Copper(II) defect-cubane water oxidation electrocatalysts: from molecular tetramers to oxidic nanostructures.
Adiyeri Saseendran, Devi Prasad; Fischer, Jörg W A; Müller, Lea; Abbott, Daniel F.; Mougel, Victor; Jeschke, Gunnar; Triana, Carlos A.; Patzke, Greta R.; Chemical communications (Cambridge, England) 59 (2023) 5866–5869; doi:10.1039/d3cc01005h

data_7131587
_publ_section_title
;
 Copper(II) defect-cubane water oxidation electrocatalysts: from molecular
 tetramers to oxidic nanostructures.
;
_journal_issue                   39
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5866
_journal_page_last               5869
_journal_paper_doi               10.1039/d3cc01005h
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety
'2(C40 H52 Cu4 N4 O12), 4(C6 H16 N), 4(Cl O3.75), 6(H2 O)'
_chemical_formula_sum            'C104 H180 Cl4 Cu8 N12 O45'
_chemical_formula_weight         2968.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-21 deposited with the CCDC.	2023-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.8590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   9.15690(10)
_cell_length_b                   31.5203(3)
_cell_length_c                   11.78070(10)
_cell_measurement_reflns_used    21572
_cell_measurement_temperature    160.00(10)
_cell_measurement_theta_max      73.0270
_cell_measurement_theta_min      4.8900
_cell_volume                     3368.31(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9b (Rigaku OD, 2015)'
_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      160.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.978
_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    -54.00  20.00   0.50   10.26    --    0.00 -75.00  45.00  148
  2  \w    -60.00 -15.00   0.50   10.26    --  -88.50  75.00 172.00   90
  3  \w   -145.00-114.00   0.50   10.26    --  -88.50 -75.00  45.00   62
  4  \w   -103.00 -69.00   0.50   10.26    --  -88.50  75.00 172.00   68
  5  \w     58.00  83.00   0.50   10.26    --   97.44 -75.00  45.00   50
  6  \w     79.00 113.00   0.50   10.26    --   97.44  75.00 172.00   68
  7  \w    -48.00   6.00   0.50   10.26    --    0.00 -57.00 -90.00  108
  8  \w     40.00  72.00   0.50   10.26    --    0.00  37.00 150.00   64
  9  \w    -15.00  17.00   0.50   10.26    --    0.00  37.00 150.00   64
 10  \w    -78.00  10.00   0.50   10.26    --    0.00 -37.00-180.00  176
 11  \w     16.00  41.00   0.50   10.26    --    0.00  75.00 172.00   50
 12  \w   -104.00  -9.00   0.50   10.26    --  -88.50  30.00 150.00  190
 13  \w   -164.00 -81.00   0.50   10.26    --  -88.50-111.00   0.00  166
 14  \w   -145.00-114.00   0.50   10.26    --  -88.50 -30.00  90.00   62
 15  \w    -55.00 -11.00   0.50   10.26    --  -88.50 111.00 -90.00   88
 16  \w   -103.00 -73.00   0.50   10.26    --  -88.50 -30.00  90.00   60
 17  \w   -130.00 -78.00   0.50   10.26    --  -88.50 -45.00 -60.00  104
 18  \w    -83.00 -12.00   0.50   10.26    --  -88.50 111.00 -60.00  142
 19  \w    -87.00 -61.00   0.50   10.26    --  -88.50  45.00-180.00   52
 20  \w   -117.00 -91.00   0.50   10.26    --  -88.50 -94.00 150.00   52
 21  \w     86.00 117.00   0.50   10.26    --   97.44  61.00 -60.00   62
 22  \w     73.00 143.00   0.50   10.26    --   97.44 178.00 -30.00  140
 23  \w     90.00 130.00   0.50   10.26    --   97.44  45.00 -60.00   80
 24  \w    130.00 176.00   0.50   10.26    --   97.44  15.00 -30.00   92
 25  \w     82.00 175.00   0.50   10.26    --   97.44  30.00 -90.00  186
 26  \w     59.00 107.00   0.50   10.26    --   97.44-111.00  30.00   96
 27  \w     24.00  50.00   0.50   10.26    --   97.44-111.00  30.00   52
 28  \w     39.00 109.00   0.50   10.26    --   97.44-111.00 120.00  140
 29  \w     84.00 170.00   0.50   10.26    --   97.44  45.00-180.00  172
 30  \w    113.00 162.00   0.50   10.26    --   97.44  61.00  90.00   98
 31  \w     83.00 108.00   0.50   10.26    --   97.44 -45.00 -90.00   50
 32  \w     21.00  96.00   0.50   10.26    --   97.44 -45.00   0.00  150
 33  \w     82.00 171.00   0.50   10.26    --   97.44  30.00-120.00  178
 34  \w     22.00  76.00   0.50   10.26    --   97.44 -45.00 -90.00  108
 35  \w    138.00 163.00   0.50   10.26    --   97.44  61.00 -60.00   50
 36  \w     80.00 107.00   0.50   10.26    --   97.44  61.00  90.00   54
 37  \w     48.00  73.00   0.50   10.26    --   97.44 -75.00  45.00   50
 38  \w      1.00  26.00   0.50   10.26    --    0.00  75.00 172.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1221246000
_diffrn_orient_matrix_UB_12      -0.0131255000
_diffrn_orient_matrix_UB_13      0.0967976000
_diffrn_orient_matrix_UB_21      -0.0389083000
_diffrn_orient_matrix_UB_22      0.0380672000
_diffrn_orient_matrix_UB_23      0.0722146000
_diffrn_orient_matrix_UB_31      -0.1114068000
_diffrn_orient_matrix_UB_32      -0.0276936000
_diffrn_orient_matrix_UB_33      0.0533666000
_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  0.0373
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            43173
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.569
_diffrn_reflns_theta_min         2.804
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.789
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.812
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9b (Rigaku Oxford Diffraction, 2015)
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_density_diffrn    1.464
_exptl_crystal_description       block
_exptl_crystal_F_000             1548
_exptl_crystal_size_max          0.091
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.894
_refine_diff_density_min         -0.471
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     412
_refine_ls_number_reflns         6646
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0360
_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^)+(0.0644P)^2^+2.7649P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1072
_refine_ls_wR_factor_ref         0.1113
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5758
_reflns_number_total             6646
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc01005h2.cif
_cod_data_source_block           Cu(pyalk)4(OAc)4_tetramer
_cod_depositor_comments
'Adding full bibliography for 7131586--7131587.cif.'
_cod_database_code               7131587
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H92 Cl2 Cu4 N6 O24'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Others
 Fixed Sof: O8(0.75) O12A(0.5) H12A(0.5) H12B(0.5)
3.a Free rotating group:
 O11(H11A,H11B), O12A(H12A,H12B)
3.b Ternary CH refined with riding coordinates:
 N3(H3A)
3.c Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C23(H23A,H23B), C21(H21A,H21B)
3.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C11(H11), C4(H4), C3(H3), C14(H14), C12(H12), C13(H13)
3.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C17(H17A,H17B,H17C), C10(H10A,H10B,H10C), C7(H7A,H7B,
 H7C), C20(H20A,H20B,H20C), C8(H8A,H8B,H8C), C22(H22A,H22B,H22C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              27824
_shelx_hkl_checksum              51678
_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 3.348
_oxdiff_exptl_absorpt_empirical_full_min 0.671