<i>meta</i>-C-H arylation of fluoroarenes <i>via</i> traceless directing group relay strategy.
Font, Marc; Spencer, Andrew R. A.; Larrosa, Igor; Chemical science 9 (2018) 7133–7137; doi:10.1039/c8sc02417k

data_1549724
_publ_section_title
;
 <i>meta</i>-C-H arylation of fluoroarenes <i>via</i> traceless directing
 group relay strategy.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              7133
_journal_page_last               7137
_journal_paper_doi               10.1039/c8sc02417k
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         '0.9(C15 H9 F7), 0.1(C15 H9 F7.49)'
_chemical_formula_sum            'C15 H9 F7.05'
_chemical_formula_weight         323.08
_space_group_crystal_system      orthorhombic
_space_group_IT_number           57
_space_group_name_Hall           '-P 2c 2b'
_space_group_name_H-M_alt        'P b c m'
_symmetry_space_group_name_Hall  '-P 2c 2b'
_symmetry_space_group_name_H-M   'P b c m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-10-23 deposited with the CCDC.
2018-07-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            40
_cell_length_a                   12.0690(5)
_cell_length_b                   30.5791(11)
_cell_length_c                   36.076(2)
_cell_measurement_reflns_used    5263
_cell_measurement_temperature    150.02(10)
_cell_measurement_theta_max      23.5930
_cell_measurement_theta_min      3.5680
_cell_volume                     13314.2(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41q (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41q (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41q (Rigaku OD, 2015)'
_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      150.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.939
_diffrn_measured_fraction_theta_max 0.997
_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     52.00  88.00   0.75   15.00    --   18.86  77.00-180.00   48
  2  \w     -4.00  83.00   0.75   15.00    --   18.86  77.00  90.00  116
  3  \w    -20.00  57.25   0.75   15.00    --   18.86 -99.00 -60.00  103
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0520476000
_diffrn_orient_matrix_UB_12      -0.0105582000
_diffrn_orient_matrix_UB_13      0.0016710000
_diffrn_orient_matrix_UB_21      -0.0271203000
_diffrn_orient_matrix_UB_22      0.0196105000
_diffrn_orient_matrix_UB_23      -0.0053094000
_diffrn_orient_matrix_UB_31      0.0030662000
_diffrn_orient_matrix_UB_32      -0.0064713000
_diffrn_orient_matrix_UB_33      -0.0188596000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0882
_diffrn_reflns_av_unetI/netI     0.0997
_diffrn_reflns_Laue_measured_fraction_full 0.939
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            43850
_diffrn_reflns_point_group_measured_fraction_full 0.939
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.712
_diffrn_reflns_theta_min         3.205
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.163
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64360
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41q (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.612
_exptl_crystal_description       plate
_exptl_crystal_F_000             6496
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.819
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1151
_refine_ls_number_reflns         11520
_refine_ls_number_restraints     285
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.2122
_refine_ls_R_factor_gt           0.1041
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1615P)^2^+7.2807P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2713
_refine_ls_wR_factor_ref         0.3542
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4828
_reflns_number_total             11520
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc02417k2.cif
_cod_data_source_block           ail15
_cod_depositor_comments
'Adding full bibliography for 1549724--1549725.cif.'
_cod_original_cell_volume        13314.1(10)
_cod_database_code               1549724
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         CFNOH
_chemical_oxdiff_usercomment     MJ/STL
_reflns_odcompleteness_completeness 99.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Restrained distances
 F70-F69
 2.1 with sigma of 0.02
 F68-F69 = F68-F70
 2.1 with sigma of 0.02
 F65-F66
 2.1 with sigma of 0.02
 F66-F64
 2.1 with sigma of 0.02
 F64-F65
 2.1 with sigma of 0.02
 F93-F92
 2.1 with sigma of 0.02
 C108-C106 \\sim C111-C106
 with sigma of 0.002
 F109-C108 \\sim F113-C111 \\sim F110-C108 \\sim F112-C111
 with sigma of 0.002
 C63-C57 \\sim C67-C57
 with sigma of 0.002
 F65-C63 \\sim F64-C63 \\sim F66-C63 \\sim F68-C67 \\sim F70-C67 \\sim F69-C67
 with sigma of 0.002
 F93-C89 \\sim F91-C89 \\sim F92-C89 \\sim F90-C89
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C111: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C108 \\sim C111: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
4. Rigid body (RIGU) restrains
 F93, F92, F91, F90, C89, C80
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F65, C63, F64, F66, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F70, C67, F69, F68, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F112, F113, C108, C106
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C99, C98, C97, C96, C95, C94, F100
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F51, C45, C50, C49, C48, C47, C46, C52
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C84, F86, F85, F87, F88, C82
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C89, F90, F93, F91, F92, C80
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F113, F112, C108, C106
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F110, F109, C108, C106
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(F87)=1-FVAR(1)
 Sof(F88)=0.5*(1-FVAR(2))
 Sof(F85)=0.5*FVAR(2)
 Sof(F86)=FVAR(1)
 Sof(F109)=1-FVAR(2)
 Sof(F110)=Sof(C108)=0.5*(1-FVAR(3))
 Sof(F112)=Sof(C111)=0.5*FVAR(3)
 Sof(F113)=FVAR(2)
 Sof(C67)=Sof(F70)=Sof(F68)=Sof(F69)=1-FVAR(3)
 Sof(F66)=Sof(F65)=Sof(F64)=Sof(C63)=FVAR(3)
 Sof(F90)=Sof(F91)=1-FVAR(4)
 Sof(F92)=0.5*FVAR(5)
 Sof(F93)=FVAR(4)
 Fixed Sof: H77A(0.5) H77B(0.5) H77C(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C103(H103), C105(H105), C107(H107), C10(H10), C83(H83), C74(H74), C126(H126),
 C6(H6), C73(H73), C36(H36), C54(H54), C32(H32), C14(H14), C26(H26), C28(H28),
 C12(H12), C130(H130), C128(H128), C25(H25), C96(H96), C122(H122), C4(H4),
 C2AA(H2AA), C34(H34), C3(H3), C58(H58), C50(H50), C119(H119), C120(H120),
 C97(H97), C48(H48), C79(H79), C47(H47), C56(H56), C99(H99), C81(H81)
6.b Idealised Me refined as rotating group:
 C77(H77A,H77B,H77C), C124(H12A,H12B,H12C), C8(H8A,H8B,H8C), C101(H10A,H10B,
 H10C), C30(H30A,H30B,H30C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              96483
_olex2_date_sample_data_collection 2016-11-01
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.565
_oxdiff_exptl_absorpt_empirical_full_min 0.720