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_7713267
_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         '2(C20 H32 F N), C20 H32 N, F2 H'
_chemical_formula_sum            'C60 H97 F4 N3'
_chemical_formula_weight         936.40
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                96.869(3)
_cell_angle_beta                 96.961(3)
_cell_angle_gamma                93.453(3)
_cell_formula_units_Z            2
_cell_length_a                   9.3894(3)
_cell_length_b                   17.6755(7)
_cell_length_c                   17.8951(7)
_cell_measurement_reflns_used    7046
_cell_measurement_temperature    150.01(11)
_cell_measurement_theta_max      72.0660
_cell_measurement_theta_min      3.3470
_cell_volume                     2918.44(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_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)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.6426
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.972
_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    -19.00  32.00   1.00   30.61    --  -40.98  58.00 -65.00   51
  2  \w   -112.00 -15.00   1.00   30.61    --  -40.98 -58.00 153.00   97
  3  \w     19.00  64.00   1.00   30.61    --   40.98  58.00 -65.00   45
  4  \w     -5.00  20.00   1.00   30.61    --   40.98 -58.00 153.00   25
  5  \w     76.00 174.00   1.00  122.43    --  103.58  58.00 -65.00   98
  6  \w     30.00  57.00   1.00  122.43    --  103.58 -58.00 153.00   27
  7  \w    -73.00  34.00   1.00   30.61    --  -40.98  77.00  30.00  107
  8  \w    -19.00  67.00   1.00   30.61    --   40.98 -77.00-120.00   86
  9  \w    -10.00  72.00   1.00   30.61    --   40.98 -77.00-180.00   82
 10  \w     44.00  74.00   1.00   30.61    --   40.98 -77.00  30.00   30
 11  \w     95.00 121.00   1.00  122.43    --  103.58  61.00 120.00   26
 12  \w     28.00 110.00   1.00  122.43    --  103.58 -80.00  70.42   82
 13  \w     33.00  60.00   1.00  122.43    --  103.58 -79.00 -60.58   27
 14  \w     77.00 105.00   1.00  122.43    --  103.58 -79.00-164.31   28
 15  \w    103.00 175.00   1.00  122.43    --  103.58  77.00   0.00   72
 16  \w    111.00 163.00   1.00  122.43    --  103.58  77.00  30.00   52
 17  \w     27.00  60.00   1.00  122.43    --  103.58 -79.00-164.31   33
 18  \w    131.00 161.00   1.00  122.43    --  103.58  61.00 120.00   30
 19  \w     89.00 122.00   1.00  122.43    --  103.58 -80.00  34.51   33
 20  \w     68.00 108.00   1.00  122.43    --  103.58 -80.00-101.19   40
 21  \w     36.00 136.00   1.00  122.43    --  103.58 -80.00 152.42  100
 22  \w    106.00 142.00   1.00  122.43    --  103.58  77.00 150.00   36
 23  \w     79.00 136.00   1.00  122.43    --  103.58 -79.00 -60.58   57
 24  \w    105.00 178.00   1.00  122.43    --  103.58  77.00-120.00   73
 25  \w     75.00 102.00   1.00  122.43    --  103.58 -80.00  21.66   27
 26  \w    122.00 149.00   1.00  122.43    --  103.58  77.00-150.00   27
 27  \w     31.00 122.00   1.00  122.43    --  103.58 -45.00 -60.00   91
;
_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_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            11761
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        70.000
_diffrn_reflns_theta_max         72.552
_diffrn_reflns_theta_min         3.324
_exptl_absorpt_coefficient_mu    0.546
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94916
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
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    1.066
_exptl_crystal_description       block
_exptl_crystal_F_000             1028
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile and t-BuOH'
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.266
_exptl_crystal_size_min          0.121
_refine_diff_density_max         0.357
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     702
_refine_ls_number_reflns         11761
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0762
_refine_ls_R_factor_gt           0.0566
_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^)+(0.0982P)^2^+0.0761P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1491
_refine_ls_wR_factor_ref         0.1600
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8607
_reflns_number_total             11761
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.8280\% 
around [0.00 1.00 0.00] (reciprocal) or [0.14 0.98 0.13] (direct)
;
_cod_data_source_file            d3dt01476b2.cif
_cod_data_source_block           exp_1438_caachf_tbuoh_mecn_twin1_hklf4
_cod_original_cell_volume        2918.4(2)
_cod_database_code               7713267
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7935(10)
 0.2065(10)
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, All F(H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C47B) = Uanis(C47A)
Uanis(C44B) = Uanis(C44A)
4. Others
 Sof(F21B)=Sof(H22A)=1-FVAR(1)
 Sof(F21A)=Sof(H22)=FVAR(1)
 Sof(F41B)=Sof(H42A)=1-FVAR(2)
 Sof(F41A)=Sof(H42)=FVAR(2)
 Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=Sof(H27D)=Sof(H27E)=
 Sof(H27F)=1-FVAR(3)
 Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=FVAR(3)
 Sof(C24B)=Sof(H24C)=Sof(H24D)=1-FVAR(4)
 Sof(C24A)=Sof(H24A)=Sof(H24B)=FVAR(4)
 Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47B)=Sof(H47D)=Sof(H47E)=
 Sof(H47F)=1-FVAR(5)
 Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47A)=Sof(H47A)=Sof(H47B)=
 Sof(H47C)=FVAR(5)
 Sof(C44B)=Sof(H44C)=Sof(H44D)=1-FVAR(6)
 Sof(C44A)=Sof(H44A)=Sof(H44B)=FVAR(6)
5.a Ternary CH refined with riding coordinates:
 C22(H22), C22(H22A), C36(H36), C39(H39), C42(H42), C42(H42A), C56(H56),
 C59(H59), C16(H16), C19(H19)
5.b Secondary CH2 refined with riding coordinates:
 C24A(H24A,H24B), C24B(H24C,H24D), C44A(H44A,H44B), C44B(H44C,H44D), C4(H4A,H4B)
5.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C33(H33), C34(H34), C52(H52), C53(H53), C54(H54), C2(H2), C12(H12),
 C13(H13), C14(H14)
5.d Idealised Me refined as rotating group:
 C26A(H26A,H26B,H26C), C26B(H26D,H26E,H26F), C27A(H27A,H27B,H27C), C27B(H27D,
 H27E,H27F), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C37(H37A,H37B,H37C),
 C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C46A(H46A,H46B,
 H46C), C46B(H46D,H46E,H46F), C47A(H47A,H47B,H47C), C47B(H47D,H47E,H47F),
 C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C57(H57A,H57B,H57C), C58(H58A,H58B,
 H58C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), 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              32833
_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
;