Robust and efficient transfer hydrogenation of carbonyl compounds catalyzed by NN-Mn(I) complexes
Wang, Zheng; Ma, Ning; Lu, Xiaochi; Liu, Ming; Liu, Tian; Liu, Qingbin; Solan, Gregory; Sun, Wen Hua; Dalton Transactions  (2023) –; doi:10.1039/D3DT02022C

data_7713441
_publ_section_title
;
 Robust and efficient transfer hydrogenation of carbonyl compounds
 catalyzed by NN-Mn(I) complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02022C
_journal_year                    2023
_chemical_formula_moiety         '2(Br), 2(C12 H19 N2)'
_chemical_formula_sum            'C24 H38 Br2 N4'
_chemical_formula_weight         542.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-03-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-03-13 deposited with the CCDC.	2023-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.023(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.4207(4)
_cell_length_b                   7.60980(10)
_cell_length_c                   19.8264(4)
_cell_measurement_reflns_used    8875
_cell_measurement_temperature    169.98(10)
_cell_measurement_theta_max      73.2110
_cell_measurement_theta_min      3.5170
_cell_volume                     2618.25(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.98(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 0.968
_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    -28.00  20.00   0.50    0.20    --  -47.57  44.00 121.00   96
  2  \w   -111.00 -37.00   0.50    0.20    --  -47.57 -44.00 -28.00  148
  3  \w     38.00 100.00   0.50    0.20    --   47.57  44.00 121.00  124
  4  \w    -11.00  34.00   0.50    0.20    --   47.57 -44.00 -28.00   90
  5  \w   -164.00 -97.00   0.50    1.00    --  -99.00 -44.00 -28.00  134
  6  \w     91.00 130.00   0.50    1.00    --  103.25  44.00 121.00   78
  7  \w    -20.00  26.00   0.50    0.20    --  -47.57  19.00 -90.00   92
  8  \w   -112.00 -77.00   0.50    0.20    --  -47.57-125.00  60.00   70
  9  \w   -130.00 -85.00   0.50    1.00    --  -99.00 -94.00  90.00   90
 10  \w    -64.00 -27.00   0.50    1.00    --  -99.00  61.00 -60.00   74
 11  \w    -63.00 -27.00   0.50    1.00    --  -99.00  61.00-150.00   72
 12  \w    -67.00 -27.00   0.50    1.00    --  -99.00  61.00 -90.00   80
 13  \w    -55.00 -26.00   0.50    1.00    --  -99.00  61.00  60.00   58
 14  \w   -163.00-133.00   0.50    1.00    --  -99.00 -94.00  90.00   60
 15  \w    -61.00 -26.00   0.50    1.00    --  -99.00  61.00 150.00   70
 16  \w    -68.00 -27.00   0.50    1.00    --  -99.00  61.00 -30.00   82
 17  \w    -66.00 -32.00   0.50    1.00    --  -99.00  61.00 120.00   68
 18  \w     67.00 111.00   0.50    1.00    --  103.25-125.00-120.00   88
 19  \w     32.00  74.00   0.50    1.00    --  103.25 -61.00  90.00   84
 20  \w     32.00  64.00   0.50    1.00    --  103.25 -61.00 -60.00   64
 21  \w     42.00  73.00   0.50    1.00    --  103.25 -61.00   0.00   62
 22  \w    140.00 168.00   0.50    1.00    --  103.25  15.00  60.00   56
 23  \w     31.00  71.00   0.50    1.00    --  103.25 -61.00 -30.00   80
 24  \w    111.00 167.00   0.50    1.00    --  103.25  30.00-180.00  112
 25  \w     89.00 165.00   0.50    1.00    --  103.25  61.00-150.00  152
 26  \w     96.00 122.00   0.50    1.00    --  103.25  15.00  60.00   52
 27  \w     70.00 108.00   0.50    1.00    --  103.25 -77.00  90.00   76
 28  \w     31.00  59.00   0.50    1.00    --  103.25 -77.00  90.00   56
;
_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      -0.0167236000
_diffrn_orient_matrix_UB_12      -0.0775765000
_diffrn_orient_matrix_UB_13      0.0690201000
_diffrn_orient_matrix_UB_21      0.0811814000
_diffrn_orient_matrix_UB_22      -0.0817615000
_diffrn_orient_matrix_UB_23      0.0078355000
_diffrn_orient_matrix_UB_31      0.0318118000
_diffrn_orient_matrix_UB_32      0.1681519000
_diffrn_orient_matrix_UB_33      0.0354930000
_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  0.0422
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            21032
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.285
_diffrn_reflns_theta_min         3.240
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.045
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64912
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.006
_refine_diff_density_min         -0.823
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     295
_refine_ls_number_reflns         5239
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0511
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0528P)^2^+5.6904P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1248
_refine_ls_wR_factor_ref         0.1299
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4484
_reflns_number_total             5239
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02022c2.cif
_cod_data_source_block           L1
_cod_database_code               7713441
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_usercomment     'C H N O Mn Br'
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.498
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 Br1A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(Br1A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
4. Others
 Sof(Br1A)=1-FVAR(1)
 Sof(Br1)=FVAR(1)
 Sof(Br2A)=1-FVAR(2)
 Sof(Br2)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C20(H20), C10(H10), C22(H22)
5.b Secondary CH2 refined with riding coordinates:
 N2(H2a,H2b), N4(H4a,H4b), C7(H7a,H7b), C6(H6a,H6b), C5(H5a,H5b), C19(H19a,
 H19b), C18(H18a,H18b), C17(H17a,H17b)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C15(H15), C1(H1), C14(H14), C13(H13)
5.d Idealised Me refined as rotating group:
 C12(H12a,H12b,H12c), C11(H11a,H11b,H11c), C23(H23a,H23b,H23c), C24(H24a,H24b,
 H24c)
;
_shelx_res_checksum              77723
_shelx_fab_checksum              8066
_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 1.491
_oxdiff_exptl_absorpt_empirical_full_min 0.711