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_7713263
_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, F3 H2'
_chemical_formula_sum            'C20 H34 F3 N'
_chemical_formula_weight         345.48
_chemical_properties_physical    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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-17
_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                 103.161(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8109(4)
_cell_length_b                   9.4778(3)
_cell_length_c                   20.4419(7)
_cell_measurement_reflns_used    4945
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      71.7950
_cell_measurement_theta_min      4.2480
_cell_volume                     2039.53(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(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 0.986
_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    -73.00  35.00   1.00    2.46    --  -41.11  77.00 -20.00  108
  2  \w    -21.00  50.00   1.00    2.46    --   41.11 -77.00-146.00   71
  3  \w     51.00  82.00   1.00    9.84    --  103.58 -77.00-146.00   31
  4  \w    110.00 178.00   1.00    9.84    --  103.58  77.00 -20.00   68
  5  \w    -73.00  28.00   1.00    2.46    --  -41.11  77.00 120.00  101
  6  \w     38.00 112.00   1.00    2.46    --   41.11  57.00  90.00   74
  7  \w     20.00  63.00   1.00    2.46    --   41.11  57.00  60.00   43
  8  \w     57.00 109.00   1.00    2.46    --   41.11  57.00   0.00   52
  9  \w    103.00 178.00   1.00    9.84    --  103.58  77.00  60.00   75
 10  \w     26.00 116.00   1.00    9.84    --  103.58 -80.00 165.57   90
 11  \w     99.00 176.00   1.00    9.84    --  103.58  45.00  30.00   77
 12  \w     76.00 103.00   1.00    9.84    --  103.58 -79.00 131.21   27
 13  \w     64.00 115.00   1.00    9.84    --  103.58 -80.00-106.30   51
 14  \w     35.00  60.00   1.00    9.84    --  103.58 -80.00-106.30   25
 15  \w     86.00 173.00   1.00    9.84    --  103.58  45.00 120.00   87
 16  \w     76.00 103.00   1.00    9.84    --  103.58 -80.00  91.02   27
 17  \w     30.00  55.00   1.00    9.84    --  103.58 -79.00 -32.50   25
 18  \w     88.00 124.00   1.00    9.84    --  103.58 -79.00 -32.50   36
 19  \w     32.00  67.00   1.00    9.84    --  103.58 -45.00  30.00   35
 20  \w    104.00 150.00   1.00    9.84    --  103.58  77.00 150.00   46
 21  \w     81.00 108.00   1.00    9.84    --  103.58 -45.00  30.00   27
 22  \w     58.00  85.00   1.00    9.84    --  103.58 -79.00  47.66   27
 23  \w    118.00 168.00   1.00    9.84    --  103.58  45.00 -60.00   50
 24  \w     27.00 124.00   1.00    9.84    --  103.58 -80.00   5.22   97
 25  \w     41.00  66.00   1.00    9.84    --  103.58 -45.00   0.00   25
;
_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      -0.1431681000
_diffrn_orient_matrix_UB_12      0.0251236000
_diffrn_orient_matrix_UB_13      -0.0069948000
_diffrn_orient_matrix_UB_21      0.0050320000
_diffrn_orient_matrix_UB_22      -0.0856080000
_diffrn_orient_matrix_UB_23      0.0646251000
_diffrn_orient_matrix_UB_31      0.0297611000
_diffrn_orient_matrix_UB_32      0.1359131000
_diffrn_orient_matrix_UB_33      0.0420024000
_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  0.0388
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            16584
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        70.000
_diffrn_reflns_theta_max         72.274
_diffrn_reflns_theta_min         4.281
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.684
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.951
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.125
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.459
_exptl_crystal_size_mid          0.222
_exptl_crystal_size_min          0.197
_refine_diff_density_max         0.469
_refine_diff_density_min         -0.163
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         3973
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0498
_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^)+(0.0650P)^2^+0.6968P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1289
_refine_ls_wR_factor_ref         0.1391
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3211
_reflns_number_total             3973
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01476b2.cif
_cod_data_source_block           exp_698_573_mecaach+h2f3-
_cod_original_cell_volume        2039.53(12)
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               7713263
_shelxl_version_number           2017/1
_chemical_oxdiff_formula         'C20 H32 N F3'
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.744
_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. Others
 Fixed Uiso: H2B(0.05135)
3.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), 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(H21B,H21A,H21C)
;
_shelx_res_checksum              11119
_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 1.227
_oxdiff_exptl_absorpt_empirical_full_min 0.840