Macrocycle- and metal-centered reduction of cobalt trithiadodecaazahexaphyrin (Hhp). Metal-to-ligand charge transfer in {(CoI2CoIIO)(Hhp˙4−)}2−
Nazarov, Dmitry I.; Kuzmin, Alexey V.; Islyaikin, Mikhail K.; Ivanov, Evgenii N.; Shestakov, Alexander F.; Faraonov, Maxim A.; Khasanov, Salavat S.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Konarev, Dmitri V.; New Journal of Chemistry 49 (2025) 1631–1639; doi:10.1039/D4NJ04896B

data_7063582
_publ_section_title
;
 Macrocycle- and metal-centered reduction of cobalt
 trithiadodecaazahexaphyrin (Hhp). Metal-to-ligand charge transfer in
 {(CoI2CoIIO)(Hhp&#x02D9;4&#x2212;)}2&#x2212;
;
_journal_issue                   5
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              1631
_journal_page_last               1639
_journal_paper_doi               10.1039/D4NJ04896B
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety
'C30 H12 Co3 N15 O S3, 2(C18 H36 K N2 O6), 2(C6 H4 Cl2)'
_chemical_formula_sum            'C78 H92 Cl4 Co3 K2 N19 O13 S3'
_chemical_formula_weight         1996.67
_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             2024-08-28
_audit_creation_method
;FinalCif V139 by Daniel Kratzert, Freiburg 2024, 
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2024-08-28 deposited with the CCDC.	2024-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                95.465(2)
_cell_angle_beta                 92.670(2)
_cell_angle_gamma                90.759(3)
_cell_formula_units_Z            2
_cell_length_a                   15.6198(6)
_cell_length_b                   15.6415(6)
_cell_length_c                   17.9376(4)
_cell_measurement_reflns_used    14447
_cell_measurement_temperature    126(18)
_cell_measurement_theta_max      28.4910
_cell_measurement_theta_min      2.0960
_cell_volume                     4357.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 39.46 (release 15-03-2018))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      126(18)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.834
_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    -15.00  85.00   1.00   96.00    --   10.59  57.00 -60.00  100
  2  \w    -12.00  72.00   1.00   96.00    --   10.59  57.00  90.00   84
  3  \w    -82.00 -46.00   1.00   96.00    --  -10.83 -57.00   0.00   36
  4  \w    -22.00   3.00   1.00   96.00    --  -10.83 -57.00  30.00   25
  5  \w    -35.00  60.00   1.00   96.00    --  -10.83  37.00-180.00   95
  6  \w    -87.00 -53.00   1.00   96.00    --  -10.83 -37.00  30.00   34
  7  \w    -82.00 -57.00   1.00   96.00    --  -10.83 -37.00  90.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0386659000
_diffrn_orient_matrix_UB_12      -0.0243181000
_diffrn_orient_matrix_UB_13      -0.0001119000
_diffrn_orient_matrix_UB_21      0.0167347000
_diffrn_orient_matrix_UB_22      -0.0209840000
_diffrn_orient_matrix_UB_23      0.0307250000
_diffrn_orient_matrix_UB_31      -0.0170920000
_diffrn_orient_matrix_UB_32      0.0323133000
_diffrn_orient_matrix_UB_33      0.0252499000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0508
_diffrn_reflns_av_unetI/netI     0.0845
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.834
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            45605
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.834
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.094
_diffrn_reflns_theta_min         1.775
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.927
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94744
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_description       block
_exptl_crystal_F_000             2064
_exptl_crystal_size_max          0.401
_exptl_crystal_size_mid          0.257
_exptl_crystal_size_min          0.087
_refine_diff_density_max         1.087
_refine_diff_density_min         -0.875
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1208
_refine_ls_number_reflns         19528
_refine_ls_number_restraints     360
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0982
_refine_ls_R_factor_gt           0.0588
_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^)+(0.0613P)^2^+4.7296P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1282
_refine_ls_wR_factor_ref         0.1545
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13351
_reflns_number_total             19528
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj04896b2.cif
_cod_data_source_block           exp_2037_int1
_cod_depositor_comments          'Adding full bibliography for 7063582.cif.'
_cod_database_code               7063582
_chemical_oxdiff_formula         'C78 H78 N19 O13 S3 Cl4 K2 Co3 '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl41-C41 \\sim Cl71-C71
 with sigma of 0.02
 C41-C42 \\sim C71-C72
 with sigma of 0.02
 C41-C46 \\sim C71-C76
 with sigma of 0.02
 Cl42-C42 \\sim Cl72-C72
 with sigma of 0.02
 C42-C43 \\sim C72-C73
 with sigma of 0.02
 C43-C44 \\sim C73-C74
 with sigma of 0.02
 C44-C45 \\sim C74-C75
 with sigma of 0.02
 C45-C46 \\sim C75-C76
 with sigma of 0.02
 Cl41-C42 \\sim Cl71-C72
 with sigma of 0.04
 Cl41-C46 \\sim Cl71-C76
 with sigma of 0.04
 C41-Cl42 \\sim C71-Cl72
 with sigma of 0.04
 C41-C43 \\sim C71-C73
 with sigma of 0.04
 C41-C45 \\sim C71-C75
 with sigma of 0.04
 Cl42-C43 \\sim Cl72-C73
 with sigma of 0.04
 C42-C44 \\sim C72-C74
 with sigma of 0.04
 C42-C46 \\sim C72-C76
 with sigma of 0.04
 C43-C45 \\sim C73-C75
 with sigma of 0.04
 C44-C46 \\sim C74-C76
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C71 \\sim C72 \\sim
C76 \\sim C73 \\sim C75 \\sim C74: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
Cl42 \\sim Cl72: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Cl41 \\sim Cl71: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C64 \\sim C65 \\sim C66 \\sim C61 \\sim C62 \\sim C63: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002 within 2A
C55 \\sim C56 \\sim C51 \\sim C52 \\sim C53 \\sim C54: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002 within 2A
Uanis(C46) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C71) \\sim Ueq,
Uanis(C72) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C75)
\\sim Ueq, Uanis(C74) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
4. Others
 Sof(Cl71)=Sof(C71)=Sof(C72)=Sof(C76)=Sof(H76)=Sof(Cl72)=Sof(C73)=Sof(H73)=
 Sof(C75)=Sof(H75)=Sof(C74)=Sof(H74)=1-FVAR(1)
 Sof(Cl41)=Sof(C41)=Sof(Cl42)=Sof(C42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=
 Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=FVAR(1)
 Fixed Sof: Cl52(0.5) Cl51(0.5) C51(0.5) C52(0.5) C53(0.5) H53(0.5) C54(0.5)
 H54(0.5) C55(0.5) H55(0.5) C56(0.5) H56(0.5) Cl62(0.5) Cl61(0.5) C61(0.5)
 C62(0.5) C63(0.5) H63(0.5) C64(0.5) H64(0.5) C65(0.5) H65(0.5) C66(0.5)
 H66(0.5)
5.a Free rotating group:
 Cl52(Cl51,C51,C52,C53,C54,C55,C56), Cl62(Cl61,C61,C62,C63,C64,C65,C66)
5.b Secondary CH2 refined with riding coordinates:
 C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,H30H), C305(H30I,
 H30J), C306(H30K,H30L), C307(H30M,H30N), C308(H30O,H30P), C309(H30Q,H30R),
 C310(H31A,H31B), C311(H31C,H31D), C312(H31E,H31F), C313(H31G,H31H), C314(H31I,
 H31J), C315(H31K,H31L), C316(H31M,H31N), C317(H31O,H31P), C318(H31Q,H31R),
 C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C205(H20I,
 H20J), C206(H20K,H20L), C207(H20M,H20N), C208(H20O,H20P), C209(H20Q,H20R),
 C210(H21A,H21B), C211(H21C,H21D), C212(H21E,H21F), C213(H21G,H21H), C214(H21I,
 H21J), C215(H21K,H21L), C216(H21M,H21N), C217(H21O,H21P), C218(H21Q,H21R)
5.c Aromatic/amide H refined with riding coordinates:
 C104(H104), C105(H105), C106(H106), C107(H107), C114(H114), C115(H115),
 C116(H116), C117(H117), C124(H124), C125(H125), C126(H126), C127(H127),
 C43(H43), C44(H44), C45(H45), C46(H46), C53(H53), C54(H54), C55(H55), C56(H56),
  C63(H63), C64(H64), C65(H65), C66(H66), C76(H76), C73(H73), C75(H75), C74(H74)
;
_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 1.134
_oxdiff_exptl_absorpt_empirical_full_min 0.897
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.708
_shelx_estimated_absorpt_t_max   0.924
_shelx_res_checksum              75698
_shelx_hkl_checksum              96094