Reactivity and stability synergism directed by the electron transfer between polyoxometalates and metal–organic frameworks
Lu, Xinlin; Cheng, Ting; Geletii, Yurii V.; Bacsa, John; Hill, Craig L.; Catalysis Science & Technology 13 (2023) 5094–5103; doi:10.1039/D3CY00569K

data_1569617
_publ_section_title
;
 Reactivity and stability synergism directed by the electron transfer
 between polyoxometalates and metal--organic frameworks
;
_journal_issue                   17
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              5094
_journal_page_last               5103
_journal_paper_doi               10.1039/D3CY00569K
_journal_volume                  13
_journal_year                    2023
_chemical_absolute_configuration unk
_chemical_formula_moiety
'Mo10 O40 P V2, C72 H48 Cu12 O60, 5(C4 H12 N), 16(O)'
_chemical_formula_sum            'C92 H108 Cu12 Mo10 N5 O116 P V2'
_chemical_formula_weight         4994.56
_space_group_crystal_system      cubic
_space_group_IT_number           196
_space_group_name_Hall           'F 2 2 3'
_space_group_name_H-M_alt        'F 2 3'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-15
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-04-15 deposited with the CCDC.	2023-07-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.2487(4)
_cell_length_b                   26.2487(4)
_cell_length_c                   26.2487(4)
_cell_measurement_reflns_used    2078
_cell_measurement_temperature    106(9)
_cell_measurement_theta_max      74.4830
_cell_measurement_theta_min      3.3820
_cell_volume                     18085.2(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.74a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.74a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.74a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      106(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.934
_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   -160.00 -76.00   0.50   27.29    --  -88.50 -91.00-127.00  168
  2  \w   -119.00 -70.00   0.50    6.82    --  -47.12-125.00-180.00   98
  3  \w   -119.00 -72.00   0.50    6.82    --  -47.12-125.00-120.00   94
  4  \w     35.00  81.00   0.50   27.29    --  105.44 -61.00-150.00   92
  5  \w    114.00 160.00   0.50   27.29    --  107.31  99.00 176.00   92
  6  \w    -98.00 -71.00   0.50    6.82    --  -47.12-125.00-120.00   54
  7  \w    -82.00 -54.00   0.50   27.29    --  -88.50  45.00-180.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0307655000
_diffrn_orient_matrix_UB_12      0.0495461000
_diffrn_orient_matrix_UB_13      -0.0065819000
_diffrn_orient_matrix_UB_21      0.0462720000
_diffrn_orient_matrix_UB_22      0.0252635000
_diffrn_orient_matrix_UB_23      -0.0259297000
_diffrn_orient_matrix_UB_31      -0.0190582000
_diffrn_orient_matrix_UB_32      -0.0186215000
_diffrn_orient_matrix_UB_33      -0.0522360000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0268
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.934
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            10093
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.903
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.486
_diffrn_reflns_theta_min         2.916
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.780
_exptl_absorpt_correction_T_max  0.740
_exptl_absorpt_correction_T_min  0.459
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.74a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.834
_exptl_crystal_description       prism
_exptl_crystal_F_000             9808
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.817
_refine_diff_density_min         -0.753
_refine_diff_density_rms         0.133
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.49(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     179
_refine_ls_number_reflns         2902
_refine_ls_number_restraints     182
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0552
_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^)+(0.1151P)^2^+40.7463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1605
_refine_ls_wR_factor_ref         0.1682
_reflns_Friedel_coverage         0.811
_reflns_Friedel_fraction_full    0.970
_reflns_Friedel_fraction_max     0.868
_reflns_number_gt                2461
_reflns_number_total             2902
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy00569k2.cif
_cod_data_source_block           mof199-pmo10v2_chiral
_cod_depositor_comments          'Adding full bibliography for 1569617.cif.'
_cod_original_cell_volume        18085.2(8)
_cod_database_code               1569617
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C288  H192  Cu48  Mo48  O416  P4  '
_shelx_estimated_absorpt_t_max   0.578
_shelx_estimated_absorpt_t_min   0.373
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.51(4)
 0.49(4)
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,H) groups
3. Restrained distances
 O1W-H1WA = O1W-H1WB
 0.955 with sigma of 0.001
 N1_1-C1_1 = N1_1-C3_1 = N1_1-C2_1 = N1_1-C4_1
 1.5 with sigma of 0.01
 C5-C4 \\sim C2-C1
 with sigma of 0.002
 O1-C5 \\sim O10-C2
 with sigma of 0.002
 C3-C2 \\sim C6-C5
 with sigma of 0.002
 O4-C1 \\sim O2-C4
 with sigma of 0.002
 O10-C1 \\sim O1-C4
 with sigma of 0.002
 N1_1-C1_1 \\sim N1_1-C2_1 \\sim N1_1-C3_1 \\sim N1_1-C4_1
 with sigma of 0.02
 N1_1-C1_1 \\sim N1_1-C4_1 \\sim N1_1-C3_1 \\sim N1_1-C2_1
 with sigma of 0.002
 C3_1-C2_1 \\sim C4_1-C2_1 \\sim C2_1-C1_1 \\sim C4_1-C3_1 \\sim C3_1-C1_1
\\sim C4_1-C1_1
 with sigma of 0.002
 C1_1-C3_1 \\sim C1_1-C2_1 \\sim C1_1-C4_1 \\sim C2_1-C3_1 \\sim C2_1-C4_1
\\sim C3_1-C4_1
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1A
Uanis(Mo1) \\sim Ueq, Uanis(V1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1_1) \\sim Ueq, Uanis(N1_1) \\sim Ueq, Uanis(C4_1) \\sim Ueq, Uanis(O2W)
\\sim Ueq, Uanis(O3W) \\sim Ueq: with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(Mo1) = Uanis(V1)
Uanis(C2) = Uanis(C5)
Uanis(C4) = Uanis(C1)
Uanis(C6) = Uanis(C3)
Uanis(O2W) = Uanis(C4_1)
Uanis(C3_1) = Uanis(C2_1) = Uanis(C1_1) = Uanis(C4_1)
5. Rigid body (RIGU) restrains
 O10, C1, O4, C2, C3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C1, C2, C3, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, C4, O2, C5, C6
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N1T, C1T
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N1_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4_1, N1_1, C1_1, C2_1, C3_1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
6. Others
 Fixed Sof: Mo1(0.833333) V1(0.166667) H1TA(0.333333) H1TB(0.333333)
 H1TC(0.333333) O3W(0.666667) O2W(0.666667) N1(0.333333) C1(0.333333)
 H1A(0.333333) H1B(0.333333) H1C(0.333333) C2(0.333333) H2A(0.333333)
 H2B(0.333333) H2C(0.333333) C3(0.333333) H3A(0.333333) H3B(0.333333)
 H3C(0.333333) C4(0.333333) H4A(0.333333) H4B(0.333333) H4C(0.333333)
 Fixed X: H1WA(0.385921) H1WB(0.387409)
 Fixed Y: H1WA(0.61461) H1WB(0.613111)
 Fixed Z: H1WA(0.274639) H1WB(0.21715)
7.a Me refined with riding coordinates:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6)
7.c Idealised Me refined as rotating group:
 C1T(H1TA,H1TB,H1TC)
;
_shelx_res_checksum              41481
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone'
_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 1.467
_oxdiff_exptl_absorpt_empirical_full_min 0.770