Ligand-free nickel catalyzed perfluoroalkylation of arenes and heteroarenes.
Deolka, Shubham; Govindarajan, Ramadoss; Vasylevskyi, Serhii; Roy, Michael C.; Khusnutdinova, Julia R.; Khaskin, Eugene; Chemical science 13 (2022) 12971–12979; doi:10.1039/d2sc03879j

data_1567793
_publ_section_title
;
 Ligand-free nickel catalyzed perfluoroalkylation of arenes and
 heteroarenes.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              12971
_journal_page_last               12979
_journal_paper_doi               10.1039/d2sc03879j
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C20 H18 F5 N O5'
_chemical_formula_sum            'C20 H18 F5 N O5'
_chemical_formula_weight         447.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-06-20 deposited with the CCDC.	2022-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.999(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.3374(7)
_cell_length_b                   7.1756(3)
_cell_length_c                   14.0098(7)
_cell_measurement_reflns_used    5142
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.3460
_cell_measurement_theta_min      3.7280
_cell_volume                     2041.69(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.978
_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    -40.00  53.00   1.00   29.74    --   49.60 -82.00-180.00   93
  2  \w    -36.00  69.00   1.00   29.74    --   49.60 -19.00 -90.00  105
  3  \w     26.00  80.00   1.00   29.74    --   49.60  37.00 -90.00   54
  4  \w    -39.00  41.00   1.00   29.74    --   49.60 -57.00  60.00   80
  5  \w     86.00 138.00   1.00   29.74    --   49.60  37.00 -90.00   52
  6  \w     49.00  76.00   1.00   29.74    --   49.60  37.00 -60.00   27
  7  \w     58.00 111.00   1.00   29.74    --   49.60  37.00-180.00   53
  8  \w     93.00 135.00   1.00  118.94    --  110.20  77.00 -30.00   42
  9  \w    125.00 152.00   1.00  118.94    --  110.20  82.00 150.00   27
 10  \w    170.00 198.00   1.00  118.94    --  110.20  61.00-120.00   28
 11  \w     83.00 166.00   1.00  118.94    --  110.20  61.00-120.00   83
 12  \w    131.00 197.00   1.00  118.94    --  110.20  30.00  90.00   66
 13  \w    114.00 192.00   1.00  118.94    --  110.20  15.00 -60.00   78
 14  \w    132.00 199.00   1.00  118.94    --  110.20  45.00 150.00   67
 15  \w     22.00 138.00   1.00  118.94    --  110.20 -61.00  60.00  116
 16  \w     83.00 198.00   1.00  118.94    --  110.20  30.00 -30.00  115
 17  \w    133.00 166.00   1.00  118.94    --  110.20  45.00-180.00   33
 18  \w     71.00  96.00   1.00  118.94    --  110.20  15.00 -60.00   25
 19  \w     88.00 126.00   1.00  118.94    --  110.20  45.00-180.00   38
 20  \w    110.00 199.00   1.00  118.94    --  110.20  45.00 120.00   89
 21  \w     22.00 142.00   1.00  118.94    --  110.20 -82.00  60.00  120
 22  \w     78.00 104.00   1.00  118.94    --  110.20  82.00 150.00   26
 23  \w     89.00 117.00   1.00  118.94    --  110.20  45.00 150.00   28
 24  \w     83.00 160.00   1.00  118.94    --  110.20  61.00-150.00   77
 25  \w     31.00  56.00   1.00  118.94    --  110.20 -45.00  60.00   25
 26  \w     96.00 130.00   1.00  118.94    --  110.20  30.00 120.00   34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0540096000
_diffrn_orient_matrix_UB_12      0.1203210000
_diffrn_orient_matrix_UB_13      0.0422544000
_diffrn_orient_matrix_UB_21      -0.0037689000
_diffrn_orient_matrix_UB_22      -0.1371867000
_diffrn_orient_matrix_UB_23      0.0838097000
_diffrn_orient_matrix_UB_31      0.0531317000
_diffrn_orient_matrix_UB_32      0.1134748000
_diffrn_orient_matrix_UB_33      0.0574026000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            11116
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.509
_diffrn_reflns_theta_min         3.742
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.174
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83998
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
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    1.455
_exptl_crystal_description       plate
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.418
_refine_diff_density_min         -0.413
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1632 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.25(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     353
_refine_ls_number_reflns         4292
_refine_ls_number_restraints     251
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0567
_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^)+(0.0772P)^2^+2.3568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1515
_refine_ls_wR_factor_ref         0.1549
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.939
_reflns_number_gt                3939
_reflns_number_total             4292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03879j2.cif
_cod_data_source_block           jk1392a
_cod_depositor_comments
'Adding full bibliography for 1567790--1567793.cif.'
_cod_database_code               1567793
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C10 H10 F5'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.872
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C20B-C19B
 1.5 with sigma of 0.02
 F2B-C20B \\sim F2B-F1B \\sim C20B-F1B
 with sigma of 0.04
 C19B-C5 \\sim C19B-F2B \\sim C19B-C20B \\sim C19B-F1B
 with sigma of 0.02
 F5B-F4B \\sim F5B-F3B \\sim F4B-F3B
 with sigma of 0.04
 C20B-F5B \\sim C20B-F4B \\sim C20B-C19B \\sim C20B-F3B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1A \\sim F2A \\sim F3A \\sim F4A \\sim F5A \\sim C19A \\sim C20A \\sim F1B
\\sim F2B \\sim F3B \\sim F4B \\sim F5B \\sim C19B \\sim C20B: within 2A with
sigma of 0.002 and sigma for terminal atoms of 0.004 within 2A
4. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(C19B)=Sof(C20B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(C19A)=Sof(C20A)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1b)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b), C12(H12a,H12b)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C8(H8), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18)
5.d Idealised Me refined as rotating group:
 C10(H10a,H10b,H10c)
;
_shelx_res_checksum              51563
_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 1.198
_oxdiff_exptl_absorpt_empirical_full_min 0.860