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_7716872
_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_formula_moiety         'C20 H34 F3 Fe N4 O, 2.4[H2O]'
_chemical_formula_sum            'C20 H34 F3 Fe N4 O'
_chemical_formula_weight         459.360
_chemical_name_systematic
'[FeF3(1,4-diisopropyl-7-phenylacetamide-1,4,7-triazacyclononane)]'
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_symmetry_Int_Tables_number      148
_audit_creation_date             2024-01-17
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_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            18
_cell_length_a                   33.7472(5)
_cell_length_b                   33.7472(5)
_cell_length_c                   10.2893(2)
_cell_measurement_reflns_used    58387
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.8360
_cell_measurement_theta_min      2.0780
_cell_volume                     10148.3(3)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (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 0.9998
_diffrn_measured_fraction_theta_max 0.9998
_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    -55.00   0.00   0.50   11.95    --  -10.97 -58.00  90.00  110
  2  \w    -23.00  62.00   0.50   11.95    --  -10.97  58.00-128.00  170
  3  \w      3.00  61.00   0.50   11.95    --   13.32  58.00-128.00  116
  4  \w    -56.00  25.00   0.50   11.95    --   13.32 -58.00  90.00  162
  5  \w    -40.00   9.00   0.50   11.95    --  -10.97  95.00 173.68   98
  6  \w    -40.00   9.00   0.50   11.95    --  -10.97  95.00 144.68   98
  7  \w    -56.00   1.00   0.50   11.95    --  -10.97 -57.00  30.00  114
  8  \w    -56.00   1.00   0.50   11.95    --  -10.97 -57.00 -60.00  114
  9  \w    -39.00  11.00   0.50   11.95    --  -10.97  93.00 -53.14  100
 10  \w    -88.00 -17.00   0.50   11.95    --  -10.97 -19.00   0.00  142
 11  \w    -88.00 -17.00   0.50   11.95    --  -10.97 -19.00   0.00  142
 12  \w    -86.00  -5.00   0.50   11.95    --  -10.97 -38.00 120.00  162
 13  \w    -40.00   9.00   0.50   11.95    --  -10.97  95.00 -20.04   98
 14  \w    -40.00   9.00   0.50   11.95    --  -10.97  95.00-123.45   98
 15  \w    -40.00   9.00   0.50   11.95    --  -10.97  95.00  85.01   98
 16  \w    -40.00   9.00   0.50   11.95    --  -10.97  95.00  32.86   98
 17  \w     21.00  92.00   0.50   11.95    --   13.32  19.00 -30.00  142
 18  \w      2.00  62.00   0.50   11.95    --   13.32  57.00 -90.00  120
 19  \w     -9.00  18.00   0.50   11.95    --   13.32  83.00 -64.96   54
 20  \w    -64.00 -17.00   0.50   11.95    --   13.32 -19.00 150.00   94
 21  \w     21.00  67.00   0.50   11.95    --  -10.97  19.00 -60.00   92
 22  \w    -40.00  -1.00   0.50   11.95    --  -10.97  95.00 -74.88   78
 23  \w    -65.00 -21.00   0.50   11.95    --  -10.97 140.00  92.16   88
 24  \w    -64.00 -20.00   0.50   11.95    --  -10.97 139.00 -27.25   88
 25  \w    -39.00  11.00   0.50   11.95    --  -10.97  93.00-148.85  100
 26  \w    -44.00   3.00   0.50   11.95    --  -10.97 104.00-104.11   94
 27  \w     21.00  67.00   0.50   11.95    --  -10.97  19.00 -90.00   92
 28  \w    -40.00   9.00   0.50   11.95    --  -10.97  95.00  55.71   98
 29  \w      2.00  62.00   0.50   11.95    --   13.32  57.00 -60.00  120
 30  \w      2.00  62.00   0.50   11.95    --   13.32  57.00  30.00  120
;
_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      -0.0165226333
_diffrn_orient_matrix_UB_12      -0.0107131667
_diffrn_orient_matrix_UB_13      0.0498384333
_diffrn_orient_matrix_UB_21      -0.0068887333
_diffrn_orient_matrix_UB_22      0.0165728333
_diffrn_orient_matrix_UB_23      -0.0078157667
_diffrn_orient_matrix_UB_31      -0.0163817333
_diffrn_orient_matrix_UB_32      -0.0141223667
_diffrn_orient_matrix_UB_33      -0.0469891667
_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  0.0522
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 0.9998
_diffrn_reflns_Laue_measured_fraction_max 0.9998
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            147068
_diffrn_reflns_point_group_measured_fraction_full 0.9998
_diffrn_reflns_point_group_measured_fraction_max 0.9998
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.70
_diffrn_reflns_theta_min         2.09
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.711
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57363
_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    1.353
_exptl_crystal_description       block
_exptl_crystal_F_000             4383.574
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.015
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.3753
_refine_diff_density_min         -0.3946
_refine_diff_density_rms         0.0668
_refine_ls_d_res_high            0.7401
_refine_ls_d_res_low             9.7420
_refine_ls_goodness_of_fit_ref   1.1033
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     568
_refine_ls_number_reflns         5824
_refine_ls_number_restraints     1209
_refine_ls_restrained_S_all      0.9948
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0275
_refine_ls_shift/su_max          -0.0006
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0201P)^2^+13.8343P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0574
_refine_ls_wR_factor_ref         0.0614
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              38
_reflns_limit_h_min              0
_reflns_limit_k_max              39
_reflns_limit_k_min              0
_reflns_limit_l_max              13
_reflns_limit_l_min              -13
_reflns_number_gt                4943
_reflns_number_total             5824
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4dt02074j2.cif
_cod_data_source_block           CB9494_73_FeF3L3_REPROCESSEDcopy3
_cod_depositor_comments
'Adding full bibliography for 7716867--7716872.cif.'
_cod_original_sg_symbol_H-M      'R -3'
_cod_original_formula_sum        'C20 H34 F3 Fe1 N4 O1'
_cod_database_code               7716872
_chemical_oxdiff_formula         C20H34F3FeN4O
_olex2_refinement_description
;
1. Rigid body (RIGU) restrains
 C11, H11C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, Fe1, F1, F2, F3, N1, N2, N3, C1, C6, C2, C3, C10, C13, C4, C5, H7, H1a,
 H1b, H6a, H6b, C8, C9, H5b, H2a, H2b, H3a, H3b, H10, C11, C12, H13a, H13b, C14,
  H4a, H4b, H5a, H8a, H8b, H8c, H9a, H9b, H9c, H11A, H11B, H11C, H, H12B, H12C,
 O1, N4, H4, C15, C16, C20, H16, C17, C19, H20, H17, C18, H19, H18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Fe1, F1, F2, F3, N1, N2, N3, C1, C6, C7, C2, C3, C10, C13, C4, C5, H7, H1a,
 H1b, H6a, H6b, C8, C9, H5b, H2a, H2b, H3a, H3b, H10, C11, C12, H13a, H13b, C14,
  H4a, H4b, H5a, H8a, H8b, H8c, H9a, H9b, H9c, H11A, H11B, H11C, H, H12B, H12C,
 O1, N4, H4, C15, C16, C20, H16, C17, C19, H20, H17, C18, H19, H18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 24 electrons were 
found in a volume of 813\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
2.4[H2O] per Unit Cell 
which account for 24 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         PBE
   BASIS SET:      def2-TZVP
   CHARGE:         0
   MULTIPLICITY:   2
   DATE:           2024-01-16_17-14-45
;
_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 2.025
_oxdiff_exptl_absorpt_empirical_full_min 0.601