Stabilization of Radical Active Species in a MOF Nanospace to Exploit Unique Reaction Pathways
Harada, Yuki; Kusaka, Shinpei; Nakajo, Toshinobu; Kumagai, Jun; Kim, Cho Rong; Shim, Joo Young; Hori, Akihiro; Ma, Yunsheng; Matsuda, Ryotaro; Chemical Communications  (2021) –; doi:10.1039/D1CC04267J

data_7129114
_publ_section_title
;
 Stabilization of Radical Active Species in a MOF Nanospace to Exploit
 Unique Reaction Pathways
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC04267J
_journal_year                    2021
_chemical_formula_moiety         'C20 H16 I2 O11 Zn2'
_chemical_formula_sum            'C20 H16 I2 O11 Zn2'
_chemical_formula_weight         816.87
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-04 deposited with the CCDC.	2021-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   27.5610(10)
_cell_length_b                   27.5610(10)
_cell_length_c                   17.9581(6)
_cell_measurement_reflns_used    11961
_cell_measurement_temperature    233
_cell_measurement_theta_max      29.2600
_cell_measurement_theta_min      2.8010
_cell_volume                     11813.6(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      233
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.840
_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     22.00  86.00   0.50    2.33    --   -3.70  19.00 -30.00  128
  2  \w    -20.00  49.00   0.50    2.33    --    4.20  57.00  30.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0233047000
_diffrn_orient_matrix_UB_12      -0.0041418000
_diffrn_orient_matrix_UB_13      0.0036603000
_diffrn_orient_matrix_UB_21      0.0180631000
_diffrn_orient_matrix_UB_22      0.0293402000
_diffrn_orient_matrix_UB_23      0.0033717000
_diffrn_orient_matrix_UB_31      -0.0037381000
_diffrn_orient_matrix_UB_32      -0.0021232000
_diffrn_orient_matrix_UB_33      0.0391886000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0228
_diffrn_reflns_av_unetI/netI     0.0268
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.840
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            17180
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.840
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.279
_diffrn_reflns_theta_min         2.049
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.232
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51712
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.067
_exptl_crystal_description       needle
_exptl_crystal_F_000             7020
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         5.966
_refine_diff_density_min         -2.839
_refine_diff_density_rms         0.294
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.823
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         6025
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.864
_refine_ls_R_factor_all          0.1167
_refine_ls_R_factor_gt           0.1068
_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          0.3737
_refine_ls_wR_factor_ref         0.3887
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5111
_reflns_number_total             6025
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc04267j2.cif
_cod_data_source_block           zni2_-40deg
_cod_original_cell_volume        11813.6(9)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7129114
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.569
_shelx_estimated_absorpt_t_min   0.470
_reflns_odcompleteness_completeness 98.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 O(H,H) groups
2. Restrained distances
 C19-C20
 1.487 with sigma of 0.02
 H1A-C1
 0.98 with sigma of 0.001
 H1B-C1
 0.98 with sigma of 0.001
 H20B-H20A
 1.6 with sigma of 0.001
 H20B-C20
 0.98 with sigma of 0.001
 H20A-C20
 0.98 with sigma of 0.001
 H1A-H1B
 1.6 with sigma of 0.001
 H20A-C19
 2 with sigma of 0.02
 H20B-C19
 2 with sigma of 0.02
 H20A-I3
 2.3 with sigma of 0.02
 H1A-I1
 2.3 with sigma of 0.02
 I2-H1A
 2 with sigma of 0.02
 H20B-I3
 2.3 with sigma of 0.02
 H20A-I4
 2.3 with sigma of 0.02
 H1A-I2
 2.3 with sigma of 0.02
 H1B-I1
 2.3 with sigma of 0.02
 H1B-I2
 2.3 with sigma of 0.02
 I3-C20 \\sim I4-C20
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O11 \\sim C19 \\sim C20 \\sim I3: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O1 \\sim C2 \\sim C1 \\sim I2 \\sim I1: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 1.7A
Uanis(Zn1) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq,
Uanis(O9) \\sim Ueq, Uanis(Zn2) \\sim Ueq, Uanis(O10) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(Zn1) = Uanis(Zn2)
4. Rigid body (RIGU) restrains
 O11, C19, C20, I3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(I2)=Sof(I4)=1-FVAR(1)
 Sof(I1)=Sof(I3)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C19(H19A,H19B)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C4(H4), C13(H13), C9(H9), C16(H16), C18(H18)
6.c X=CH2 refined with riding coordinates:
 O10(H10A,H10B)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78229
_shelx_fab_checksum              59825
_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 1.599
_oxdiff_exptl_absorpt_empirical_full_min 0.819