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_1569790
_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         'C82 H88 Ag N O6 P2 S4 Ti'
_chemical_formula_sum            'C82 H88 Ag N O6 P2 S4 Ti'
_chemical_formula_weight         1529.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_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                 110.243(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.8480(12)
_cell_length_b                   11.2724(3)
_cell_length_c                   25.8452(10)
_cell_measurement_reflns_used    26695
_cell_measurement_temperature    150
_cell_measurement_theta_max      32.0630
_cell_measurement_theta_min      2.2630
_cell_volume                     7885.4(5)
_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 0.998
_diffrn_measured_fraction_theta_max 0.863
_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    -79.00  -6.00   0.50    2.94    --  -14.57 -58.00  27.00  146
  2  \w     -6.00  20.00   0.50    2.94    --  -14.57 -99.00  60.00   52
  3  \w    -25.00   1.00   0.50    2.94    --   13.79 -37.00 150.00   52
  4  \w    -31.00  55.00   0.50    2.94    --  -14.57  58.00 167.00  172
  5  \w      8.00  55.00   0.50    2.94    --  -14.57  57.00-150.00   94
  6  \w     39.00  81.00   0.50    2.94    --   13.79 178.00   0.00   84
  7  \w    -26.00   9.00   0.50    2.94    --  -14.57 -99.00-180.00   70
;
_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      0.0242537000
_diffrn_orient_matrix_UB_12      0.0052312000
_diffrn_orient_matrix_UB_13      -0.0007077000
_diffrn_orient_matrix_UB_21      -0.0055230000
_diffrn_orient_matrix_UB_22      -0.0436284000
_diffrn_orient_matrix_UB_23      -0.0210387000
_diffrn_orient_matrix_UB_31      -0.0081850000
_diffrn_orient_matrix_UB_32      0.0450077000
_diffrn_orient_matrix_UB_33      -0.0203427000
_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  0.0392
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.863
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            90492
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.863
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.752
_diffrn_reflns_theta_min         2.064
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.547
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58129
_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    1.288
_exptl_crystal_description       block
_exptl_crystal_F_000             3192
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.710
_refine_diff_density_min         -0.834
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     964
_refine_ls_number_reflns         27255
_refine_ls_number_restraints     145
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0969
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0548P)^2^+1.9480P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1125
_refine_ls_wR_factor_ref         0.1336
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15871
_reflns_number_total             27255
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02793g2.cif
_cod_data_source_block           TiAg
_cod_depositor_comments
'Adding full bibliography for 1569790--1569794.cif.'
_cod_original_cell_volume        7885.4(6)
_cod_database_code               1569790
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         CHONPSAgTi
_shelx_estimated_absorpt_t_max   0.853
_shelx_estimated_absorpt_t_min   0.772
_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. Rigid bond restraints
 C1, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
C1 \\sim C7: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C47 \\sim C45 \\sim C44 \\sim C46 \\sim N1: 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(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1) \\sim
Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Others
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=1-FVAR(1)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=1-FVAR(2)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(2)
 Sof(C48)=Sof(H48)=1-FVAR(3)
 Sof(C49)=Sof(H49)=FVAR(3)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=1-FVAR(4)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(4)
 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(5)
 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(5)
5.a Ternary CH refined with riding coordinates:
 C50(H50)
5.b Aromatic/amide H refined with riding coordinates:
 C39(H39), C9(H9), C33(H33), C58(H58), C57(H57), C28(H28), C37(H37), C84(H84),
 C30(H30), C56(H56), C82(H82), C88(H88), C54(H54), C78(H78), C68(H68), C55(H55),
  C69(H69), C81(H81), C61(H61), C71(H71), C14(H14), C67(H67), C85(H85),
 C79(H79), C16(H16), C59(H59), C66(H66), C87(H87), C65(H65), C64(H64), C86(H86),
  C75(H75), C63(H63), C80(H80), C73(H73), C72(H72), C62(H62), C74(H74),
 C49(H49), C48(H48)
5.c Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C51(H51A,H51B,H51C), C42(H42A,H42B,H42C), C43(H43A,H43B,
 H43C), C26(H26A,H26B,H26C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C41(H41A,
 H41B,H41C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C47(H47A,H47B,H47C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C45(H45A,H45B,
 H45C), C25(H25A,H25B,H25C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C2(H2A,H2B,H2C),
 C5(H5A,H5B,H5C), C3(H3A,H3B,H3C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              75860
_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 1.849
_oxdiff_exptl_absorpt_empirical_full_min 0.650