Preparation, X-ray Structures, Spectroscopic, and Redox Properties of Di- and Trinuclear Iron-Zirconium and Iron-Hafnium Porphyrinoclathrochelates.
Dudkin, Semyon V.; Erickson, Nathan R.; Vologzhanina, Anna V.; Novikov, Valentin V.; Rhoda, Hannah M.; Holstrom, Cole D.; Zatsikha, Yuriy V.; Yusubov, Mekhman S.; Voloshin, Yan Z.; Nemykin, Victor N.; Inorganic chemistry 55 (2016) 11867–11882; doi:10.1021/acs.inorgchem.6b01936

data_4349133
_publ_section_title
;
 Preparation, X-ray Structures, Spectroscopic, and Redox Properties of Di-
 and Trinuclear Iron-Zirconium and Iron-Hafnium Porphyrinoclathrochelates.
;
_journal_issue                   22
_journal_name_full               'Inorganic chemistry'
_journal_page_first              11867
_journal_page_last               11882
_journal_paper_doi               10.1021/acs.inorgchem.6b01936
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C106 H80 Fe N14 O6 Zr2, C8 H18, 0.25(C7 H8)'
_chemical_formula_sum            'C115.75 H100 Fe N14 O6 Zr2'
_chemical_formula_weight         2021.38
_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
_audit_creation_date             2016-09-23
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                65.2780(10)
_cell_angle_beta                 80.8680(10)
_cell_angle_gamma                73.5230(10)
_cell_formula_units_Z            2
_cell_length_a                   15.0421(2)
_cell_length_b                   20.6793(2)
_cell_length_c                   21.0501(3)
_cell_measurement_reflns_used    5874
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      61.59
_cell_measurement_theta_min      3.07
_cell_volume                     5697.43(13)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.921
_diffrn_measured_fraction_theta_max 0.931
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0661
_diffrn_reflns_av_unetI/netI     0.0766
_diffrn_reflns_Laue_measured_fraction_full 0.921
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            53969
_diffrn_reflns_point_group_measured_fraction_full 0.921
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        68.000
_diffrn_reflns_theta_max         67.499
_diffrn_reflns_theta_min         3.067
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.925
_exptl_absorpt_correction_T_max  0.2264
_exptl_absorpt_correction_T_min  0.0470
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1506 before and 0.0687 after correction.
The Ratio of minimum to maximum transmission is 0.2076.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.178
_exptl_crystal_description       plate
_exptl_crystal_F_000             2093
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.266
_refine_diff_density_min         -2.304
_refine_diff_density_rms         0.209
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1093
_refine_ls_number_reflns         19118
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.1128
_refine_ls_R_factor_gt           0.0953
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+5.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2558
_refine_ls_wR_factor_ref         0.2870
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14838
_reflns_number_total             19118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b01936_si_002.cif
_cod_data_source_block           4a
_cod_database_code               4349133
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.800
_shelx_estimated_absorpt_t_min   0.540
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C6-C5A
 1.5 with sigma of 0.02
 C14S-C10S
 1.5 with sigma of 0.02
 C15S-C14S
 2.5 with sigma of 0.02
 C14S-C9S
 2.5 with sigma of 0.02
 C15S-C10S
 1.5 with sigma of 0.02
 C2S-C6S
 1.5 with sigma of 0.02
 C2S-C1S
 1.5 with sigma of 0.02
 C23S-C17S
 1.5 with sigma of 0.02
 C5-C4A = C4A-C3 = C5A-C4
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C4) = Uiso(C4A) = Uiso(C5) = Uiso(C5A)
Uanis(C1S) = Uanis(C2S) = Uanis(C7S) = Uanis(C6S) = Uanis(C3S) = Uanis(C4S) =
Uanis(C8S) = Uanis(C5S)
Uanis(C14S) = Uanis(C10S) = Uanis(C15S) = Uanis(C9S) = Uanis(C11S) =
Uanis(C12S) = Uanis(C16S) = Uanis(C13S)
Uanis(C23S) = Uanis(C17S) = Uanis(C18S) = Uanis(C19S) = Uanis(C20S) =
Uanis(C21S) = Uanis(C22S)
4. Others
 Fixed Sof: H3BC(0.5) H3BD(0.5) H3AA(0.5) H3AB(0.5) C5(0.5) H5A(0.5) H5B(0.5)
 H6AA(0.5) H6AB(0.5) H6BC(0.5) H6BD(0.5) C45(0.75) C50(0.75) H50(0.75)
 C49(0.75) H49(0.75) C48(0.75) H48(0.75) C47(0.75) H47(0.75) C46(0.75)
 H46(0.75) C51(0.5) C56(0.5) H56(0.5) C55(0.5) H55(0.5) C54(0.5) H54(0.5)
 C53(0.5) H53(0.5) C52(0.5) H52(0.5) C89(0.5) C94(0.5) H94(0.5) C93(0.5)
 H93(0.5) C92(0.5) H92(0.5) C91(0.5) H91(0.5) C90(0.5) H90(0.5) C4(0.5)
 H4A(0.5) H4B(0.5) C4S(0.5) H4S(0.5) C12S(0.5) H12S(0.5) C2S(0.5) C8S(0.5)
 H8SA(0.5) H8SB(0.5) H8SC(0.5) C7S(0.5) H7SA(0.5) H7SB(0.5) H7SC(0.5) C5S(0.5)
 H5SA(0.5) H5SB(0.5) H5SC(0.5) C11S(0.5) H11C(0.5) H11D(0.5) C10S(0.5)
 C13S(0.5) H13A(0.5) H13B(0.5) H13C(0.5) C16S(0.5) H16C(0.5) H16D(0.5)
 H16E(0.5) C9S(0.5) H9SA(0.5) H9SB(0.5) H9SC(0.5) C6S(0.5) H6SA(0.5) H6SB(0.5)
 H6SC(0.5) C14S(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C15S(0.5) H15C(0.5)
 H15D(0.5) H15E(0.5) C46A(0.25) H46A(0.25) C47A(0.25) H47A(0.25) C48A(0.25)
 H48A(0.25) C49A(0.25) H49A(0.25) C50A(0.25) H50A(0.25) C45A(0.25) C90A(0.5)
 H90A(0.5) C89A(0.5) C94A(0.5) H94A(0.5) C93A(0.5) H93A(0.5) C92A(0.5)
 H92A(0.5) C91A(0.5) H91A(0.5) C51A(0.5) C52A(0.5) H52A(0.5) C53A(0.5)
 H53A(0.5) C54A(0.5) H54A(0.5) C55A(0.5) H55A(0.5) C56A(0.5) H56A(0.5) C5A(0.5)
 H5AA(0.5) H5AB(0.5) C4A(0.5) H4AA(0.5) H4AB(0.5) C3S(0.5) H3SA(0.5) H3SB(0.5)
 C1S(0.5) H1SA(0.5) H1SB(0.5) H1SC(0.5) C23S(0.25) H23A(0.25) H23B(0.25)
 H23C(0.25) C22S(0.25) H22S(0.25) C17S(0.25) C18S(0.25) H18S(0.25) C19S(0.25)
 H19S(0.25) C20S(0.25) H20S(0.25) C21S(0.25) H21S(0.25)
5.a Ternary CH refined with riding coordinates:
 C4S(H4S), C12S(H12S)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3BC,H3BD), C3(H3AA,H3AB), C5(H5A,H5B), C6(H6AA,H6AB), C6(H6BC,H6BD),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C15(H15A,H15B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C4(H4A,H4B), C11S(H11C,H11D),
 C5A(H5AA,H5AB), C4A(H4AA,H4AB), C3S(H3SA,H3SB)
5.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C25(H25), C26(H26), C30(H30), C31(H31), C35(H35),
 C36(H36), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C50(H50), C49(H49),
  C48(H48), C47(H47), C46(H46), C56(H56), C55(H55), C54(H54), C53(H53),
 C52(H52), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C64(H64), C65(H65),
  C69(H69), C70(H70), C74(H74), C75(H75), C79(H79), C80(H80), C84(H84),
 C85(H85), C86(H86), C87(H87), C88(H88), C94(H94), C93(H93), C92(H92), C91(H91),
  C90(H90), C96(H96), C97(H97), C98(H98), C99(H99), C100(H100), C106(H106),
 C105(H105), C104(H104), C103(H103), C102(H102), C46A(H46A), C47A(H47A),
 C48A(H48A), C49A(H49A), C50A(H50A), C90A(H90A), C94A(H94A), C93A(H93A),
 C92A(H92A), C91A(H91A), C52A(H52A), C53A(H53A), C54A(H54A), C55A(H55A),
 C56A(H56A), C22S(H22S), C18S(H18S), C19S(H19S), C20S(H20S), C21S(H21S)
5.d Fitted hexagon refined as free rotating group:
 C39(C40,C41,C42,C43,C44), C45(C50,C49,C48,C47,C46), C51(C56,C55,C54,C53,C52),
 C57(C58,C59,C60,C61,C62), C83(C84,C85,C86,C87,C88), C89(C94,C93,C92,C91,C90),
 C95(C96,C97,C98,C99,C100), C101(C106,C105,C104,C103,C102), C46A(C47A,C48A,C49A,
 C50A,C45A), C90A(C89A,C94A,C93A,C92A,C91A), C51A(C52A,C53A,C54A,C55A,C56A),
 C22S(C17S,C18S,C19S,C20S,C21S)
5.e Idealised Me refined as rotating group:
 C8S(H8SA,H8SB,H8SC), C7S(H7SA,H7SB,H7SC), C5S(H5SA,H5SB,H5SC), C13S(H13A,H13B,
 H13C), C16S(H16C,H16D,H16E), C9S(H9SA,H9SB,H9SC), C6S(H6SA,H6SB,H6SC),
 C14S(H14A,H14B,H14C), C15S(H15C,H15D,H15E), C1S(H1SA,H1SB,H1SC), C23S(H23A,
 H23B,H23C)
;
_shelx_res_checksum              23212
_shelx_hkl_checksum              57783
_shelx_fab_checksum              86645
_olex2_submission_special_instructions 'No special instructions were received'