<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_1574875
_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 ad
_chemical_formula_moiety         '1(C14 H14 O)'
_chemical_formula_sum            'C14 H14 O'
_chemical_formula_weight         198.25
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-12-27 deposited with the CCDC.	2025-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                91.263(8)
_cell_angle_beta                 91.912(7)
_cell_angle_gamma                91.077(8)
_cell_formula_units_Z            4
_cell_length_a                   5.5996(14)
_cell_length_b                   8.103(2)
_cell_length_c                   23.254(6)
_cell_measurement_reflns_used    4520
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      26.85
_cell_measurement_theta_min      2.51
_cell_volume                     1054.1(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0872
_diffrn_reflns_av_unetI/netI     0.1312
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            21323
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.226
_diffrn_reflns_theta_min         2.515
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6085
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1377 before and 0.0909 after correction.
The Ratio of minimum to maximum transmission is 0.8160.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       plate
_exptl_crystal_F_000             424
_refine_diff_density_max         0.469
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 1623 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     658
_refine_ls_number_reflns         10075
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.1669
_refine_ls_R_factor_gt           0.0977
_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^)+(0.1411P)^2^+0.5029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2414
_refine_ls_wR_factor_ref         0.2970
_reflns_Friedel_coverage         0.958
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                5600
_reflns_number_total             10075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02606g2.cif
_cod_data_source_block           23mayb_0m
_cod_depositor_comments
'Adding full bibliography for 1574873--1574875.cif.'
_cod_database_code               1574875
_shelx_shelxl_version_number     2019/3
_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, All O(H) groups
2. Restrained distances
 C012-C01G \\sim C8-C10
 with sigma of 0.04
 C01I-C01N \\sim C9-C7
 with sigma of 0.04
 C01N-C01O \\sim C7-C01P
 with sigma of 0.02
 C012-C01I \\sim C8-C9
 with sigma of 0.02
 C019-C01G \\sim C0-C10
 with sigma of 0.02
 C01G-C01I \\sim C10-C9
 with sigma of 0.02
 C00R-C01I \\sim C00R-C9
 with sigma of 0.04
 C019-C01I \\sim C0-C9
 with sigma of 0.04
 C01D-C01O \\sim C01D-C01P
 with sigma of 0.04
 C00R-C012 \\sim C00R-C8
 with sigma of 0.02
 C012-C01N \\sim C8-C7
 with sigma of 0.02
 C019-C01D \\sim C0-C01D
 with sigma of 0.02
 C019-C01O \\sim C0-C01P
 with sigma of 0.02
 C00R-C01N \\sim C00R-C7
 with sigma of 0.04
 C012-C01O \\sim C8-C01P
 with sigma of 0.04
 C019-C01N \\sim C0-C7
 with sigma of 0.04
 C01D-C01G \\sim C01D-C10
 with sigma of 0.04
 C01G-C01O \\sim C10-C01P
 with sigma of 0.04
 C01B-C01L \\sim C2-C6
 with sigma of 0.04
 C00V-C01L \\sim C00V-C6
 with sigma of 0.04
 C00S-C01M \\sim C5-C1
 with sigma of 0.04
 C01C-C01M \\sim C01C-C1
 with sigma of 0.04
 C00S-C00V \\sim C5-C00V
 with sigma of 0.02
 C00S-C01H \\sim C5-C4
 with sigma of 0.02
 C01J-C01M \\sim C3-C1
 with sigma of 0.04
 C00S-C01L \\sim C5-C6
 with sigma of 0.02
 C01B-C01C \\sim C2-C01C
 with sigma of 0.02
 C01B-C01J \\sim C2-C3
 with sigma of 0.02
 C01B-C01M \\sim C2-C1
 with sigma of 0.02
 C00V-C01H \\sim C00V-C4
 with sigma of 0.04
 C01B-C01H \\sim C2-C4
 with sigma of 0.04
 C01H-C01J \\sim C4-C3
 with sigma of 0.02
 C01C-C01J \\sim C01C-C3
 with sigma of 0.04
 C01H-C01L \\sim C4-C6
 with sigma of 0.04
 C01L-C01M \\sim C6-C1
 with sigma of 0.02
 C00S-C01J \\sim C5-C3
 with sigma of 0.04
 C01D-C01F \\sim C01D-C11
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C012) \\sim Ueq, Uanis(C00S) \\sim Ueq, Uanis(C5)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C1) \\sim
Ueq, Uanis(C6) \\sim Ueq, Uanis(C012) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C01G) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C01I) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C01N) \\sim Ueq, Uanis(C01O) \\sim Ueq,
Uanis(C01P) \\sim Ueq, Uanis(C0) \\sim Ueq, Uanis(C019) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
Uanis(C11) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C01F) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C8) = Uanis(C012)
Uanis(C00S) = Uanis(C5)
4. Others
 Sof(H01A)=Sof(C0)=Sof(C01P)=Sof(H01P)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(C9)=Sof(H9)=
 Sof(C10)=Sof(H10)=1-FVAR(1)
 Sof(C012)=Sof(C019)=Sof(H01D)=Sof(C01G)=Sof(H01G)=Sof(C01I)=Sof(H01I)=
 Sof(C01N)=Sof(H01N)=Sof(C01O)=Sof(H01O)=FVAR(1)
 Sof(H01J)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4A)=Sof(C5)=
 Sof(C6)=Sof(H6)=1-FVAR(2)
 Sof(C00S)=Sof(C01B)=Sof(H01H)=Sof(C01H)=Sof(H01K)=Sof(C01J)=Sof(H01L)=
 Sof(C01L)=Sof(H01S)=Sof(C01M)=Sof(H01T)=FVAR(2)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=1-FVAR(3)
 Sof(C01F)=Sof(H01B)=Sof(H01C)=Sof(H01E)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C00H(H00H), C00M(H00M), C01C(H01H), C01C(H01J), C01D(H01D), C01D(H01A)
5.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C25(H25), C22(H22), C21(H21), C00E(H00E), C00G(H00G), C00I(H00I),
 C00J(H00J), C00K(H00K), C00L(H00L), C00N(H00N), C00O(H00O), C00P(H00P),
 C00Q(H00Q), C00T(H00T), C00U(H00U), C00W(H00W), C00X(H00X), C00Y(H00Y),
 C00Z(H00Z), C010(H010), C011(H011), C013(H013), C015(H015), C016(H016),
 C017(H017), C018(H018), C01A(H01F), C01G(H01G), C01H(H01K), C01I(H01I),
 C01J(H01L), C01L(H01S), C01M(H01T), C01N(H01N), C01O(H01O), C01P(H01P), C7(H7),
  C9(H9), C10(H10), C1(H1), C3(H3), C4(H4A), C6(H6)
5.c Idealised Me refined as rotating group:
 C014(H01U,H01V,H01W), C01E(H01X,H01Y,H), C01F(H01B,H01C,H01E), C01K(H01M,H01Q,
 H01R), C11(H11A,H11B,H11C)
5.d Idealised tetrahedral OH refined as rotating group:
 O001(H001), O002(H002), O003(H003), O4(H4)
;
_shelx_res_checksum              68891
_olex2_submission_special_instructions 'No special instructions were received'