Structural and reactivity insights into high-valent Co(III)-(μ-peroxo)-Co(IV) and its electromer Co(III)-(μ-superoxo)-Co(III).
Sharma, Parkhi; Gupta, Sikha; Kumar, Rakesh; Charisiadis, Asterios; Sauvan, Maxime; Velasco, Lucia; Saini, Abhishek; Moonshiram, Dooshaye; Draksharapu, Apparao; Chemical communications (Cambridge, England) 60 (2024) 14846–14849; doi:10.1039/d4cc04658g

data_7133985
_publ_section_title
;
 Structural and reactivity insights into high-valent
 Co(III)-(&#x3bc;-peroxo)-Co(IV) and its electromer
 Co(III)-(&#x3bc;-superoxo)-Co(III).
;
_journal_issue                   99
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14846
_journal_page_last               14849
_journal_paper_doi               10.1039/d4cc04658g
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety
'C54 H73 Co2 N8 O9, Cl O3.98, 2(Cl O4), 4[H2O], 0.6[H2O]'
_chemical_formula_sum            'C54 H82.2 Cl3 Co2 N8 O25.58'
_chemical_formula_weight         1476.96
_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
_audit_creation_date             2024-10-01
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-01 deposited with the CCDC.	2024-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.9520(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.9896(6)
_cell_length_b                   22.9608(8)
_cell_length_c                   17.9997(7)
_cell_measurement_reflns_used    9227
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.050
_cell_measurement_theta_min      1.853
_cell_volume                     6527.8(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 1K area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0868
_diffrn_reflns_av_unetI/netI     0.0552
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            83478
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.050
_diffrn_reflns_theta_max         25.050
_diffrn_reflns_theta_min         1.853
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.718
_exptl_absorpt_correction_T_max  0.965
_exptl_absorpt_correction_T_min  0.860
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'brownish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.503
_exptl_crystal_description       block
_exptl_crystal_F_000             3087
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.974
_refine_diff_density_min         -0.712
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     843
_refine_ls_number_reflns         11553
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0974
_refine_ls_R_factor_gt           0.0776
_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^)+(0.0567P)^2^+26.8421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1651
_refine_ls_wR_factor_ref         0.1741
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9227
_reflns_number_total             11553
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04658g2.cif
_cod_data_source_block           2381919
_cod_depositor_comments          'Adding full bibliography for 7133985.cif.'
_cod_original_formula_sum        'C54 H82.20 Cl3 Co2 N8 O25.58'
_cod_database_code               7133985
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.864
_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. Others
 Fixed Sof: O21A(0.66) O20A(0.66) C15A(0.5) H15A(0.5) H15B(0.5) H15C(0.5)
 O20B(0.33) O21B(0.33) C15B(0.5) H15D(0.5) H15E(0.5) H15F(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C36(H36A,H36B), C20(H20A,H20B), C9(H9A,H9B), C10(H10A,H10B),
 C37(H37A,H37B)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1A), C18(H18), C54(H54), C45(H45), C27(H27), C28(H28)
3.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C22(H22A,H22B,H22C), C7(H7A,H7B,H7C), C3(H3A,H3B,H3C),
 C44(H44A,H44B,H44C), C49(H49A,H49B,H49C), C40(H40A,H40B,H40C), C53(H53A,H53B,
 H53C), C30(H30A,H30B,H30C), C24(H24A,H24B,H24C), C51(H51A,H51B,H51C), C17(H17A,
 H17B,H17C), C42(H42A,H42B,H42C), C5(H5A,H5B,H5C), C34(H34A,H34B,H34C),
 C13(H13A,H13B,H13C), C32(H32A,H32B,H32C), C15A(H15A,H15B,H15C), C15B(H15D,H15E,
 H15F)
;
_shelx_res_checksum              77588
_shelx_hkl_checksum              28283
_shelx_fab_checksum              85420
_olex2_submission_special_instructions 'No special instructions were received'