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_1571291
_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         '2(C45 H52 Na O6 S4 Zr), 2(C2 H3 N)'
_chemical_formula_sum            'C94 H110 N2 Na2 O12 S8 Zr2'
_chemical_formula_weight         1944.73
_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   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                65.104(3)
_cell_angle_beta                 85.720(3)
_cell_angle_gamma                69.053(3)
_cell_formula_units_Z            2
_cell_length_a                   15.2188(5)
_cell_length_b                   19.6877(7)
_cell_length_c                   20.5242(6)
_cell_measurement_reflns_used    24304
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.3040
_cell_measurement_theta_min      2.6940
_cell_volume                     5188.5(3)
_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      293(2)
_diffrn_detector                 'Image Plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku IP'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.950
_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    -42.00  21.00   0.50    0.28    --  -47.32  60.00 -76.00  126
  2  \w    -18.00   9.00   0.50    0.28    --  -47.32  19.00-150.00   54
  3  \w    -24.00  20.00   0.50    0.28    --  -47.32  19.00 -90.00   88
  4  \w    -42.00  18.00   0.50    0.28    --  -47.32  37.00  30.00  120
  5  \w    -51.00 -15.00   0.50    1.12    --  -86.25  45.00  90.00   72
  6  \w    -43.00 -17.00   0.50    1.12    --  -86.25  45.00 120.00   52
  7  \w    -39.00 -14.00   0.50    1.12    --  -86.25  45.00 150.00   50
  8  \w    -71.00 -31.00   0.50    1.12    --  -86.25  61.00 -30.00   80
  9  \w    -66.00 -40.00   0.50    1.12    --  -86.25  60.00 -76.00   52
 10  \w   -118.00 -31.00   0.50    0.28    --  -47.32 -60.00 144.00  174
 11  \w   -119.00 -77.00   0.50    0.28    --  -47.32-125.00  90.00   84
 12  \w   -154.00-112.00   0.50    1.12    --  -86.25 -60.00 144.00   84
 13  \w    -12.00  18.00   0.50    0.28    --   47.32 -57.00 -90.00   60
 14  \w     32.00  60.00   0.50    0.28    --   47.32 -57.00 -90.00   56
 15  \w     36.00  85.00   0.50    0.28    --   47.32-125.00-180.00   98
 16  \w     60.00 112.00   0.50    1.12    --  104.28-125.00-180.00  104
 17  \w     67.00 105.00   0.50    1.12    --  104.28 -94.00 -90.00   76
 18  \w     56.00 102.00   0.50    1.12    --  104.28-125.00   0.00   92
 19  \w     47.00 117.00   0.50    1.12    --  104.28-125.00  30.00  140
 20  \w     93.00 125.00   0.50    1.12    --  104.28-135.00 130.96   64
 21  \w     66.00 117.00   0.50    1.12    --  104.28-125.00  90.00  102
 22  \w     34.00  69.00   0.50    1.12    --  104.28 -60.00 144.00   70
 23  \w     46.00  71.00   0.50    1.12    --  104.28 -77.00 150.00   50
 24  \w     39.00  89.00   0.50    1.12    --  104.28-135.00 130.96  100
 25  \w     34.00  62.00   0.50    1.12    --  104.28 -77.00  30.00   56
 26  \w     33.00  70.00   0.50    1.12    --  104.28 -61.00  60.00   74
 27  \w     40.00  70.00   0.50    1.12    --  104.28 -61.00 -30.00   60
 28  \w     33.00  70.00   0.50    1.12    --  104.28 -61.00 -60.00   74
 29  \w     37.00 117.00   0.50    1.12    --  104.28-125.00 -60.00  160
 30  \w     35.00 116.00   0.50    1.12    --  104.28-125.00-120.00  162
 31  \w     32.00 102.00   0.50    1.12    --  104.28-125.00  60.00  140
 32  \w     34.00  99.00   0.50    1.12    --  104.28-125.00 150.00  130
 33  \w     -2.00  57.00   0.50    0.28    --   47.32 -60.00 144.00  118
 34  \w    138.00 176.00   0.50    1.12    --  104.28  45.00 150.00   76
 35  \w     93.00 163.00   0.50    1.12    --  104.28 125.00   0.00  140
 36  \w    140.00 166.00   0.50    1.12    --  104.28  60.00 -76.00   52
 37  \w    131.00 175.00   0.50    1.12    --  104.28  45.00 -60.00   88
 38  \w    115.00 164.00   0.50    1.12    --  104.28  30.00-120.00   98
 39  \w    147.00 172.00   0.50    1.12    --  104.28  61.00-180.00   50
 40  \w     95.00 121.00   0.50    1.12    --  104.28  60.00 -76.00   52
 41  \w     93.00 176.00   0.50    1.12    --  104.28  30.00 -30.00  166
 42  \w     93.00 169.00   0.50    1.12    --  104.28 125.00 -30.00  152
 43  \w    102.00 128.00   0.50    1.12    --  104.28 125.00-150.00   52
 44  \w     92.00 117.00   0.50    1.12    --  104.28  61.00-180.00   50
 45  \w     93.00 158.00   0.50    1.12    --  104.28  30.00 -90.00  130
 46  \w     94.00 126.00   0.50    1.12    --  104.28  45.00 150.00   64
 47  \w     38.00  63.00   0.50    0.28    --   47.32  60.00 -76.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku R-AXIS SPIDER IP'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0826599000
_diffrn_orient_matrix_UB_12      -0.0040347000
_diffrn_orient_matrix_UB_13      0.0478117000
_diffrn_orient_matrix_UB_21      0.0441809000
_diffrn_orient_matrix_UB_22      -0.0923719000
_diffrn_orient_matrix_UB_23      0.0344952000
_diffrn_orient_matrix_UB_31      0.0553081000
_diffrn_orient_matrix_UB_32      0.0021536000
_diffrn_orient_matrix_UB_33      0.0585416000
_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  0.0558
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            71680
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.697
_diffrn_reflns_theta_min         2.713
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.668
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37330
_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 whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.245
_exptl_crystal_description       block
_exptl_crystal_F_000             2028
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.5
_refine_diff_density_max         0.708
_refine_diff_density_min         -1.247
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1326
_refine_ls_number_reflns         20759
_refine_ls_number_restraints     336
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0642P)^2^+5.9407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1372
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17034
_reflns_number_total             20759
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc07005k2.cif
_cod_data_source_block           Zr2Na2
_cod_depositor_comments
'Adding full bibliography for 1571291--1571294.cif.'
_cod_database_code               1571291
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.261
_shelx_estimated_absorpt_t_min   0.261
_reflns_odcompleteness_completeness 99.45
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C63-C70
 2.2 with sigma of 0.01
 C67-C66
 1.45 with sigma of 0.01
 C62-C55
 2.2 with sigma of 0.01
 C025-C74 \\sim C025-C75
 with sigma of 0.02
 C025-C64 \\sim C025-C76
 with sigma of 0.02
 C025-C60 \\sim C025-C73
 with sigma of 0.02
 C02G-C80 \\sim C02G-C79
 with sigma of 0.02
 C02G-C77 \\sim C02G-C40
 with sigma of 0.02
 C02G-C52 \\sim C02G-C51
 with sigma of 0.02
 C61-C78 \\sim C61-C62
 with sigma of 0.02
 C61-C54 \\sim C61-C56
 with sigma of 0.02
 C61-C65 \\sim C61-C55
 with sigma of 0.02
 C021-C57 \\sim C021-C25A
 with sigma of 0.02
 C021-C59 \\sim C021-C27A
 with sigma of 0.02
 C021-C58 \\sim C021-C26A
 with sigma of 0.02
 C72-C71 \\sim C72-C63
 with sigma of 0.02
 C72-C53 \\sim C72-C68
 with sigma of 0.02
 C72-C69 \\sim C72-C70
 with sigma of 0.02
 C89-C81 \\sim C89-C87
 with sigma of 0.02
 C89-C83 \\sim C89-C82
 with sigma of 0.02
 C89-C88 \\sim C89-C86
 with sigma of 0.02
 C7-C4 \\sim C7-C3
 with sigma of 0.02
 C7-C6 \\sim C7-C5
 with sigma of 0.02
 C7-C2 \\sim C7-C1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C61 \\sim C62: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C66 \\sim C67 \\sim N3: 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 C7: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C40) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80)
\\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C60) \\sim Ueq,
Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C64)
\\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C78)
\\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C63) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C81) \\sim
Ueq, Uanis(C88) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C58) \\sim Ueq,
Uanis(C86) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C87) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C4, C6, C2
 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
5. Others
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=1-FVAR(1)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=
 Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=1-FVAR(2)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=FVAR(2)
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=1-FVAR(3)
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(3)
 Sof(C25A)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26A)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(H27C)=1-FVAR(4)
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=FVAR(4)
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=1-FVAR(5)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=FVAR(5)
 Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=
 Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=1-FVAR(6)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=
 Sof(C88)=Sof(H88A)=Sof(H88B)=Sof(H88C)=FVAR(6)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C1)=
 Sof(H1A)=Sof(H1B)=Sof(H1C)=1-FVAR(7)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(H2C)=FVAR(7)
6.a Riding coordinates:
 C82(H82A,H82B,H82C), C87(H87A,H87B,H87C)
6.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C48(H48A,H48B)
6.c Aromatic/amide H refined with riding coordinates:
 C44(H44), C24(H24), C42(H42), C21(H21), C34(H34), C28(H28), C01N(H01N),
 C01O(H01O), C36(H36), C01W(H01W), C01X(H01X), C27(H27), C020(H020), C19(H19),
 C024(H024), C17(H17)
6.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C13(H13A,H13B,H13C), C4(H4A,H4B,H4C), C38(H38A,H38B,H38C),
 C37(H37A,H37B,H37C), C47(H47A,H47B,H47C), C8(H8A,H8B,H8C), C6(H6A,H6B,H6C),
 C02N(H02A,H02B,H02C), C78(H78A,H78B,H78C), C81(H81A,H81B,H81C), C2(H2A,H2B,
 H2C), C83(H83A,H83B,H83C), C88(H88A,H88B,H88C), C74(H74A,H74B,H74C), C64(H64A,
 H64B,H64C), C52(H52A,H52B,H52C), C77(H77A,H77B,H77C), C65(H65A,H65B,H65C),
 C54(H54A,H54B,H54C), C60(H60A,H60B,H60C), C80(H80A,H80B,H80C), C73(H73A,H73B,
 H73C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C40(H40A,H40B,H40C), C51(H51A,
 H51B,H51C), C79(H79A,H79B,H79C), C56(H56A,H56B,H56C), C55(H55A,H55B,H55C),
 C62(H62A,H62B,H62C), C58(H58A,H58B,H58C), C57(H57A,H57B,H57C), C59(H59A,H59B,
 H59C), C25A(H25A,H25B,H25C), C26A(H26A,H26B,H26C), C27A(H27A,H27B,H27C),
 C53(H53A,H53B,H53C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C63(H63A,H63B,
 H63C), C70(H70A,H70B,H70C), C68(H68A,H68B,H68C), C66(H66A,H66B,H66C), C86(H86A,
 H86B,H86C), C84(H84A,H84B,H84C), C5(H5A,H5B,H5C), C3(H3A,H3B,H3C), C1(H1A,H1B,
 H1C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              95635
_shelx_fab_checksum              27453
_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 2.240
_oxdiff_exptl_absorpt_empirical_full_min 0.341