Soluble Gd<sub>6</sub>Cu<sub>24</sub> clusters: effective molecular electrocatalysts for water oxidation.
Chen, Jia-Nan; Pan, Zhong-Hua; Qiu, Qi-Hao; Wang, Cheng; Long, La-Sheng; Zheng, Lan-Sun; Kong, Xiang-Jian; Chemical science 15 (2024) 511–515; doi:10.1039/d3sc05849b

data_1570495
_publ_section_title
;
 Soluble Gd<sub>6</sub>Cu<sub>24</sub> clusters: effective molecular
 electrocatalysts for water oxidation.
;
_journal_issue                   2
_journal_name_full               'Chemical science'
_journal_page_first              511
_journal_page_last               515
_journal_paper_doi               10.1039/d3sc05849b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C73 H156 Cu24 Gd6 N36 O87, 16(Cl1 O4)'
_chemical_formula_sum            'C73 H156 Cl16 Cu24 Gd6 N36 O151'
_chemical_formula_weight         6989.99
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-02-06
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-25 deposited with the CCDC.	2023-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   20.0889(6)
_cell_length_b                   20.0889(6)
_cell_length_c                   57.4977(9)
_cell_measurement_reflns_used    10027
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      67.0960
_cell_measurement_theta_min      3.9780
_cell_volume                     20095.3(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -63.00  44.00   1.00    8.00    --  -36.19  37.00-180.00  107
  2  \w   -128.00 -82.00   1.00    8.00    --  -36.19 -77.00-120.00   46
  3  \w   -123.00 -95.00   1.00    8.00    --  -36.19 -77.00 150.00   28
  4  \w    -74.00  42.00   1.00    8.00    --  -36.19  77.00-120.00  116
  5  \w      8.00  57.00   1.00    8.00    --   36.19 -99.00 -30.00   49
  6  \w     -1.00  37.00   1.00    8.00    --   36.19  77.00  60.00   38
  7  \w     -2.00  42.00   1.00    8.00    --   36.19  77.00 120.00   44
  8  \w    103.00 136.00   1.00   13.57    --   99.62  77.00-120.00   33
  9  \w     64.00 172.00   1.00   13.57    --   99.62  45.00  30.00  108
 10  \w     63.00 134.00   1.00   13.57    --   99.62 178.00 -60.00   71
 11  \w    117.00 165.00   1.00   13.57    --   99.62  45.00 -30.00   48
 12  \w     32.00 108.00   1.00   13.57    --   99.62-111.00 -90.00   76
 13  \w     65.00 104.00   1.00   13.57    --   99.62  45.00 -30.00   39
 14  \w     30.00  57.00   1.00   13.57    --   99.62-111.00   0.00   27
 15  \w     64.00 135.00   1.00   13.57    --   99.62 178.00-120.00   71
 16  \w     24.00  55.00   1.00   13.57    --   99.62-111.00  90.00   31
 17  \w     82.00 108.00   1.00   13.57    --   99.62-111.00   0.00   26
 18  \w     64.00 144.00   1.00   13.57    --   99.62 178.00-180.00   80
 19  \w    105.00 159.00   1.00   13.57    --   99.62 111.00 -60.00   54
 20  \w     33.00  67.00   1.00   13.57    --   99.62-111.00 150.00   34
 21  \w     83.00 108.00   1.00   13.57    --   99.62-111.00 150.00   25
 22  \w     98.00 178.00   1.00   13.57    --   99.62  30.00 120.00   80
 23  \w     16.00 139.00   1.00   13.57    --   99.62 -77.00 -90.00  123
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0075225000
_diffrn_orient_matrix_UB_12      -0.0412194000
_diffrn_orient_matrix_UB_13      0.0215683000
_diffrn_orient_matrix_UB_21      -0.0708817000
_diffrn_orient_matrix_UB_22      -0.0015196000
_diffrn_orient_matrix_UB_23      0.0108747000
_diffrn_orient_matrix_UB_31      -0.0526356000
_diffrn_orient_matrix_UB_32      -0.0783222000
_diffrn_orient_matrix_UB_33      -0.0115581000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0619
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -68
_diffrn_reflns_number            43102
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.505
_diffrn_reflns_theta_max         67.505
_diffrn_reflns_theta_min         3.989
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.733
_exptl_absorpt_correction_T_max  0.399
_exptl_absorpt_correction_T_min  0.106
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.733
_exptl_crystal_description       block
_exptl_crystal_F_000             10218
_exptl_crystal_size_max          0.275
_exptl_crystal_size_mid          0.215
_exptl_crystal_size_min          0.158
_refine_diff_density_max         2.208
_refine_diff_density_min         -1.252
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         7987
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.1122
_refine_ls_R_factor_gt           0.0920
_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^)+(0.1806P)^2^+202.1831P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2772
_refine_ls_wR_factor_ref         0.3022
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5823
_reflns_number_total             7987
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05849b2.cif
_cod_data_source_block           Gd6Cu24-IM
_cod_depositor_comments
'Adding full bibliography for 1570494--1570495.cif.'
_cod_original_cell_volume        20095.2(12)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1570495
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C73H150Cl16Cu24Gd6N36O145
_shelx_estimated_absorpt_t_max   0.220
_shelx_estimated_absorpt_t_min   0.116
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H11 of O11, All N(H) groups, All N(H,H) groups, All N(H,H,
  H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H10 of O10, H24 of O24, H4 of O4, H16 of O16, H12 of O12
2. Restrained distances
 C4A-C10B = C4B-C10A
 1.52 with sigma of 0.01
 N1-C10A = N1-C10B
 1.47 with sigma of 0.01
 Cl3-O2
 1.46 with sigma of 0.01
 Cl3-O2 \\sim Cl3-O7
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Others
 Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=1-FVAR(1)
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=FVAR(1)
 Fixed Sof: H1BC(0.5) H1BD(0.5) H1AA(0.5) H1AB(0.5) C10B(0.5) H10B(0.5)
 O15(0.5) C10A(0.5) H10A(0.5)
5.a Ternary CH refined with riding coordinates:
 O4(H4), O10(H10), O12(H12), O16(H16), O24(H24), C6(H6), C10B(H10B), C10A(H10A)
5.b Secondary CH2 refined with riding coordinates:
 N1(H1BC,H1BD), N1(H1AA,H1AB), N7(H7A,H7B)
5.c Me refined with riding coordinates:
 C4B(H4BA,H4BB,H4BC), C4A(H4AA,H4AB,H4AC)
5.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C15(H15), N5(H5A), C2(H2), N23(H23), C7(H7), C3(H3), C19(H19), O11(H11)
5.e Fitted pentagon refined as free rotating group:
 N11(C5,C15,N5,C2), N23(C7,N17,C3,C19)
5.f Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              14471
_shelx_fab_checksum              65435
_platon_squeeze_void_probe_radius 1.20
_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 1.418
_oxdiff_exptl_absorpt_empirical_full_min 0.734