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C46 H40 Mn N2 O2 P2'
_chemical_formula_sum            'C46 H40 Mn N2 O2 P2'
_chemical_formula_weight         769.68
_chemical_properties_physical    Oxygen-sensitive,Light-sensitive
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-14
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-12-06 deposited with the CCDC.	2025-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   17.5937(3)
_cell_length_b                   17.5937(3)
_cell_length_c                   29.4019(7)
_cell_measurement_reflns_used    14196
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      74.0640
_cell_measurement_theta_min      3.2520
_cell_volume                     7881.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_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)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.961
_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     34.00 111.00   0.50    1.00    --   47.20  56.00 145.00  154
  2  \w     90.00 178.00   0.50    9.00    --  103.25  32.00 130.00  176
  3  \w    128.00 155.00   0.50    9.00    --  103.25  23.00  81.00   54
  4  \w   -114.00 -86.00   0.50    1.00    --  -47.20-125.00 150.00   56
  5  \w    -18.00  18.00   0.50    1.00    --  -47.20  19.00-150.00   72
  6  \w   -119.00 -82.00   0.50    1.00    --  -47.20-125.00-180.00   74
  7  \w     42.00  74.00   0.50    9.00    --  103.25 -61.00 120.00   64
  8  \w     31.00  56.00   0.50    9.00    --  103.25 -61.00 -60.00   50
  9  \w     46.00  75.00   0.50    9.00    --  103.25 -61.00  90.00   58
 10  \w    -65.00 -35.00   0.50    9.00    -- -104.50  61.00 120.00   60
 11  \w   -173.00 -92.00   0.50    9.00    -- -104.50 -30.00 -60.00  162
 12  \w    -67.00 -38.00   0.50    9.00    -- -104.50  61.00  60.00   58
 13  \w    -62.00 -33.00   0.50    9.00    -- -104.50  61.00  30.00   58
 14  \w   -147.00 -85.00   0.50    9.00    -- -104.50 -94.00  90.00  124
 15  \w    -68.00 -41.00   0.50    9.00    -- -104.50  61.00 -30.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0079135000
_diffrn_orient_matrix_UB_12      0.0308853000
_diffrn_orient_matrix_UB_13      -0.0497080000
_diffrn_orient_matrix_UB_21      0.0861653000
_diffrn_orient_matrix_UB_22      -0.0019646000
_diffrn_orient_matrix_UB_23      -0.0050353000
_diffrn_orient_matrix_UB_31      -0.0522619000
_diffrn_orient_matrix_UB_32      -0.0962609000
_diffrn_orient_matrix_UB_33      -0.0157878000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0627
_diffrn_reflns_av_unetI/netI     0.0589
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            34069
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.877
_diffrn_reflns_theta_min         2.900
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.853
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36964
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    0.973
_exptl_crystal_description       block
_exptl_crystal_F_000             2406
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.653
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.102(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         10455
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0796
_refine_ls_R_factor_gt           0.0674
_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^)+(0.1019P)^2^+7.3199P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1839
_refine_ls_wR_factor_ref         0.1940
_reflns_Friedel_coverage         0.763
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.893
_reflns_number_gt                8698
_reflns_number_total             10455
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra03062e2.cif
_cod_data_source_block           tx12157_auto
_cod_database_code               7250660
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O P Br Mn'
_shelx_estimated_absorpt_t_max   0.804
_shelx_estimated_absorpt_t_min   0.674
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.898(9)
 0.102(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1) \\sim
Ueq, Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C41) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C22(H22), C27(H27)
4.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C26(H26A,H26B), C24(H24A,H24B), C25(H25A,H25B)
4.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C19(H19), C28(H28), C42(H42), C43(H43), C44(H44), C45(H45),
 C46(H46), C33(H33), C31(H31), C30(H30), C14(H14), C17(H17), C36(H36), C16(H16),
  C15(H15), C40(H40), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C39(H39),
 C37(H37), C38(H38), C4(H4), C5(H5), C6(H6), C2(H2), C3(H3)
4.d Fitted hexagon refined as free rotating group:
 C41(C42,C43,C44,C45,C46), C8(C9,C10,C11,C12,C7), C4(C5,C6,C1,C2,C3)
;
_shelx_res_checksum              80968
_shelx_fab_checksum              88862
_platon_squeeze_special_details
;
A solvent mask was calculated and 1082 electrons were 
found in a volume of 2788\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.45[CH2Cl2] per Formula Unit 
which account for 1096 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_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 2.303
_oxdiff_exptl_absorpt_empirical_full_min 0.294