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_1575548
_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_absolute_configuration ad
_chemical_formula_moiety         'C36 H24 Fe3'
_chemical_formula_sum            'C36 H24 Fe3'
_chemical_formula_weight         624.10
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-08-06 deposited with the CCDC.	2025-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   10.3956(2)
_cell_length_b                   10.3956(2)
_cell_length_c                   20.2799(6)
_cell_measurement_reflns_used    10502
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      31.0380
_cell_measurement_theta_min      2.9970
_cell_volume                     1898.00(8)
_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      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -17.00  35.00   0.50    1.16    --    4.00 -99.00  90.00  104
  2  \w    -17.00  35.00   0.50    1.16    --    4.00 -99.00 -90.00  104
  3  \w    -67.00  18.00   0.50    1.16    --    4.00 -56.00 -41.00  170
  4  \w    -10.00  15.00   0.50    1.16    --    4.00  57.00 -90.00   50
;
_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      0.0369164000
_diffrn_orient_matrix_UB_12      -0.0086436000
_diffrn_orient_matrix_UB_13      -0.0275973000
_diffrn_orient_matrix_UB_21      -0.0506541000
_diffrn_orient_matrix_UB_22      -0.0776246000
_diffrn_orient_matrix_UB_23      0.0000832000
_diffrn_orient_matrix_UB_31      -0.0476143000
_diffrn_orient_matrix_UB_32      0.0106862000
_diffrn_orient_matrix_UB_33      -0.0215147000
_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  0.0376
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            13094
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.679
_diffrn_reflns_theta_min         2.262
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.723
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77399
_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_density_diffrn    1.638
_exptl_crystal_description       block
_exptl_crystal_F_000             954
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.261
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.15(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     419
_refine_ls_number_reflns         2399
_refine_ls_number_restraints     1836
_refine_ls_restrained_S_all      0.773
_refine_ls_R_factor_all          0.0236
_refine_ls_R_factor_gt           0.0220
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0278P)^2^+0.6445P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0514
_refine_ls_wR_factor_ref         0.0520
_reflns_Friedel_coverage         0.700
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                2311
_reflns_number_total             2399
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02322j2.cif
_cod_data_source_block           alk_fc_auto
_cod_depositor_comments
'Adding full bibliography for 1575546--1575548.cif.'
_cod_original_cell_volume        1898.00(9)
_cod_database_code               1575548
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.820
_diffrn_oxdiff_digest_hkl
;
0166d319df20ba2f526d6a56012e4118f103a6
;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.85(3)
 0.15(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Uiso/Uaniso restraints and constraints
: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
All non-hydrogen atoms have similar U: within 1A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1A
All non-hydrogen atoms have similar U: within 3A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 3A
Uanis(C1_1) \\sim Ueq, Uanis(C2_1) \\sim Ueq, Uanis(C3_1) \\sim Ueq,
Uanis(C4_1) \\sim Ueq, Uanis(C5_1) \\sim Ueq, Uanis(C6_1) \\sim Ueq,
Uanis(C7_1) \\sim Ueq, Uanis(C8_1) \\sim Ueq, Uanis(C9_1) \\sim Ueq,
Uanis(C10_1) \\sim Ueq, Uanis(C11_1) \\sim Ueq, Uanis(C12_1) \\sim Ueq,
Uanis(C13_1) \\sim Ueq, Uanis(C14_1) \\sim Ueq, Uanis(C15_1) \\sim Ueq,
Uanis(C16_1) \\sim Ueq, Uanis(C17_1) \\sim Ueq, Uanis(C18_1) \\sim Ueq,
Uanis(C19_1) \\sim Ueq, Uanis(C20_1) \\sim Ueq, Uanis(C21_1) \\sim Ueq,
Uanis(C22_1) \\sim Ueq, Uanis(C23_1) \\sim Ueq, Uanis(C24_1) \\sim Ueq,
Uanis(C25_1) \\sim Ueq, Uanis(C26_1) \\sim Ueq, Uanis(C27_1) \\sim Ueq,
Uanis(C28_1) \\sim Ueq, Uanis(C29_1) \\sim Ueq, Uanis(C30_1) \\sim Ueq,
Uanis(C31_1) \\sim Ueq, Uanis(C32_1) \\sim Ueq, Uanis(C33_1) \\sim Ueq,
Uanis(C34_1) \\sim Ueq, Uanis(C35_1) \\sim Ueq, Uanis(C36_1) \\sim Ueq,
Uanis(Fe1_1) \\sim Ueq, Uanis(Fe2_1) \\sim Ueq, Uanis(Fe3_1) \\sim Ueq: with
sigma of 0.002 and sigma for terminal atoms of 0.004
4. Rigid body (RIGU) restrains
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
6. Others
 Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(C7)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(C19)=Sof(C20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(C26)=
 Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=
 Sof(C31)=Sof(C32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=
 Sof(C36)=Sof(H36)=Sof(Fe1)=Sof(Fe2)=Sof(Fe3)=0.5*(1-FVAR(2))
 Sof(Fe1)=0.5*FVAR(2)
 Sof(Fe2)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=
 Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=
 Sof(H10)=Sof(C11)=Sof(C12)=Sof(C13)=Sof(C14)=Sof(C15)=Sof(H15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=FVAR(1)
7.a Free rotating group:
 C1(C2,C3,C4,C5,C6,C7,C8,C9,C10,C11,C12,C13,C14,C15,C16,C17,C18,C19,C20,C21,
 C22,C23,C24,C25,C26,C27,C28,C29,C30,C31,C32,C33,C34,C35,C36,Fe1,Fe2,Fe3)
7.b Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C15(H15),
 C16(H16), C17(H17), C18(H18), C2(H2), C3(H3), C4(H4), C5(H5), C14(H14),
 C15(H15), C16(H16), C17(H17), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
  C27(H27), C28(H28), C29(H29), C33(H33), C34(H34), C35(H35), C36(H36)
;
_shelx_res_checksum              60947
_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 1.595
_oxdiff_exptl_absorpt_empirical_full_min 0.691