Multistep synthesis and X-ray structure of the carboxyl-terminated hybrid iron(II) phthalocyaninatoclathrochelates and their postsynthetic transformation into polytopic carboranyl-containing derivatives
Chuprin, Alexander S.; Pavlov, Alexander A.; Vologzhanina, Anna V. V.; Dorovatovskii, Pavel; Makarenkov, Anton V.; Ol'shevskaya, Valentina Antonovna; Dudkin, Semyon V.; Voloshin, Yan Z.; Dalton Transactions  (2023) –; doi:10.1039/D3DT00076A

data_7712328
_publ_section_title
;
 Multistep synthesis and X-ray structure of the carboxyl-terminated hybrid
 iron(II) phthalocyaninatoclathrochelates and their postsynthetic
 transformation into polytopic carboranyl-containing derivatives
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00076A
_journal_year                    2023
_chemical_formula_moiety         'C63 H61 B11 Fe N18 O7 Zr'
_chemical_formula_sum            'C63 H61 B11 Fe N18 O7 Zr'
_chemical_formula_weight         1448.27
_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             2022-09-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-09-07 deposited with the CCDC.	2023-02-16 downloaded from the CCDC.
;
_cell_angle_alpha                71.88(3)
_cell_angle_beta                 69.88(3)
_cell_angle_gamma                87.44(3)
_cell_formula_units_Z            4
_cell_length_a                   19.422(4)
_cell_length_b                   20.591(4)
_cell_length_c                   21.089(4)
_cell_measurement_reflns_used    841
_cell_measurement_temperature    100
_cell_measurement_theta_max      17.94
_cell_measurement_theta_min      1.53
_cell_volume                     7508(3)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Rayonix CCD'
_diffrn_measurement_method       'phi scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.745
_diffrn_reflns_av_R_equivalents  0.1508
_diffrn_reflns_av_unetI/netI     0.1506
_diffrn_reflns_Laue_measured_fraction_full 0.961
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            27240
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        18.085
_diffrn_reflns_theta_max         18.085
_diffrn_reflns_theta_min         1.093
_diffrn_source                   'Belok beamline of NRC Kurchatov Institute'
_exptl_absorpt_coefficient_mu    0.444
_exptl_absorpt_correction_T_max  0.984
_exptl_absorpt_correction_T_min  0.942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'XDS (Kabsch, 2010)'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.281
_exptl_crystal_description       plate
_exptl_crystal_F_000             2968
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.590
_refine_diff_density_min         -1.093
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.700
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1419
_refine_ls_number_reflns         8746
_refine_ls_number_restraints     1013
_refine_ls_restrained_S_all      1.628
_refine_ls_R_factor_all          0.1771
_refine_ls_R_factor_gt           0.1088
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0050P)^2^+26.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1911
_refine_ls_wR_factor_ref         0.2086
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4791
_reflns_number_total             8746
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00076a2.cif
_cod_data_source_block           ac129
_cod_database_code               7712328
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.920
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups,
  All N(H) groups
2. Restrained distances
 C120-C117
 1.5 with sigma of 0.02
 O14-C120
 1.2 with sigma of 0.02
 C125-C124
 1.5 with sigma of 0.02
 N33-C121 = C122-C121
 1.5 with sigma of 0.02
 N33-C120
 1.4 with sigma of 0.02
 N15-C58
 1.45 with sigma of 0.02
 C57-C54
 1.5 with sigma of 0.02
 C57-N15
 1.45 with sigma of 0.02
 N33-C121 \\sim N33-C120
 with sigma of 0.02
3. Restrained planarity
 C117, C120, O14, N33
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C51 \\sim C56 \\sim C55 \\sim C54 \\sim C53 \\sim C52 \\sim O7 \\sim C57 \\sim
N15: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim
C34 \\sim C33 \\sim C32 \\sim C31 \\sim C30 \\sim C29 \\sim C28 \\sim C27 \\sim
N9 \\sim N10 \\sim N8 \\sim C26 \\sim N7 \\sim C19 \\sim N14 \\sim C20 \\sim
C25 \\sim C24 \\sim C23 \\sim C22 \\sim C21 \\sim N12 \\sim N13 \\sim N11:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C2 \\sim C4 \\sim C6 \\sim C5 \\sim C1 \\sim C13 \\sim C14 \\sim C15 \\sim C16
\\sim C17 \\sim C18 \\sim C8 \\sim C7 \\sim C12 \\sim C11 \\sim C10 \\sim C9
\\sim C3: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
N20 \\sim C65 \\sim C66 \\sim C69 \\sim C64 \\sim N19 \\sim C72 \\sim C71 \\sim
N21 \\sim N22 \\sim C70 \\sim C75 \\sim N23 \\sim C77 \\sim C78 \\sim C81 \\sim
C76 \\sim N24: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
N28 \\sim C98 \\sim N29 \\sim C105 \\sim N30 \\sim C106 \\sim N31 \\sim C104
\\sim C103 \\sim C102 \\sim C101 \\sim C100 \\sim C99 \\sim N27 \\sim C97 \\sim
C96 \\sim C95 \\sim C93 \\sim C94 \\sim C92 \\sim C91 \\sim C90 \\sim N26 \\sim
N32 \\sim C113 \\sim C112 \\sim C111 \\sim C110 \\sim C109 \\sim C108 \\sim
C107 \\sim N25 \\sim C89 \\sim C88 \\sim C87 \\sim C86 \\sim C85 \\sim C84
\\sim C83 \\sim C82: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
C114 \\sim C115 \\sim C119 \\sim B12 \\sim C118 \\sim C117 \\sim C116 \\sim
C120 \\sim O14 \\sim N33 \\sim C121: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C115 \\sim C114 \\sim C119 \\sim C118 \\sim C117 \\sim C116 \\sim B12: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C27) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(N9) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C6) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C86) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C89) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C113) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C106) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.002
Uanis(C54) \\sim Ueq, : with sigma of 0.005 and sigma for terminal atoms of
0.005
Uanis(C65) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(N19)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(N24) \\sim Ueq, Uanis(C83) \\sim Ueq,
Uanis(C79) \\sim Ueq, Uanis(N26) \\sim Ueq, Uanis(C84) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.005
Uanis(C52) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(N21) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(C107) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of
0.008 and sigma for terminal atoms of 0.016
Uanis(N23) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C98) \\sim Ueq, Uanis(C97) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
5. Others
 Fixed Sof: O1(0.6) N1(0.4) N1A(0.6) O2(0.6) N2(0.6) N2A(0.4) O3(0.6) N3(0.6)
 N3A(0.4) O4(0.6) O04D(0.4) O04J(0.4) O04W(0.4) N4(0.4) N4A(0.6) O5(0.6)
 N5(0.6) N5A(0.4) O6(0.6) N6(0.4) N6A(0.6) O15(0.4) O048(0.4) O058(0.4)
 H66C(0.5) H66D(0.5) H66A(0.5) H66B(0.5) C67(0.5) H67A(0.5) H67B(0.5) C67A(0.5)
 H67C(0.5) H67D(0.5) C68(0.5) H68A(0.5) H68B(0.5) C68A(0.5) H68C(0.5) H68D(0.5)
 H69C(0.5) H69D(0.5) H69A(0.5) H69B(0.5) H72A(0.5) H72B(0.5) H72C(0.5)
 H72D(0.5) C73(0.5) H73A(0.5) H73B(0.5) C73A(0.5) H73C(0.5) H73D(0.5) C74(0.5)
 H74A(0.5) H74B(0.5) C74A(0.5) H74C(0.5) H74D(0.5) H75A(0.5) H75B(0.5)
 H75C(0.5) H75D(0.5)
 Fixed Uiso: C57(0.15) N15(0.15) N16(0.15) N17(0.15) N18(0.15) O7(0.15)
 C58(0.15) C59(0.15) C60(0.15) C61(0.15) C62(0.15) B5(0.15) C63(0.15) B9(0.15)
 B10(0.15) B11(0.15) B6(0.15) B7(0.15) B8(0.15) B2(0.15) B4(0.15) B3(0.15)
 O14(0.15) N33(0.15) N34(0.15) N35(0.15) N36(0.15) C114(0.12) C115(0.12)
 C116(0.12) C117(0.12) C118(0.12) C119(0.12) C120(0.15) C121(0.15) C122(0.15)
 C123(0.15) C124(0.15) C125(0.15) B13(0.15) B14(0.15) C126(0.15) B16(0.15)
 B17(0.15) B18(0.15) B19(0.15) B20(0.15) B21(0.15) B22(0.15) B15(0.15)
6.a Riding coordinates:
 N15(H15A), N33(H33)
6.b Free rotating group:
 C62(B5,C63,B9,B10,B11,B6,B7,B8,B2,B4,B3), C125(B13,B14,C126,B16,B17,B18,B19,
 B20,B21,B22,B15)
6.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C12(H12E,H12F), C15(H15B,H15C), C16(H16A,H16B),
 C17(H17A,H17B), C18(H18A,H18B), C58(H58A,H58B), C61(H61A,H61B), C66(H66C,H66D),
  C66(H66A,H66B), C67(H67A,H67B), C67A(H67C,H67D), C68(H68A,H68B), C68A(H68C,
 H68D), C69(H69C,H69D), C69(H69A,H69B), C72(H72A,H72B), C72(H72C,H72D),
 C73(H73A,H73B), C73A(H73C,H73D), C74(H74A,H74B), C74A(H74C,H74D), C75(H75A,
 H75B), C75(H75C,H75D), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B),
 C81(H81A,H81B), C121(H12A,H12B), C124(H12C,H12D)
6.d Aromatic/amide H refined with riding coordinates:
 C21(H21A), C22(H22A), C23(H23), C24(H24), C29(H29), C30(H30), C31(H31),
 C32(H32), C37(H37), C38(H38), C39(H39), C40(H40), C45(H45), C46(H46), C47(H47),
  C48(H48), C52(H52), C53(H53), C55(H55), C56(H56), C60(H60), C84(H84),
 C85(H85), C86(H86), C87(H87), C92(H92), C93(H93), C94(H94), C95(H95),
 C100(H100), C101(H101), C102(H102), C103(H103), C108(H108), C109(H109),
 C110(H110), C111(H111), C115(H115), C116(H116), C118(H118), C119(H119),
 C123(H123)
6.e Fitted hexagon refined as free rotating group:
 C51(C52,C53,C54,C55,C56), C114(C115,C116,C117,C118,C119)
6.f Boron cage BH refined with riding coordinates:
 B5(H5), C63(H63), B9(H9), B10(H10), B11(H11), B6(H6), B7(H7), B8(H8), B2(H2),
 B4(H4), B3(H3), B13(H13), B14(H14), C126(H126), B16(H16), B17(H17), B18(H18),
 B19(H19), B20(H20), B21(H21), B22(H22), B15(H15)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              5086
_shelx_hkl_checksum              16375
_shelx_fab_checksum              71548
_olex2_submission_special_instructions 'No special instructions were received'