Substituent-controlled, Mild Oxidative Fluorination of Iodoarenes: Synthesis and Structural Study of Aryl I(III)- and I(V)-Fluorides
Häfliger, Joel; Pitts, Cody Ross; Bornemann, Dustin; Käser, Roland; Santschi, Nico; Charpentier, Julie; Otth, Elisabeth; Trapp, Nils; Verel, René; Lüthi, Hans Peter; Togni, Antonio; Chemical Science  (2019) –; doi:10.1039/C9SC02162K

data_1551252
_publ_section_title
;
 Substituent-controlled, Mild Oxidative Fluorination of Iodoarenes:
 Synthesis and Structural Study of Aryl I(III)- and I(V)-Fluorides
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02162K
_journal_year                    2019
_chemical_formula_moiety         'C10 H9 Br F3 I'
_chemical_formula_sum            'C10 H9 Br F3 I'
_chemical_formula_weight         392.98
_chemical_name_systematic
(4-Bromo-8-fluoro-5,6,7,8-tetrahydronaphthalen-1-yl)difluoro-\l3-iodane
_chemical_properties_physical    Moisture-sensitive
_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'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-30 deposited with the CCDC.    2019-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 134.610(17)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.483(2)
_cell_length_b                   8.4119(3)
_cell_length_c                   15.9818(15)
_cell_measurement_reflns_used    7333
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      77.7190
_cell_measurement_theta_min      5.5340
_cell_volume                     2247.5(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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     84.00 170.00   0.50    1.10    --  105.75  77.00  90.00  172
  2  \w     84.00 170.00   0.50    1.10    --  105.75  77.00   0.00  172
  3  \w     92.00 176.00   0.50    1.10    --  105.75  57.00 -30.00  168
  4  \w     98.00 178.00   0.50    1.10    --  105.75  38.00 -60.00  160
  5  \w     98.00 178.00   0.50    1.10    --  105.75  38.00-120.00  160
  6  \w     98.00 178.00   0.50    1.10    --  105.75  38.00-180.00  160
  7  \w    -68.00  20.00   0.50    0.27    --    0.88   0.00-180.00  176
  8  \w    -83.00   1.00   0.50    1.10    --  -70.00  57.00  30.00  168
  9  \w    -22.00  64.00   0.50    0.27    --   -0.88  77.00 120.00  172
 10  \w     38.00 111.00   0.50    1.10    --  105.75 -99.00  60.00  146
 11  \w     41.00 127.00   0.50    1.10    --  105.75 -77.00-120.00  172
 12  \w     35.00 119.00   0.50    1.10    --  105.75 -57.00-120.00  168
 13  \w     35.00 119.00   0.50    1.10    --  105.75 -57.00  90.00  168
 14  \w    -69.00  14.00   0.50    0.27    --    0.88 -57.00   0.00  166
 15  \w    -75.00   8.00   0.50    0.27    --   -0.88 -19.00  30.00  166
 16  \w   -134.00 -48.00   0.50    1.10    --  -70.00 -77.00  90.00  172
 17  \w   -140.00 -66.00   0.50    1.10    --  -70.00-130.00 169.00  148
 18  \w   -134.00 -62.00   0.50    1.10    --  -70.00 -77.00-180.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0829433000
_diffrn_orient_matrix_UB_12      0.0726918000
_diffrn_orient_matrix_UB_13      -0.0682971000
_diffrn_orient_matrix_UB_21      -0.0400031000
_diffrn_orient_matrix_UB_22      -0.1442049000
_diffrn_orient_matrix_UB_23      -0.0834916000
_diffrn_orient_matrix_UB_31      -0.0030605000
_diffrn_orient_matrix_UB_32      -0.0865388000
_diffrn_orient_matrix_UB_33      0.0817089000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11254
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.444
_diffrn_reflns_theta_min         5.292
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    26.661
_exptl_absorpt_correction_T_max  0.821
_exptl_absorpt_correction_T_min  0.086
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.323
_exptl_crystal_description       plate
_exptl_crystal_F_000             1472
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM/n-hexane'
_exptl_crystal_size_max          0.129
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.014
_refine_diff_density_max         0.981
_refine_diff_density_min         -1.493
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         2383
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0310
_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^)+(0.0453P)^2^+12.0548P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0841
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2271
_reflns_number_total             2383
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02162k2.cif
_cod_data_source_block           lac250219_1_1
_cod_original_cell_volume        2247.4(6)
_cod_database_code               1551252
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C10H9BrF3I
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C9-C8 \\sim C9A-C8A
 with sigma of 0.02
 C8A-C7 \\sim C8-C7
 with sigma of 0.02
 F3A-C10A \\sim F3-C10
 with sigma of 0.02
 C6-C10 \\sim C6-C10A
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F3, F3A, C5, C6, C7, C8, C8A, C9, C9A, C10, C10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F3A)=Sof(H7BC)=Sof(H7BD)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9AA)=
 Sof(H9AB)=Sof(C10A)=Sof(H10A)=1-FVAR(1)
 Sof(F3)=Sof(H7AA)=Sof(H7AB)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=
 Sof(H9B)=Sof(C10)=Sof(H10)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C10A(H10A)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7AA,H7AB), C7(H7BC,H7BD), C8(H8A,H8B), C8A(H8AA,H8AB), C9(H9A,H9B),
 C9A(H9AA,H9AB)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
;
_shelx_res_checksum              21169
_olex2_submission_original_sample_id lac250219_1_1
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.076
_oxdiff_exptl_absorpt_empirical_full_min 0.603