Ag<sup>1+</sup> incorporation <i>via</i> a Zr<sup>4+</sup>-anchored metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic clusters for enhanced eCO<sub>2</sub>RR-to-CO activity.
Li, Liang-Jun; Mu, Wen-Lei; Tian, Yi-Qi; Yu, Wei-Dong; Li, Lan-Yan; Yan, Jun; Liu, Chao; Chemical science 15 (2024) 7643–7650; doi:10.1039/d3sc07005k

data_1571292
_publ_section_title
;
 Ag<sup>1+</sup> incorporation <i>via</i> a Zr<sup>4+</sup>-anchored
 metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic
 clusters for enhanced eCO<sub>2</sub>RR-to-CO activity.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              7643
_journal_page_last               7650
_journal_paper_doi               10.1039/d3sc07005k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety
'C90 H102 Ag2 O12 S8 Zr2, 2(C3 H7 N O), 2(C2 H3 N)'
_chemical_formula_sum            'C100 H122 Ag2 N4 O14 S8 Zr2'
_chemical_formula_weight         2258.67
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-25 deposited with the CCDC.	2024-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.4396(2)
_cell_length_b                   12.29540(11)
_cell_length_c                   32.4346(3)
_cell_measurement_reflns_used    20610
_cell_measurement_temperature    150
_cell_measurement_theta_max      72.8870
_cell_measurement_theta_min      2.7090
_cell_volume                     10544.02(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.933
_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    -69.00 -30.00   0.50    0.29    --  -47.57 116.00 171.00   78
  2  \w    -11.00  28.00   0.50    0.29    --  -47.57  19.00  90.00   78
  3  \w    -44.00 -18.00   0.50    1.16    --  -86.25  57.00 -30.00   52
  4  \w    -39.00 -14.00   0.50    1.16    --  -86.25  37.00-120.00   50
  5  \w    -42.00 -17.00   0.50    1.16    --  -86.25  37.00-180.00   50
  6  \w    -12.00  26.00   0.50    0.29    --  -47.57  19.00-180.00   76
  7  \w    109.00 151.00   0.50    1.16    --   98.15 129.00-105.00   84
  8  \w     35.00  60.00   0.50    1.16    --   98.15 -57.00  60.00   50
  9  \w     70.00 109.00   0.50    1.16    --   98.15 -99.00  90.00   78
 10  \w     32.00 100.00   0.50    1.16    --   98.15-116.00  82.00  136
 11  \w     29.00  55.00   0.50    1.16    --   98.15 -57.00 150.00   52
 12  \w     27.00  58.00   0.50    1.16    --   98.15 -99.00  90.00   62
 13  \w   -119.00 -75.00   0.50    0.29    --  -47.57-125.00 -60.00   88
 14  \w   -160.00 -73.00   0.50    1.16    --  -86.25 -12.00-123.00  174
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0459546000
_diffrn_orient_matrix_UB_12      0.0751782000
_diffrn_orient_matrix_UB_13      0.0061178000
_diffrn_orient_matrix_UB_21      0.0356719000
_diffrn_orient_matrix_UB_22      -0.0983908000
_diffrn_orient_matrix_UB_23      -0.0046307000
_diffrn_orient_matrix_UB_31      0.0024456000
_diffrn_orient_matrix_UB_32      0.0195014000
_diffrn_orient_matrix_UB_33      -0.0468872000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            39225
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.065
_diffrn_reflns_theta_min         2.725
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.479
_exptl_absorpt_correction_T_max  0.583
_exptl_absorpt_correction_T_min  0.124
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             4656
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.417
_refine_diff_density_min         -0.571
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     698
_refine_ls_number_reflns         9834
_refine_ls_number_restraints     169
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0418
_refine_ls_R_factor_gt           0.0354
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0509P)^2^+7.1404P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.0957
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8489
_reflns_number_total             9834
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc07005k2.cif
_cod_data_source_block           Zr2Ag2
_cod_depositor_comments
'Adding full bibliography for 1571291--1571294.cif.'
_cod_original_cell_volume        10544.00(15)
_cod_database_code               1571292
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.247
_shelx_estimated_absorpt_t_min   0.140
_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
 C2-C6
 2.2 with sigma of 0.01
 C015-C11 \\sim C015-C9
 with sigma of 0.02
 C015-C8 \\sim C015-C24
 with sigma of 0.02
 C015-C22 \\sim C015-C23
 with sigma of 0.02
 C016-C20 \\sim C016-C13
 with sigma of 0.02
 C016-C19 \\sim C016-C7
 with sigma of 0.02
 C016-C18 \\sim C016-C21
 with sigma of 0.02
 C012-C12 \\sim C012-C16
 with sigma of 0.02
 C012-C17 \\sim C012-C14
 with sigma of 0.02
 C012-C10 \\sim C012-C15
 with sigma of 0.02
 C017-C3 \\sim C017-C2
 with sigma of 0.02
 C017-C5 \\sim C017-C4
 with sigma of 0.02
 C017-C1 \\sim C017-C6
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C14 \\sim C10 \\sim C15 \\sim C12 \\sim C16 \\sim C17: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C18 \\sim C7 \\sim C19 \\sim C13 \\sim C20 \\sim C21: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C3 \\sim C5 \\sim C1: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
C8 \\sim C9 \\sim C11 \\sim C23 \\sim C22 \\sim C24: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C11: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C15) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C4) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C11, C8, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C9, C24, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C19, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C7, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12, C17, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C14, C15
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3, C5, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2, C4, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=1-FVAR(1)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=1-FVAR(2)
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(2)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=1-FVAR(3)
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(3)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(H2C)=1-FVAR(4)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C1)=
 Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(4)
6.a Riding coordinates:
 C018(H01A,H01B,H01C), C01A(H01D,H01E,H01F), C12(H12A,H12B,H12C), C3(H3A,H3B,
 H3C), C5(H5A,H5B,H5C), C20(H20A,H20B,H20C), C01H(H01N,H01O,H01P), C17(H17A,
 H17B,H17C), C19(H19A,H19B,H19C), C1(H1A,H1B,H1C), C11(H11A,H11B,H11C),
 C10(H10A,H10B,H10C), C01N(H01H,H01I,H01J), C18(H18A,H18B,H18C), C01R(H01K,H01L,
 H01M), C8(H8A,H8B,H8C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C9(H9A,H9B,
 H9C), C24(H24A,H24B,H24C), C21(H21A,H21B,H21C), C13(H13A,H13B,H13C), C7(H7A,
 H7B,H7C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C6(H6A,H6B,H6C), C4(H4A,H4B,H4C), C2(H2A,H2B,H2C)
6.b Aromatic/amide H refined with riding coordinates:
 C00G(H00G), C00M(H00M), C00U(H00U), C00V(H00V), C00X(H00X), C00Y(H00Y),
 C011(H011), C013(H013), C014(H014), C01F(H01G)
;
_shelx_res_checksum              33727
_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 1.753
_oxdiff_exptl_absorpt_empirical_full_min 0.544