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_7713266
_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         '3(F H), 2(F3 H2), 2(C20 H32 N)'
_chemical_formula_sum            'C40 H71 F9 N2'
_chemical_formula_weight         750.98
_chemical_properties_physical    Moisture-sensitive,Heat-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
_audit_creation_date             2023-04-11
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-16 deposited with the CCDC.	2023-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.3955(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.90751(18)
_cell_length_b                   31.7144(5)
_cell_length_c                   12.95482(18)
_cell_measurement_reflns_used    11730
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.1580
_cell_measurement_theta_min      3.6290
_cell_volume                     4481.29(12)
_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 2016/6 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.00
_diffrn_detector_area_resol_mean 10.6426
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_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    -60.00   3.00   1.00   15.37    --  -41.11  47.00  61.00   63
  2  \w   -111.00 -33.00   1.00   15.37    --  -41.11 -73.00 101.00   78
  3  \w     68.00  94.00   1.00   61.47    --  103.58 -73.00 101.00   26
  4  \w    117.00 175.00   1.00   61.47    --  103.58  47.00  61.00   58
  5  \w     99.00 125.00   1.00   61.47    --  103.58 -73.00 101.00   26
  6  \w     72.00 117.00   1.00   61.47    --  103.58  73.00-129.00   45
  7  \w     54.00 130.00   1.00   61.47    --  103.58 -47.00 -87.00   76
  8  \w    -53.00 -27.00   1.00   15.37    --  -41.11  73.00-129.00   26
  9  \w    -21.00  22.00   1.00   15.37    --   41.11 -77.00-180.00   43
 10  \w    103.00 177.00   1.00   61.47    --  103.58  77.00 -90.00   74
 11  \w    105.00 131.00   1.00   61.47    --  103.58  77.00 -30.00   26
 12  \w    106.00 178.00   1.00   61.47    --  103.58  77.00 -60.00   72
 13  \w     39.00  98.00   1.00   15.37    --   41.23-133.00-137.00   59
 14  \w     61.00  87.00   1.00   61.47    --  103.58 178.00  60.00   26
 15  \w    107.00 133.00   1.00   61.47    --  103.58 178.00  60.00   26
 16  \w     41.00 101.00   1.00   61.47    --  103.58-111.00  90.00   60
 17  \w    -76.00 -51.00   1.00   15.37    --  -41.23 133.00 -69.00   25
 18  \w   -102.00 -24.00   1.00   15.37    --  -41.23 -38.00-150.00   78
 19  \w    -84.00 -27.00   1.00   15.37    --  -41.23 -38.00 -90.00   57
 20  \w    139.00 165.00   1.00   61.47    --  103.58  77.00   0.00   26
 21  \w     68.00 104.00   1.00   61.47    --  103.58-111.00  30.00   36
 22  \w     78.00 131.00   1.00   61.47    --  103.58  45.00  90.00   53
 23  \w    148.00 174.00   1.00   61.47    --  103.58  45.00  90.00   26
 24  \w     57.00 109.00   1.00   61.47    --  103.58-111.00-150.00   52
 25  \w     27.00  75.00   1.00   61.47    --  103.58 -94.00 120.00   48
 26  \w     78.00 109.00   1.00   61.47    --  103.58-111.00 -60.00   31
 27  \w     99.00 175.00   1.00   61.47    --  103.58  61.00-180.00   76
 28  \w     73.00 123.00   1.00   61.47    --  103.58 -61.00-180.00   50
 29  \w     84.00 109.00   1.00   61.47    --  103.58-111.00  90.00   25
 30  \w     31.00  57.00   1.00   61.47    --  103.58 -61.00 -60.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            38097
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        70.000
_diffrn_reflns_theta_max         72.376
_diffrn_reflns_theta_min         2.787
_exptl_absorpt_coefficient_mu    0.756
_exptl_absorpt_correction_T_max  0.917
_exptl_absorpt_correction_T_min  0.872
_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            'dull light colourless'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.113
_exptl_crystal_description       block
_exptl_crystal_F_000             1624
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: HF'
_exptl_crystal_size_max          0.344
_exptl_crystal_size_mid          0.288
_exptl_crystal_size_min          0.216
_refine_diff_density_max         0.414
_refine_diff_density_min         -0.292
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     518
_refine_ls_number_reflns         8757
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0775
_refine_ls_R_factor_gt           0.0607
_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^)+(0.0885P)^2^+1.6771P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1666
_refine_ls_wR_factor_ref         0.1811
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6680
_reflns_number_total             8757
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01476b2.cif
_cod_data_source_block           exp_773
_cod_original_cell_volume        4481.30(12)
_cod_database_code               7713266
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9812(5)
 0.0188(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H7A,H7B,H7C} of C7, All C(H,H) groups
 At 1.5 times of:
  {H21A,H21B,H21C} of C21, {H27A,H27B,H27C} of C27, {H29A,H29B,H29C} of C29,
  {H17A,H17B,H17C} of C17, {H26A,H26B,H26C} of C26, {H28A,H28B,H28C} of C28,
  {H18A,H18B,H18C} of C18, {H20A,H20B,H20C} of C20, {H37A,H37B,H37C} of C37,
  {H38A,H38B,H38C} of C38, {H41A,H41B,H41C} of C41, {H40A,H40B,H40C} of C40,
  {H8A,H8B,H8C} of C8, {H6A,H6B,H6C} of C6, {H9A,H9B,H9C} of C9
3. Others
 Sof(F1B)=Sof(F2B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=FVAR(1)
 Fixed X: H23(0.71897) H1A(0.78908)
 Fixed Y: H23(0.53831) H1A(0.27568)
 Fixed Z: H23(0.91218) H1A(0.20184)
4.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C36(H36), C39(H39)
4.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C24(H24A,H24B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C12(H12), C13(H13), C14(H14), C22(H22), C32(H32), C33(H33), C34(H34)
4.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),
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C)
;
_shelx_res_checksum              38558
_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
;