A water-soluble heterometallic iron(IV)-ruthenium(IV) μ-nitrido porphyrin complex: synthesis, structure and catalytic activity.
Ng, Rain; Cheung, Wai-Man; Leung, Cheuk-Pui; Au, Chun Kit; So, Yat-Ming; Sung, Herman H.-Y.; Chan, Wan; Williams, Ian D.; Leung, Wa-Hung; Dalton transactions (Cambridge, England : 2003) 54 (2025) 9359–9367; doi:10.1039/d5dt00712g

data_7718658
_publ_section_title
;
 A water-soluble heterometallic iron(IV)-ruthenium(IV) &#x3bc;-nitrido
 porphyrin complex: synthesis, structure and catalytic activity.
;
_journal_issue                   23
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9359
_journal_page_last               9367
_journal_paper_doi               10.1039/d5dt00712g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'C61 H60 Cl2 Co Fe N5 O22 P3 Ru S4, 4(C24 H20 P), 9(H2 O), 0.918(O)'
_chemical_formula_sum            'C157 H158 Cl2 Co Fe N5 O31.92 P7 Ru S4'
_chemical_formula_weight         3257.37
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-15
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7205)
;
_audit_update_record
;
2025-04-22 deposited with the CCDC.	2025-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                79.900(3)
_cell_angle_beta                 80.703(3)
_cell_angle_gamma                78.930(3)
_cell_formula_units_Z            2
_cell_length_a                   13.3216(5)
_cell_length_b                   20.9058(7)
_cell_length_c                   28.0045(9)
_cell_measurement_reflns_used    7197
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.3620
_cell_measurement_theta_min      3.5680
_cell_volume                     7469.2(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.3577
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.949
_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     30.00 135.00   1.00   12.00    --  104.49 -61.00-180.00  105
  2  \w   -114.00 -22.00   1.00    6.00    --  -40.45 -57.00 -90.00   92
  3  \w    -70.00  38.00   1.00    6.00    --  -40.45  77.00  30.00  108
  4  \w    -70.00  34.00   1.00    6.00    --  -40.45  57.00-180.00  104
  5  \w     74.00 176.00   1.00   12.00    --  104.49  30.00 120.00  102
  6  \w     53.00 112.00   1.00   12.00    --  104.49-111.00-180.00   59
  7  \w    138.00 178.00   1.00   12.00    --  104.49  61.00  30.00   40
  8  \w     74.00 109.00   1.00   12.00    --  104.49  61.00  30.00   35
  9  \w     34.00 133.00   1.00   12.00    --  104.49-146.00  50.00   99
 10  \w     29.00 108.00   1.00   12.00    --  104.49-111.00  90.00   79
 11  \w     81.00 169.00   1.00   12.00    --  104.49  30.00-150.00   88
 12  \w     56.00 131.00   1.00   12.00    --  104.49 -45.00  30.00   75
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0660
_diffrn_reflns_av_unetI/netI     0.1066
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            45207
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.688
_diffrn_reflns_theta_min         3.576
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    4.638
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69695
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       needle
_exptl_crystal_F_000             3381
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.971
_refine_diff_density_min         -0.908
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2103
_refine_ls_number_reflns         28191
_refine_ls_number_restraints     428
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1132
_refine_ls_R_factor_gt           0.0652
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0757P)^2^+4.7826P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1514
_refine_ls_wR_factor_ref         0.1797
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18131
_reflns_number_total             28191
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00712g2.cif
_cod_data_source_block           wai240cult
_cod_depositor_comments          'Adding full bibliography for 7718658.cif.'
_cod_database_code               7718658
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.429
_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, All O(H,H) groups
2. Restrained distances
 O18-O19
 2.4 with sigma of 0.04
 O17A-O19A
 2.4 with sigma of 0.04
 O17-O19
 2.4 with sigma of 0.04
 O18A-O17A
 2.4 with sigma of 0.04
 C72A-C76A
 2.4 with sigma of 0.02
 C75A-C71A
 2.4 with sigma of 0.02
 C73A-C71A
 2.4 with sigma of 0.02
 O18A-O19A
 2.4 with sigma of 0.04
 O17-O18
 2.4 with sigma of 0.04
 C72A-C74A
 2.4 with sigma of 0.02
 C75A-C73A
 2.4 with sigma of 0.02
 C52-C51 \\sim C53-C52 \\sim C54-C53 \\sim C55-C54 \\sim C56-C55 \\sim C56-C51
 with sigma of 0.02
 C75A-C74A \\sim C74A-C73A \\sim C73A-C72A \\sim C72A-C71A \\sim C76A-C71A
\\sim C76A-C75A
 with sigma of 0.02
 S1-O11 \\sim S1-O12 \\sim S1-O13
 with sigma of 0.02
3. Restrained planarity
 S3A, C71A, C72A, C73A, C74A, C75A, C76A
 with sigma of 0.02
 C51, C52, C53, C54, C55, C56
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(O15) \\sim Ueq, Uanis(S2) \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(O14)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.012
Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.012
Uanis(C71A) \\sim Ueq, Uanis(C72A) \\sim Ueq, Uanis(C73A) \\sim Ueq,
Uanis(C74A) \\sim Ueq, Uanis(C75A) \\sim Ueq, Uanis(C76A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.012
Uanis(O13A) \\sim Ueq, Uanis(O11A) \\sim Ueq, Uanis(O12A) \\sim Ueq: with sigma
of 0.008 and sigma for terminal atoms of 0.012
Uanis(O17A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.012
Uanis(O7W) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 S3, O17, O18, O19, C74
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S3A, O17A, O18A, O19A, C74
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S3A, O17A, O18A, O19A, C71A, C72A, C73A, C74A, C75A, C76A, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C50, C51A, C52A, C53A, C54A, C55A, C56A, S1A, O13A, O12A, O11A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O13, O11, O12, S1, C54, C55, C56, C51, C52, C53, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(S1A)=Sof(O11A)=Sof(O12A)=Sof(O13A)=Sof(C51A)=Sof(C52A)=Sof(H52A)=
 Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=
 Sof(O10W)=1-FVAR(1)
 Sof(S1)=Sof(O11)=Sof(O12)=Sof(O13)=Sof(C51)=Sof(C52)=Sof(H52)=Sof(C53)=
 Sof(H53)=Sof(C54)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56)=FVAR(1)
 Sof(S3A)=Sof(O17A)=Sof(O18A)=Sof(O19A)=Sof(C71A)=Sof(C72A)=Sof(H72A)=
 Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(C75A)=Sof(H75A)=Sof(C76A)=Sof(H76A)=1-FVAR(2)
 Sof(S3)=Sof(O17)=Sof(O18)=Sof(O19)=Sof(C71)=Sof(C72)=Sof(H72)=Sof(C73)=
 Sof(H73)=Sof(C74)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=FVAR(2)
 Fixed Sof: O11W(0.5)
7.a Riding coordinates:
 O10(H10A,H10B), O8W(H8WA,H8WB), O3W(H3WA,H3WB), O7W(H7WA,H7WB), O9W(H9WA,H9WB)
7.b Free rotating group:
 O6W(H6WA,H6WB), O5W(H5WA,H5WB), O4W(H4WA,H4WB), O1W(H1WA,H1WB), O2W(H2WA,H2WB)
7.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B), C17(H17A,H17B), C19(H19A,H19B), C21(H21A,H21B)
7.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C15(H15), C32(H32), C33(H33),
 C37(H37), C38(H38), C42(H42), C43(H43), C47(H47), C48(H48), C52(H52),
 C52A(H52A), C53(H53), C53A(H53A), C55(H55), C55A(H55A), C56(H56), C56A(H56A),
 C62(H62), C63(H63), C65(H65), C66(H66), C72(H72), C73(H73), C75(H75), C76(H76),
  C82(H82), C83(H83), C85(H85), C86(H86), C116(H116), C117(H117), C118(H118),
 C119(H119), C120(H120), C122(H122), C123(H123), C124(H124), C125(H125),
 C126(H126), C128(H128), C129(H129), C130(H130), C131(H131), C132(H132),
 C134(H134), C135(H135), C136(H136), C137(H137), C138(H138), C140(H140),
 C141(H141), C142(H142), C143(H143), C144(H144), C146(H146), C147(H147),
 C148(H148), C149(H149), C150(H150), C152(H152), C153(H153), C154(H154),
 C155(H155), C156(H156), C158(H158), C159(H159), C160(H160), C161(H161),
 C162(H162), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96), C98(H98),
 C99(H99), C100(H100), C101(H101), C102(H102), C104(H104), C105(H105),
 C106(H106), C107(H107), C108(H108), C110(H110), C111(H111), C112(H112),
 C113(H113), C114(H114), C164(H164), C165(H165), C166(H166), C167(H167),
 C168(H168), C170(H170), C171(H171), C172(H172), C173(H173), C174(H174),
 C176(H176), C177(H177), C178(H178), C179(H179), C180(H180), C182(H182),
 C183(H183), C184(H184), C185(H185), C186(H186), C72A(H72A), C73A(H73A),
 C75A(H75A), C76A(H76A)
7.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              74462
_shelx_hkl_checksum              79185
_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 1.705
_oxdiff_exptl_absorpt_empirical_full_min 0.680