Single Metal‒Organic Cage Decorated with an Ir(III) Complex for CO2 Photoreduction
Qi, Xiangjuan; Zhong, Ronglin; Chen, Mengmeng; Sun, Chunyi; You, Siqi; Gu, Jianxia; Shan, Guogang; Cui, Dongxu; Wang, Xinlong; Su, Zhongmin; ACS Catalysis 11 (2021) 7241–7248; doi:10.1021/acscatal.1c01974

data_4518777
_publ_section_title
;
 Single Metal--Organic Cage Decorated with an Ir(III) Complex for CO2
 Photoreduction
;
_journal_issue                   12
_journal_name_full               'ACS Catalysis'
_journal_page_first              7241
_journal_page_last               7248
_journal_paper_doi               10.1021/acscatal.1c01974
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C139.5 H65.5 Ir0.5 N13.5 O40 Zr12, 5(Cl1)'
_chemical_formula_sum            'C151 H130 Cl5 Ir0.5 N7.5 O40 Zr12'
_chemical_formula_weight         4057.61
_space_group_crystal_system      cubic
_space_group_IT_number           225
_space_group_name_Hall           '-F 4 2 3'
_space_group_name_H-M_alt        'F m -3 m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-04-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   43.339(6)
_cell_length_b                   43.339(6)
_cell_length_c                   43.339(6)
_cell_measurement_reflns_used    2027
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      57.000
_cell_measurement_theta_min      1.953
_cell_volume                     81402(2)
_computing_cell_refinement       'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker D8 VENTURE'
_diffrn_measured_fraction_theta_full 0.918
_diffrn_measured_fraction_theta_max 0.918
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '0.60\ % \ w and 0.6\ % \ f scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1092
_diffrn_reflns_av_unetI/netI     0.0604
_diffrn_reflns_Laue_measured_fraction_full 0.918
_diffrn_reflns_Laue_measured_fraction_max 0.918
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            22607
_diffrn_reflns_point_group_measured_fraction_full 0.918
_diffrn_reflns_point_group_measured_fraction_max 0.918
_diffrn_reflns_theta_full        51.114
_diffrn_reflns_theta_max         51.114
_diffrn_reflns_theta_min         2.039
_exptl_absorpt_coefficient_mu    3.274
_exptl_absorpt_correction_T_max  0.86
_exptl_absorpt_correction_T_min  0.84
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    0.662
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             16096
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.744
_refine_diff_density_min         -1.154
_refine_diff_density_rms         0.193
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.337
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         2027
_refine_ls_number_restraints     1023
_refine_ls_restrained_S_all      2.209
_refine_ls_R_factor_all          0.2263
_refine_ls_R_factor_gt           0.1908
_refine_ls_shift/su_max          0.004
_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          0.4761
_refine_ls_wR_factor_ref         0.5176
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1449
_reflns_number_total             2027
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01974_si_002.cif
_cod_data_source_block           1_a_sq
_cod_depositor_comments          'Adding full bibliography for 4518777.cif.'
_cod_original_cell_volume        81401(34)
_cod_original_formula_sum        'C151 H130 Cl5 Ir0.50 N7.50 O40 Zr12'
_cod_database_code               4518777
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.560
_shelx_estimated_absorpt_t_min   0.507
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Shared sites
{C5, N4}
3. Restrained distances
 C19-C13
 1.5 with sigma of 0.01
 C9-C18
 1.5 with sigma of 0.01
 Ir1-N1 = Ir1-N2 = Ir1-N3
 2 with sigma of 0.01
 N3-N2
 2.58 with sigma of 0.01
 N2-N1
 2.58 with sigma of 0.01
 N1-N3
 4 with sigma of 0.01
 C5-C4 = C2-C1 = C5-C2
 1.38 with sigma of 0.001
 Ir1_$2-C5_$2
 1.9 with sigma of 0.02
 N2-C18
 2.65 with sigma of 0.01
 C19-N2
 2.65 with sigma of 0.01
 N4-N4_$5
 2.35 with sigma of 0.01
 N2-C13 \\sim N2-C9 \\sim N3-C18 \\sim N3-C14
 with sigma of 0.02
 C12-C11 \\sim C11-C10 \\sim C10-C9 \\sim C18-C17 \\sim C17-C16 \\sim C16-C15
\\sim C15-C14
 with sigma of 0.02
 N2-C10 \\sim N2-C12 \\sim N3-C17 \\sim N3-C15
 with sigma of 0.04
 C13-C9 \\sim C13-C11 \\sim C12-C10 \\sim C11-C9 \\sim C18-C14 \\sim C18-C16
\\sim C17-C15
 with sigma of 0.04
 N1-C19 \\sim N1-C23
 with sigma of 0.02
 C19-C20 \\sim C20-C21 \\sim C21-C22 \\sim C22-C23
 with sigma of 0.02
 N1-C22 \\sim N1-C20
 with sigma of 0.04
 C21-C23 \\sim C21-C19 \\sim C22-C20 \\sim C23-C19
 with sigma of 0.04
4. Restrained planarity
 N2, N3, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18
 with sigma of 0.1
 N1, C19, C20, C21, C22, C23
 with sigma of 0.1
 N1, N2, N3, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21,
 C22, C23
 with sigma of 0.01
 Ir1, N1, N2, N3, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20,
 C21, C22, C23
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
N2 \\sim N3 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim
C15 \\sim C16 \\sim C17 \\sim C18: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
N1 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C9 \\sim C10 \\sim C11 \\sim
C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C1 \\sim
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim O1 \\sim O2
\\sim O3: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.03
Ir1 \\sim Zr1 \\sim O1 \\sim O2 \\sim O3 \\sim C1 \\sim C2 \\sim C3 \\sim C4
\\sim C5 \\sim C6 \\sim C7 \\sim C8: within 4A with sigma of 0.01 and sigma for
terminal atoms of 0.03
Ir1 \\sim Zr1 \\sim O1 \\sim O2 \\sim O3 \\sim N1 \\sim N2 \\sim N3 \\sim C1
\\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim
C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim
C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23: within 4A with sigma of
0.01 and sigma for terminal atoms of 0.03
Uanis(Cl1) \\sim Ueq: with sigma of 0.008 and sigma for terminal atoms of 0.005
Uanis(C5) = Uanis(N4)
6. Rigid body (RIGU) restrains
 N2, N3, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C19, C20, C21, C22, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: Ir1(0.02083) N1(0.02083) C19(0.02083) C20(0.02083) H20(0.02083)
 C21(0.02083) H21(0.02083) C22(0.02083) H22(0.02083) C23(0.02083) H23(0.02083)
 N2(0.02083) C9(0.02083) C10(0.02083) H10(0.02083) C11(0.02083) H11(0.02083)
 C12(0.02083) H12(0.02083) C13(0.02083) N3(0.02083) C14(0.02083) H14(0.02083)
 C15(0.02083) H15(0.02083) C16(0.02083) H16(0.02083) C17(0.02083) H17(0.02083)
 C18(0.02083) N4(0.5) C5(0.5) Cl1(0.20833)
8.a Riding coordinates:
 C6(H6), C7(H7), C8(H8)
8.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C22(H22), C23(H23), C10(H10), C11(H11), C12(H12),
 C14(H14), C15(H15), C16(H16), C17(H17)
8.c Fitted hexagon refined as free rotating group:
 N1(C19,C20,C21,C22,C23), N2(C9,C10,C11,C12,C13), N3(C14,C15,C16,C17,C18)
;
_shelx_res_checksum              25428
_shelx_hkl_checksum              22274
_shelx_fab_checksum              70650
_olex2_submission_special_instructions 'No special instructions were received'