An acetylene-bridged ferrocene macrocycle: efficient synthesis and electron transfer mechanism in mixed-valence systems.
Li, Longfei; Zhang, Beijing; Xie, Yi; Xiong, Qi; Zhong, Yuanbo; Jiang, Yansong; Wang, Yu; Wang, Haobing; Jiang, Shang-Da; Zhou, Shen; Jiang, Xing; Chemical science 16 (2025) 17268–17275; doi:10.1039/d5sc02322j

data_1575546
_publ_section_title
;
 An acetylene-bridged ferrocene macrocycle: efficient synthesis and
 electron transfer mechanism in mixed-valence systems.
;
_journal_issue                   37
_journal_name_full               'Chemical science'
_journal_page_first              17268
_journal_page_last               17275
_journal_paper_doi               10.1039/d5sc02322j
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C36 H36 Fe3'
_chemical_formula_sum            'C36 H36 Fe3'
_chemical_formula_weight         636.20
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-05-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-05-23 deposited with the CCDC.	2025-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                102.0480(10)
_cell_angle_beta                 97.6720(10)
_cell_angle_gamma                104.6740(10)
_cell_formula_units_Z            8
_cell_length_a                   13.3346(2)
_cell_length_b                   17.6109(2)
_cell_length_c                   25.4209(3)
_cell_measurement_reflns_used    63386
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      31.2140
_cell_measurement_theta_min      2.0590
_cell_volume                     5537.10(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.825
_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     -8.00  76.00   0.50    3.33    --    4.15  47.00-120.00  168
  2  \w    -67.00  16.00   0.50    3.33    --    4.15 -47.00  90.00  166
  3  \w    -17.00  35.00   0.50    3.33    --    4.15 -99.00 150.00  104
  4  \w    -17.00  35.00   0.50    3.33    --    4.15 -99.00  60.00  104
  5  \w    -17.00  35.00   0.50    3.33    --    4.15 -99.00-120.00  104
  6  \w    -17.00  35.00   0.50    3.33    --    4.15 -99.00  30.00  104
  7  \w    -17.00  76.00   0.50    3.33    --    4.15  77.00 120.00  186
  8  \w    -77.00   9.00   0.50    3.33    --   -5.09 -57.00 -60.00  172
  9  \w    -17.00   8.00   0.50    3.33    --    4.15 -99.00-180.00   50
 10  \w    -17.00  35.00   0.50    3.33    --    4.15 -99.00 -60.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0464031000
_diffrn_orient_matrix_UB_12      0.0294645000
_diffrn_orient_matrix_UB_13      0.0163155000
_diffrn_orient_matrix_UB_21      -0.0219871000
_diffrn_orient_matrix_UB_22      0.0313497000
_diffrn_orient_matrix_UB_23      -0.0044824000
_diffrn_orient_matrix_UB_31      -0.0225585000
_diffrn_orient_matrix_UB_32      -0.0009875000
_diffrn_orient_matrix_UB_33      0.0236765000
_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  0.0435
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.825
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            129604
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.825
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.183
_diffrn_reflns_theta_min         1.912
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.576
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81176
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       block
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.161
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1405
_refine_ls_number_reflns         29597
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.146
_refine_ls_R_factor_all          0.0579
_refine_ls_R_factor_gt           0.0435
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0191P)^2^+8.0671P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0932
_refine_ls_wR_factor_ref         0.0974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24002
_reflns_number_total             29597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02322j2.cif
_cod_data_source_block           etfc-cyclictrimer_auto
_cod_depositor_comments
'Adding full bibliography for 1575546--1575548.cif.'
_cod_database_code               1575546
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H Fe'
_shelx_estimated_absorpt_t_max   0.743
_shelx_estimated_absorpt_t_min   0.649
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C90(H90A,H90B), C31(H31A,H31B), C30(H30A,H30B), C66(H66A,H66B), C19(H19A,
 H19B), C18(H18A,H18B), C91(H91A,H91B), C43(H43A,H43B), C114(H11A,H11B),
 C67(H67A,H67B), C42(H42A,H42B), C78(H78A,H78B), C103(H10A,H10B), C102(H10C,
 H10D), C54(H54A,H54B), C79(H79A,H79B), C115(H11C,H11D), C55(H55A,H55B),
 C127(H12A,H12B), C126(H12C,H12D), C150(H15A,H15B), C151(H15C,H15D), C139(H13A,
 H13B), C138(H13C,H13D)
2.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C93(H93), C45(H45), C29(H29), C107(H107), C33(H33), C96(H96),
 C17(H17), C24(H24), C15(H15), C22(H22), C108(H108), C105(H105), C110(H110),
 C132(H132), C21(H21), C14(H14), C53(H53), C16(H16), C48(H48), C60(H60),
 C27(H27), C36(H36), C131(H131), C141(H141), C77(H77), C98(H98), C106(H106),
 C23(H23), C113(H113), C76(H76), C86(H86), C50(H50), C87(H87), C71(H71),
 C72(H72), C144(H144), C28(H28), C94(H94), C47(H47), C34(H34), C41(H41),
 C143(H143), C112(H112), C75(H75), C35(H35), C65(H65), C69(H69), C111(H111),
 C99(H99), C89(H89), C142(H142), C38(H38), C95(H95), C101(H101), C149(H149),
 C59(H59), C125(H125), C84(H84), C146(H146), C46(H46), C88(H88), C124(H124),
 C148(H148), C40(H40), C147(H147), C74(H74), C120(H120), C156(H156), C62(H62),
 C153(H153), C137(H137), C39(H39), C52(H52), C130(H130), C57(H57), C117(H117),
 C100(H100), C129(H129), C155(H155), C118(H118), C134(H134), C123(H123),
 C70(H70), C64(H64), C135(H135), C81(H81), C63(H63), C154(H154), C122(H122),
 C119(H119), C58(H58), C51(H51), C136(H136), C82(H82), C83(H83)
;
_shelx_res_checksum              78445
_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 2.618
_oxdiff_exptl_absorpt_empirical_full_min 0.493