Fast, solvent-free synthesis of ferrocene-containing organic cages <i>via</i> dynamic covalent chemistry in the solid state.
Kunde, Tom; Pausch, Tobias; Guńka, Piotr A; Krzyżanowski, Maurycy; Kasprzak, Artur; Schmidt, Bernd M.; Chemical science 13 (2022) 2877–2883; doi:10.1039/d1sc06372c

data_1566277
_publ_section_title
;
 Fast, solvent-free synthesis of ferrocene-containing organic cages
 <i>via</i> dynamic covalent chemistry in the solid state.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              2877
_journal_page_last               2883
_journal_paper_doi               10.1039/d1sc06372c
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C72 H54 Fe3 N8, 0.5(H2 O), C3 H3'
_chemical_formula_sum            'C75 H58 Fe3 N8 O0.5'
_chemical_formula_weight         1246.84
_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
_audit_creation_date             2021-05-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-11-15 deposited with the CCDC.	2022-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                107.9320(10)
_cell_angle_beta                 90.985(2)
_cell_angle_gamma                106.8140(10)
_cell_formula_units_Z            2
_cell_length_a                   10.8575(2)
_cell_length_b                   16.0366(2)
_cell_length_c                   19.8722(3)
_cell_measurement_reflns_used    43293
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.2900
_cell_measurement_theta_min      2.8200
_cell_volume                     3129.76(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3347
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.922
_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 -45.00 39.00 0.50 45.00 -- -11.24 77.00 120.00 168
 2 \w -64.00 38.00 0.50 45.00 -- 11.71 -38.00-120.00 204
 3 \w -22.00 39.00 0.50 45.00 -- 11.71 77.00 90.00 122
 4 \w -18.00 45.00 0.50 45.00 -- 11.71 -77.00 -60.00 126
 5 \w -70.00 58.00 0.50 45.00 -- 11.71 -19.00 -60.00 256
 6 \w -22.00 39.00 0.50 45.00 -- 11.71 77.00 -90.00 122
 7 \w -64.00 38.00 0.50 45.00 -- 11.71 -38.00 150.00 204
 8 \w -18.00 45.00 0.50 45.00 -- 11.71 -77.00 30.00 126
 9 \w -22.00 39.00 0.50 45.00 -- 11.71 77.00-180.00 122
 10 \w -22.00 39.00 0.50 45.00 -- 11.71 77.00 -30.00 122
 11 \w -22.00 39.00 0.50 45.00 -- 11.71 77.00 0.00 122
 12 \w -45.00 39.00 0.50 45.00 -- -11.24 77.00 60.00 168
 13 \w -15.00 88.00 0.50 45.00 -- 11.71 38.00 0.00 206
 14 \w 34.00 80.00 0.50 45.00 -- 11.71-143.00 154.00 92
 15 \w 24.00 54.00 0.50 45.00 -- 11.71-127.00 -34.00 60
 16 \w 1.00 54.00 0.50 45.00 -- 11.71 -99.00-120.00 106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0031363000
_diffrn_orient_matrix_UB_12      -0.0141262000
_diffrn_orient_matrix_UB_13      -0.0376705000
_diffrn_orient_matrix_UB_21      -0.0588058000
_diffrn_orient_matrix_UB_22      0.0105248000
_diffrn_orient_matrix_UB_23      -0.0019281000
_diffrn_orient_matrix_UB_31      0.0354086000
_diffrn_orient_matrix_UB_32      0.0456074000
_diffrn_orient_matrix_UB_33      0.0020137000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.922
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            99448
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.569
_diffrn_reflns_theta_min         2.360
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.738
_exptl_absorpt_correction_T_max  0.910
_exptl_absorpt_correction_T_min  0.808
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       block
_exptl_crystal_F_000             1292
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.487
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     928
_refine_ls_number_reflns         16169
_refine_ls_number_restraints     41
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0602
_refine_ls_R_factor_gt           0.0414
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0566P)^2^+1.1318P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1062
_refine_ls_wR_factor_ref         0.1178
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12353
_reflns_number_total             16169
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06372c2.cif
_cod_data_source_block           pg160smartsb_sq
_cod_depositor_comments
'Adding full bibliography for 1566274--1566277.cif.'
_cod_original_cell_volume        3129.75(9)
_cod_original_formula_sum        'C75 H58 Fe3 N8 O0.50'
_cod_database_code               1566277
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C72 H54 N7 Fe3'
_chemical_oxdiff_usercomment     'AK1016 kryst z benzen/(CH2Cl2 lub CHCl3)'
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.762
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All H(H) groups
2. Restrained distances
 C12-C11 = C11-C10 = C9-C10 = C8-C9 = C8-C7 = C12-C7
 1.39 with sigma of 0.001
 C92-C93 = C91-C92 = C91-C93_$1
 1.39 with sigma of 0.001
 C58-C59 = C59-C60 = C61-C60 = C62-C61 = C62-C57 = C58-C57
 1.39 with sigma of 0.001
 C59A-C58A = C60A-C59A = C61A-C60A = C61A-C62A = C62A-C57A = C58A-C57A
 1.39 with sigma of 0.001
 N51-C60A = N51-C60 = N1-C10 = N1-C10A
 1.42 with sigma of 0.001
3. Restrained planarity
 N2A, C7A, C8A, C9A, C10A, C11A, C12A
 with sigma of 0.1
 N2, C7, C8, C9, C10, C11, C12
 with sigma of 0.1
 N52A, C57A, C58A, C59A, C60A, C61A, C62A
 with sigma of 0.1
 N52, C57, C58, C59, C60, C61, C62
 with sigma of 0.1
4. Others
 Sof(N2)=Sof(C6)=Sof(H6)=Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=
 Sof(C10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=1-FVAR(1)
 Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=
 Sof(H12)=Sof(N2A)=Sof(C6A)=Sof(H6A)=FVAR(1)
 Sof(N52A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=
 Sof(H59A)=Sof(C60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62A)=1-FVAR(2)
 Sof(N52)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=
 Sof(C60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62)=FVAR(2)
 Fixed Sof: H1A(0.5) H1B(0.5)
 Fixed X: H1A(0.05422) H1B(0.00077)
 Fixed Y: H1A(0.551961) H1B(0.466649)
 Fixed Z: H1A(0.52303) H1B(0.52589)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28),
  C29(H29), C30(H30), C32(H32), C33(H33), C35(H35), C36(H36), C52(H52),
 C53(H53), C54(H54), C55(H55), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68),
  C70(H70), C71(H71), C73(H73), C74(H74), C76(H76), C77(H77), C78(H78),
 C79(H79), C80(H80), C82(H82), C83(H83), C85(H85), C86(H86), C6(H6), C8(H8),
 C9(H9), C11(H11), C12(H12), C6A(H6A), C8A(H8A), C9A(H9A), C11A(H11A),
 C12A(H12A), C56(H56), C58(H58), C59(H59), C61(H61), C62(H62), C56A(H56A),
 C58A(H58A), C59A(H59A), C61A(H61A), C62A(H62A), C91(H91), C92(H92), C93(H93)
;
_shelx_res_checksum              98487
_shelx_fab_checksum              47139
_platon_squeeze_void_probe_radius 1.20
_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 1.114
_oxdiff_exptl_absorpt_empirical_full_min 0.852