Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne "umpolung".
Bonfante, Sara; Tanner, Theo F. N.; Lorber, Christian; Lynam, Jason M.; Simonneau, Antoine; Slattery, John M.; Chemical science 16 (2025) 3552–3559; doi:10.1039/d4sc08522a

data_1573704
_publ_section_title
;
 Zirconium-mediated carbon-fluorine bond functionalisation through
 cyclohexyne "umpolung".
;
_journal_issue                   8
_journal_name_full               'Chemical science'
_journal_page_first              3552
_journal_page_last               3559
_journal_paper_doi               10.1039/d4sc08522a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C21 H20 F3 N Zr'
_chemical_formula_sum            'C21 H20 F3 N Zr'
_chemical_formula_weight         434.60
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-03-12 deposited with the CCDC.	2025-01-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.4290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.17660(10)
_cell_length_b                   15.5546(2)
_cell_length_c                   14.6671(2)
_cell_measurement_reflns_used    8675
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      76.2160
_cell_measurement_theta_min      4.1470
_cell_volume                     1840.21(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.957
_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   -113.00 -56.00   0.50    0.40    --  -48.70 165.00-121.00  114
  2  \w    -68.00 -29.00   0.50    0.40    --  -48.70 116.00  90.00   78
  3  \w   -108.00 -83.00   0.50    0.40    --  -48.70-165.00-145.00   50
  4  \w     34.00  59.00   0.50    0.40    --   48.70-116.00   2.00   50
  5  \w     65.00  90.00   0.50    0.40    --   48.70-165.00-145.00   50
  6  \w     69.00 118.00   0.50    1.61    --  107.75 165.00-121.00   98
  7  \w     96.00 125.00   0.50    1.61    --  107.75-165.00-145.00   58
  8  \w     79.00 105.00   0.50    1.61    --  107.75-116.00   2.00   52
  9  \w    106.00 167.00   0.50    1.61    --  107.75 116.00  90.00  122
 10  \w   -118.00 -74.00   0.50    0.40    --  -48.70-125.00  60.00   88
 11  \w    -61.00  24.00   0.50    0.40    --  -48.70  19.00-120.00  170
 12  \w   -105.00 -73.00   0.50    0.40    --  -48.70-125.00  30.00   64
 13  \w   -118.00 -90.00   0.50    0.40    --  -48.70-125.00 150.00   56
 14  \w     12.00  37.00   0.50    0.40    --   48.70 -99.00-180.00   50
 15  \w     43.00  99.00   0.50    1.61    --  107.75-125.00 -60.00  112
 16  \w     48.00  73.00   0.50    1.61    --  107.75 -77.00-180.00   50
 17  \w     39.00 106.00   0.50    1.61    --  107.75 -99.00-180.00  134
 18  \w     40.00 100.00   0.50    1.61    --  107.75 -99.00  60.00  120
 19  \w     89.00 114.00   0.50    1.61    --  107.75 -19.00 -60.00   50
 20  \w    132.00 171.00   0.50    1.61    --  107.75  57.00 150.00   78
 21  \w     91.00 130.00   0.50    1.61    --  107.75 -77.00-180.00   78
 22  \w     32.00  57.00   0.50    1.61    --  107.75 -19.00 -60.00   50
 23  \w     94.00 124.00   0.50    1.61    --  107.75  57.00 150.00   60
 24  \w     97.00 164.00   0.50    1.61    --  107.75  57.00-180.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0769238000
_diffrn_orient_matrix_UB_12      0.0668839000
_diffrn_orient_matrix_UB_13      0.0578794000
_diffrn_orient_matrix_UB_21      0.0357759000
_diffrn_orient_matrix_UB_22      0.0714525000
_diffrn_orient_matrix_UB_23      -0.0667467000
_diffrn_orient_matrix_UB_31      -0.1711812000
_diffrn_orient_matrix_UB_32      -0.0151058000
_diffrn_orient_matrix_UB_33      -0.0593791000
_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  0.0375
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12546
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.951
_diffrn_reflns_theta_min         4.173
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.188
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76005
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.569
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.475
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         3722
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0247
_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^)+(0.0180P)^2^+1.1752P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0608
_refine_ls_wR_factor_ref         0.0621
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3429
_reflns_number_total             3722
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08522a2.cif
_cod_data_source_block           jms23002
_cod_depositor_comments          'Adding full bibliography for 1573704.cif.'
_cod_database_code               1573704
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     'Sara Bonfante SB36c'
_shelx_estimated_absorpt_t_max   0.652
_shelx_estimated_absorpt_t_min   0.357
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C2(H2A,H2B), C4(H4A,H4B), C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C17(H17), C18(H18), C19(H19), C13(H13), C21(H21), C15(H15),
 C20(H20), C14(H14), C12(H12), C16(H16)
;
_shelx_res_checksum              11179
_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 1.314
_oxdiff_exptl_absorpt_empirical_full_min 0.802