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_4349134
_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 Hf2 N14 O6, 0.33(C8 H18)'
_chemical_formula_sum            'C108.67 H86 Fe Hf2 N14 O6'
_chemical_formula_weight         2096.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 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                90
_cell_angle_beta                 139.9030(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.6505(4)
_cell_length_b                   17.5395(4)
_cell_length_c                   39.0049(6)
_cell_measurement_reflns_used    9834
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      66.65
_cell_measurement_theta_min      3.03
_cell_volume                     9980.6(4)
_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      120.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type  apex
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0627
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            109772
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.808
_diffrn_reflns_theta_min         2.290
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    5.373
_exptl_absorpt_correction_T_max  0.2208
_exptl_absorpt_correction_T_min  0.0700
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1307 before and 0.0708 after correction.
The Ratio of minimum to maximum transmission is 0.3170.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.395
_exptl_crystal_description       prism
_exptl_crystal_F_000             4216
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.592
_refine_diff_density_min         -0.839
_refine_diff_density_rms         0.130
_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     1070
_refine_ls_number_reflns         17581
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0780
_refine_ls_R_factor_gt           0.0564
_refine_ls_shift/su_max          0.017
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0840P)^2^+46.5990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1493
_refine_ls_wR_factor_ref         0.1680
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13324
_reflns_number_total             17581
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b01936_si_002.cif
_cod_data_source_block           4b
_cod_database_code               4349134
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.542
_shelx_estimated_absorpt_t_min   0.336
_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
 C1E-C1H
 1.5 with sigma of 0.02
 C1G-C1H
 1.5 with sigma of 0.02
 C1H-C1I
 1.5 with sigma of 0.02
 C1G-C1E
 2.5 with sigma of 0.02
 C1E-C1I
 2.5 with sigma of 0.02
 C13-C1E
 1.5 with sigma of 0.02
 C17-C13 = C1B-C13 = C16-C13
 1.5 with sigma of 0.02
 C1H-C13
 2.5 with sigma of 0.02
 C17B-C18 \\sim C17B-C16B \\sim C17A-C16A \\sim C17A-C18 \\sim C16B-C15 \\sim
C16A-C15
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C5) = Uiso(C5A)
Uiso(C16A) = Uiso(C16B) = Uiso(C17A) = Uiso(C17B)
Uanis(C30) = Uanis(C26) = Uanis(C27) = Uanis(C28) = Uanis(C29)
Uanis(C17) = Uanis(C1B) = Uanis(C13) = Uanis(C16) = Uanis(C1E) = Uanis(C1H) =
Uanis(C1G) = Uanis(C1I)
4. Others
 Fixed Sof: H4AA(0.5) H4AB(0.5) H4BC(0.5) H4BD(0.5) C5(0.5) H5A(0.5) H5B(0.5)
 H6AA(0.5) H6AB(0.5) H6BC(0.5) H6BD(0.5) H15A(0.5) H15B(0.5) H15C(0.5)
 H15D(0.5) H18C(0.5) H18D(0.5) H18A(0.5) H18B(0.5) C5A(0.5) H5AA(0.5) H5AB(0.5)
 C16A(0.5) H16A(0.5) H16B(0.5) C16B(0.5) H16C(0.5) H16D(0.5) C17B(0.5)
 H17A(0.5) H17B(0.5) C17A(0.5) H17C(0.5) H17D(0.5) C13(0.33333) C16(0.33333)
 H16E(0.33333) H16F(0.33333) H16G(0.33333) C17(0.33333) H17E(0.33333)
 H17F(0.33333) H17G(0.33333) C1B(0.33333) H1BA(0.33333) H1BB(0.33333)
 H1BC(0.33333) C1E(0.33333) H1EA(0.33333) H1EB(0.33333) C1G(0.33333)
 H1GA(0.33333) H1GB(0.33333) H1GC(0.33333) C1H(0.33333) H1H(0.33333)
 C1I(0.33333) H1IA(0.33333) H1IB(0.33333) H1IC(0.33333)
5.a Ternary CH refined with riding coordinates:
 C1H(H1H)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4AA,H4AB), C4(H4BC,H4BD), C5(H5A,H5B), C6(H6AA,H6AB),
 C6(H6BC,H6BD), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C15(H15A,H15B), C15(H15C,H15D), C18(H18C,H18D), C18(H18A,H18B), C5A(H5AA,H5AB),
  C16A(H16A,H16B), C16B(H16C,H16D), C17B(H17A,H17B), C17A(H17C,H17D), C1E(H1EA,
 H1EB)
5.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C22(H22), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
 C32(H32), C33(H33), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C43(H43),
  C44(H44), C52(H52), C51(H51), C50(H50), C49(H49), C48(H48), C54(H54),
 C55(H55), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C65(H65), C66(H66),
  C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C76(H76), C77(H77),
 C85(H85), C84(H84), C83(H83), C82(H82), C81(H81), C87(H87), C88(H88), C96(H96),
  C95(H95), C94(H94), C93(H93), C92(H92), C98(H98), C99(H99), C107(H107),
 C106(H106), C105(H105), C104(H104), C103(H103)
5.d Fitted hexagon refined as free rotating group:
 C25(C26,C27,C28,C29,C30), C36(C37,C38,C39,C40,C41), C47(C52,C51,C50,C49,C48),
 C58(C59,C60,C61,C62,C63), C69(C70,C71,C72,C73,C74), C80(C85,C84,C83,C82,C81),
 C91(C96,C95,C94,C93,C92), C102(C107,C106,C105,C104,C103)
5.e Idealised Me refined as rotating group:
 C16(H16E,H16F,H16G), C17(H17E,H17F,H17G), C1B(H1BA,H1BB,H1BC), C1G(H1GA,H1GB,
 H1GC), C1I(H1IA,H1IB,H1IC)
;
_shelx_res_checksum              20617
_shelx_hkl_checksum              18795
_shelx_fab_checksum              86420
_olex2_submission_special_instructions 'No special instructions were received'