Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized Olefins Using Fluoride Ion.
Lu, Deng-Fu; Zhu, Cheng-Liang; Sears, Jeffrey D.; Xu, Hao; Journal of the American Chemical Society 138 (2016) 11360–11367; doi:10.1021/jacs.6b07221

data_4130824
_publ_section_title
;
 Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized
 Olefins Using Fluoride Ion.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11360
_journal_page_last               11367
_journal_paper_doi               10.1021/jacs.6b07221
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12.67 H10 F6 N O2, 0.33(C F3)'
_chemical_formula_sum            'C13 H10 F7 N O2'
_chemical_formula_weight         345.22
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-08-07
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2015.08.05 svn.r3207 for OlexSys, GUI svn.r5081)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.3576(15)
_cell_length_b                   13.3576(15)
_cell_length_c                   16.362(2)
_cell_measurement_reflns_used    8681
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      65.100
_cell_measurement_theta_min      4.272
_cell_volume                     2919.4(6)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0224
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            14349
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        65.095
_diffrn_reflns_theta_max         65.095
_diffrn_reflns_theta_min         4.273
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.491
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.5975
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0914 before and 0.0425 after correction.
The Ratio of minimum to maximum transmission is 0.7939.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.571
_exptl_crystal_description       prism
_exptl_crystal_F_000             1392
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and hexane by slow evaporation'
_exptl_crystal_size_max          0.854
_exptl_crystal_size_mid          0.349
_exptl_crystal_size_min          0.261
_refine_diff_density_max         0.180
_refine_diff_density_min         -0.180
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 971 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     258
_refine_ls_number_reflns         2480
_refine_ls_number_restraints     134
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0333
_refine_ls_R_factor_gt           0.0326
_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^)+(0.0559P)^2^+0.7108P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0882
_refine_ls_wR_factor_ref         0.0889
_reflns_Friedel_coverage         0.681
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                2419
_reflns_number_total             2480
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b07221_si_004.cif
_cod_data_source_block           af-indene-mjr
_cod_original_cell_volume        2919.4(8)
_cod_database_code               4130824
_shelx_estimated_absorpt_t_max   0.697
_shelx_estimated_absorpt_t_min   0.362
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 C11B-H11B
 0.999 with sigma of 0.01
 C13B-C11B \\sim C13A-C11A
 with sigma of 0.004
3. Uiso/Uaniso restraints and constraints
Uanis(C12C) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C11A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(F4A) = Uanis(F4B)
Uanis(F6A) = Uanis(F6B)
Uanis(C13A) = Uanis(C13B)
Uanis(F5A) = Uanis(F5B)
Uanis(C12C) = Uanis(C12B)
Uanis(F3C) = Uanis(F3B)
Uanis(F1C) = Uanis(F1B)
Uanis(F2C) = Uanis(F2B)
Uanis(F2A) = Uanis(F2C)
Uanis(F1A) = Uanis(F1C)
Uanis(F3A) = Uanis(F3C)
Uanis(F2A) = Uanis(F2C) = Uanis(F2B)
Uanis(C11B) = Uanis(C11A)
4. Rigid body (RIGU) restrains
 C11B, C13B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F4B, F5B, F6B, C13B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F1B, F2B, F3B, C12B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C11B, F1A, F2A, F3A, C12A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C12B, C11B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Same fragment restrains
{F1A, F2A, F3A, C12A} sigma for 1-2: 0.002, 1-3: 0.002
as
{F1B, F2B, F3B, C12B}
{F1A, F2A, F3A, C12A} sigma for 1-2: 0.002, 1-3: 0.002
as
{F1C, F2C, F3C, C12C}
{F1A, F2A, F3A, C12A} sigma for 1-2: 0.002, 1-3: 0.002
as
{F4B, F5B, F6B, C13B}
{F1A, F2A, F3A, C12A} sigma for 1-2: 0.002, 1-3: 0.002
as
{F4A, F5A, F6A, C13A}
6. Others
 Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(C13B)=Sof(C11B)=Sof(H11B)=1-FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(C13A)=Sof(C11A)=Sof(H11A)=FVAR(1)
 Fixed Sof: F1B(0.33333) F2B(0.33333) F3B(0.33333) C12B(0.33333) F1C(0.33333)
 F2C(0.33333) F3C(0.33333) C12C(0.33333) F1A(0.33333) F2A(0.33333) F3A(0.33333)
 C12A(0.33333)
7.a Ternary CH refined with riding coordinates:
 C1(H1A), C2(H2), C11A(H11A)
7.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
7.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C6(H6), C7(H7), C8(H8), C9(H9)
;
_shelx_res_checksum              10320
_shelx_hkl_checksum              21489
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id AF-indene-major
_olex2_submission_special_instructions 'No special instructions were received'