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_4134005
_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         'C50 H45 F4 P2, 2(C2 F6 N O4 S2)'
_chemical_formula_sum            'C54 H45 F16 N2 O8 P2 S4'
_chemical_formula_weight         1344.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-11-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.633(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.6718(5)
_cell_length_b                   13.9968(7)
_cell_length_c                   17.3742(9)
_cell_measurement_reflns_used    9984
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.10
_cell_measurement_theta_min      2.35
_cell_volume                     2829.1(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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            45199
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         2.186
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.334
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6974
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1095 before and 0.0644 after correction. The Ratio of minimum to maximum transmission is 0.9350. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.578
_exptl_crystal_description       block
_exptl_crystal_F_000             1370
_exptl_crystal_size_max          0.394
_exptl_crystal_size_mid          0.312
_exptl_crystal_size_min          0.219
_refine_diff_density_max         0.968
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.087
_refine_ls_abs_structure_details
;
 Flack x determined using 3525 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     838
_refine_ls_number_reflns         9472
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0643
_refine_ls_R_factor_gt           0.0549
_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^)+(0.0879P)^2^+4.2653P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1436
_refine_ls_wR_factor_ref         0.1515
_reflns_Friedel_coverage         0.997
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8483
_reflns_number_total             9472
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12167_si_002.cif
_cod_data_source_block           mo_ry_dm_3_262_0m_a
_cod_database_code               4134005
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.65(12)
 0.35(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 S4B-C36B
 1.821 with sigma of 0.02
 S3B-C35B
 1.821 with sigma of 0.02
4. Others
 Fixed Sof: S3A(0.85) S4A(0.85) F13A(0.85) F14A(0.85) F15A(0.85) F17A(0.85)
 F18A(0.85) F19A(0.85) O0AA(0.85) O6A(0.85) O8A(0.85) N2A(0.85) C35A(0.85)
 C36A(0.85) S3B(0.15) S4B(0.15) F13B(0.15) F14B(0.15) F15B(0.15) F17B(0.15)
 F18B(0.15) F19B(0.15) O6B(0.15) O7B(0.15) O8B(0.15) N2B(0.15) C35B(0.15)
 C36B(0.15)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C13(H13), C14(H14), C15(H15), C16(H16),
 C21(H21), C22(H22), C23(H23), C27(H27), C28(H28), C29(H29), C30(H30),
 C212(H212), C213(H213), C214(H214), C215(H215), C219(H219), C220(H220),
 C221(H221), C222(H222), C226(H226), C227(H227), C228(H228), C229(H229)
5.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C25(H25A,H25B,H25C), C32(H32A,H32B,H32C), C217(H21A,H21B,
 H21C), C224(H22A,H22B,H22C), C231(H23A,H23B,H23C)
;
_shelx_res_checksum              76641
_shelx_hkl_checksum              47332
_olex2_submission_special_instructions 'No special instructions were received'