A metallosupramolecular-based ring-in-ring complex showing reversible host-guest dynamics and switchable electrochemical properties.
Martínez-Visiedo, Joel; Ibáñez, Susana; Dawe, Louise N.; Peris, Eduardo; Nanoscale 17 (2025) 20089–20095; doi:10.1039/d5nr02758f

data_1575232
_publ_section_title
;
 A metallosupramolecular-based ring-in-ring complex showing reversible
 host-guest dynamics and switchable electrochemical properties.
;
_journal_issue                   35
_journal_name_full               Nanoscale
_journal_page_first              20089
_journal_page_last               20095
_journal_paper_doi               10.1039/d5nr02758f
_journal_volume                  17
_journal_year                    2025
_chemical_formula_moiety         'C160 H188 Ir4 N20, C38 H28 N2 O8, 0.25[]'
_chemical_formula_sum            'C198 H216 Ir4 N22 O8'
_chemical_formula_weight         3800.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-06-16 deposited with the CCDC.	2025-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90.0
_cell_angle_beta                 117.491(5)
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   34.3083(13)
_cell_length_b                   25.6152(4)
_cell_length_c                   41.4962(18)
_cell_measurement_reflns_used    20026
_cell_measurement_temperature    200.15
_cell_measurement_theta_max      71.5100
_cell_measurement_theta_min      4.1180
_cell_volume                     32350(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_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_environment      N~2~
_diffrn_ambient_temperature      200.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4051
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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     -5.00  38.00   0.25    5.00    --  -42.50  19.00 -60.00  172
  2  \w    -87.00  -6.00   0.25    5.00    --  -42.50 125.00  30.00  324
  3  \w     -5.00  38.00   0.25    5.00    --  -42.50  19.00 -90.00  172
  4  \w     -5.00  38.00   0.25    5.00    --  -42.50  19.00 150.00  172
  5  \w     -5.00  38.00   0.25    5.00    --  -42.50  19.00   0.00  172
  6  \w     26.00  57.00   0.25   27.50    --  102.61 -30.00 -30.00  124
  7  \w     97.00 174.00   0.25   27.50    --  102.61 125.00 -30.00  308
  8  \w     30.00  72.00   0.25   27.50    --  102.61 -45.00 120.00  168
  9  \w     26.00  57.00   0.25   27.50    --  102.61 -30.00-120.00  124
 10  \w     26.00  57.00   0.25   27.50    --  102.61 -30.00 -90.00  124
 11  \w     91.00 173.00   0.25   27.50    --  102.61  30.00 -60.00  328
 12  \w     30.00  72.00   0.25   27.50    --  102.61 -45.00 -60.00  168
 13  \w    103.00 178.00   0.25   27.50    --  102.61  77.00 -30.00  300
 14  \w     26.00  57.00   0.25   27.50    --  102.61 -30.00  30.00  124
 15  \w     26.00  57.00   0.25   27.50    --  102.61 -30.00   0.00  124
 16  \w     91.00 173.00   0.25   27.50    --  102.61  30.00 -60.00  328
 17  \w     30.00  86.00   0.25   27.50    --  102.61 -61.00-150.00  224
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0372245000
_diffrn_orient_matrix_UB_12      -0.0373189000
_diffrn_orient_matrix_UB_13      -0.0040981000
_diffrn_orient_matrix_UB_21      0.0113716000
_diffrn_orient_matrix_UB_22      0.0093122000
_diffrn_orient_matrix_UB_23      0.0400391000
_diffrn_orient_matrix_UB_31      -0.0323818000
_diffrn_orient_matrix_UB_32      0.0462361000
_diffrn_orient_matrix_UB_33      -0.0114235000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0896
_diffrn_reflns_av_unetI/netI     0.0772
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            84744
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         3.638
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.196
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.680
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.104a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    0.780
_exptl_crystal_description       prism
_exptl_crystal_F_000             7720
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Tetrachloroethane/hexane'
_exptl_crystal_size_max          0.306
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.115
_refine_diff_density_max         3.208
_refine_diff_density_min         -1.977
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.154
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     812
_refine_ls_number_reflns         28462
_refine_ls_number_restraints     844
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.1395
_refine_ls_R_factor_gt           0.1080
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3056
_refine_ls_wR_factor_ref         0.3566
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17060
_reflns_number_total             28462
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nr02758f2.cif
_cod_data_source_block           str2317_sq
_cod_depositor_comments
'Adding full bibliography for 1575231--1575232.cif.'
_cod_database_code               1575232
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Ir B  F'
_cell_oxdiff_angle_alpha         89.9581(12)
_cell_oxdiff_angle_beta          117.477(2)
_cell_oxdiff_angle_gamma         89.9802(14)
_cell_oxdiff_length_a            34.2941(8)
_cell_oxdiff_length_b            25.6154(3)
_cell_oxdiff_length_c            41.5078(7)
_cell_oxdiff_measurement_reflns_used 20147
_cell_oxdiff_volume              32350(1)
_shelx_estimated_absorpt_t_max   0.697
_shelx_estimated_absorpt_t_min   0.424
_diffrn_oxdiff_digest_hkl
;
4334efe3cd2b3301419e686fa1eb1f1edd0493
;
_reflns_odcompleteness_completeness 99.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C52-C51
 1.54 with sigma of 0.02
 C53-C52
 1.54 with sigma of 0.02
 C53-C54
 1.54 with sigma of 0.02
 C41-C42
 1.54 with sigma of 0.02
 N1-C31 \\sim N8-C51
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C136) = Uiso(O102) = Uiso(C119) = Uiso(C118) = Uiso(C120) = Uiso(C117) =
Uiso(N101) = Uiso(O101) = Uiso(C121) = Uiso(C122) = Uiso(C101) = Uiso(O103) =
Uiso(C132) = Uiso(O104) = Uiso(C123) = Uiso(C102) = Uiso(C114) = Uiso(C133) =
Uiso(C131) = Uiso(C124) = Uiso(C103) = Uiso(C113) = Uiso(C134) = Uiso(C130) =
Uiso(C125) = Uiso(C115) = Uiso(C104) = Uiso(C112) = Uiso(C126) = Uiso(C129) =
Uiso(C116) = Uiso(C105) = Uiso(C111) = Uiso(C127) = Uiso(C128) = Uiso(C110) =
Uiso(C106) = Uiso(O105) = Uiso(N102) = Uiso(O106) = Uiso(C109) = Uiso(C107) =
Uiso(C135) = Uiso(C108) = Uiso(O108) = Uiso(O107) = Uiso(C138) = Uiso(C137)
Uanis(C31) = Uanis(C51)
Uanis(C34) = Uanis(C53)
Uanis(C32) = Uanis(C52)
Uanis(C34) = Uanis(C54)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: O102(0.5) O101(0.5) O103(0.5) O104(0.5) O105(0.5) O106(0.5)
 O107(0.5) O108(0.5) N101(0.5) N102(0.5) C101(0.5) C102(0.5) H102(0.5)
 C103(0.5) C104(0.5) H104(0.5) C105(0.5) H105(0.5) C106(0.5) C107(0.5)
 H107(0.5) C108(0.5) C109(0.5) H109(0.5) C110(0.5) C111(0.5) H111(0.5)
 C112(0.5) H112(0.5) C113(0.5) C114(0.5) H114(0.5) C115(0.5) C116(0.5)
 C117(0.5) H11A(0.5) H11B(0.5) C118(0.5) H11C(0.5) H11D(0.5) C119(0.5)
 H11E(0.5) H11F(0.5) C120(0.5) H12A(0.5) H12B(0.5) C121(0.5) C122(0.5)
 C123(0.5) C124(0.5) H124(0.5) C125(0.5) H125(0.5) C126(0.5) C127(0.5)
 C128(0.5) C129(0.5) C130(0.5) H130(0.5) C131(0.5) H131(0.5) C132(0.5)
 C133(0.5) C134(0.5) C135(0.5) H13A(0.5) H13B(0.5) C136(0.5) H13C(0.5)
 H13D(0.5) C137(0.5) H13E(0.5) H13F(0.5) C138(0.5) H13G(0.5) H13H(0.5)
 Fixed Uiso: O102(0.15143) O101(0.15143) O103(0.15143) O104(0.15143)
 O105(0.15143) O106(0.15143) O107(0.15143) O108(0.15143) N101(0.15143)
 N102(0.15143) C101(0.15143) C102(0.15143) C103(0.15143) C104(0.15143)
 C105(0.15143) C106(0.15143) C107(0.15143) C108(0.15143) C109(0.15143)
 C110(0.15143) C111(0.15143) C112(0.15143) C113(0.15143) C114(0.15143)
 C115(0.15143) C116(0.15143) C117(0.15143) C118(0.15143) C119(0.15143)
 C120(0.15143) C121(0.15143) C122(0.15143) C123(0.15143) C124(0.15143)
 C125(0.15143) C126(0.15143) C127(0.15143) C128(0.15143) C129(0.15143)
 C130(0.15143) C131(0.15143) C132(0.15143) C133(0.15143) C134(0.15143)
 C135(0.15143) C136(0.15143) C137(0.15143) C138(0.15143)
6.a Free rotating group:
 O102(O101,O103,O104,O105,O106,O107,O108,N101,N102,C101,C102,C103,C104,C105,
 C106,C107,C108,C109,C110,C111,C112,C113,C114,C115,C116,C117,C118,C119,C120,
 C121,C122,C123,C124,C125,C126,C127,C128,C129,C130,C131,C132,C133,C134,C135,
 C136,C137,C138)
6.b Ternary CH refined with riding coordinates:
 C55(H55), C58(H58), C59(H59), C62(H62), C63(H63), C66(H66), C67(H67), C70(H70)
6.c Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C39(H39A,H39B), C40(H40A,
 H40B), C41(H41A,H41B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B),
 C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C56(H56A,H56B), C57(H57A,H57B),
  C60(H60A,H60B), C61(H61A,H61B), C64(H64A,H64B), C65(H65A,H65B), C68(H68A,
 H68B), C69(H69A,H69B), C117(H11A,H11B), C118(H11C,H11D), C119(H11E,H11F),
 C120(H12A,H12B), C135(H13A,H13B), C136(H13C,H13D), C137(H13E,H13F), C138(H13G,
 H13H)
6.d Me refined with riding coordinates:
 C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C42(H42A,H42B,H42C), C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,
 H49B,H49C), C50(H50A,H50B,H50C)
6.e Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C9(H9), C14(H14), C18(H18), C22(H22), C24(H24), C29(H29),
 C71(H71), C72(H72), C75(H75), C76(H76), C77(H77), C78(H78), C79(H79), C80(H80),
  C102(H102), C104(H104), C105(H105), C107(H107), C109(H109), C111(H111),
 C112(H112), C114(H114), C124(H124), C125(H125), C130(H130), C131(H131)
6.f Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C)
;
_shelx_res_checksum              95922
_shelx_fab_checksum              15026
_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 2.443
_oxdiff_exptl_absorpt_empirical_full_min 0.534