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_1570494
_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
'C48 H126 Cu24 Gd6 N12 O96, 10(Cl O4), Cl, O, H2 O'
_chemical_formula_sum            'C48 H128 Cl11 Cu24 Gd6 N12 O138'
_chemical_formula_weight         5940.03
_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
_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                65.084(3)
_cell_angle_beta                 76.898(2)
_cell_angle_gamma                60.275(3)
_cell_formula_units_Z            1
_cell_length_a                   18.7431(5)
_cell_length_b                   18.7639(5)
_cell_length_c                   19.9485(6)
_cell_measurement_reflns_used    20585
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.1230
_cell_measurement_theta_min      2.9350
_cell_volume                     5524.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.965
_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    -58.00 -12.00   1.00    2.00    --  -41.00 -57.00   0.00   46
  2  \w   -113.00 -15.00   1.00    2.00    --  -41.00 -37.00 -60.00   98
  3  \w   -116.00 -19.00   1.00    2.00    --  -41.00 -37.00-150.00   97
  4  \w     13.00  40.00   1.00    2.00    --   41.00  57.00 150.00   27
  5  \w    -21.00  74.00   1.00    2.00    --   41.00 -77.00 120.00   95
  6  \w     50.00  98.00   1.00    2.00    --   41.00-125.00 -60.00   48
  7  \w     88.00 114.00   1.00    2.00    --   41.00  57.00 150.00   26
  8  \w    103.00 178.00   1.00   15.00    --  110.83  77.00   0.00   75
  9  \w    111.00 165.00   1.00   15.00    --  110.83  77.00 150.00   54
 10  \w    104.00 170.00   1.00   15.00    --  110.83  77.00-150.00   66
 11  \w    104.00 144.00   1.00   15.00    --  110.83  77.00  60.00   40
 12  \w     64.00 107.00   1.00   15.00    --  110.83-100.00 137.00   43
 13  \w     64.00  97.00   1.00   15.00    --  110.83 -94.00 -60.00   33
 14  \w    106.00 132.00   1.00   15.00    --  110.83 100.00-116.00   26
 15  \w     37.00 129.00   1.00   15.00    --  110.83 -45.00  60.00   92
 16  \w     41.00  68.00   1.00   15.00    --  110.83-125.00-120.00   27
 17  \w     27.00  96.00   1.00   15.00    --  110.83 -94.00  60.00   69
 18  \w     45.00 135.00   1.00   15.00    --  110.83 -45.00-150.00   90
 19  \w     99.00 170.00   1.00   15.00    --  110.83  45.00 -60.00   71
 20  \w     68.00 129.00   1.00   15.00    --  110.83-148.00  69.13   61
 21  \w     82.00 107.00   1.00   15.00    --  110.83 -94.00  30.00   25
 22  \w     82.00 107.00   1.00   15.00    --  110.83 -94.00 150.00   25
 23  \w     53.00 108.00   1.00   15.00    --  110.83-103.00-126.56   55
;
_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      -0.0171376000
_diffrn_orient_matrix_UB_12      -0.0009447000
_diffrn_orient_matrix_UB_13      0.0795553000
_diffrn_orient_matrix_UB_21      -0.0548190000
_diffrn_orient_matrix_UB_22      -0.0451093000
_diffrn_orient_matrix_UB_23      0.0148501000
_diffrn_orient_matrix_UB_31      0.0752560000
_diffrn_orient_matrix_UB_32      -0.0910014000
_diffrn_orient_matrix_UB_33      0.0265367000
_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  0.0423
_diffrn_reflns_av_unetI/netI     0.0581
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            41320
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.509
_diffrn_reflns_theta_min         2.913
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.900
_exptl_absorpt_correction_T_max  0.393
_exptl_absorpt_correction_T_min  0.135
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
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    1.786
_exptl_crystal_description       block
_exptl_crystal_F_000             2871
_exptl_crystal_size_max          0.193
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.131
_refine_diff_density_max         1.945
_refine_diff_density_min         -0.988
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1199
_refine_ls_number_reflns         22102
_refine_ls_number_restraints     848
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0674P)^2^+22.4498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1395
_refine_ls_wR_factor_ref         0.1447
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19976
_reflns_number_total             22102
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05849b2.cif
_cod_data_source_block           Gd6Cu24-AC
_cod_depositor_comments
'Adding full bibliography for 1570494--1570495.cif.'
_cod_database_code               1570494
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C88Cl6Cu24Gd6N32O141
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H25 of O25, H39 of O39, H5 of O5, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H1 of O1, H30 of O30, H32 of O32, H22 of O22, H50 of
  O50, H6 of O6, H20 of O20, H10 of O10, H16 of O16, H36 of O36, H8 of O8, H18
  of O18, H56 of O56, H12 of O12, H54 of O54, All O(H,H) groups
2. Restrained distances
 Cl5-O67
 1.45 with sigma of 0.01
 Cl5-O65 = Cl3-O69
 1.45 with sigma of 0.01
 O2-O67 \\sim O65-O67 \\sim O33-O67
 with sigma of 0.02
 O2-O67 \\sim O17-O71
 with sigma of 0.04
 O17-O35 \\sim O17-O71 \\sim O69-O71 \\sim O35-O71
 with sigma of 0.02
 O65-O67 \\sim O69-O71
 with sigma of 0.04
 Cl5-O2 \\sim Cl3-O17
 with sigma of 0.02
 O33-O67 \\sim O35-O71
 with sigma of 0.04
 Cl5-O65 \\sim Cl3-O69
 with sigma of 0.02
 O65-O33 \\sim O69-O35
 with sigma of 0.04
 Cl5-O33 \\sim Cl3-O35
 with sigma of 0.02
 O2-O33 \\sim O2-O67 \\sim O65-O67 \\sim O33-O67
 with sigma of 0.02
 Cl5-O2 \\sim Cl5-O65 \\sim Cl5-O33 \\sim Cl5-O67
 with sigma of 0.01
 Cl5-O67 \\sim Cl3-O71
 with sigma of 0.02
 Cl3-O17 \\sim Cl3-O69 \\sim Cl3-O35 \\sim Cl3-O71
 with sigma of 0.01
 O2-O65 \\sim O17-O69
 with sigma of 0.04
 O2-O33 \\sim O17-O35
 with sigma of 0.04
 C40-C20 \\sim C52-C20
 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(Cl3)=Sof(O17)=Sof(O69)=Sof(O35)=Sof(O71)=1-FVAR(1)
 Sof(Cl5)=Sof(O2)=Sof(O65)=Sof(O33)=Sof(O67)=FVAR(1)
 Fixed Sof: H14A(0.5) H14(0.5) H16B(0.5) H16A(0.5) H18B(0.5) H18A(0.5)
 H20B(0.5) H20A(0.5) H24(0.5) H24A(0.5) H7A(0.75) H7B(0.25) C2(0.5) H2C(0.5)
 H2D(0.5) H2E(0.5) C9(0.5) H9A(0.5) H9B(0.5) H9C(0.5) C19(0.5) H19A(0.5)
 H19B(0.5) H19C(0.5) C21(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C11(0.5) H11A(0.5)
 H11B(0.5) H11C(0.5) C23(0.5) H23A(0.5) H23B(0.5) H23C(0.5) C3(0.5) H3C(0.5)
 H3D(0.5) H3E(0.5) C13(0.5) H13A(0.5) H13B(0.5) H13C(0.5) C27(0.5) H27A(0.5)
 H27B(0.5) H27C(0.5) C34(0.5) H34A(0.5) H34B(0.5) H34C(0.5) C40(0.5) H40A(0.5)
 H40B(0.5) H40C(0.5) C52(0.5) H52A(0.5) H52B(0.5) H52C(0.5) O51(0.5) H51A(0.5)
 H51B(0.5)
5.a Riding coordinates:
 O5(H5), O51(H51A,H51B)
5.b Ternary CH refined with riding coordinates:
 O1(H1), O6(H6), O8(H8), O10(H10), O12(H12), O16(H16), O18(H18), O20(H20),
 O22(H22), O30(H30), O32(H32), O36(H36), O50(H50), O54(H54), O56(H56),
 C14(H14A), C14(H14), C16(H16B), C16(H16A), C18(H18B), C18(H18A), C20(H20B),
 C20(H20A), C24(H24), C24(H24A), C7(H7A), C7(H7B)
5.c Secondary CH2 refined with riding coordinates:
 N43(H43A,H43B), N1(H1A,H1B), N4(H4A,H4B), N5(H5A,H5B), N3(H3A,H3B), N2(H2A,H2B)
5.d Aromatic/amide H refined with riding coordinates:
 O39(H39), O25(H25)
5.e Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C2(H2C,H2D,H2E), C17(H17A,H17B,H17C), C9(H9A,H9B,H9C),
 C19(H19A,H19B,H19C), C5(H5C,H5D,H5E), C21(H21A,H21B,H21C), C11(H11A,H11B,H11C),
  C23(H23A,H23B,H23C), C3(H3C,H3D,H3E), C13(H13A,H13B,H13C), C27(H27A,H27B,
 H27C), C34(H34A,H34B,H34C), C40(H40A,H40B,H40C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              48755
_shelx_fab_checksum              28908
_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 2.066
_oxdiff_exptl_absorpt_empirical_full_min 0.596