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_1575197
_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_absolute_configuration rmad
_chemical_formula_moiety         'C33 H75 Ce I N4 Si3, C16 H32 Li O4'
_chemical_formula_sum            'C49 H107 Ce I Li N4 O4 Si3'
_chemical_formula_weight         1174.61
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-09-25
_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
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.7985(6)
_cell_length_b                   17.8628(8)
_cell_length_c                   19.3154(6)
_cell_measurement_reflns_used    59840
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.05
_cell_measurement_theta_min      2.28
_cell_volume                     6141.0(4)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.175.0 (STOE, 2021)
;
_computing_data_reduction
;
X-Area Integrate 2.5.1.0 (STOE, 2021)
X-Area X-Red 2.3.0.0 (STOE, 2021)
;
_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 2.0, Darmstadt 2021
;
_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 0.953
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measurement_details
;
 593 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  0.0214
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.953
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            42273
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.280
_diffrn_source                   Axo_Mo
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.342
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.270
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2468
_refine_diff_density_max         1.114
_refine_diff_density_min         -0.917
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.134(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     619
_refine_ls_number_reflns         11846
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0417
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0535P)^2^+2.6586P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0849
_refine_ls_wR_factor_ref         0.0888
_reflns_Friedel_coverage         0.915
_reflns_Friedel_fraction_full    0.929
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                10465
_reflns_number_total             11846
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03626g3.cif
_cod_data_source_block           1_LiI_THF4
_cod_depositor_comments
'Adding full bibliography for 1575197--1575202.cif.'
_cod_database_code               1575197
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.866(17)
 0.134(17)
2. 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
3. Restrained distances
 C10-C12 \\sim C10-C12A
 with sigma of 0.02
 C13-C15 \\sim C13-C15A
 with sigma of 0.02
 C13-C14 \\sim C13-C14A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C35 \\sim C34 \\sim C36 \\sim C37: within 2A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 2A
C39 \\sim C40 \\sim C38 \\sim C41: within 2A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 2A
C49 \\sim C46 \\sim C47 \\sim C48: within 2A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 2A
C45 \\sim C42 \\sim C44 \\sim C43: within 2A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 2A
C10 \\sim C11 \\sim C12 \\sim C12A: within 2A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 2A
C13 \\sim C15 \\sim C14 \\sim C15A \\sim C14A: within 2A with sigma of 0.004
and sigma for terminal atoms of 0.008 within 2A
5. Others
 Sof(H10A)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(H10)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
 Sof(H13A)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C14A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=1-FVAR(2)
 Sof(H13)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C16(H16), C28(H28), C25(H25), C22(H22), C31(H31), C19(H19), C10(H10),
 C10(H10A), C13(H13), C13(H13A), C7(H7)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C1(H1A,H1B), C3(H3A,H3B), C6(H6A,H6B), C5(H5A,H5B), C4(H4A,H4B),
 C45(H45A,H45B), C35(H35A,H35B), C39(H39A,H39B), C41(H41A,H41B), C40(H40A,H40B),
  C42(H42A,H42B), C38(H38A,H38B), C34(H34A,H34B), C44(H44A,H44B), C49(H49A,
 H49B), C46(H46A,H46B), C47(H47A,H47B), C43(H43A,H43B), C36(H36A,H36B),
 C37(H37A,H37B), C48(H48A,H48B)
6.c Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C23(H23A,H23B,H23C), C29(H29A,H29B,H29C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C18(H18A,H18B,H18C), C33(H33A,H33B,H33C), C15(H15A,
 H15B,H15C), C17(H17A,H17B,H17C), C21(H21A,H21B,H21C), C30(H30A,H30B,H30C),
 C24(H24A,H24B,H24C), C20(H20A,H20B,H20C), C14(H14A,H14B,H14C), C11(H11A,H11B,
 H11C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C9(H9A,H9B,H9C), C12A(H12D,H12E,
 H12F), C15A(H15D,H15E,H15F), C14A(H14D,H14E,H14F)
;
_shelx_res_checksum              60911
_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 6
_stoe_evaluation_lana_bos_l_odd_max 3
_stoe_evaluation_lana_completeness 93.6
_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 58.0
_stoe_evaluation_lana_max_2theta_desired 58.0
_stoe_evaluation_lana_mean_redundancy 6.1
_stoe_evaluation_lana_number_refls_after_or 47819
_stoe_evaluation_lana_number_refls_outliers 10183
_stoe_evaluation_lana_number_refls_total 58002
_stoe_evaluation_lana_number_refls_unique 7887
_stoe_evaluation_lana_number_refls_written 47819
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group mmm
_stoe_evaluation_lana_table
;
2Theta           7.2   13.2   19.2   25.2   31.2   37.2   43.2   49.2   55.2
<Resolution>    4.94   3.05   2.15   1.61   1.32   1.11   0.97   0.85   0.78
N(total)         802   2639   3380   5432   8085  10052  10835  11338   5439
<Redundancy>    11.3   12.7    7.9    7.6    7.7    7.2    6.4    5.4    3.1
Complet. [%%]   100.0  100.0  100.0  100.0  100.0  100.0  100.0   99.9   74.8
<I/sigma>      161.9  123.0   75.3   51.6   28.8   16.6   10.1    5.8    3.6
R(int)         0.020  0.018  0.020  0.020  0.026  0.031  0.045  0.072  0.106
;
_stoe_measurement_identifier     SC001
_stoe_measurement_max_exposure_per_frame '80.0 s'
_stoe_measurement_mean_exposure_per_frame '80.0 s'
_stoe_measurement_min_exposure_per_frame '80.0 s'
_stoe_measurement_total_exposure_time '13.2 h'
_stoe_measurement_total_frame_number 593
_stoe_measurement_total_run_number 13
_stoe_measurement_tube_power     '50.0 W'