Evaluation of CH4 oxidation activity of high-valent iron-oxo species of a μ-nitrido-bridged heterodimer of iron porphycene and iron phthalocyanine
Yamada, Yasuyuki; Miwa, Yusuke; Toyoda, Yuka; Phung, Quan Manh; Oyama, Kin-ichi; Tanaka, Kentaro; Catalysis Science & Technology 13 (2023) 1725–1734; doi:10.1039/D2CY01980A

data_1568404
_publ_section_title
;
 Evaluation of CH4 oxidation activity of high-valent iron-oxo species of a
 \m-nitrido-bridged heterodimer of iron porphycene and iron phthalocyanine
;
_journal_issue                   6
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              1725
_journal_page_last               1734
_journal_paper_doi               10.1039/D2CY01980A
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety
'0.707(I3), 0.8(C86 H54 Fe2 N15), 4.8(C H Cl3), C0.4 H0.4 Cl1.2 I0.278'
_chemical_formula_sum            'C74 H48.4 Cl15.6 Fe1.6 I2.4 N12'
_chemical_formula_weight         2053.882
_chemical_name_systematic        FePcNFePpcI3
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-11-03 deposited with the CCDC.	2023-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                64.380(1)
_cell_angle_beta                 69.270(1)
_cell_angle_gamma                68.880(1)
_cell_formula_units_Z            5
_cell_length_a                   20.6469(2)
_cell_length_b                   23.6627(3)
_cell_length_c                   24.8965(3)
_cell_measurement_reflns_used    103671
_cell_measurement_temperature    123
_cell_measurement_theta_max      31.2830
_cell_measurement_theta_min      2.4200
_cell_volume                     9942.9(2)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.9981
_diffrn_measured_fraction_theta_max 0.8733
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_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  0.0499
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.9981
_diffrn_reflns_Laue_measured_fraction_max 0.8733
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            293619
_diffrn_reflns_point_group_measured_fraction_full 0.9981
_diffrn_reflns_point_group_measured_fraction_max 0.8733
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         31.40
_diffrn_reflns_theta_min         2.46
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.802
_exptl_absorpt_correction_T_max  31.0431
_exptl_absorpt_correction_T_min  2.4568
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.715
_exptl_crystal_description       block
_exptl_crystal_F_000             5069.081
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: CHCl3'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         3.4801
_refine_diff_density_min         -2.2847
_refine_diff_density_rms         0.3212
_refine_ls_d_res_high            0.6820
_refine_ls_d_res_low             8.2902
_refine_ls_goodness_of_fit_ref   1.1096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    253
_refine_ls_number_parameters     2544
_refine_ls_number_reflns         57310
_refine_ls_number_restraints     824
_refine_ls_restrained_S_all      1.1013
_refine_ls_R_factor_all          0.1465
_refine_ls_R_factor_gt           0.1207
_refine_ls_shift/su_max          0.0199
_refine_ls_shift/su_mean         0.0002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1018P)^2^+258.9181P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3236
_refine_ls_wR_factor_ref         0.3581
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              30
_reflns_limit_h_min              -27
_reflns_limit_k_max              33
_reflns_limit_k_min              -30
_reflns_limit_l_max              36
_reflns_limit_l_min              0
_reflns_number_gt                43714
_reflns_number_total             57310
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d2cy01980a2.cif
_cod_data_source_block           FePcNFePpcI3
_cod_depositor_comments          'Adding full bibliography for 1568404.cif.'
_cod_database_code               1568404
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C1-Cl1
 1.78 with sigma of 0.02
 Cl1-Cl2
 2.9 with sigma of 0.02
 C2-Cl4
 1.78 with sigma of 0.02
 Cl4-Cl5
 2.9 with sigma of 0.02
 C3-Cl7
 1.78 with sigma of 0.02
 Cl7-Cl8
 2.9 with sigma of 0.02
 C4-Cl10
 1.78 with sigma of 0.02
 Cl10-Cl11
 2.9 with sigma of 0.02
 C5-Cl13
 1.78 with sigma of 0.02
 Cl13-Cl14
 2.9 with sigma of 0.02
 C6-Cl16
 1.78 with sigma of 0.02
 Cl16-Cl17
 2.9 with sigma of 0.02
 C7-Cl19
 1.78 with sigma of 0.02
 Cl19-Cl20
 2.9 with sigma of 0.02
 C8-Cl22
 1.78 with sigma of 0.02
 Cl22-Cl23
 2.9 with sigma of 0.02
 C9-Cl25
 1.78 with sigma of 0.02
 Cl25-Cl26
 2.9 with sigma of 0.02
 C10-Cl28
 1.78 with sigma of 0.02
 Cl28-Cl29
 2.9 with sigma of 0.02
 C11-Cl31
 1.78 with sigma of 0.02
 Cl31-Cl32
 2.9 with sigma of 0.02
 C12-Cl34
 1.78 with sigma of 0.02
 Cl34-Cl35
 2.9 with sigma of 0.02
 C13-Cl37
 1.78 with sigma of 0.02
 Cl37-Cl38
 2.9 with sigma of 0.02
 C14-Cl40
 1.78 with sigma of 0.02
 Cl40-Cl41
 2.9 with sigma of 0.02
 C15-Cl
 1.78 with sigma of 0.02
 C1-Cl1 \\sim C1-Cl2 \\sim C1-Cl3
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl2-Cl3 \\sim Cl3-Cl1
 with sigma of 0.02
 C2-Cl4 \\sim C2-Cl5 \\sim C2-Cl6
 with sigma of 0.02
 Cl4-Cl5 \\sim Cl5-Cl6 \\sim Cl6-Cl4
 with sigma of 0.02
 C3-Cl7 \\sim C3-Cl8 \\sim C3-Cl9
 with sigma of 0.02
 Cl7-Cl8 \\sim Cl8-Cl9 \\sim Cl9-Cl7
 with sigma of 0.02
 C4-Cl10 \\sim C4-Cl11 \\sim C4-Cl12
 with sigma of 0.02
 Cl10-Cl11 \\sim Cl11-Cl12 \\sim Cl12-Cl10
 with sigma of 0.02
 C5-Cl13 \\sim C5-Cl14 \\sim C5-Cl15
 with sigma of 0.02
 Cl13-Cl14 \\sim Cl14-Cl15 \\sim Cl15-Cl13
 with sigma of 0.02
 C6-Cl16 \\sim C6-Cl17 \\sim C6-Cl18
 with sigma of 0.02
 Cl16-Cl17 \\sim Cl17-Cl18 \\sim Cl18-Cl16
 with sigma of 0.02
 C7-Cl19 \\sim C7-Cl20 \\sim C7-Cl21
 with sigma of 0.02
 Cl19-Cl20 \\sim Cl20-Cl21 \\sim Cl21-Cl19
 with sigma of 0.02
 C8-Cl22 \\sim C8-Cl23 \\sim C8-Cl24
 with sigma of 0.02
 Cl22-Cl23 \\sim Cl23-Cl24 \\sim Cl24-Cl22
 with sigma of 0.02
 C9-Cl25 \\sim C9-Cl26 \\sim C9-Cl27
 with sigma of 0.02
 Cl25-Cl26 \\sim Cl26-Cl27 \\sim Cl27-Cl25
 with sigma of 0.02
 C10-Cl28 \\sim C10-Cl29 \\sim C10-Cl30
 with sigma of 0.02
 Cl28-Cl29 \\sim Cl29-Cl30 \\sim Cl30-Cl28
 with sigma of 0.02
 C11-Cl31 \\sim C11-Cl32 \\sim C11-Cl33
 with sigma of 0.02
 Cl31-Cl32 \\sim Cl32-Cl33 \\sim Cl33-Cl31
 with sigma of 0.02
 C12-Cl34 \\sim C12-Cl35 \\sim C12-Cl36
 with sigma of 0.02
 Cl34-Cl35 \\sim Cl35-Cl36 \\sim Cl36-Cl34
 with sigma of 0.02
 C13-Cl37 \\sim C13-Cl38 \\sim C13-Cl39
 with sigma of 0.02
 Cl37-Cl38 \\sim Cl38-Cl39 \\sim Cl39-Cl37
 with sigma of 0.02
 C14-Cl40 \\sim C14-Cl41 \\sim C14-Cl42
 with sigma of 0.02
 Cl40-Cl41 \\sim Cl41-Cl42 \\sim Cl42-Cl40
 with sigma of 0.02
 C15-Cl \\sim C15-Cl1A \\sim C15-Cl1B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim Cl1 \\sim Cl2 \\sim Cl3: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
C2 \\sim Cl5 \\sim Cl4 \\sim Cl6: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
C3 \\sim Cl9 \\sim Cl7 \\sim Cl8: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
C4 \\sim Cl10 \\sim Cl11 \\sim Cl12: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C5 \\sim Cl13 \\sim Cl14 \\sim Cl15: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C6 \\sim Cl16 \\sim Cl17 \\sim Cl18: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C7 \\sim Cl19 \\sim Cl20 \\sim Cl21: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C8 \\sim Cl22 \\sim Cl23 \\sim Cl24: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C9 \\sim Cl25 \\sim Cl26 \\sim Cl27: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C10 \\sim Cl28 \\sim Cl29 \\sim Cl30: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C11 \\sim Cl31 \\sim Cl32 \\sim Cl33: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C12 \\sim Cl34 \\sim Cl35 \\sim Cl36: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C13 \\sim Cl37 \\sim Cl38 \\sim Cl39: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C14 \\sim Cl40 \\sim Cl41 \\sim Cl42: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
I6A \\sim I5A \\sim I4A: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 1.7A
C15 \\sim Cl \\sim Cl1A \\sim Cl1B: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C17 \\sim Cl8A \\sim Cl9A \\sim Cl7A: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
Uanis(C1) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C2) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(Cl6)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C3) \\sim Ueq, Uanis(Cl9) \\sim Ueq, Uanis(Cl7) \\sim Ueq, Uanis(Cl8)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C4) \\sim Ueq, Uanis(Cl10) \\sim Ueq, Uanis(Cl11) \\sim Ueq, Uanis(Cl12)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C5) \\sim Ueq, Uanis(Cl13) \\sim Ueq, Uanis(Cl14) \\sim Ueq, Uanis(Cl15)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C6) \\sim Ueq, Uanis(Cl16) \\sim Ueq, Uanis(Cl17) \\sim Ueq, Uanis(Cl18)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C7) \\sim Ueq, Uanis(Cl19) \\sim Ueq, Uanis(Cl20) \\sim Ueq, Uanis(Cl21)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C8) \\sim Ueq, Uanis(Cl22) \\sim Ueq, Uanis(Cl23) \\sim Ueq, Uanis(Cl24)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C9) \\sim Ueq, Uanis(Cl25) \\sim Ueq, Uanis(Cl26) \\sim Ueq, Uanis(Cl27)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C10) \\sim Ueq, Uanis(Cl28) \\sim Ueq, Uanis(Cl29) \\sim Ueq, Uanis(Cl30)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C11) \\sim Ueq, Uanis(Cl31) \\sim Ueq, Uanis(Cl32) \\sim Ueq, Uanis(Cl33)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C12) \\sim Ueq, Uanis(Cl34) \\sim Ueq, Uanis(Cl35) \\sim Ueq, Uanis(Cl36)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C13) \\sim Ueq, Uanis(Cl37) \\sim Ueq, Uanis(Cl38) \\sim Ueq, Uanis(Cl39)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C14) \\sim Ueq, Uanis(Cl40) \\sim Ueq, Uanis(Cl41) \\sim Ueq, Uanis(Cl42)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(I6A) \\sim Ueq, Uanis(I5A) \\sim Ueq, Uanis(I4A) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
Uanis(C15) \\sim Ueq, Uanis(Cl) \\sim Ueq, Uanis(Cl1A) \\sim Ueq, Uanis(Cl1B)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C17) \\sim Ueq, Uanis(Cl8A) \\sim Ueq, Uanis(Cl9A) \\sim Ueq, Uanis(Cl7A)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(I6A)=Sof(I5A)=Sof(I4A)=1-FVAR(1)
 Sof(I5)=Sof(I4)=Sof(I6)=FVAR(1)
 Sof(Cl37)=Sof(C13)=Sof(H13)=Sof(Cl38)=Sof(Cl39)=1-FVAR(2)
 Sof(Cl40)=Sof(C14)=Sof(H14)=Sof(Cl41)=Sof(Cl42)=FVAR(2)
 Sof(I3A)=Sof(I2A)=Sof(I1A)=1-FVAR(3)
 Sof(I2)=Sof(I1)=Sof(I3)=FVAR(3)
 Sof(C15)=Sof(H15)=Sof(Cl)=Sof(Cl1A)=Sof(Cl1B)=1-FVAR(4)
 Sof(Cl12)=Sof(Cl10)=Sof(Cl11)=Sof(C4)=Sof(H4)=FVAR(4)
 Sof(C17)=Sof(H17)=Sof(Cl9A)=Sof(Cl8A)=Sof(Cl7A)=1-FVAR(5)
 Sof(Cl7)=Sof(Cl9)=Sof(Cl8)=Sof(C3)=Sof(H3)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C9(H9), C11(H11), C2(H2), C3(H3), C12(H12), C8(H8), C1(H1), C5(H5),
 C4(H4), C14(H14), C7(H7), C6(H6), C13(H13), C15(H15), C17(H17)
5.b Aromatic/amide H refined with riding coordinates:
 C8B(H8B), C15A(H15A), C80B(H80B), C5A(H5A), C81B(H81B), C9B(H9B), C8A(H8A),
 C22A(H22A), C24A(H24A), C23A(H23A), C14B(H14B), C18B(H18B), C14A(H14A),
 C77A(H77A), C78A(H78A), C58B(H58B), C15B(H15B), C4A(H4A), C74A(H74A),
 C64B(H64B), C19B(H19B), C71A(H71A), C78B(H78B), C9A(H9A), C28B(H28B),
 C41B(H41B), C4B(H4B), C30B(H30B), C24B(H24B), C40B(H40B), C55A(H55A),
 C74B(H74B), C5B(H5B), C77B(H77B), C80A(H80A), C79B(H79B), C19A(H19A),
 C36A(H36A), C35A(H35A), C29B(H29B), C42B(H42B), C86B(H86B), C79A(H79A),
 C47B(H47B), C82B(H82B), C72A(H72A), C18A(H18A), C25A(H25A), C73A(H73A),
 C83B(H83B), C34B(H34B), C55B(H55B), C63B(H63B), C49A(H49A), C47A(H47A),
 C65B(H65B), C50A(H50A), C26A(H26A), C57B(H57B), C25B(H25B), C81A(H81A),
 C34A(H34A), C36B(H36B), C38B(H38B), C66B(H66B), C48B(H48B), C30A(H30A),
 C23B(H23B), C22B(H22B), C31B(H31B), C86A(H86A), C50B(H50B), C84B(H84B),
 C48A(H48A), C32B(H32B), C44B(H44B), C58A(H58A), C63A(H63A), C38A(H38A),
 C37A(H37A), C82A(H82A), C43B(H43B), C73B(H73B), C32A(H32A), C49B(H49B),
 C26B(H26B), C37B(H37B), C56A(H56A), C71B(H71B), C85B(H85B), C28A(H28A),
 C66A(H66A), C29A(H29A), C72B(H72B), C31A(H31A), C56B(H56B), C57A(H57A),
 C85A(H85A), C83A(H83A), C84A(H84A), C64A(H64A), C43A(H43A), C40A(H40A),
 C35B(H35B), C65A(H65A), C44A(H44A), C42A(H42A), C41A(H41A)
;
_olex2_submission_special_instructions 'No special instructions were received'