Visible-light driven photoreduction of carbon dioxide to syngas with decatungstate-based metal-organic frameworks
Li, Hua; Fu, Yaomei; Wu, Shuangxue; Liu, Li; Wang, Xinlong; Qin, Chao; Su, Zhong-Min; Physical Chemistry Chemical Physics  (2025) –; doi:10.1039/D5CP02729B

data_7250829
_publ_section_title
;
 Visible-light driven photoreduction of carbon dioxide to syngas with
 decatungstate-based metal-organic frameworks
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP02729B
_journal_year                    2025
_chemical_formula_moiety         'C40 H36 Co2 N12 O40 W10'
_chemical_formula_sum            'C40 H36 Co2 N12 O40 W10'
_chemical_formula_weight         3281.17
_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_block_doi                 10.5517/ccdc.csd.cc2fcyqh
_audit_creation_date             2023-03-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-02 deposited with the CCDC.	2025-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                105.86(7)
_cell_angle_beta                 106.92(7)
_cell_angle_gamma                103.27(5)
_cell_formula_units_Z            1
_cell_length_a                   10.665(9)
_cell_length_b                   12.477(11)
_cell_length_c                   15.956(18)
_cell_measurement_reflns_used    2444
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      20.71
_cell_measurement_theta_min      2.68
_cell_volume                     1840(3)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      294.91
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1931
_diffrn_reflns_av_unetI/netI     0.0927
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            32864
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        20.984
_diffrn_reflns_theta_max         20.984
_diffrn_reflns_theta_min         2.611
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    16.084
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    2.960
_exptl_crystal_description       block
_exptl_crystal_F_000             1474
_refine_diff_density_max         2.978
_refine_diff_density_min         -1.806
_refine_diff_density_rms         0.364
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     457
_refine_ls_number_reflns         3862
_refine_ls_number_restraints     1015
_refine_ls_restrained_S_all      0.969
_refine_ls_R_factor_all          0.1208
_refine_ls_R_factor_gt           0.0559
_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^)+(0.0459P)^2^+136.1846P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1157
_refine_ls_wR_factor_ref         0.1504
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2389
_reflns_number_total             3862
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp02729b2.cif
_cod_data_source_block           1_sq
_cod_original_cell_volume        1841(3)
_cod_database_code               7250829
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 H19_$1-H9_$2
 2.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C4 \\sim C6 \\sim C16 \\sim C12 \\sim C14 \\sim C2 \\sim C3 \\sim C5
\\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C13 \\sim C15 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim N1 \\sim N4 \\sim N2 \\sim N3 \\sim N6
\\sim N5 \\sim O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7 \\sim
O8 \\sim O9 \\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim O15 \\sim
O16 \\sim O17 \\sim O18 \\sim O19 \\sim O20: within 3.8A with sigma of 0.01 and
sigma for terminal atoms of 0.03
Uanis(O18) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(W2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a :
 N1(N4,C1,C4,C6)
4.b Aromatic/amide H refined with riding coordinates:
 N4(H4), C1(H1), N6(H6), C14(H14), C3(H3), C7(H7), C10(H10), C13(H13),
 C18(H18), C20(H20)
4.c Fitted pentagon refined as free rotating group:
 N3(C16,C12,N6,C14)
4.d Tetrahedral OH refined with riding coordinates:
 O9(H9), O19(H19)
4.e Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              8215
_shelx_fab_checksum              19842
_olex2_submission_special_instructions 'No special instructions were received'