Frustrated Lewis pair meditated selective single fluoride substitution in trifluoromethyl groups.
Mandal, Dipendu; Gupta, Richa; Jaiswal, Amit K.; Young, Rowan D.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b12167

data_4134006
_publ_section_title
;
 Frustrated Lewis pair meditated selective single fluoride substitution in
 trifluoromethyl groups.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b12167
_journal_year                    2020
_chemical_formula_moiety         'C29 H28 F2 P, C2 F6 N O4 S2'
_chemical_formula_sum            'C31 H28 F8 N O4 P S2'
_chemical_formula_weight         725.63
_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             2019-07-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.9460(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5732(4)
_cell_length_b                   16.6147(6)
_cell_length_c                   16.7556(6)
_cell_measurement_reflns_used    9776
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.61
_cell_measurement_theta_min      2.45
_cell_volume                     3198.2(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.99
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0531
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            61809
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.719
_diffrn_reflns_theta_min         2.583
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.301
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.7087
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1070 before and 0.0640 after correction. The Ratio of minimum to maximum transmission is 0.9503. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_description       block
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.372
_exptl_crystal_size_mid          0.294
_exptl_crystal_size_min          0.218
_refine_diff_density_max         0.567
_refine_diff_density_min         -0.496
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     458
_refine_ls_number_reflns         8274
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0598
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0338P)^2^+2.6958P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0864
_refine_ls_wR_factor_ref         0.1013
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6474
_reflns_number_total             8274
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12167_si_005.cif
_cod_data_source_block           mo_ry_bt_1_3a_0m
_cod_database_code               4134006
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.896
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C24B(0.4) H24B(0.4) C28A(0.6) H28A(0.6) C27B(0.4) H27B(0.4)
 C25B(0.4) H25B(0.4) C26B(0.4) H26B(0.4) C29A(0.6) H29A(0.6) H29B(0.6)
 H29C(0.6) C29B(0.4) H29D(0.4) H29E(0.4) H29F(0.4) C24A(0.6) C25A(0.6)
 H25A(0.6) C26A(0.6) H26A(0.6) C27A(0.6) H27A(0.6) C28B(0.4)
3.a Aromatic/amide H refined with riding coordinates:
 C24B(H24B), C7(H7), C28A(H28A), C10(H10), C3(H3), C18(H18), C6(H6), C21(H21),
 C4(H4), C11(H11), C13(H13), C20(H20), C19(H19), C27B(H27B), C12(H12),
 C25B(H25B), C26B(H26B), C25A(H25A), C26A(H26A), C27A(H27A)
3.b Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C22(H22A,H22B,H22C), C8(H8A,H8B,H8C), C29A(H29A,H29B,
 H29C), C29B(H29D,H29E,H29F)
;
_shelx_res_checksum              96745
_shelx_hkl_checksum              18673
_olex2_submission_special_instructions 'No special instructions were received'