Precisely Embedding Active Sites into a Mesoporous Zr-Framework through Linker Installation for High-Efficiency Photocatalysis.
Pang, Jiandong; Di, Zhengyi; Qin, Jun-Sheng; Yuan, Shuai; Lollar, Christina T.; Li, Jialuo; Zhang, Peng; Wu, Mingyan; Yuan, Daqiang; Hong, Maochun; Zhou, Hong-Cai; Journal of the American Chemical Society 142 (2020) 15020–15026; doi:10.1021/jacs.0c05758

data_4135204
_publ_section_title
;
 Precisely Embedding Active Sites into a Mesoporous Zr-Framework through
 Linker Installation for High-Efficiency Photocatalysis.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15020
_journal_page_last               15026
_journal_paper_doi               10.1021/jacs.0c05758
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C14.65 H8 N0.45 O4.75 Ru0.13 Zr0.75'
_chemical_formula_sum            'C14.65 H8.2 Cl0 N0.45 O4.75 Ru0.12 Zr0.75'
_chemical_formula_weight         347.56
_space_group_crystal_system      hexagonal
_space_group_IT_number           191
_space_group_name_Hall           '-P 6 2'
_space_group_name_H-M_alt        'P 6/m m m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-01-27
_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                120
_cell_formula_units_Z            24
_cell_length_a                   40.8928(8)
_cell_length_b                   40.893
_cell_length_c                   19.2023(4)
_cell_measurement_reflns_used    9913
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      59.2788
_cell_measurement_theta_min      2.3009
_cell_volume                     27808.6(8)
_computing_cell_refinement       'SAINT+ ver. (Bruker, 2001)'
_computing_data_collection       'APEX2  (Bruker, 2008)'
_computing_data_reduction        'SAINT+ ver. (Bruker, 2001)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.99
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART APEX II CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1180
_diffrn_reflns_av_unetI/netI     0.0887
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            61099
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        60.148
_diffrn_reflns_theta_max         60.148
_diffrn_reflns_theta_min         2.161
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    1.878
_exptl_absorpt_correction_T_max  0.7518
_exptl_absorpt_correction_T_min  0.6000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1082 before and 0.0534 after correction.
The Ratio of minimum to maximum transmission is 0.7981.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Red
_exptl_crystal_density_diffrn    0.498
_exptl_crystal_description       needle
_exptl_crystal_F_000             4146
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.610
_refine_diff_density_min         -1.556
_refine_diff_density_rms         0.127
_refine_ls_extinction_coef       0.00008(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     178
_refine_ls_number_reflns         7699
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.337
_refine_ls_R_factor_all          0.1354
_refine_ls_R_factor_gt           0.1002
_refine_ls_shift/su_max          0.000
_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          0.3012
_refine_ls_wR_factor_ref         0.3272
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4484
_reflns_number_total             7699
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05758_si_003.cif
_cod_data_source_block           PCN-808-BDBR
_cod_depositor_comments
'Adding full bibliography for 4135202--4135205.cif.'
_cod_original_cell_volume        27808.5(12)
_cod_original_formula_sum        'C14.65 H8.20 Cl0 N0.45 O4.75 Ru0.12 Zr0.75'
_cod_database_code               4135204
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C11-C8
 1.4 with sigma of 0.005
 O8-C10
 1.42 with sigma of 0.005
 C21-C20
 2.2 with sigma of 0.005
 C20-C20_$1
 1.5 with sigma of 0.005
 O3-C16
 1.25 with sigma of 0.005
 O3-O4
 2.24 with sigma of 0.005
 C18-C17
 1.4 with sigma of 0.005
 C19-C17
 2.2 with sigma of 0.005
 Ru1-C28_$2
 2.95 with sigma of 0.005
 C29-C29_$2
 2.2 with sigma of 0.005
 C28-C28_$2
 2.2 with sigma of 0.005
 Ru1-C27_$2
 3.1 with sigma of 0.005
 Ru1-N1
 2.1 with sigma of 0.005
 N2-C28_$2
 1.4 with sigma of 0.005
 C30-N2
 2.78 with sigma of 0.005
 C13-C15
 1.39 with sigma of 0.02
 C15-C15_$3
 1.39 with sigma of 0.02
 C15_$3-C13_$3
 1.39 with sigma of 0.02
 C13_$3-C14_$3
 1.39 with sigma of 0.02
 C14_$3-C14
 1.39 with sigma of 0.02
 C14-C13
 1.39 with sigma of 0.02
 C13-C15_$3
 2.4 with sigma of 0.02
 C15-C13_$3
 2.4 with sigma of 0.02
 C15_$3-C14_$3
 2.4 with sigma of 0.02
 C13_$3-C14
 2.4 with sigma of 0.02
 C14_$3-C13
 2.4 with sigma of 0.02
 C14-C15
 2.4 with sigma of 0.02
 C13-C13_$3
 2.8 with sigma of 0.02
 C15-C14_$3
 2.8 with sigma of 0.02
 C15_$3-C14
 2.8 with sigma of 0.02
3. Restrained planarity
 O8, C9, C8, C11, C12
 with sigma of 0.1
 N1, C20, C19, C18, C17, C21, C16
 with sigma of 0.1
 N2, Ru1, N1, C20, C19, C21, C17, C18
 with sigma of 0.1
 C30, C29, C28, N2, Ru1
 with sigma of 0.1
 C13, C15, C15_$3, C13_$3, C14_$3, C14
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C10) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O4) = Uanis(C16) = Uanis(C17) = Uanis(C18) = Uanis(C21) = Uanis(N1) =
Uanis(C20) = Uanis(C19)
Uanis(C15) = Uanis(C13) = Uanis(C14) = Uanis(C12) = Uanis(C11) = Uanis(C9) =
Uanis(C8)
Uanis(N26) = Uanis(C3) = Uanis(C22) = Uanis(C23) = Uanis(C25) = Uanis(C24) =
Uanis(Ru1) = Uanis(N2) = Uanis(C28) = Uanis(C27) = Uanis(C29) = Uanis(C30)
Uanis(C13) = Uanis(C14) = Uanis(C14) = Uanis(C13) = Uanis(C15) = Uanis(C15)
Uanis(C10) = Uanis(O8) = Uanis(C9) = Uanis(C8) = Uanis(C11) = Uanis(C12) =
Uanis(C11) = Uanis(C8)
5. Others
 Fixed Sof: H10A(0.5) H10B(0.5) H10C(0.5) Ru1(0.125) O4(0.25) N1(0.25)
 C21(0.25) C17(0.25) C18(0.25) C19(0.25) C20(0.5) C16(0.25) N2(0.1) C28(0.1)
 C30(0.1) C29(0.1) C27(0.1) C3(0.1) H3(0.1) C22(0.1) H22(0.1) C23(0.1) H23(0.1)
 C24(0.1) H24(0.1) C25(0.1) H25(0.1) N26(0.1)
6.a Free rotating group:
 C3(C22,C23,C24,C25,N26)
6.b Aromatic/amide H refined with riding coordinates:
 C0AA(H0AA), C4(H4), C11(H11), C6(H6), C7(H7), C14(H14), C15(H15), C3(H3),
 C22(H22), C23(H23), C24(H24), C25(H25)
6.c Fitted hexagon refined as free rotating group:
 N1(C21,C17,C18,C19,C20)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_olex2_submission_special_instructions 'No special instructions were received'