BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant
Luo, Zhenli; Pan, Yixiao; Yao, Zhen; Yang, Ji; Zhang, Xin; Liu, Xintong; Xu, Lijin; Fan, Qing-Hua; Green Chemistry 23 (2021) 5205–5211; doi:10.1039/D1GC01468D

data_7243079
_publ_section_title
;
 BF3&#x00B7;Et2O as a metal-free catalyst for direct reductive amination
 of aldehydes with amines using formic acid as a reductant
;
_journal_issue                   14
_journal_name_full               'Green Chemistry'
_journal_page_first              5205
_journal_page_last               5211
_journal_paper_doi               10.1039/D1GC01468D
_journal_volume                  23
_journal_year                    2021
_chemical_formula_moiety         'C21 H18 N2'
_chemical_formula_sum            'C21 H18 N2'
_chemical_formula_weight         298.37
_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     dual
_audit_creation_date             2020-12-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-03-16 deposited with the CCDC.	2021-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.078(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.6432(3)
_cell_length_b                   13.2799(2)
_cell_length_c                   17.6411(4)
_cell_measurement_temperature    272(1)
_cell_volume                     3345.90(12)
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      272(1)
_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 0.958
_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    -29.00  70.00   1.00    0.20    --   43.77 -84.00 -71.00   99
  2  \w     33.00 116.00   1.00    2.00    --  107.00-125.00 -60.00   83
  3  \w     36.00 137.00   1.00    2.00    --  107.00 -84.00 -71.00  101
  4  \w     33.00  73.00   1.00    2.00    --  107.00 -61.00 -60.00   40
  5  \w     75.00 177.00   1.00    2.00    --  107.00  15.00 -30.00  102
  6  \w     85.00 149.00   1.00    2.00    --  107.00  84.00  48.00   64
  7  \w     33.00 104.00   1.00    2.00    --  107.00 -77.00  90.00   71
  8  \w    -36.00  25.00   1.00    0.20    --  -43.77  37.00 150.00   61
  9  \w    -67.00 -42.00   1.00    2.00    -- -102.00  61.00 150.00   25
 10  \w    -69.00 -34.00   1.00    2.00    -- -102.00  61.00 120.00   35
 11  \w    -69.00 -28.00   1.00    2.00    -- -102.00  61.00  60.00   41
 12  \w    -69.00 -33.00   1.00    2.00    -- -102.00  61.00-120.00   36
 13  \w    -68.00 -28.00   1.00    2.00    -- -102.00  61.00-180.00   40
 14  \w   -175.00-150.00   1.00    2.00    -- -102.00 -45.00 -30.00   25
 15  \w   -166.00-141.00   1.00    2.00    -- -102.00 -45.00   0.00   25
 16  \w   -133.00 -90.00   1.00    2.00    -- -102.00 -45.00   0.00   43
 17  \w    -56.00  30.00   1.00    0.20    --  -43.77  84.00  48.00   86
 18  \w   -104.00 -79.00   1.00    2.00    -- -102.00  84.00  48.00   25
 19  \w   -111.00 -81.00   1.00    2.00    -- -102.00 -45.00 -30.00   30
 20  \w   -168.00-143.00   1.00    2.00    -- -102.00 -84.00 -71.00   25
 21  \w   -115.00 -74.00   1.00    0.20    --  -43.77-125.00  60.00   41
 22  \w   -115.00 -90.00   1.00    0.20    --  -43.77-125.00-180.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0462846000
_diffrn_orient_matrix_UB_12      -0.1001526000
_diffrn_orient_matrix_UB_13      0.0063602000
_diffrn_orient_matrix_UB_21      0.0245227000
_diffrn_orient_matrix_UB_22      0.0209316000
_diffrn_orient_matrix_UB_23      0.0924846000
_diffrn_orient_matrix_UB_31      -0.0942877000
_diffrn_orient_matrix_UB_32      0.0545890000
_diffrn_orient_matrix_UB_33      -0.0237520000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0257
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22664
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.948
_diffrn_reflns_theta_min         4.315
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.537
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_description       block
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.150
_refine_diff_density_max         0.110
_refine_diff_density_min         -0.156
_refine_diff_density_rms         0.025
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     415
_refine_ls_number_reflns         6695
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0611P)^2^+0.2627P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1198
_refine_ls_wR_factor_ref         0.1279
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5370
_reflns_number_total             6695
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1gc01468d2.cif
_cod_data_source_block           exp_3044
_cod_depositor_comments
;
         Adding full bibliography for 7243079.cif.

2024-06-28
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C42 H36 N4'
_cod_original_formula_weight         596.75
_cod_original_formula_moiety         '2(C21 H18 N2)'
_cod_original_formula_units_Z            4
_cod_database_code               7243079
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N'
_reflns_odcompleteness_completeness 99.87
_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
2.a Secondary CH2 refined with riding coordinates:
 C00O(H00A,H00D), C00R(H00Q,H00R), C00V(H00F,H00I), C00Z(H00V,H00Y)
2.b Aromatic/amide H refined with riding coordinates:
 C006(H006), C007(H007), C00B(H00B), C00C(H00C), C00D(H00J), C00E(H00E),
 C00G(H00G), C00H(H00H), C00I(H00L), C00J(H00M), C00K(H00K), C00L(H00N),
 C00M(H00O), C00P(H00P), C00S(H00S), C00T(H00T), C00U(H00U), C00W(H00W),
 C00X(H00X), C010(H010), C011(H011), C012(H012), C013(H013), C014(H014),
 C015(H015), C016(H016), C017(H017), C018(H018)
;
_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 1.222
_oxdiff_exptl_absorpt_empirical_full_min 0.699