Visible light activation of C-Cl and C-F bonds in persistent organic pollutants using cerium(iii) triamidoamine complex.
Combourieu, Adrien; Christodoulou, Stella; Maron, Laurent; Assendjee, Eachann; Casaretto, Nicolas; Phung, Bich Tuyen; Banyasz, Akos; Maury, Olivier; Gregson, Matthew; Wooles, Ashley J.; Liddle, Stephen T.; Tard, Cédric; Nocton, Grégory; Danoun, Grégory; Chemical science 16 (2025) 15510–15517; doi:10.1039/d5sc03626g

data_1575202
_publ_section_title
;
 Visible light activation of C-Cl and C-F bonds in persistent organic
 pollutants using cerium(iii) triamidoamine complex.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              15510
_journal_page_last               15517
_journal_paper_doi               10.1039/d5sc03626g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '8(C33 H75 Ce F N4 Si3)'
_chemical_formula_sum            'C264 H600 Ce8 F8 N32 Si24'
_chemical_formula_weight         6170.84
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-14
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-27 deposited with the CCDC.	2025-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.739(4)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   20.3562(10)
_cell_length_b                   19.9580(9)
_cell_length_c                   20.6752(11)
_cell_measurement_reflns_used    29348
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.95
_cell_measurement_theta_min      1.59
_cell_volume                     8159.4(7)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.186.0 (STOE, 2022)
;
_computing_data_reduction
;
X-Area Integrate 2.5.3.0 (STOE, 2021)
X-Area LANA 2.7.5.0 (STOE, 2022)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 2.1, Darmstadt 2022
;
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'EIGER2 1M CDTE'
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.902
_diffrn_measurement_details
;
 553 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.902
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            77535
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.902
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.644
_diffrn_reflns_theta_min         2.270
_diffrn_source                   Axo_Mo
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.234
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  1.0000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3280
_refine_diff_density_max         0.677
_refine_diff_density_min         -0.873
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1214
_refine_ls_number_reflns         22744
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0371
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0397P)^2^+7.1942P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0869
_refine_ls_wR_factor_ref         0.0998
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16506
_reflns_number_total             22744
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03626g3.cif
_cod_data_source_block           2_F
_cod_depositor_comments
'Adding full bibliography for 1575197--1575202.cif.'
_cod_database_code               1575202
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2.a Idealised Me refined as rotating group:
 C27B(H27A,H27B,H27C), C20B(H20A,H20B,H20C), C26A(H26D,H26E,H26F), C14B(H14A,
 H14B,H14C), C15A(H15D,H15E,H15F), C8A(H8AA,H8AB,H8AC), C8B(H8BA,H8BB,H8BC),
 C14A(H14D,H14E,H14F), C9B(H9BA,H9BB,H9BC), C18A(H18D,H18E,H18F), C17A(H17D,
 H17E,H17F), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F)
;
_shelx_res_checksum              10397
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '60.0 mm'
_stoe_detector_pixelsize_x       '0.075 mm'
_stoe_detector_pixelsize_y       '0.075 mm'
_stoe_detector_size_x            '8.0 cm'
_stoe_detector_size_y            '7.7 cm'
_stoe_evaluation_integration_a   14.5
_stoe_evaluation_integration_b   0.7
_stoe_evaluation_integration_ems 0.013
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 90.2
_stoe_evaluation_lana_dxs_max_order 3
_stoe_evaluation_lana_dys_max_order 3
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 61.3
_stoe_evaluation_lana_max_2theta_desired 61.3
_stoe_evaluation_lana_mean_redundancy 3.4
_stoe_evaluation_lana_number_refls_after_or 78608
_stoe_evaluation_lana_number_refls_outliers 6628
_stoe_evaluation_lana_number_refls_total 85236
_stoe_evaluation_lana_number_refls_unique 23354
_stoe_evaluation_lana_number_refls_written 78608
_stoe_evaluation_lana_or_c1      0.050
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      1.0
_stoe_evaluation_lana_point_group 2/m
_stoe_evaluation_lana_table
;
2Theta           7.3   13.7   20.1   26.5   32.9   39.3   45.7   52.1   58.5
<Resolution>    4.89   2.90   2.02   1.52   1.25   1.05   0.91   0.81   0.74
N(total)        1317   3149   5293   6081  10663  14780  17290  17993   8670
<Redundancy>     7.5    5.6    4.5    3.2    3.8    3.9    3.5    3.1    2.2
Complet. [%%]   100.0  100.0   99.5   97.1   99.7  100.0  100.0   99.8   61.3
<I/sigma>       98.7   87.0   51.9   38.3   21.0   13.7    8.6    5.3    3.5
R(int)         0.018  0.020  0.024  0.023  0.028  0.035  0.051  0.077  0.104
;
_stoe_measurement_identifier     FCeTRENTIPS
_stoe_measurement_max_exposure_per_frame '130.0 s'
_stoe_measurement_mean_exposure_per_frame '130.0 s'
_stoe_measurement_min_exposure_per_frame '130.0 s'
_stoe_measurement_total_exposure_time '20.0 h'
_stoe_measurement_total_frame_number 553
_stoe_measurement_total_run_number 7
_stoe_measurement_tube_power     '50.0 W'