A conductive catecholate-based framework coordinated with unsaturated bismuth boosts CO<sub>2</sub> electroreduction to formate.
Gao, Zengqiang; Hou, Man; Shi, Yongxia; Li, Li; Sun, Qisheng; Yang, Shuyuan; Jiang, Zhiqiang; Yang, Wenjuan; Zhang, Zhicheng; Hu, Wenping; Chemical science 14 (2023) 6860–6866; doi:10.1039/d3sc01876h

data_1569257
_publ_section_title
;
 A conductive catecholate-based framework coordinated with unsaturated
 bismuth boosts CO<sub>2</sub> electroreduction to formate.
;
_journal_issue                   25
_journal_name_full               'Chemical science'
_journal_page_first              6860
_journal_page_last               6866
_journal_paper_doi               10.1039/d3sc01876h
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C36 H18 Bi4 O15.294, H2 O'
_chemical_formula_sum            'C36 H20 Bi4 O16.3'
_chemical_formula_weight         1549.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-01-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-16 deposited with the CCDC.	2023-05-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 143.57(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.9776(17)
_cell_length_b                   14.3793(4)
_cell_length_c                   26.623(3)
_cell_measurement_reflns_used    7474
_cell_measurement_temperature    159.99(10)
_cell_measurement_theta_max      74.4090
_cell_measurement_theta_min      3.0630
_cell_volume                     3859.6(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.68a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      159.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -27.00  10.00   0.50    0.15    --   47.02 -19.00-150.00   74
  2  \w    -27.00  21.00   0.50    0.15    --   47.02 -19.00-120.00   96
  3  \w    -18.00  38.00   0.50    0.15    --   47.02 -37.00 -60.00  112
  4  \w    -10.00  20.00   0.50    0.15    --   47.02 -19.00   0.00   60
  5  \w     -9.00  39.00   0.50    0.15    --   47.02 -37.00 120.00   96
  6  \w    101.00 133.00   0.50    0.59    --  105.17  45.00  30.00   64
  7  \w     89.00 175.00   0.50    0.59    --  105.17  61.00-150.00  172
  8  \w    104.00 130.00   0.50    0.59    --  105.17 113.00-112.00   52
  9  \w     31.00 102.00   0.50    0.15    --   47.02  57.00 120.00  142
 10  \w     35.00  60.00   0.50    0.59    --  105.17 -61.00   0.00   50
 11  \w      9.00  69.00   0.50    0.15    --   47.02-113.00 155.00  120
 12  \w     87.00 112.00   0.50    0.59    --  105.17-125.00   0.00   50
 13  \w     42.00  84.00   0.50    0.59    --  105.17-125.00   0.00   84
 14  \w     41.00  70.00   0.50    0.59    --  105.17-125.00 -60.00   58
 15  \w     87.00 112.00   0.50    0.59    --  105.17-125.00 -60.00   50
 16  \w     69.00 110.00   0.50    0.59    --  105.17-125.00-150.00   82
 17  \w     32.00  63.00   0.50    0.59    --  105.17 -94.00-180.00   62
 18  \w     33.00  61.00   0.50    0.59    --  105.17 -61.00 -90.00   56
 19  \w     32.00 105.00   0.50    0.59    --  105.17 -94.00 -60.00  146
 20  \w     47.00  99.00   0.50    0.59    --  105.17-113.00 155.00  104
 21  \w    -92.00 -33.00   0.50    0.59    -- -100.00 144.00  62.97  118
 22  \w    -60.00 -33.00   0.50    0.59    -- -100.00 139.00  -0.66   54
 23  \w    -57.00 -32.00   0.50    0.59    -- -100.00 125.00 -60.00   50
 24  \w    -57.00 -30.00   0.50    0.59    -- -100.00 125.00   0.00   54
 25  \w   -126.00-101.00   0.50    0.59    -- -100.00 144.00  62.97   50
 26  \w   -109.00 -30.00   0.50    0.59    -- -100.00 125.00  60.00  158
 27  \w    -86.00 -60.00   0.50    0.59    -- -100.00 125.00   0.00   52
 28  \w   -122.00 -70.00   0.50    0.59    -- -100.00 139.00  -0.66  104
 29  \w   -110.00 -84.00   0.50    0.59    -- -100.00 125.00 -60.00   52
 30  \w   -108.00 -49.00   0.50    0.59    -- -100.00 113.00-112.00  118
 31  \w   -110.00 -67.00   0.50    0.59    -- -100.00 125.00-180.00   86
 32  \w    -67.00 -16.00   0.50    0.15    --  -47.02 113.00-112.00  102
 33  \w    -72.00 -27.00   0.50    0.59    -- -100.00  61.00-150.00   90
 34  \w    -54.00 -27.00   0.50    0.59    -- -100.00  45.00-150.00   54
 35  \w    -72.00 -36.00   0.50    0.59    -- -100.00  61.00-120.00   72
 36  \w    -53.00 -28.00   0.50    0.59    -- -100.00  45.00 -90.00   50
 37  \w    -74.00 -30.00   0.50    0.59    -- -100.00  61.00 -90.00   88
 38  \w    -54.00 -29.00   0.50    0.59    -- -100.00  45.00  60.00   50
 39  \w    -53.00 -28.00   0.50    0.59    -- -100.00  45.00  90.00   50
 40  \w    -53.00 -27.00   0.50    0.59    -- -100.00  45.00  30.00   52
 41  \w    -28.00  25.00   0.50    0.15    --  -47.02  19.00-120.00  106
 42  \w    -53.00 -27.00   0.50    0.59    -- -100.00  45.00 -30.00   52
 43  \w   -127.00 -97.00   0.50    0.59    -- -100.00 -30.00  90.00   60
 44  \w   -165.00-135.00   0.50    0.59    -- -100.00 -30.00  90.00   60
 45  \w   -162.00 -85.00   0.50    0.59    -- -100.00 -45.00  60.00  154
 46  \w   -158.00 -84.00   0.50    0.59    -- -100.00 -77.00-180.00  148
 47  \w   -119.00 -34.00   0.50    0.15    --  -47.02 -57.00-120.00  170
 48  \w   -172.00 -84.00   0.50    0.59    -- -100.00 -30.00 -30.00  176
 49  \w   -135.00-109.00   0.50    0.59    -- -100.00-113.00 155.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0330434000
_diffrn_orient_matrix_UB_12      -0.0979400000
_diffrn_orient_matrix_UB_13      -0.0028172000
_diffrn_orient_matrix_UB_21      -0.0083350000
_diffrn_orient_matrix_UB_22      -0.0386611000
_diffrn_orient_matrix_UB_23      0.0496067000
_diffrn_orient_matrix_UB_31      -0.1490147000
_diffrn_orient_matrix_UB_32      -0.0195337000
_diffrn_orient_matrix_UB_33      -0.0838182000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0441
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            50191
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.621
_diffrn_reflns_theta_min         2.703
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    35.795
_exptl_absorpt_correction_T_max  0.609
_exptl_absorpt_correction_T_min  0.283
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.68a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light black'
_exptl_crystal_density_diffrn    2.666
_exptl_crystal_description       block
_exptl_crystal_F_000             2793
_exptl_crystal_size_max          0.076
_exptl_crystal_size_mid          0.032
_exptl_crystal_size_min          0.027
_refine_diff_density_max         6.951
_refine_diff_density_min         -1.854
_refine_diff_density_rms         0.317
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     522
_refine_ls_number_reflns         7747
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0612
_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^)+(0.1008P)^2^+76.1877P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1756
_refine_ls_wR_factor_ref         0.1804
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6779
_reflns_number_total             7747
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01876h2.cif
_cod_data_source_block           059252-gzq-bihhtp_20230128n
_cod_depositor_comments          'Adding full bibliography for 1569257.cif.'
_cod_original_cell_volume        3859.8(13)
_cod_original_formula_sum        'C36 H20 Bi4 O16.30'
_cod_database_code               1569257
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C36 H26.8 Bi4 O19.4'
_shelx_estimated_absorpt_t_max   0.445
_shelx_estimated_absorpt_t_min   0.172
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups, All O(H,H,H,H,H,H) groups
2. Rigid bond restraints
 Bi42, O23
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
Bi42 \\sim O23: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
Uanis(Bi60) \\sim Ueq, Uanis(O5) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O11) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O23) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(H5A)=Sof(H5B)=Sof(Bi74)=Sof(Bi47)=1-FVAR(1)
 Sof(Bi34)=Sof(Bi60)=Sof(O5)=Sof(O72)=Sof(H72A)=Sof(H72B)=FVAR(1)
 Fixed X: O5(0.19733) H5A(0.280169) H5B(0.18377) O11(-0.73135) O72(-0.12798)
 O78(0.070419) H78A(0.08876) H78B(0.05585) H72A(-0.059351) H72B(-0.102799)
 H11A(-0.73098) H11B(-0.79506)
 Fixed Y: O5(-1.029311) H5A(-1.014501) H5B(-1.02072) O11(-0.63147) O72(-
 0.59861) O78(-0.5864) H78A(-0.527431) H78B(-0.595461) H72A(-0.59072) H72B(-
 0.6403) H11A(-0.589451) H11B(-0.61454)
 Fixed Z: O5(0.30207) H5A(0.34905) H5B(0.26317) O11(0.61205) O72(0.396429)
 O78(0.58123) H78A(0.58835) H78B(0.60559) H72A(0.45098) H72B(0.38767)
 H11A(0.58873) H11B(0.599409)
5.a Rotating group:
 O23(H23A,H23B)
5.b Aromatic/amide H refined with riding coordinates:
 C24(H24), C4(H4), C68(H68), C13(H13), C2(H2), C55(H55), C33(H33), C65(H65),
 C9(H9), C30(H30), C35(H35), C71(H71)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 146 electrons were 
found in a volume of 546\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
3[H2O], 1[H2O] per Asymmetric Unit 
which account for 160 electrons 
per unit cell.
;
_shelx_res_checksum              33627
_shelx_hkl_checksum              37989
_shelx_fab_checksum              84431
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.106
_oxdiff_exptl_absorpt_empirical_full_min 0.615