Stepwise assembly of thiacalix[4]arene-protected Ag/Ti bimetallic nanoclusters: accurate identification of catalytic Ag sites in CO<sub>2</sub> electroreduction.
Tian, Yi-Qi; Mu, Wen-Lei; Wu, Lin-Lin; Yi, Xiao-Yi; Yan, Jun; Liu, Chao; Chemical science 14 (2023) 10212–10218; doi:10.1039/d3sc02793g

data_1569791
_publ_section_title
;
 Stepwise assembly of thiacalix[4]arene-protected Ag/Ti bimetallic
 nanoclusters: accurate identification of catalytic Ag sites in
 CO<sub>2</sub> electroreduction.
;
_journal_issue                   37
_journal_name_full               'Chemical science'
_journal_page_first              10212
_journal_page_last               10218
_journal_paper_doi               10.1039/d3sc02793g
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C80 H88 Ag4 O10 S8 Ti2, 0.5(C8 H12 N4)'
_chemical_formula_sum            'C84 H94 Ag4 N2 O10 S8 Ti2'
_chemical_formula_weight         2075.37
_space_group_crystal_system      tetragonal
_space_group_IT_number           132
_space_group_name_Hall           '-P 4c 2c'
_space_group_name_H-M_alt        'P 42/m c m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-05-13 deposited with the CCDC.	2023-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.9991(4)
_cell_length_b                   15.9991(4)
_cell_length_c                   18.5546(12)
_cell_measurement_reflns_used    6989
_cell_measurement_temperature    150
_cell_measurement_theta_max      32.2410
_cell_measurement_theta_min      2.1500
_cell_volume                     4749.4(4)
_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 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.909
_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     15.00  78.00   0.50   20.00    --   13.79  20.00 -39.00  126
  2  \w    -16.00  10.00   0.50   20.00    --  -14.57 -99.00 -30.00   52
  3  \w    -26.00  17.00   0.50   20.00    --  -14.57 -99.00  60.00   86
  4  \w    -52.00  -5.00   0.50   20.00    --   13.79 -20.00 153.00   94
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 6000 area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0056914000
_diffrn_orient_matrix_UB_12      -0.0078898000
_diffrn_orient_matrix_UB_13      0.0373197000
_diffrn_orient_matrix_UB_21      -0.0094049000
_diffrn_orient_matrix_UB_22      0.0427914000
_diffrn_orient_matrix_UB_23      0.0056769000
_diffrn_orient_matrix_UB_31      -0.0429585000
_diffrn_orient_matrix_UB_32      -0.0083574000
_diffrn_orient_matrix_UB_33      -0.0061425000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0762
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.909
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            29248
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.697
_diffrn_reflns_theta_min         2.108
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.196
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30902
_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    1.451
_exptl_crystal_description       block
_exptl_crystal_F_000             2104
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.570
_refine_diff_density_min         -0.642
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     154
_refine_ls_number_reflns         4597
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0823
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0624P)^2^+1.1044P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1170
_refine_ls_wR_factor_ref         0.1339
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2819
_reflns_number_total             4597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02793g2.cif
_cod_data_source_block           Ti2Ag4
_cod_depositor_comments
'Adding full bibliography for 1569790--1569794.cif.'
_cod_database_code               1569791
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         CHONAgTiS
_shelx_estimated_absorpt_t_max   0.715
_shelx_estimated_absorpt_t_min   0.586
_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
 C15-C16
 1.45 with sigma of 0.01
3. Rigid bond restraints
 C1, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C15 \\sim C16: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C1 \\sim C2 \\sim C3: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
Uanis(C15) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
5. Others
 Fixed Sof: H15B(0.25) H15C(0.25) H15A(0.25) H11A(0.5) H11C(0.5) H11B(0.5)
 H1A(0.5) H1B(0.5) H1C(0.5)
6.a Riding coordinates:
 C15(H15B,H15C,H15A)
6.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C5(H5)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C3(H3A,H3B,H3C), C11(H11A,H11C,H11B), C1(H1A,H1B,H1C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              62716
_shelx_fab_checksum              68547
_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 2.517
_oxdiff_exptl_absorpt_empirical_full_min 0.699