Highly efficient photoelectrocatalytic oxidation of arsenic(iii) with a polyoxometalate-thiacalix[4]arene-based metal–organic complex-modified bismuth vanadate photoanode
Song, Yuting; Zhang, Jia-Yi; Yang, Jin; Bo, Tao; Ma, Jian-Fang; Green Chemistry 26 (2024) 3874–3883; doi:10.1039/D3GC04755E

data_7248212
_publ_section_title
;
 Highly efficient photoelectrocatalytic oxidation of arsenic(iii) with a
 polyoxometalate-thiacalix[4]arene-based metal--organic complex-modified
 bismuth vanadate photoanode
;
_journal_issue                   7
_journal_name_full               'Green Chemistry'
_journal_page_first              3874
_journal_page_last               3883
_journal_paper_doi               10.1039/D3GC04755E
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety
'O40 P W12, C112 H145 Ag2 N32 O8 S16, 2[C2H5OH], 2[CH3CN]'
_chemical_formula_sum            'C120 H163 Ag2 N34 O50 P S16 W12'
_chemical_formula_weight         5847.70
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-04-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-09-12 deposited with the CCDC.	2024-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                75.711(4)
_cell_angle_beta                 77.491(4)
_cell_angle_gamma                88.110(4)
_cell_formula_units_Z            1
_cell_length_a                   12.6937(6)
_cell_length_b                   18.4490(8)
_cell_length_c                   19.5975(7)
_cell_measurement_reflns_used    6952
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.3130
_cell_measurement_theta_min      3.5160
_cell_volume                     4340.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.118a (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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0541
_diffrn_reflns_av_unetI/netI     0.0993
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            27986
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         3.281
_exptl_absorpt_coefficient_mu    8.418
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39633
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.237
_exptl_crystal_description       block
_exptl_crystal_F_000             2774
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         2.004
_refine_diff_density_min         -1.446
_refine_diff_density_rms         0.207
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1040
_refine_ls_number_reflns         15233
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0969
_refine_ls_R_factor_gt           0.0556
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0343P)^2^+2.3809P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1062
_refine_ls_wR_factor_ref         0.1277
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10064
_reflns_number_total             15233
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc04755e2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7248212.cif.'
_cod_database_code               7248212
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.432
_shelx_estimated_absorpt_t_min   0.202
_olex2_refinement_description
;
1. Restrained distances
 H9-H17A
 2.2 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
C35 \\sim C36 \\sim C37 \\sim C38: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C48 \\sim C50: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(P1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C49) \\sim Ueq, Uanis(C53) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: O15(0.5) O16(0.5) O17(0.5) O26(0.5) H9(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C17(H17A,H17B), C18(H18A,H18B), C39(H39A,H39B),
 C40(H40A,H40B), C52(H52A,H52B), C53(H53A,H53B)
4.b Aromatic/amide H refined with riding coordinates:
 N9(H9), C7(H7), C9(H9A), C21(H21), C23(H23), C32(H32), C34(H34), C46(H46),
 C56(H56)
4.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,
 H28B,H28C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C42(H42A,H42B,H42C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,
 H51C), C55(H55A,H55B,H55C)
;
_shelx_res_checksum              9817
_shelx_hkl_checksum              90016
_shelx_fab_checksum              17965
_platon_squeeze_special_details
;
A solvent mask was calculated and 269 electrons were 
found in a volume of 545\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C2H5OH] and 1[CH3CN] per Asymmetric Unit 
which account for 96 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'