Direct synthesis of N-perfluoro-tert-butyl secondary amines from N-trifluoromethyl secondary amines
Wang, leibing; Feng, Zhongyu; Luo, Zhen; Guo, Zihao; Wang , Jieping; Yi, WenBin; Chemical Science  (2024) –; doi:10.1039/D4SC06335J

data_1573072
_publ_section_title
;
 Direct synthesis of N-perfluoro-tert-butyl secondary amines from
 N-trifluoromethyl secondary amines
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D4SC06335J
_journal_year                    2024
_chemical_formula_moiety         '2(C16 H10 F9 N)'
_chemical_formula_sum            'C32 H20 F18 N2'
_chemical_formula_weight         774.50
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-04-14 deposited with the CCDC.	2024-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.282(2)
_cell_length_b                   7.7234(5)
_cell_length_c                   10.7769(6)
_cell_measurement_reflns_used    9704
_cell_measurement_temperature    193.15
_cell_measurement_theta_max      53.172
_cell_measurement_theta_min      4.119
_cell_volume                     3103.1(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0526
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            18441
_diffrn_reflns_point_group_measured_fraction_full 0.949
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.123
_diffrn_reflns_theta_min         4.122
_diffrn_source_current           2.86
_diffrn_source_power             0.19937059999999998
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.003
_exptl_absorpt_correction_T_max  0.7506
_exptl_absorpt_correction_T_min  0.5301
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1025 before and 0.0721 after correction.
The Ratio of minimum to maximum transmission is 0.7062.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_description       block
_exptl_crystal_F_000             1552
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.283
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 1478 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.34(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     578
_refine_ls_number_reflns         5369
_refine_ls_number_restraints     148
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.0916
_refine_ls_R_factor_gt           0.0721
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0167P)^2^+6.5043P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1499
_refine_ls_wR_factor_ref         0.1597
_reflns_Friedel_coverage         0.799
_reflns_Friedel_fraction_full    0.899
_reflns_Friedel_fraction_max     0.887
_reflns_number_gt                4233
_reflns_number_total             5369
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06335j2.cif
_cod_data_source_block           230412lu_nlg_lmf2_0m
_cod_database_code               1573072
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.881
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
2. Restrained distances
 F10A-C29A \\sim F10B-C29B
 with sigma of 0.04
 F13A-C29A \\sim F13B-C29B
 with sigma of 0.04
 F15A-C29A \\sim F15B-C29B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
F10A \\sim F11A \\sim F12A \\sim F13A \\sim F14A \\sim F15A \\sim F16A \\sim
F17A \\sim F18A \\sim C29A \\sim C30A \\sim C31A \\sim C32A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
F10B \\sim F11B \\sim F12B \\sim F13B \\sim F14B \\sim F15B \\sim F16B \\sim
F17B \\sim F18B \\sim C29B \\sim C30B \\sim C31B \\sim C32B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(F13B)=Sof(F14B)=Sof(F15B)=Sof(F16B)=
 Sof(F17B)=Sof(F18B)=Sof(H2B)=Sof(C29B)=Sof(C30B)=Sof(C31B)=Sof(C32B)=1-FVAR(1)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=
 Sof(F17A)=Sof(F18A)=Sof(H2A)=Sof(C29A)=Sof(C30A)=Sof(C31A)=Sof(C32A)=FVAR(1)
5.a Everything fixed:
 F17B
5.b Aromatic/amide H refined with riding coordinates:
 N2(H2A), N2(H2B), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C24(H24),
 C25(H25), C27(H27), C28(H28), N1(H1), C1(H1A), C2(H2), C3(H3), C5(H5), C6(H6),
 C8(H8), C9(H9), C11(H11), C12(H12)
;
_shelx_res_checksum              18179
_olex2_submission_special_instructions 'No special instructions were received'