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_1557285
_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         'Mo12 O40 P, 3(C15 H11 Mn N3 O3), 2(C2 H3 N)'
_chemical_formula_sum            'C49 H39 Mn3 Mo12 N11 O49 P'
_chemical_formula_weight         2912.98
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2019-01-23
_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                79.875(2)
_cell_angle_beta                 88.908(2)
_cell_angle_gamma                87.011(2)
_cell_formula_units_Z            2
_cell_length_a                   13.0340(6)
_cell_length_b                   15.6737(6)
_cell_length_c                   20.2719(9)
_cell_measurement_reflns_used    9857
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      27.08
_cell_measurement_theta_min      2.58
_cell_volume                     4071.1(3)
_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      273.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_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  0.0736
_diffrn_reflns_av_unetI/netI     0.0611
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            74286
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.201
_diffrn_reflns_theta_min         2.229
_exptl_absorpt_coefficient_mu    2.351
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.376
_exptl_crystal_description       block
_exptl_crystal_F_000             2792
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.26
_refine_diff_density_max         1.137
_refine_diff_density_min         -1.314
_refine_diff_density_rms         0.157
_refine_ls_extinction_coef       0.00027(3)
_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   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1132
_refine_ls_number_reflns         17989
_refine_ls_number_restraints     4334
_refine_ls_restrained_S_all      0.974
_refine_ls_R_factor_all          0.0955
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0231P)^2^+27.1647P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0871
_refine_ls_wR_factor_ref         0.1070
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11784
_reflns_number_total             17989
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05392a2.cif
_cod_data_source_block           1
_cod_depositor_comments
;Adding full bibliography for 1557284--1557286.cif.

 Adding full bibliography for 1557284--1557286.cif.
;
_cod_database_code               1557285
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.580
_shelx_estimated_absorpt_t_min   0.529
_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
 N10-C46
 1.14 with sigma of 0.01
 C47-C46
 1.38 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C27 \\sim C6 \\sim C5 \\sim C7 \\sim C4 \\sim C11 \\sim C20 \\sim C35 \\sim C10
\\sim C17 \\sim C38 \\sim C40 \\sim C44 \\sim C28 \\sim C3 \\sim C36 \\sim C2
\\sim C29 \\sim C39 \\sim C19 \\sim C32 \\sim C16 \\sim C30 \\sim C45 \\sim C37
\\sim C25 \\sim C18 \\sim C1 \\sim C21 \\sim C43 \\sim C33 \\sim C8 \\sim C9
\\sim C31 \\sim C12 \\sim C34 \\sim C14 \\sim C22 \\sim C23 \\sim C24 \\sim C15
\\sim C26 \\sim C13 \\sim C46 \\sim C47 \\sim C49 \\sim C48 \\sim C41 \\sim C42
\\sim N9 \\sim N2 \\sim N8 \\sim N4 \\sim N1 \\sim N5 \\sim N7 \\sim N6 \\sim
N3 \\sim N11 \\sim N10: within 5A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O10 \\sim O15 \\sim O26 \\sim O30 \\sim O3 \\sim O33 \\sim O29 \\sim O9 \\sim
O21 \\sim O34 \\sim O24 \\sim O38 \\sim O8 \\sim O12 \\sim O19 \\sim O32 \\sim
O20 \\sim O40 \\sim O13 \\sim O4 \\sim O5 \\sim O2 \\sim O23 \\sim O27 \\sim
O16 \\sim O37 \\sim O22 \\sim O17 \\sim O28 \\sim O11 \\sim O36 \\sim O39 \\sim
O31 \\sim O7 \\sim O1 \\sim O14 \\sim O35 \\sim O25 \\sim O45 \\sim O46 \\sim
O41 \\sim O18 \\sim O49 \\sim O6 \\sim O42 \\sim O44 \\sim O43 \\sim O47 \\sim
O48: within 5A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(O49) \\sim Ueq, Uanis(N10)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C4(H4), C10(H10), C17(H17), C38(H38), C40(H40), C3(H3), C2(H2),
 C39(H39), C19(H19), C32(H32), C16(H16), C37(H37), C25(H25), C18(H18), C1(H1),
 C33(H33), C8(H8), C9(H9), C31(H31), C34(H34), C22(H22), C23(H23), C24(H24)
4.b Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C45(H45A,H45B,H45C), C15(H15A,H15B,H15C), C47(H47A,H47B,
 H47C), C49(H49A,H49B,H49C)
;
_shelx_res_checksum              59069
_olex2_submission_special_instructions 'No special instructions were received'