From cyclic (alkyl)(amino)carbene (CAAC) precursors to fluorinating reagents. Experimental and theoretical study.
Gruden, Evelin; Prinčič, Griša Grigorij; Hočevar, Jan; Iskra, Jernej; Kvíčala, Jaroslav; Tavčar, Gašper; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt01476b

data_7713264
_publ_section_title
;
 From cyclic (alkyl)(amino)carbene (CAAC) precursors to fluorinating
 reagents. Experimental and theoretical study.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt01476b
_journal_year                    2023
_chemical_formula_moiety         'C20 H32 F N'
_chemical_formula_sum            'C20 H32 F N'
_chemical_formula_weight         305.46
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-11
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2023-05-16 deposited with the CCDC.	2023-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.4960(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.33810(10)
_cell_length_b                   12.42200(10)
_cell_length_c                   12.3701(2)
_cell_measurement_reflns_used    22440
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.3070
_cell_measurement_theta_min      3.5370
_cell_volume                     1817.85(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6426
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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     -6.00  24.00   1.00    3.12    --  -40.98  77.00   0.00   30
  2  \w    -64.00  30.00   1.00    3.12    --  -40.98  57.00-120.00   94
  3  \w    -74.00 -44.00   1.00    3.12    --  -40.98  77.00   0.00   30
  4  \w   -109.00 -18.00   1.00    3.12    --  -40.98 -57.00  90.00   91
  5  \w    -20.00  74.00   1.00    3.12    --   40.98 -77.00 -30.00   94
  6  \w     79.00 165.00   1.00   12.46    --  103.58  45.00   0.00   86
  7  \w     32.00  95.00   1.00   12.46    --  103.58 -45.00-180.00   63
  8  \w     92.00 119.00   1.00   12.46    --  103.58 -80.00 -89.12   27
  9  \w    106.00 177.00   1.00   12.46    --  103.58  77.00-150.00   71
 10  \w    102.00 130.00   1.00   12.46    --  103.58 -80.00 -47.70   28
 11  \w     90.00 173.00   1.00   12.46    --  103.58  45.00 -60.00   83
 12  \w    104.00 163.00   1.00   12.46    --  103.58  77.00-120.00   59
 13  \w     91.00 117.00   1.00   12.46    --  103.58  61.00-180.00   26
 14  \w    140.00 176.00   1.00   12.46    --  103.58  61.00-180.00   36
 15  \w     31.00 125.00   1.00   12.46    --  103.58 -80.00  12.23   94
 16  \w     76.00 101.00   1.00   12.46    --  103.58 -77.00  90.00   25
 17  \w     33.00  84.00   1.00   12.46    --  103.58 -80.00 -47.70   51
 18  \w     80.00 107.00   1.00   12.46    --  103.58 -80.00-124.76   27
 19  \w     78.00 103.00   1.00   12.46    --  103.58 -77.00  60.00   25
 20  \w     30.00  94.00   1.00   12.46    --  103.58 -77.00 120.00   64
 21  \w     27.00 117.00   1.00   12.46    --  103.58 -80.00 173.00   90
 22  \w     43.00  86.00   1.00   12.46    --  112.00 -56.00-168.00   43
 23  \w    -92.00 -14.00   1.00    3.12    --  -41.23 -57.00 -30.00   78
 24  \w    -74.00 -13.00   1.00    3.12    --  -41.23 -57.00 150.00   61
 25  \w   -114.00 -79.00   1.00    3.12    --  -41.23 -57.00 150.00   35
 26  \w   -113.00 -14.00   1.00    3.12    --  -41.23 -57.00 -90.00   99
 27  \w     10.00  40.00   1.00    3.12    --   41.23  76.00 -75.45   30
 28  \w     13.00  40.00   1.00    3.12    --   41.23  79.00 -30.13   27
 29  \w      8.00  40.00   1.00    3.12    --   41.23  80.00  67.44   32
 30  \w      9.00  41.00   1.00    3.12    --   41.23  80.00-127.42   32
 31  \w    -12.00  63.00   1.00    3.12    --   41.23 -77.00 120.00   75
 32  \w      9.00  41.00   1.00    3.12    --   41.23  77.00 114.90   32
 33  \w    -31.00  31.00   1.00    3.12    --   41.23 -57.00  30.00   62
 34  \w     83.00 108.00   1.00   12.46    --  112.00  61.00-150.00   25
 35  \w     86.00 114.00   1.00   12.46    --  112.00  45.00  30.00   28
 36  \w    141.00 174.00   1.00   12.46    --  112.00  61.00-150.00   33
 37  \w     86.00 134.00   1.00   12.46    --  112.00  45.00  90.00   48
 38  \w    140.00 178.00   1.00   12.46    --  112.00  56.00 -26.00   38
 39  \w     83.00 174.00   1.00   12.46    --  112.00  61.00 -90.00   91
 40  \w     86.00 144.00   1.00   12.46    --  112.00  45.00-120.00   58
 41  \w     35.00  74.00   1.00   12.46    --  112.00 -80.00  -3.09   39
 42  \w    133.00 166.00   1.00   12.46    --  112.00  45.00 -30.00   33
 43  \w    116.00 178.00   1.00   12.46    --  112.00  61.00 -60.00   62
 44  \w     84.00 126.00   1.00   12.46    --  112.00  56.00 -26.00   42
 45  \w     83.00 108.00   1.00   12.46    --  112.00  61.00 -60.00   25
 46  \w     39.00 118.00   1.00   12.46    --  112.00 -80.00 143.87   79
 47  \w     83.00 172.00   1.00   12.46    --  112.00  61.00 120.00   89
 48  \w     83.00 108.00   1.00   12.46    --  112.00  61.00  30.00   25
 49  \w    120.00 177.00   1.00   12.46    --  112.00  61.00  30.00   57
 50  \w     83.00 133.00   1.00   12.46    --  112.00  61.00-180.00   50
 51  \w    140.00 170.00   1.00   12.46    --  112.00  61.00-180.00   30
 52  \w     83.00 109.00   1.00   12.46    --  112.00  61.00  60.00   26
 53  \w     86.00 111.00   1.00   12.46    --  112.00  45.00 -30.00   25
 54  \w    121.00 147.00   1.00   12.46    --  112.00  45.00-180.00   26
 55  \w    120.00 178.00   1.00   12.46    --  112.00  61.00   0.00   58
 56  \w     86.00 158.00   1.00   12.46    --  112.00  45.00-150.00   72
 57  \w     35.00 130.00   1.00   12.46    --  112.00 -78.00 -40.78   95
 58  \w     83.00 109.00   1.00   12.46    --  112.00  61.00   0.00   26
 59  \w     89.00 142.00   1.00   12.46    --  112.00  45.00 -90.00   53
 60  \w     39.00  82.00   1.00   12.46    --  112.00 -77.00-180.00   43
 61  \w     98.00 143.00   1.00   12.46    --  112.00 -77.00-180.00   45
 62  \w     41.00 129.00   1.00   12.46    --  112.00 -45.00   0.00   88
 63  \w     94.00 122.00   1.00   12.46    --  112.00 -56.00-168.00   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0962935000
_diffrn_orient_matrix_UB_12      0.0635811000
_diffrn_orient_matrix_UB_13      -0.0815797000
_diffrn_orient_matrix_UB_21      -0.0863163000
_diffrn_orient_matrix_UB_22      -0.0828442000
_diffrn_orient_matrix_UB_23      0.0177205000
_diffrn_orient_matrix_UB_31      -0.0153452000
_diffrn_orient_matrix_UB_32      0.0669221000
_diffrn_orient_matrix_UB_33      0.0994782000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0083
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_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       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            4451
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        70.000
_diffrn_reflns_theta_max         76.382
_diffrn_reflns_theta_min         3.736
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.548
_exptl_absorpt_correction_T_max  0.902
_exptl_absorpt_correction_T_min  0.858
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.88a (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.116
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.307
_exptl_crystal_size_min          0.226
_refine_diff_density_max         0.369
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         4451
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0414
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0777P)^2^+0.2618P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1158
_refine_ls_wR_factor_ref         0.1182
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4089
_reflns_number_total             4451
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9965\% 
around [-0.27 -0.00 0.96] (reciprocal) or [-0.00 0.00 1.00] (direct)
;
_cod_data_source_file            d3dt01476b2.cif
_cod_data_source_block           exp_910_605_mecaach+h2f3-_csf_twin1_hklf4
_cod_database_code               7713264
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C20 H30 N F'
_shelx_estimated_absorpt_t_max   0.886
_shelx_estimated_absorpt_t_min   0.836
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7790(15)
 0.2210(15)
2. 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
3.a Ternary CH refined with riding coordinates:
 C2(H2), C16(H16), C19(H19)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
3.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14)
3.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C17(H17A,
 H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              46267
_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 1.229
_oxdiff_exptl_absorpt_empirical_full_min 0.878
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2