Different paths lead to the same destination: a highly efficient TMSOTf/HFIP catalytic system for large-scale synthesis of fluoroalkyl-containing 4,4′-methylenedianiline (MDA) monomers
Wu, Ziyan; Fang, Guodong; Li, Xindi; Wu, Yuhao; Li, Jinshan; Feng, Yan; Xie, Jialin; Zhou, Xueqing; Wen, Zhenchang; Jia, Chunman; Green Chemistry 27 (2025) 13751–13761; doi:10.1039/D5GC03637B

data_7251021
_publ_section_title
;
 Different paths lead to the same destination: a highly efficient
 TMSOTf/HFIP catalytic system for large-scale synthesis of
 fluoroalkyl-containing 4,4&#x2032;-methylenedianiline (MDA) monomers
;
_journal_issue                   43
_journal_name_full               'Green Chemistry'
_journal_page_first              13751
_journal_page_last               13761
_journal_paper_doi               10.1039/D5GC03637B
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C18 H21 F3 N2'
_chemical_formula_sum            'C18 H21 F3 N2'
_chemical_formula_weight         322.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-12-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-06-17 deposited with the CCDC.	2025-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.613(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.2009(5)
_cell_length_b                   8.2531(2)
_cell_length_c                   14.6469(2)
_cell_measurement_reflns_used    6770
_cell_measurement_temperature    152.99(10)
_cell_measurement_theta_max      77.2100
_cell_measurement_theta_min      3.2550
_cell_volume                     3286.81(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      152.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.942
_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    107.00 132.00   0.50    0.14    --  106.55  86.00-160.00   50
  2  \w     -4.00  25.00   0.50    0.05    --   45.64 -19.00 -90.00   58
  3  \w    -25.00  44.00   0.50    0.05    --   45.64 -38.00 -30.00  138
  4  \w     35.00  60.00   0.50    0.14    --  106.55 -57.00-150.00   50
  5  \w     34.00  59.00   0.50    0.14    --  106.55 -57.00-120.00   50
  6  \w     37.00  62.00   0.50    0.14    --  106.55 -57.00 -90.00   50
  7  \w     39.00  64.00   0.50    0.14    --  106.55 -57.00  90.00   50
  8  \w     36.00 131.00   0.50    0.14    --  106.55 -86.00  81.00  190
  9  \w     37.00 110.00   0.50    0.14    --  106.55-125.00 -60.00  146
 10  \w     36.00  93.00   0.50    0.14    --  106.55 -99.00 -60.00  114
 11  \w    -25.00  51.00   0.50    0.05    --   45.64 -86.00  81.00  152
 12  \w    -47.00 -22.00   0.50    0.05    --  -45.64  86.00-160.00   50
 13  \w    -87.00 -36.00   0.50    0.05    --  -45.64 125.00-180.00  102
 14  \w    -84.00 -58.00   0.50    0.14    -- -104.00  86.00-160.00   52
 15  \w    -63.00 -31.00   0.50    0.14    -- -104.00  57.00-150.00   64
 16  \w    -63.00 -34.00   0.50    0.14    -- -104.00  57.00-180.00   58
 17  \w   -100.00 -75.00   0.50    0.14    -- -104.00  77.00  30.00   50
 18  \w    -68.00 -32.00   0.50    0.14    -- -104.00  77.00  30.00   72
 19  \w    -23.00  19.00   0.50    0.05    --  -45.64  19.00 -90.00   84
 20  \w    -56.00 -31.00   0.50    0.14    -- -104.00  57.00  60.00   50
 21  \w    -64.00 -32.00   0.50    0.14    -- -104.00  57.00 120.00   64
 22  \w    -64.00 -38.00   0.50    0.14    -- -104.00  57.00 150.00   52
 23  \w   -174.00 -98.00   0.50    0.14    -- -104.00 -38.00 120.00  152
 24  \w   -175.00 -84.00   0.50    0.14    -- -104.00 -86.00  81.00  182
;
_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      0.0286714000
_diffrn_orient_matrix_UB_12      0.1277877000
_diffrn_orient_matrix_UB_13      -0.0536992000
_diffrn_orient_matrix_UB_21      -0.0046872000
_diffrn_orient_matrix_UB_22      -0.1058506000
_diffrn_orient_matrix_UB_23      -0.0864524000
_diffrn_orient_matrix_UB_31      -0.0486487000
_diffrn_orient_matrix_UB_32      0.0854319000
_diffrn_orient_matrix_UB_33      -0.0267585000
_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  0.0416
_diffrn_reflns_av_unetI/netI     0.0389
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            10927
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.432
_diffrn_reflns_theta_min         3.251
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.845
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59898
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.140a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.303
_exptl_crystal_description       block
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.194
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         3298
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0424
_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^)+(0.0643P)^2^+1.5569P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1163
_refine_ls_wR_factor_ref         0.1223
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2781
_reflns_number_total             3298
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc03637b2.cif
_cod_data_source_block           wzy-2_auto
_cod_depositor_comments
'Adding full bibliography for 7251021--7251022.cif.'
_cod_database_code               7251021
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNF
_chemical_oxdiff_usercomment     CHNF
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.849
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Rotating group:
 N1(H1A,H1B)
2.b Ternary CH refined with riding coordinates:
 C10(H10)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C17(H17), C12(H12)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C16(H16A,H16B,H16C), C1(H1C,H1D,H1E), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              43358
_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 1.708
_oxdiff_exptl_absorpt_empirical_full_min 0.427