A 20-core copper(I) nanocluster as electron-hole recombination inhabitor on TiO2 nanosheet for enhancing photocatalytic H2 evolution
Cao, Yun-Dong; Hao, Hui-Ping; Liu, Huashi; Yin, Di; Wang, Mingliang; Gao, Guanggang; Fan, Lin-Lin; Liu, Hong; Nanoscale  (2021) –; doi:10.1039/D1NR04683G

data_1564595
_publ_section_title
;
 A 20-core copper(I) nanocluster as electron-hole recombination inhabitor
 on TiO2 nanosheet for enhancing photocatalytic H2 evolution
;
_journal_name_full               Nanoscale
_journal_paper_doi               10.1039/D1NR04683G
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C252 H294 Cu20 O37'
_chemical_formula_sum            'C252 H294 Cu20 O37'
_chemical_formula_weight         5185.65
_space_group_crystal_system      hexagonal
_space_group_IT_number           182
_space_group_name_Hall           'P 6c 2c'
_space_group_name_H-M_alt        'P 63 2 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-06-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-06-22 deposited with the CCDC.	2021-09-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   20.0197(6)
_cell_length_b                   20.0197(6)
_cell_length_c                   38.877(3)
_cell_measurement_reflns_used    6898
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      20.8220
_cell_measurement_theta_min      3.5190
_cell_volume                     13493.9(12)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
  1 omega   -1.00   44.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.1717   57.0000 -180.0000 45

  2 omega  -11.00   84.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.1717   77.0000  -60.0000 95

  3 omega    8.00   35.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.1717  -99.0000   90.0000 27

  4 omega  -50.00   43.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.1717  -77.0000 -180.0000 93

  5 omega   17.00   55.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.1717  -99.0000   60.0000 38

  6 omega  -39.00   46.00   1.0000   90.0000
omega____ theta____ kappa____ phi______ frames
    -       16.1717  -19.0000    0.0000 85
;
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_UB_11      0.0180880000
_diffrn_orient_matrix_UB_12      0.0046219000
_diffrn_orient_matrix_UB_13      -0.0162036000
_diffrn_orient_matrix_UB_21      -0.0175832000
_diffrn_orient_matrix_UB_22      0.0209595000
_diffrn_orient_matrix_UB_23      -0.0060589000
_diffrn_orient_matrix_UB_31      0.0322223000
_diffrn_orient_matrix_UB_32      0.0348325000
_diffrn_orient_matrix_UB_33      0.0057886000
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoKa
_diffrn_radiation_wavelength     0.710
_diffrn_reflns_av_R_equivalents  0.2011
_diffrn_reflns_av_unetI/netI     0.1082
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            97042
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         25.318
_diffrn_reflns_theta_min         3.353
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    1.599
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             5364
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.768
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 1388 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.043(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.909
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         8207
_refine_ls_number_restraints     203
_refine_ls_restrained_S_all      0.915
_refine_ls_R_factor_all          0.1329
_refine_ls_R_factor_gt           0.0678
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0941P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1514
_refine_ls_wR_factor_ref         0.1693
_reflns_Friedel_coverage         0.731
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4553
_reflns_number_total             8207
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1nr04683g2.cif
_cod_data_source_block           2018031212hy
_cod_original_cell_volume        13494.0(13)
_cod_database_code               1564595
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.856
_shelx_estimated_absorpt_t_min   0.740
_reflns_odcompleteness_completeness 89.52
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups
2. Restrained distances
 O1-C41
 1.45 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O6 \\sim O8 \\sim O5 \\sim O2 \\sim O7 \\sim O1 \\sim O4 \\sim O3: within 10A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 10A
Uanis(C38) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(O8) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3) \\sim Ueq, Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O8) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O3) = Uanis(O4)
4. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O4, O3, Cu4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O8, O1, C2, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Fixed Sof: O4(0.05556) O3(0.11111)
6.a Riding coordinates:
 O1(H1A)
6.b Ternary CH refined with riding coordinates:
 C10(H10), C11(H11), C28(H28), C33(H), C34(H34), C9(H9)
6.c Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C15(H15A,H15B), C27(H27A,H27), C14(H14A,H14B), C35(H35A,H35B),
  C8(H8A,H8B), C17(H17A,H17B), C32(H32A,H32B), C31(HA,H31B), C26(H26A,H26B),
 C36(H36A,H36B), C7(H7A,H7B)
6.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C1(H1), C3(H3), C42(H42), C39(H39), C40(H40)
6.e Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C30(H30A,H30B,H30C), C13(H13A,H13B,H13C)
6.f Idealised tetrahedral OH refined as rotating group:
 O8(H8), O2(HB), O7(H7)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6104
_shelx_fab_checksum              37125
_olex2_submission_special_instructions 'No special instructions were received'