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_1575201
_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         'C33 H75 Ce Cl N4 Si3'
_chemical_formula_sum            'C33 H75 Ce Cl N4 Si3'
_chemical_formula_weight         787.81
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-23
_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                 90.572(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9683(8)
_cell_length_b                   15.5387(9)
_cell_length_c                   20.3785(12)
_cell_measurement_reflns_used    17273
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.82
_cell_measurement_theta_min      2.26
_cell_volume                     4106.3(4)
_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 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
 540 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  0.0760
_diffrn_reflns_av_unetI/netI     0.1053
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            31438
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.020
_diffrn_reflns_theta_min         2.270
_diffrn_source                   Axo_Mo
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.287
_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            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.274
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1672
_refine_diff_density_max         0.722
_refine_diff_density_min         -0.422
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.910
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         8013
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.910
_refine_ls_R_factor_all          0.0806
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0325P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0666
_refine_ls_wR_factor_ref         0.0737
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5194
_reflns_number_total             8013
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03626g3.cif
_cod_data_source_block           2_Cl
_cod_depositor_comments
'Adding full bibliography for 1575197--1575202.cif.'
_cod_database_code               1575201
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. 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
2.a Ternary CH refined with riding coordinates:
 C13(H13), C19(H19), C31(H31), C28(H28), C10(H10), C22(H22), C25(H25),
 C16(H16), C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C1(H1A,H1B), C4(H4A,H4B), C3(H3A,H3B), C6(H6A,H6B), C5(H5A,H5B)
2.c Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C15(H15A,H15B,H15C), C26(H26A,H26B,H26C), C12(H12A,H12B,
 H12C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C8(H8A,H8B,H8C), C24(H24A,
 H24B,H24C), C33(H33A,H33B,H33C), C14(H14A,H14B,H14C), C9(H9A,H9B,H9C),
 C20(H20A,H20B,H20C), C11(H11A,H11B,H11C), C27(H27A,H27B,H27C), C23(H23A,H23B,
 H23C), C21(H21A,H21B,H21C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              30318
_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 89.2
_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 58.6
_stoe_evaluation_lana_max_2theta_desired 58.6
_stoe_evaluation_lana_mean_redundancy 3.6
_stoe_evaluation_lana_number_refls_after_or 35934
_stoe_evaluation_lana_number_refls_outliers 1811
_stoe_evaluation_lana_number_refls_total 37745
_stoe_evaluation_lana_number_refls_unique 10003
_stoe_evaluation_lana_number_refls_written 35934
_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           6.7   12.9   19.1   25.3   31.5   37.7   43.9   50.1   56.3
<Resolution>    5.17   3.11   2.16   1.60   1.30   1.10   0.95   0.84   0.77
N(total)         434   1670   2057   3125   4975   6613   7730   8214   2927
<Redundancy>     7.9    7.9    4.4    3.9    4.3    4.1    3.7    3.2    2.0
Complet. [%%]    94.1   96.5   97.7   98.1   99.4   99.7   99.7   99.8   55.8
<I/sigma>       52.2   36.9   24.5   16.2    8.0    4.9    2.8    1.7    1.1
R(int)         0.018  0.024  0.030  0.037  0.063  0.096  0.154  0.225  0.302
;
_stoe_measurement_identifier     AC311
_stoe_measurement_max_exposure_per_frame '120.0 s'
_stoe_measurement_mean_exposure_per_frame '120.0 s'
_stoe_measurement_min_exposure_per_frame '120.0 s'
_stoe_measurement_total_exposure_time '18.0 h'
_stoe_measurement_total_frame_number 540
_stoe_measurement_total_run_number 8
_stoe_measurement_tube_power     '50.0 W'