Post-synthetic exchange (PSE) of UiO-67 frameworks with Ru/Rh half-sandwich units for visible-light-driven H2 evolution and CO2 reduction
Liao, Wei-Ming; Zhang, Jian-Hua; Wang, Zheng; Yin, Shao-Yun; Pan, Mei; Wang, Hai-Ping; Su, Cheng-Yong; Journal of Materials Chemistry A 6 (2018) 11337–; doi:10.1039/C8TA02962H

data_7237144
_publ_section_title
;
 Post-synthetic exchange (PSE) of UiO-67 frameworks with Ru/Rh
 half-sandwich units for visible-light-driven H2 evolution and CO2
 reduction
;
_journal_issue                   24
_journal_name_full               'Journal of Materials Chemistry A'
_journal_page_first              11337
_journal_paper_doi               10.1039/C8TA02962H
_journal_volume                  6
_journal_year                    2018
_chemical_formula_moiety         '2(C22 H25 N2 O5 Rh), 4(N O3), 3(H2 O)'
_chemical_formula_sum            'C44 H56 N8 O25 Rh2'
_chemical_formula_weight         1302.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_audit_update_record
;
2018-03-21 deposited with the CCDC.
2018-05-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.4400(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.18960(10)
_cell_length_b                   20.1788(2)
_cell_length_c                   15.8594(2)
_cell_measurement_reflns_used    18704
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      65.4670
_cell_measurement_theta_min      3.5210
_cell_volume                     2620.79(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6525
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_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    -82.00  39.00   1.00    1.00    --  -41.14  19.00-180.00  121
  2  \w    101.00 159.00   1.00    1.00    --   89.96 100.00  33.00   58
  3  \w    135.00 161.00   1.00    1.00    --   89.96 125.00  90.00   26
  4  \w     15.00 100.00   1.00    1.00    --   89.96 -77.00 150.00   85
  5  \w     17.00  88.00   1.00    1.00    --   89.96 -45.00  30.00   71
  6  \w     -4.00  27.00   1.00    1.00    --   34.00  91.00 -43.38   31
  7  \w    -49.00 -17.00   1.00    1.00    --  -41.33 -38.00-180.00   32
  8  \w   -110.00 -14.00   1.00    1.00    --  -41.33 -57.00 150.00   96
  9  \w    -66.00  32.00   1.00    1.00    --  -41.33  38.00 -30.00   98
 10  \w   -110.00 -22.00   1.00    1.00    --  -41.33 -38.00   0.00   88
 11  \w     45.00  90.00   1.00    1.00    --   41.33-125.00 150.00   45
 12  \w     11.00  36.00   1.00    1.00    --   46.00  84.00-147.69   25
 13  \w     11.00  37.00   1.00    1.00    --   46.00  84.00  39.17   26
 14  \w     16.00  44.00   1.00    1.00    --   50.00  82.00 153.93   28
 15  \w     21.00  46.00   1.00    1.00    --   54.00  79.00  79.35   25
 16  \w     20.00  46.00   1.00    1.00    --   54.00  81.00  -0.44   26
 17  \w     20.00  45.00   1.00    1.00    --   54.00  81.00 -54.73   25
 18  \w     21.00  47.00   1.00    1.00    --   54.00  79.00 148.33   26
 19  \w     20.00  45.00   1.00    1.00    --   54.00  81.00-109.32   25
 20  \w     33.00  64.00   1.00    1.00    --   66.00  77.00-159.09   31
 21  \w     35.00  61.00   1.00    1.00    --   66.00  74.00 -61.58   26
 22  \w     35.00  63.00   1.00    1.00    --   66.00  76.00  84.18   28
 23  \w     38.00  63.00   1.00    1.00    --   70.00  76.00 -30.24   25
 24  \w     38.00  64.00   1.00    1.00    --   70.00  74.00  13.07   26
 25  \w    119.00 145.00   1.00    1.00    --   70.00  76.00 141.13   26
 26  \w     39.00  65.00   1.00    1.00    --   70.00  75.00 -91.33   26
 27  \w     38.00  68.00   1.00    1.00    --   70.00  76.00 141.13   30
 28  \w     38.00  64.00   1.00    1.00    --   70.00  76.00  52.30   26
 29  \w     58.00  86.00   1.00    1.00    --   89.96  77.00 -60.00   28
 30  \w     95.00 124.00   1.00    1.00    --   89.96  77.00-150.00   29
 31  \w     57.00  83.00   1.00    1.00    --   89.96  77.00-150.00   26
 32  \w     90.00 165.00   1.00    1.00    --   89.96  77.00 -30.00   75
 33  \w     91.00 160.00   1.00    1.00    --   89.96  77.00 120.00   69
 34  \w     61.00  87.00   1.00    1.00    --   89.96  77.00 120.00   26
 35  \w     57.00  83.00   1.00    1.00    --   89.96  77.00 -30.00   26
 36  \w     27.00  95.00   1.00    1.00    --   89.96-125.00  60.00   68
 37  \w     69.00 118.00   1.00    1.00    --   89.96-125.00 120.00   49
 38  \w     49.00 105.00   1.00    1.00    --   89.96-125.00 -30.00   56
 39  \w     95.00 146.00   1.00    1.00    --   89.96  77.00 -90.00   51
 40  \w     59.00  69.00   1.00    1.00    --   89.96  77.00  60.00   10
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1680363000
_diffrn_orient_matrix_UB_12      0.0011780000
_diffrn_orient_matrix_UB_13      0.0442797000
_diffrn_orient_matrix_UB_21      -0.0595981000
_diffrn_orient_matrix_UB_22      0.0557673000
_diffrn_orient_matrix_UB_23      0.0585606000
_diffrn_orient_matrix_UB_31      -0.0599254000
_diffrn_orient_matrix_UB_32      -0.0521384000
_diffrn_orient_matrix_UB_33      0.0636155000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0521
_diffrn_reflns_av_unetI/netI     0.0435
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            26877
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        65.399
_diffrn_reflns_theta_max         65.399
_diffrn_reflns_theta_min         3.545
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.920
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.651
_exptl_crystal_description       block
_exptl_crystal_F_000             1332
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.419
_refine_diff_density_min         -0.774
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.374(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     742
_refine_ls_number_reflns         8559
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0315
_refine_ls_R_factor_gt           0.0308
_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^)+(0.0470P)^2^+0.5320P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0762
_refine_ls_wR_factor_ref         0.0770
_reflns_Friedel_coverage         0.940
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                8406
_reflns_number_total             8559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ta02962h2.cif
_cod_data_source_block           H2RhOH2
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               7237144
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.626(7) 0.374(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
3.a Free rotating group:
 O003(H00C,H00D), O009(H00F,H00G), O00E(H00A,H00B), O00Q(H00H,H00I), O00T(H00J,
 H00K)
3.b Aromatic/amide H refined with riding coordinates:
 C00V(H00V), C00X(H00X), C00Z(H00Z), C015(H015), C01B(H01B), C01C(H01C),
 C01D(H01D), C01O(H01O), C01P(H01P), C01V(H01V), C01X(H01X), C023(H023)
3.c Idealised Me refined as rotating group:
 C01L(H01G,H01H,H01I), C01M(H01A,H01E,H01F), C01Q(H01J,H01K,H01L), C01Y(H01M,
 H01N,H01Q), C020(H02M,H02N,H02O), C021(H02P,H02Q,H02R), C024(H02A,H02B,H02C),
 C025(H02D,H02E,H02F), C026(H02G,H02H,H02I), C027(H02J,H02K,H02L)
3.d Idealised tetrahedral OH refined as rotating group:
 O005(H005), O006(H006), O00B(H00E), O00N(H00N)
;
_shelx_shelxl_version_number     2014/7
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.678
_oxdiff_exptl_absorpt_empirical_full_min 0.632