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_7713265
_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 N, F2 H, 2(F H)'
_chemical_formula_sum            'C20 H35 F4 N'
_chemical_formula_weight         365.49
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-19
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-05-16 deposited with the CCDC.	2023-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.056(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4339(3)
_cell_length_b                   14.8964(5)
_cell_length_c                   14.3883(5)
_cell_measurement_reflns_used    5776
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.8690
_cell_measurement_theta_min      2.9320
_cell_volume                     2201.98(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (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 0.998
_diffrn_measured_fraction_theta_max 0.989
_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    -70.00  35.00   1.00    2.13    --  -40.98  77.00 -30.00  105
  2  \w   -109.00 -17.00   1.00    2.13    --  -40.98 -57.00  90.00   92
  3  \w    -65.00  29.00   1.00    2.13    --  -40.98  57.00-120.00   94
  4  \w     27.00  71.00   1.00    2.13    --   40.98 -77.00   0.00   44
  5  \w     -7.00  20.00   1.00    2.13    --   40.98 -77.00   0.00   27
  6  \w     36.00 117.00   1.00    8.53    --  103.58 -45.00-180.00   81
  7  \w     26.00 109.00   1.00    8.53    --  103.58 -80.00  31.77   83
  8  \w     73.00 107.00   1.00    8.53    --  103.58 -78.00-112.15   34
  9  \w     81.00 176.00   1.00    8.53    --  103.58  45.00-150.00   95
 10  \w     29.00 106.00   1.00    8.53    --  103.58 -80.00  87.85   77
 11  \w    115.00 178.00   1.00    8.53    --  103.58  77.00  90.00   63
 12  \w    135.00 171.00   1.00    8.53    --  103.58  77.00-180.00   36
 13  \w    103.00 161.00   1.00    8.53    --  103.58  77.00-120.00   58
 14  \w     75.00 100.00   1.00    8.53    --  103.58  61.00   0.00   25
 15  \w     78.00 177.00   1.00    8.53    --  103.58  45.00 150.00   99
 16  \w     67.00  92.00   1.00    8.53    --  103.58 -79.00 -77.52   25
 17  \w     45.00 108.00   1.00    8.53    --  103.58 -80.00 -35.09   63
 18  \w     73.00 100.00   1.00    8.53    --  103.58 -77.00-150.00   27
 19  \w     31.00 107.00   1.00    8.53    --  103.58 -80.00 160.69   76
;
_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      0.0858473000
_diffrn_orient_matrix_UB_12      -0.0748025000
_diffrn_orient_matrix_UB_13      -0.0304468000
_diffrn_orient_matrix_UB_21      0.1188645000
_diffrn_orient_matrix_UB_22      0.0629503000
_diffrn_orient_matrix_UB_23      0.0189192000
_diffrn_orient_matrix_UB_31      0.0313532000
_diffrn_orient_matrix_UB_32      -0.0337747000
_diffrn_orient_matrix_UB_33      0.1026639000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            16124
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        70.000
_diffrn_reflns_theta_max         72.330
_diffrn_reflns_theta_min         4.303
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.724
_exptl_absorpt_correction_T_max  0.858
_exptl_absorpt_correction_T_min  0.726
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.102
_exptl_crystal_description       block
_exptl_crystal_F_000             792
_exptl_crystal_size_max          0.612
_exptl_crystal_size_mid          0.42
_exptl_crystal_size_min          0.269
_refine_diff_density_max         0.313
_refine_diff_density_min         -0.149
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     243
_refine_ls_number_reflns         4295
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0715P)^2^+0.4220P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1323
_refine_ls_wR_factor_ref         0.1475
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3212
_reflns_number_total             4295
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01476b2.cif
_cod_data_source_block           exp_mecaach+h3f4-
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7713265
_shelxl_version_number           2018/1
_chemical_oxdiff_formula         'C20 H35 N F4'
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.666
_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, All F(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C12(H12), C13(H13), C14(H14)
2.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              5249
_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 1.222
_oxdiff_exptl_absorpt_empirical_full_min 0.813