Structural control of μ-hydroxo-μ-peroxodicobalt(III) complex with the 6-hpa dinucleating ligand to enhance O<sub>2</sub>-evolution activity in catalytic water oxidation.
Tanaka, Yuki; Iwanaga, Osamu; Fujikawa, Kyosuke; Shinomiya, Seina; Kitagishi, Hiroaki; Yanagisawa, Sachiko; Kubo, Minoru; Kambe, Tetsuya; Masaoka, Shigenobu; Kodera, Masahito; Dalton transactions (Cambridge, England : 2003) 54 (2025) 12130–12134; doi:10.1039/d5dt01140j

data_7719168
_publ_section_title
;
 Structural control of &#x3bc;-hydroxo-&#x3bc;-peroxodicobalt(III) complex
 with the 6-hpa dinucleating ligand to enhance O<sub>2</sub>-evolution
 activity in catalytic water oxidation.
;
_journal_issue                   32
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12130
_journal_page_last               12134
_journal_paper_doi               10.1039/d5dt01140j
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'C38 H38 Co2 N8 O3, 6(F3 P0.5), 3(C3 H3), C2 H3 N'
_chemical_formula_sum            'C49 H50 Co2 F18 N9 O3 P3'
_chemical_formula_weight         1365.75
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-26
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-07 deposited with the CCDC.	2025-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                79.551(3)
_cell_angle_beta                 76.308(3)
_cell_angle_gamma                75.548(3)
_cell_formula_units_Z            2
_cell_length_a                   10.9897(3)
_cell_length_b                   11.6010(4)
_cell_length_c                   22.6406(7)
_cell_measurement_reflns_used    13107
_cell_measurement_temperature    102.94(19)
_cell_measurement_theta_max      31.3490
_cell_measurement_theta_min      1.9350
_cell_volume                     2692.68(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      102.94(19)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -83.00   8.00   0.25    7.98    --  -12.77 -57.00 -55.00  364
  2  \w    -33.00  61.00   0.25    7.98    --  -12.77  57.00  86.00  376
  3  \w     54.00  90.00   0.25    7.98    --   11.21-178.00 120.00  144
  4  \w    -17.00  49.00   0.25    7.98    --   11.21 -99.00 -60.00  264
  5  \w     53.00  82.00   0.25    7.98    --   11.21-178.00 -90.00  116
  6  \w    -84.00 -58.00   0.25    7.98    --  -12.77 -57.00  30.00  104
  7  \w    -77.00 -51.00   0.25    7.98    --  -12.77-178.00  90.00  104
  8  \w    -32.00  10.00   0.25    7.98    --  -12.77 -57.00  30.00  168
  9  \w    -54.00  15.00   0.25    7.98    --  -12.77 -77.00 150.00  276
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0593220000
_diffrn_orient_matrix_UB_12      0.0069296000
_diffrn_orient_matrix_UB_13      0.0213002000
_diffrn_orient_matrix_UB_21      0.0084817000
_diffrn_orient_matrix_UB_22      0.0552653000
_diffrn_orient_matrix_UB_23      0.0057971000
_diffrn_orient_matrix_UB_31      -0.0322248000
_diffrn_orient_matrix_UB_32      0.0308671000
_diffrn_orient_matrix_UB_33      -0.0238810000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            35733
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         1.942
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.820
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.142a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.684
_exptl_crystal_description       block
_exptl_crystal_F_000             1384
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.475
_refine_diff_density_min         -1.308
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     761
_refine_ls_number_reflns         12336
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.1105
_refine_ls_R_factor_gt           0.0812
_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^)+(0.1388P)^2^+5.0051P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2326
_refine_ls_wR_factor_ref         0.2552
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8502
_reflns_number_total             12336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01140j2.cif
_cod_data_source_block           co6-hpa3_auto
_cod_depositor_comments          'Adding full bibliography for 7719168.cif.'
_cod_database_code               7719168
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         C47H47Co2P3F18O3N8
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.887
_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
2.a Secondary CH2 refined with riding coordinates:
 C01A(H01A,H01B), C01E(H01E,H01F), C01O(H01J,H01L), C01W(H01M,H01N), C01Y(H01O,
 H01P), C025(H02A,H02B), C027(H02C,H02D), C029(H02E,H02F)
2.b Aromatic/amide H refined with riding coordinates:
 C30(H30), C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X),
 C00Y(H00Y), C012(H012), C013(H013), C014(H014), C016(H016), C017(H017),
 C01B(H01C), C01C(H01D), C01F(H01G), C01G(H01H), C01H(H01I), C01K(H01K),
 C01Q(H01Q), C01R(H01R), C01S(H01S), C01U(H01U), C01V(H01V), C01X(H01X),
 C01Z(H01Z), C020(H020), C021(H021), C022(H022), C023(H023), C026(H026),
 C028(H028)
2.c Idealised Me refined as rotating group:
 C02B(H02G,H02H,H02I)
;
_shelx_res_checksum              2313
_shelx_hkl_checksum              14573
_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 1.081
_oxdiff_exptl_absorpt_empirical_full_min 0.922