An Ir(ppy)3 encapsulated metal–organic tetrahedral cage for photocatalytic dehydrogenation cross-couplings
Hao, Yang; Yang, Yang; Yang, Fengyu; Shi, Youpeng; Jing, Xu; Duan, Chunying; Chemical Communications 61 (2025) 8576–8579; doi:10.1039/D5CC01206F

data_7134491
_publ_section_title
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 An Ir(ppy)3 encapsulated metal--organic tetrahedral cage for
 photocatalytic dehydrogenation cross-couplings
;
_journal_issue                   47
_journal_name_full               'Chemical Communications'
_journal_page_first              8576
_journal_page_last               8579
_journal_paper_doi               10.1039/D5CC01206F
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety
'3(C42 H30 Fe N12 O3), 3(C2 F6 N O4 S2), C4 H10 O, C2 H3 N, 3[C2F6NO4S2], 2[C4H10O], 3.27[CH3CN]'
_chemical_formula_sum            'C158.54 H132.81 F36 Fe3 N46.27 O36 S12'
_chemical_formula_weight         4498.44
_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
_audit_creation_date             2025-03-02
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
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2025-03-03 deposited with the CCDC.	2025-04-30 downloaded from the CCDC.
;
_cell_angle_alpha                96.548(2)
_cell_angle_beta                 100.632(2)
_cell_angle_gamma                100.345(2)
_cell_formula_units_Z            2
_cell_length_a                   16.7218(15)
_cell_length_b                   17.6792(15)
_cell_length_c                   34.026(3)
_cell_measurement_reflns_used    9405
_cell_measurement_temperature    230.00
_cell_measurement_theta_max      27.578
_cell_measurement_theta_min      2.567
_cell_volume                     9612.3(15)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      230.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0444
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            388814
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.653
_diffrn_reflns_theta_min         2.447
_diffrn_source_current           40.0
_diffrn_source_power             1.8
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.472
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6247
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1448 before and 0.0528 after correction.
The Ratio of minimum to maximum transmission is 0.8378.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.554
_exptl_crystal_description       block
_exptl_crystal_F_000             4580
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.999
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2101
_refine_ls_number_reflns         44635
_refine_ls_number_restraints     248
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0781
_refine_ls_R_factor_gt           0.0584
_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^)+(0.0689P)^2^+10.2430P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1452
_refine_ls_wR_factor_ref         0.1568
_reflns_Friedel_coverage         0.000
_reflns_number_gt                34235
_reflns_number_total             44635
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01206f2.cif
_cod_data_source_block           a_sq
_cod_depositor_comments
'Adding full bibliography for 7134490--7134491.cif.'
_cod_original_cell_volume        9612.4(15)
_cod_database_code               7134491
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.920
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
S6 \\sim F10 \\sim F11 \\sim F12 \\sim O20 \\sim C130 \\sim S6A \\sim F10A
\\sim F11A \\sim F12A \\sim O20A \\sim C139: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
2. Rigid body (RIGU) restrains
 S6, F10, F11, F12, O20, C130, S6A, F10A, F11A, F12A, O20A, C139
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Same fragment restrains
{S6, F10, F11, F12, O20, C130} sigma for 1-2: 0.01, 1-3: 0.02
as in
{S6A, F10A, F11A, F12A, O20A, C139}
4. Others
 Sof(S6A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(O20A)=Sof(C139)=1-FVAR(1)
 Sof(S6)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(O20)=Sof(C130)=FVAR(1)
 Fixed Z: F10A(0.231999)
5.a Secondary CH2 refined with riding coordinates:
 C134(H13D,H13E), C135(H13F,H13G)
5.b Aromatic/amide H refined with riding coordinates:
 N8(H8), N10(H10), N12(H12), N20(H20A), N22(H22A), N24(H24), N32(H32A),
 N34(H34), N36(H36A), C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8A),
 C10(H10A), C11(H11), C12(H12A), C14(H14), C15(H15), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C29(H29), C30(H30),
  C31(H31), C32(H32), C33(H33), C36(H36), C38(H38), C40(H40), C43(H43),
 C44(H44), C45(H45), C46(H46), C49(H49), C50(H50), C52(H52), C53(H53), C54(H54),
  C55(H55), C56(H56), C57(H57), C60(H60), C61(H61), C63(H63), C64(H64),
 C65(H65), C66(H66), C67(H67), C68(H68), C71(H71), C72(H72), C74(H74), C75(H75),
  C78(H78), C80(H80), C82(H82), C85(H85), C86(H86), C87(H87), C88(H88),
 C91(H91), C92(H92), C94(H94), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99),
  C102(H102), C103(H103), C105(H105), C106(H106), C107(H107), C108(H108),
 C109(H109), C110(H110), C113(H113), C114(H114), C116(H116), C117(H117),
 C120(H120), C122(H122), C125(H125)
5.c Idealised Me refined as rotating group:
 C133(H13A,H13B,H13C), C136(H13H,H13I,H13J), C137(H13K,H13L,H13M)
;
_shelx_res_checksum              16704
_shelx_hkl_checksum              24852
_shelx_fab_checksum              36192
_platon_squeeze_special_details
;
A solvent mask was calculated and 1134 electrons were 
found in a volume of 3059\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[C2F6NO4S2], 2[C4H10O], 3.27[CH3CN] per Asymmetric Unit 
which account for 1134 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'