Controlled monodefluorination and alkylation of C(sp3)-F Bonds by Lanthanide Photocatalysts: Importance of Metal – Ligand Cooperativity
Kynman, Amy E.; Elghanayan, Luca; Desnoyer, Addison; Yang, Yan; Severy, Laurent; Di Giuseppe, Andrea; Tilley, T. Don; Maron, Laurent; Arnold, Polly Louise; Chemical Science  (2022) –; doi:10.1039/D2SC04192H

data_1567924
_publ_section_title
;
 Controlled monodefluorination and alkylation of C(sp3)-F Bonds by
 Lanthanide Photocatalysts: Importance of Metal -- Ligand Cooperativity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04192H
_journal_year                    2022
_chemical_formula_moiety         'C38 H55 La N2 O, C7 H8'
_chemical_formula_sum            'C45 H63 La N2 O'
_chemical_formula_weight         786.88
_chemical_properties_physical    Air-sensitive,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             2021-11-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-11-09 deposited with the CCDC.	2022-11-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.5670(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.30050(10)
_cell_length_b                   22.02780(10)
_cell_length_c                   15.63480(10)
_cell_measurement_reflns_used    110335
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.2670
_cell_measurement_theta_min      3.6260
_cell_volume                     4198.63(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_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    -79.00  25.00   0.50    0.13    --  -47.95  95.00 -93.00  208
  2  \w     -9.00  79.00   0.50    0.13    --   47.95 -95.00 156.00  176
  3  \w   -159.00 -83.00   0.50    0.50    --  -86.25 -95.00 156.00  152
  4  \w    -79.00 -13.00   0.50    0.50    --  -86.25  95.00 -93.00  132
  5  \w     35.00 105.00   0.50    0.50    --  107.75 -95.00 156.00  140
  6  \w    124.00 177.00   0.50    0.50    --  107.75  95.00 -93.00  106
  7  \w    -20.00   7.00   0.50    0.13    --   14.00 100.00-117.37   54
  8  \w     -7.00  20.00   0.50    0.13    --   18.00  83.00  38.42   54
  9  \w      5.00  30.00   0.50    0.13    --   26.00  72.00 129.21   50
 10  \w      5.00  30.00   0.50    0.13    --   26.00  72.00  25.75   50
 11  \w     14.00  40.00   0.50    0.13    --   30.00  65.00 -21.97   52
 12  \w     12.00  37.00   0.50    0.13    --   30.00  67.00 -73.41   50
 13  \w     22.00  47.00   0.50    0.13    --   38.00  61.00-152.68   50
 14  \w     22.00  49.00   0.50    0.13    --   38.00  60.00  85.44   54
 15  \w     23.00  48.00   0.50    0.13    --   38.00  60.00  21.03   50
 16  \w     22.00  47.00   0.50    0.13    --   38.00  61.00 136.07   50
 17  \w     22.00  47.00   0.50    0.13    --   38.00  60.00-113.96   50
 18  \w     22.00  47.00   0.50    0.13    --   38.00  61.00 166.52   50
 19  \w    -52.00 -26.00   0.50    0.13    --  -42.00 -59.00-116.82   52
 20  \w    -51.00 -26.00   0.50    0.13    --  -42.00 -59.00-156.92   50
 21  \w    -40.00  25.00   0.50    0.13    --  -47.95  37.00-180.00  130
 22  \w    -24.00  13.00   0.50    0.13    --   47.95 -19.00 -90.00   74
 23  \w     53.00  95.00   0.50    0.13    --   47.95-125.00-120.00   84
 24  \w     37.00  63.00   0.50    0.13    --   47.95  55.00-129.77   52
 25  \w   -120.00 -93.00   0.50    0.13    --  -50.00 -56.00-169.84   54
 26  \w    -63.00 -35.00   0.50    0.13    --  -50.00 -56.00-169.84   56
 27  \w     36.00  62.00   0.50    0.13    --   50.00  56.00 -94.43   52
 28  \w    -64.00 -39.00   0.50    0.13    --  -54.00 -55.00 103.49   50
 29  \w    -77.00 -40.00   0.50    0.13    --  -54.00 -54.00-131.60   74
 30  \w   -124.00 -88.00   0.50    0.13    --  -54.00 -54.00-131.60   72
 31  \w     40.00  78.00   0.50    0.13    --   54.00  56.00 105.93   76
 32  \w    -70.00 -43.00   0.50    0.13    --  -58.00 -56.00 -86.51   54
 33  \w    -79.00 -43.00   0.50    0.13    --  -58.00 -55.00  88.99   72
 34  \w    -97.00 -44.00   0.50    0.13    --  -58.00 -53.00   7.45  106
 35  \w     45.00  79.00   0.50    0.13    --   58.00  55.00  50.56   68
 36  \w    104.00 130.00   0.50    0.13    --   58.00  56.00  26.91   52
 37  \w     43.00  77.00   0.50    0.13    --   58.00  56.00  26.91   68
 38  \w    -83.00 -48.00   0.50    0.13    --  -62.00 -54.00 140.46   70
 39  \w     49.00  74.00   0.50    0.13    --   62.00  55.00 -27.61   50
 40  \w     89.00 115.00   0.50    0.13    --   62.00  55.00 -27.61   52
 41  \w    -78.00 -52.00   0.50    0.13    --  -66.00 -55.00  76.55   52
 42  \w     52.00  78.00   0.50    0.13    --   66.00  55.00  55.90   52
 43  \w    -89.00 -58.00   0.50    0.50    --  -70.00 -55.00 -43.49   62
 44  \w     55.00  81.00   0.50    0.13    --   70.00  56.00-118.46   52
 45  \w    -84.00 -55.00   0.50    0.50    --  -70.00 -55.00  72.19   58
 46  \w    -85.00 -59.00   0.50    0.50    --  -74.00 -55.00  44.16   52
 47  \w    -85.00 -59.00   0.50    0.50    --  -74.00 -55.00  18.85   52
 48  \w    -92.00 -60.00   0.50    0.50    --  -74.00 -54.00 -51.99   64
 49  \w    -93.00 -63.00   0.50    0.50    --  -78.00 -56.00-161.60   60
 50  \w    -89.00 -63.00   0.50    0.50    --  -78.00 -56.00-116.70   52
 51  \w    -93.00 -63.00   0.50    0.50    --  -78.00 -56.00 -25.09   60
 52  \w    -91.00 -63.00   0.50    0.50    --  -78.00 -56.00-136.98   56
 53  \w    -89.00 -63.00   0.50    0.50    --  -78.00 -56.00 111.70   52
 54  \w    -89.00 -63.00   0.50    0.50    --  -78.00 -56.00 147.40   52
 55  \w    -91.00 -63.00   0.50    0.50    --  -78.00 -55.00  12.48   56
 56  \w    -88.00 -63.00   0.50    0.50    --  -78.00 -56.00  68.34   50
 57  \w   -104.00 -68.00   0.50    0.50    --  -82.00 -55.00 -48.00   72
 58  \w    -93.00 -67.00   0.50    0.50    --  -82.00 -55.00 160.17   52
 59  \w    -93.00 -67.00   0.50    0.50    --  -82.00 -55.00 175.02   52
 60  \w    -92.00 -67.00   0.50    0.50    --  -82.00 -55.00 -95.91   50
 61  \w    -94.00 -67.00   0.50    0.50    --  -82.00 -55.00 105.13   54
 62  \w   -110.00 -68.00   0.50    0.50    --  -82.00 -53.00 -11.02   84
 63  \w    -92.00 -67.00   0.50    0.50    --  -82.00 -55.00 -73.29   50
 64  \w    -96.00 -71.00   0.50    0.50    --  -86.00 -55.00 144.38   50
 65  \w   -153.00-126.00   0.50    0.50    --  -86.00 -55.00-113.57   54
 66  \w   -112.00 -71.00   0.50    0.50    --  -86.00 -55.00-113.57   82
 67  \w    -98.00 -72.00   0.50    0.50    --  -86.25 -53.00 155.94   52
 68  \w   -122.00 -72.00   0.50    0.50    --  -86.25 -55.00   8.51  100
 69  \w   -100.00 -74.00   0.50    0.50    --  -86.25 -55.00 138.18   52
 70  \w   -104.00 -72.00   0.50    0.50    --  -86.25 -54.00  41.54   64
 71  \w    -98.00 -72.00   0.50    0.50    --  -86.25 -52.00  51.09   52
 72  \w    -97.00 -72.00   0.50    0.50    --  -86.25 -55.00 -97.48   50
 73  \w    -98.00 -72.00   0.50    0.50    --  -86.25 -54.00  82.91   52
 74  \w    -98.00 -72.00   0.50    0.50    --  -86.25 -55.00 -20.18   52
 75  \w   -104.00 -72.00   0.50    0.50    --  -86.25 -51.00 -65.80   64
 76  \w   -105.00 -72.00   0.50    0.50    --  -86.25 -54.00 -53.47   66
 77  \w    -99.00 -73.00   0.50    0.50    --  -86.25 -54.00-155.92   52
 78  \w    -98.00 -72.00   0.50    0.50    --  -86.25 -55.00 -76.04   52
 79  \w   -153.00-126.00   0.50    0.50    --  -86.25 -54.00-155.92   54
 80  \w   -159.00-109.00   0.50    0.50    --  -86.25 -55.00 -20.18  100
 81  \w     82.00 107.00   0.50    0.50    --   94.00-103.00 -86.42   50
 82  \w     28.00  64.00   0.50    0.50    --   94.00-103.00 -86.42   72
 83  \w     96.00 122.00   0.50    0.50    --  107.75  45.00 150.00   52
 84  \w    100.00 176.00   0.50    0.50    --  107.75 125.00 -30.00  152
 85  \w     35.00  69.00   0.50    0.50    --  107.75 -61.00 -90.00   68
 86  \w    145.00 178.00   0.50    0.50    --  107.75  61.00  30.00   66
 87  \w     74.00 111.00   0.50    0.50    --  107.75-125.00   0.00   74
 88  \w     37.00  63.00   0.50    0.50    --  107.75-125.00   0.00   52
 89  \w     91.00 140.00   0.50    0.50    --  107.75  61.00  30.00   98
 90  \w     97.00 123.00   0.50    0.50    --  107.75  45.00  90.00   52
 91  \w     91.00 178.00   0.50    0.50    --  107.75  61.00 120.00  174
 92  \w     65.00  97.00   0.50    0.50    --  107.75 -94.00  30.00   64
 93  \w    140.00 178.00   0.50    0.50    --  107.75  45.00  60.00   76
 94  \w     81.00 106.00   0.50    0.50    --  107.75 -94.00  60.00   50
 95  \w     36.00  69.00   0.50    0.50    --  107.75 -94.00  60.00   66
 96  \w    144.00 177.00   0.50    0.50    --  107.75  61.00-120.00   66
 97  \w     48.00  73.00   0.50    0.50    --  107.75 -61.00-120.00   50
 98  \w    147.00 174.00   0.50    0.50    --  107.75  61.00 -60.00   54
 99  \w     91.00 127.00   0.50    0.50    --  107.75  61.00-120.00   72
100  \w     35.00  61.00   0.50    0.50    --  107.75 -94.00  30.00   52
101  \w     91.00 120.00   0.50    0.50    --  107.75  61.00 -60.00   58
102  \w     96.00 130.00   0.50    0.50    --  107.75  45.00 120.00   68
103  \w    140.00 165.00   0.50    0.50    --  107.75  61.00-180.00   50
104  \w    132.00 178.00   0.50    0.50    --  107.75  45.00 -60.00   92
105  \w     35.00 112.00   0.50    0.50    --  107.75-125.00-120.00  154
106  \w     91.00 128.00   0.50    0.50    --  107.75  61.00-180.00   74
107  \w     35.00 105.00   0.50    0.50    --  107.75 -94.00   0.00  140
108  \w     96.00 126.00   0.50    0.50    --  107.75  45.00 -60.00   60
109  \w     68.00 106.00   0.50    0.50    --  107.75 -94.00 -90.00   76
110  \w     35.00 106.00   0.50    0.50    --  107.75 -94.00 -30.00  142
111  \w     96.00 123.00   0.50    0.50    --  107.75  45.00  60.00   54
112  \w     91.00 148.00   0.50    0.50    --  107.75  61.00  60.00  114
113  \w     94.00 142.00   0.50    0.50    --  107.75  61.00 -90.00   96
114  \w    146.00 171.00   0.50    0.50    --  107.75  45.00-180.00   50
115  \w    151.00 177.00   0.50    0.50    --  107.75  61.00   0.00   52
116  \w    127.00 158.00   0.50    0.50    --  107.75  45.00   0.00   62
117  \w     95.00 124.00   0.50    0.50    --  107.75  45.00   0.00   58
118  \w     91.00 134.00   0.50    0.50    --  107.75  61.00   0.00   86
119  \w     95.00 124.00   0.50    0.50    --  107.75  45.00-180.00   58
120  \w     40.00  66.00   0.50    0.50    --  107.75 -94.00 -90.00   52
121  \w     44.00  72.00   0.50    0.50    --  107.75 -61.00  90.00   56
122  \w     41.00 112.00   0.50    0.50    --  107.75-125.00-150.00  142
123  \w     35.00 108.00   0.50    0.50    --  107.75-109.00  78.63  146
124  \w    137.00 177.00   0.50    0.50    --  107.75  61.00-150.00   80
125  \w     40.00  66.00   0.50    0.50    --  107.75 -61.00   0.00   52
126  \w     91.00 133.00   0.50    0.50    --  107.75  61.00-150.00   84
127  \w    145.00 177.00   0.50    0.50    --  107.75  45.00 -30.00   64
128  \w    138.00 164.00   0.50    0.50    --  107.75  45.00  30.00   52
129  \w    101.00 127.00   0.50    0.50    --  107.75  45.00  30.00   52
130  \w     47.00 106.00   0.50    0.50    --  107.75 -94.00-120.00  118
131  \w    133.00 170.00   0.50    0.50    --  107.75  45.00 -90.00   74
132  \w     95.00 127.00   0.50    0.50    --  107.75  45.00 -90.00   64
133  \w    142.00 175.00   0.50    0.50    --  107.75  45.00-150.00   66
134  \w     91.00 141.00   0.50    0.50    --  107.75  61.00 -30.00  100
135  \w    132.00 158.00   0.50    0.50    --  107.75  45.00-120.00   52
136  \w     96.00 122.00   0.50    0.50    --  107.75  45.00-120.00   52
137  \w    149.00 177.00   0.50    0.50    --  107.75  61.00 150.00   56
138  \w     96.00 130.00   0.50    0.50    --  107.75  45.00-150.00   68
139  \w     95.00 129.00   0.50    0.50    --  107.75  45.00 -30.00   68
140  \w     91.00 145.00   0.50    0.50    --  107.75  61.00 150.00  108
141  \w     35.00 106.00   0.50    0.50    --  107.75 -97.00 163.52  142
142  \w    129.00 165.00   0.50    0.50    --  107.75   0.00-150.00   72
143  \w    138.00 176.00   0.50    0.50    --  107.75  61.00  90.00   76
144  \w     83.00 109.00   0.50    0.50    --  107.75   0.00-150.00   52
145  \w     36.00  76.00   0.50    0.50    --  107.75   0.00-150.00   80
146  \w     80.00 106.00   0.50    0.50    --  107.75 -94.00  90.00   52
147  \w     40.00 105.00   0.50    0.50    --  107.75 -94.00 120.00  130
148  \w    142.00 172.00   0.50    0.50    --  107.75  45.00 150.00   60
149  \w     41.00  74.00   0.50    0.50    --  107.75 -94.00  90.00   66
150  \w     91.00 131.00   0.50    0.50    --  107.75  61.00  90.00   80
151  \w    108.00 159.00   0.50    0.50    --  107.75 125.00-150.00  102
152  \w     45.00  73.00   0.50    0.50    --  107.75 -61.00 -60.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0683416000
_diffrn_orient_matrix_UB_12      0.0555960000
_diffrn_orient_matrix_UB_13      0.0505350000
_diffrn_orient_matrix_UB_21      -0.0384683000
_diffrn_orient_matrix_UB_22      0.0343616000
_diffrn_orient_matrix_UB_23      -0.0934921000
_diffrn_orient_matrix_UB_31      -0.0990186000
_diffrn_orient_matrix_UB_32      0.0248955000
_diffrn_orient_matrix_UB_33      0.0163883000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0535
_diffrn_reflns_av_unetI/netI     0.0171
_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       -16
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            163711
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.435
_diffrn_reflns_theta_min         3.626
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.101
_exptl_absorpt_correction_T_max  0.768
_exptl_absorpt_correction_T_min  0.368
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.116a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.245
_exptl_crystal_description       block
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.154
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.429
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     524
_refine_ls_number_reflns         8870
_refine_ls_number_restraints     289
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0226
_refine_ls_R_factor_gt           0.0214
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0255P)^2^+2.7210P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0545
_refine_ls_wR_factor_ref         0.0551
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8499
_reflns_number_total             8870
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04192h1.cif
_cod_data_source_block           pla21032_p2m
_cod_original_cell_volume        4198.63(5)
_cod_database_code               1567924
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'La N2 O C36 H60'
_shelx_estimated_absorpt_t_max   0.520
_shelx_estimated_absorpt_t_min   0.368
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C44-C45
 1.51 with sigma of 0.02
 C45-C39 = C45-C43 = C40-C41
 1.39 with sigma of 0.02
 C39-C40 = C41-C42 = C42-C43
 1.38 with sigma of 0.02
 C45-C40
 2.42 with sigma of 0.04
 C39-C41
 2.39 with sigma of 0.04
 C45-C42
 2.41 with sigma of 0.04
 C40-C42 = C41-C43
 2.4 with sigma of 0.04
 C44-C39 = C44-C43
 2.52 with sigma of 0.04
 C45-C39 \\sim C39-C40 \\sim C40-C41 \\sim C41-C42 \\sim C42-C43 \\sim C43-C45
 with sigma of 0.02
 C45-C42 \\sim C45-C40 \\sim C43-C41 \\sim C39-C43 \\sim C40-C42 \\sim C39-C41
 with sigma of 0.04
 C44-C43 \\sim C44-C39
 with sigma of 0.04
 C39-C40 \\sim C4A-C5A
 with sigma of 0.02
 C40-C41 \\sim C5A-C6A
 with sigma of 0.02
 C41-C42 \\sim C6A-C7A
 with sigma of 0.02
 C44-C45 \\sim C2A-C3A
 with sigma of 0.02
 C42-C43 \\sim C7A-C8A
 with sigma of 0.02
 C45-C39 \\sim C3A-C4A
 with sigma of 0.02
 C39-C43 \\sim C4A-C8A
 with sigma of 0.04
 C40-C42 \\sim C5A-C7A
 with sigma of 0.04
 C44-C39 \\sim C2A-C4A
 with sigma of 0.04
 C44-C43 \\sim C2A-C8A
 with sigma of 0.04
 C41-C43 \\sim C6A-C8A
 with sigma of 0.04
 C45-C40 \\sim C3A-C5A
 with sigma of 0.04
 C45-C42 \\sim C3A-C7A
 with sigma of 0.04
 C45-C43 \\sim C3A-C8A
 with sigma of 0.02
 C39-C41 \\sim C4A-C6A
 with sigma of 0.04
3. Restrained planarity
 C44, C45, C39, C40, C41, C42, C43
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C44 \\sim C45 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C44, C45, C39, C40, C41, C42, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2A, C3A, C4A, C5A, C6A, C7A, C8A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C44, C2A, C3A, C45, C8A, C7A, C42, C43, C6A, C5A, C4A, C39, C40, C41
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2A, C44, C45, C3A, C8A, C43, C42, C7A, C6A, C41, C5A, C40, C39, C4A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C41, C6A, C42, C7A, C43, C8A, C45, C3A, C39, C4A, C40, C5A, C2A, C44
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Sof(C7A)=Sof(H7A)=Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(H4A)=
 Sof(C8A)=Sof(H8AA)=Sof(C3A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=1-FVAR(1)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(C39)=Sof(H39)=Sof(C40)=
 Sof(H40)=Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C18(H18)
7.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C15(H15), C3(H3), C16(H16), C21(H21), C30(H30), C39(H39), C40(H40),
 C41(H41), C42(H42), C43(H43), C7A(H7A), C6A(H6A), C5A(H5A), C4A(H4A), C8A(H8AA)
7.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C38(H38A,H38B,H38C), C12(H12A,H12B,H12C), C8(H8A,H8B,H8C),
 C10(H10A,H10B,H10C), C19(H19A,H19B,H19C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C27(H27A,H27B,H27C), C20(H20A,H20B,H20C), C14(H14A,H14B,H14C), C13(H13A,
 H13B,H13C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C),
 C29(H29A,H29B,H29C), C44(H44A,H44B,H44C), C2A(H2AA,H2AB,H2AC)
;
_shelx_res_checksum              73367
_shelx_hkl_checksum              71760
_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 2.270
_oxdiff_exptl_absorpt_empirical_full_min 0.738