Synthesis and properties of metal trifluoride complexes with amide-functionalised tacn macrocycles and radiofluorination of [GaF<sub>3</sub>(L1)] by <sup>18</sup>F/<sup>19</sup>F isotopic exchange.
O'Callaghan, Charley; Greenacre, Victoria K.; King, Rhys P.; Grigg, Julian; Herniman, Julie M.; McRobbie, Graeme; Reid, Gillian; Dalton transactions (Cambridge, England : 2003) 53 (2024) 14897–14909; doi:10.1039/d4dt02074j

data_7716869
_publ_section_title
;
 Synthesis and properties of metal trifluoride complexes with
 amide-functionalised tacn macrocycles and radiofluorination of
 [GaF<sub>3</sub>(L1)] by <sup>18</sup>F/<sup>19</sup>F isotopic exchange.
;
_journal_issue                   35
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14897
_journal_page_last               14909
_journal_paper_doi               10.1039/d4dt02074j
_journal_volume                  53
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C24 H48 F3 In N6 O3'
_chemical_formula_sum            'C24 H48 F3 In N6 O3'
_chemical_formula_weight         640.501
_space_group_crystal_system      trigonal
_space_group_IT_number           161
_space_group_name_Hall           'R 3 -2"c'
_space_group_name_H-M_alt        'R 3 c :H'
_symmetry_Int_Tables_number      161
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-25
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.11.24 svn.r209d9fb2 for OlexSys, GUI svn.r6869)
;
_audit_update_record
;
2024-05-16 deposited with the CCDC.	2024-08-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   14.2596(2)
_cell_length_b                   14.2596(2)
_cell_length_c                   26.9863(5)
_cell_measurement_reflns_used    48857
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      33.6310
_cell_measurement_theta_min      4.3780
_cell_volume                     4752.13(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9948
_diffrn_measured_fraction_theta_max 0.9964
_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    -56.00  -3.00   0.50    8.00    --  -16.39 113.00-150.00  106
  2  \w    -27.00  40.00   0.50    8.00    --   19.52 -72.00   0.00  134
  3  \w     21.00  64.00   0.50    8.00    --  -16.39  19.00-180.00   86
  4  \w     21.00  64.00   0.50    8.00    --  -16.39  19.00 -60.00   86
  5  \w    -60.00 -17.00   0.50    8.00    --   19.52 -19.00  30.00   86
  6  \w    -56.00  -2.00   0.50    8.00    --  -16.39 -57.00   0.00  108
  7  \w    -60.00 -17.00   0.50    8.00    --   19.52 -19.00  90.00   86
  8  \w    -37.00  34.00   0.50    8.00    --  -16.39  72.00 130.00  142
  9  \w    -31.00  46.00   0.50    8.00    --  -16.39  57.00-150.00  154
 10  \w    -73.00 -21.00   0.50    8.00    --  -16.39 140.00 -59.87  104
 11  \w    -55.00  -4.00   0.50    8.00    --  -16.39 -57.00 -30.00  102
 12  \w    -70.00 -45.00   0.50    8.00    --  -16.39 135.00  -3.17   50
 13  \w     34.00  62.00   0.50    8.00    --  -16.39  19.00 150.00   56
 14  \w    -53.00 -28.00   0.50    8.00    --  -16.39 105.00 134.52   50
 15  \w    -92.00 -48.00   0.50    8.00    --  -16.39 -38.00-120.00   88
 16  \w    -28.00  -2.00   0.50    8.00    --  -16.39 -38.00-120.00   52
 17  \w    -54.00  -6.00   0.50    8.00    --  -16.39 -57.00  30.00   96
 18  \w    -48.00   7.00   0.50    8.00    --  -16.39  95.00  60.32  110
 19  \w    -53.00 -18.00   0.50    8.00    --  -16.39 105.00 -98.82   70
 20  \w      5.00  95.00   0.50    8.00    --   19.52  38.00-150.00  180
 21  \w     21.00  97.00   0.50    8.00    --   19.52  19.00 150.00  152
 22  \w      7.00  56.00   0.50    8.00    --   19.52  57.00 -60.00   98
 23  \w     -3.00  24.00   0.50    8.00    --   19.52  76.00   5.50   54
 24  \w     15.00  60.00   0.50    8.00    --   19.52  57.00-150.00   90
 25  \w     21.00  64.00   0.50    8.00    --  -16.39  19.00 -90.00   86
 26  \w    -56.00  -2.00   0.50    8.00    --  -16.39 -57.00 -60.00  108
 27  \w    -52.00   3.00   0.50    8.00    --  -16.39 104.00 161.53  110
 28  \w    -53.00   2.00   0.50    8.00    --  -16.39 105.00 -83.46  110
 29  \w    -97.00 -17.00   0.50    8.00    --  -16.39 -19.00   0.00  160
 30  \w    -72.00 -20.00   0.50    8.00    --  -16.39 139.00  90.06  104
 31  \w    -56.00  -2.00   0.50    8.00    --  -16.39 -57.00-150.00  108
 32  \w      0.00  53.00   0.50    8.00    --   19.52 -99.00  60.00  106
 33  \w     -2.00  26.00   0.50    8.00    --   19.52  75.00   0.79   56
 34  \w      5.00  97.00   0.50    8.00    --   19.52  38.00-180.00  184
 35  \w     -4.00  23.00   0.50    8.00    --   19.52  78.00 -93.06   54
 36  \w    -60.00 -17.00   0.50    8.00    --   19.52 -19.00  60.00   86
 37  \w    -60.00 -17.00   0.50    8.00    --   19.52 -19.00 -30.00   86
 38  \w      5.00  62.00   0.50    8.00    --   19.52  57.00   0.00  114
 39  \w      0.00  36.00   0.50    8.00    --   19.52  70.00-168.22   72
 40  \w    -60.00 -17.00   0.50    8.00    --   19.52 -19.00-180.00   86
 41  \w      0.00  53.00   0.50    8.00    --   19.52 -99.00 120.00  106
 42  \w     -4.00  23.00   0.50    8.00    --   19.52  78.00-165.99   54
 43  \w    -18.00   7.00   0.50    8.00    --   19.52 -72.00   0.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0284850000
_diffrn_orient_matrix_UB_12      0.0542352000
_diffrn_orient_matrix_UB_13      0.0086240000
_diffrn_orient_matrix_UB_21      0.0229924000
_diffrn_orient_matrix_UB_22      -0.0156724000
_diffrn_orient_matrix_UB_23      0.0193318000
_diffrn_orient_matrix_UB_31      0.0442803000
_diffrn_orient_matrix_UB_32      0.0105260000
_diffrn_orient_matrix_UB_33      -0.0155885000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0120
_diffrn_reflns_Laue_measured_fraction_full 0.9948
_diffrn_reflns_Laue_measured_fraction_max 0.9964
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            50509
_diffrn_reflns_point_group_measured_fraction_full 0.9948
_diffrn_reflns_point_group_measured_fraction_max 0.9960
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.70
_diffrn_reflns_theta_min         4.43
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.796
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88763
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             2001.127
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.7809
_refine_diff_density_min         -0.5152
_refine_diff_density_rms         0.0906
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   -0.018(8)
_refine_ls_d_res_high            0.7401
_refine_ls_d_res_low             4.5993
_refine_ls_goodness_of_fit_ref   1.0319
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    38
_refine_ls_number_parameters     115
_refine_ls_number_reflns         2726
_refine_ls_number_restraints     65
_refine_ls_restrained_S_all      1.0194
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0350
_refine_ls_shift/su_max          0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0611P)^2^+15.4967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0945
_refine_ls_wR_factor_ref         0.0962
_reflns_Friedel_coverage         0.996
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              9
_reflns_limit_k_min              -9
_reflns_limit_l_max              36
_reflns_limit_l_min              -36
_reflns_number_gt                2571
_reflns_number_total             2726
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4dt02074j2.cif
_cod_data_source_block           CB9494_InF3L2_reprocessed2
_cod_depositor_comments
'Adding full bibliography for 7716867--7716872.cif.'
_cod_original_sg_symbol_Hall     ' R 3 -2"c'
_cod_original_sg_symbol_H-M      'R 3 c'
_cod_database_code               7716869
_chemical_oxdiff_formula         'In F3 C24 H48 N6 O3'
_chemical_oxdiff_usercomment     'Clear Block'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C6-C7 \\sim C6-C7a
 with sigma of 0.02
 C6-C8 \\sim C6-C8a
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(C1) = Uanis(C3)
Uanis(C4) = Uanis(C3)
Uanis(C8) = Uanis(C8a)
4. Rigid body (RIGU) restrains
 In1, F1, O1, N1, N2, H2, C1, C2, C3, H3a, H3b, C4, H4a, H4b, C5, C6, H6a, H6b,
  C7, H7a, H7b, H7c, C7a, H7aa, H7ab, H7ac, C8, H8a, H8b, H8c, C8a, H8aa, H8ab,
 H8ac
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H6b)=Sof(C7a)=Sof(H7aa)=Sof(H7ab)=Sof(H7ac)=Sof(C8a)=Sof(H8aa)=Sof(H8ab)=
 Sof(H8ac)=1-FVAR(1)
 Sof(H6a)=Sof(C7)=Sof(H7a)=Sof(H7b)=Sof(H7c)=Sof(C8)=Sof(H8a)=Sof(H8b)=
 Sof(H8c)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C6(H6a), C6(H6b)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1a,H1b), C2(H2a,H2b), C3(H3a,H3b), C4(H4a,H4b)
6.c Aromatic/amide H refined with riding coordinates:
 N2(H2)
6.d Idealised Me refined with everything fixed:
 C7a(H7aa,H7ab,H7ac), C8a(H8aa,H8ab,H8ac)
6.e Idealised Me refined as rotating group:
 C7(H7a,H7b,H7c), C8(H8a,H8b,H8c)
;
_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 4.415
_oxdiff_exptl_absorpt_empirical_full_min 0.357