Polyoxometalate-based electron transfer modulation for efficient electrocatalytic carbon dioxide reduction
Du, Jing; Lang, Zhong-Ling; Ma, Yuan-Yuan; Tan, Hua-Qiao; Liu, Bai-Ling; Wang, Yong-Hui; Kang, Zhen-Hui; Li, Yang-Guang; Chemical Science 11 (2020) 3007–3015; doi:10.1039/C9SC05392A

data_1557284
_publ_section_title
;
 Polyoxometalate-based electron transfer modulation for efficient
 electrocatalytic carbon dioxide reduction
;
_journal_issue                   11
_journal_name_full               'Chemical Science'
_journal_page_first              3007
_journal_page_last               3015
_journal_paper_doi               10.1039/C9SC05392A
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'O40 Si W12, 4(C15 H11 Mn N3 O3)'
_chemical_formula_sum            'C60 H44 Mn4 N12 O52 Si W12'
_chemical_formula_weight         4219.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-01-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-24 deposited with the CCDC.	2020-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.907(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.8686(19)
_cell_length_b                   23.1581(19)
_cell_length_c                   17.7369(15)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    299(2)
_cell_measurement_theta_max      26.02
_cell_measurement_theta_min      2.42
_cell_volume                     10091.7(14)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      299.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'CCD area detector'
_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  0.0791
_diffrn_reflns_av_unetI/netI     0.0484
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            55228
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.325
_exptl_absorpt_coefficient_mu    14.199
_exptl_absorpt_correction_T_max  0.109
_exptl_absorpt_correction_T_min  0.086
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.777
_exptl_crystal_description       block
_exptl_crystal_F_000             7624
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.28
_refine_diff_density_max         3.437
_refine_diff_density_min         -2.200
_refine_diff_density_rms         0.285
_refine_ls_extinction_coef       0.000024(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     775
_refine_ls_number_reflns         8882
_refine_ls_number_restraints     1719
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0932
_refine_ls_R_factor_gt           0.0548
_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^)+(0.0205P)^2^+873.8842P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1144
_refine_ls_wR_factor_ref         0.1432
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6332
_reflns_number_total             8882
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05392a2.cif
_cod_data_source_block           1_sq
_cod_depositor_comments
;Adding full bibliography for 1557284--1557286.cif.

 Adding full bibliography for 1557284--1557286.cif.
;
_cod_database_code               1557284
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.109
_shelx_estimated_absorpt_t_min   0.086
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C21A-C22A
 1.4 with sigma of 0.02
 C22A-C23A
 1.4 with sigma of 0.02
 C23A-C24A
 1.4 with sigma of 0.02
 C24A-C25A
 1.4 with sigma of 0.02
 C25A-N5A
 1.4 with sigma of 0.02
 N5A-C21A
 1.4 with sigma of 0.02
 C21A-C20A
 1.45 with sigma of 0.02
 C20A-C19A
 1.4 with sigma of 0.02
 C19A-C18A
 1.4 with sigma of 0.02
 C18A-C17A
 1.4 with sigma of 0.02
 C17A-C16A
 1.4 with sigma of 0.02
 C16A-N4A
 1.4 with sigma of 0.02
 N4A-C20A
 1.4 with sigma of 0.02
 C17B-C18B
 1.4 with sigma of 0.02
 C18B-C19B
 1.4 with sigma of 0.02
 C19B-C20B
 1.4 with sigma of 0.02
 C20B-N4B
 1.4 with sigma of 0.02
 N4B-C16B
 1.4 with sigma of 0.02
 C16B-C17B
 1.4 with sigma of 0.02
 C20B-C21B
 1.45 with sigma of 0.02
 C21B-C22B
 1.4 with sigma of 0.02
 C22B-C23B
 1.4 with sigma of 0.02
 C21B-N5B
 1.4 with sigma of 0.02
 N5B-C25B
 1.4 with sigma of 0.02
 C23B-C24B
 1.4 with sigma of 0.02
 C24B-C25B
 1.4 with sigma of 0.02
 N6-C29A
 1.15 with sigma of 0.02
 C29A-C30A
 1.46 with sigma of 0.02
 N6B-C29B
 1.15 with sigma of 0.02
 C29B-C30B
 1.46 with sigma of 0.02
3. Rigid bond restraints
 O6, Si1, O13
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C6 \\sim C1 \\sim C12 \\sim C4 \\sim C5 \\sim C3 \\sim C2 \\sim C10 \\sim C7
\\sim C8 \\sim C11 \\sim C14 \\sim C13 \\sim C15 \\sim C9 \\sim C28 \\sim C26
\\sim C20A \\sim C21A \\sim C27 \\sim C18A \\sim C19A \\sim C16A \\sim C17A
\\sim C23A \\sim C22A \\sim C25A \\sim C24A \\sim C21B \\sim C20B \\sim C22B
\\sim C23B \\sim C16B \\sim C18B \\sim C25B \\sim C19B \\sim C17B \\sim C24B
\\sim C29A \\sim C30A \\sim C30B \\sim C29B: within 3.8A with sigma of 0.01 and
sigma for terminal atoms of 0.02
N2 \\sim N1 \\sim N3 \\sim N4A \\sim N5A \\sim N5B \\sim N4B \\sim N6 \\sim
N6B: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
Si1 \\sim O5 \\sim O10 \\sim O14 \\sim O3 \\sim O2 \\sim O4 \\sim O8 \\sim O12
\\sim O7 \\sim O19 \\sim O1 \\sim O15 \\sim O16 \\sim O20 \\sim O17 \\sim O13
\\sim O6 \\sim O11 \\sim O18 \\sim O9 \\sim O22 \\sim O21 \\sim O23 \\sim O26
\\sim O24 \\sim O25: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Others
 Fixed Sof: N4A(0.5) N5A(0.5) C20A(0.5) C21A(0.5) C18A(0.5) H18A(0.5)
 C19A(0.5) H19A(0.5) C16A(0.5) H16A(0.5) C17A(0.5) H17A(0.5) C23A(0.5)
 H23A(0.5) C22A(0.5) H22A(0.5) C25A(0.5) H25A(0.5) C24A(0.5) H24A(0.5) N5B(0.5)
 C21B(0.5) C20B(0.5) C22B(0.5) H22B(0.5) C23B(0.5) H23B(0.5) C16B(0.5)
 H16B(0.5) C18B(0.5) H18B(0.5) C25B(0.5) H25B(0.5) C19B(0.5) H19B(0.5)
 C17B(0.5) H17B(0.5) N4B(0.5) C24B(0.5) H24B(0.5) C29A(0.5) N6(0.5) C30A(0.5)
 H30A(0.5) H30B(0.5) H30C(0.5) C30B(0.5) H30D(0.5) H30E(0.5) H30F(0.5)
 C29B(0.5) N6B(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C3(H3), C2(H2), C10(H10), C7(H7), C8(H8), C9(H9), C18A(H18A),
 C19A(H19A), C16A(H16A), C17A(H17A), C23A(H23A), C22A(H22A), C25A(H25A),
 C24A(H24A), C22B(H22B), C23B(H23B), C16B(H16B), C18B(H18B), C25B(H25B),
 C19B(H19B), C17B(H17B), C24B(H24B)
6.b Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C30A(H30A,H30B,H30C), C30B(H30D,H30E,H30F)
;
_shelx_res_checksum              45803
_shelx_fab_checksum              57008
_olex2_submission_special_instructions 'No special instructions were received'