Impact of POM's coordination mode and Mo-hybrid constituents on the binding, stability, and catalytic properties of hybrid (pre)catalysts
Pisk, Jana; Vrdoljak, Višnja; Mandarić, Mirna; Hrenar, Tomica; Agustin, Dominique; Rubčić, Mirta; RSC Advances 14 (2024) 19029–19040; doi:10.1039/D4RA03563A

data_7248866
_publ_section_title
;
 Impact of POM's coordination mode and Mo-hybrid constituents on the
 binding, stability, and catalytic properties of hybrid (pre)catalysts
;
_journal_issue                   27
_journal_name_full               'RSC Advances'
_journal_page_first              19029
_journal_page_last               19040
_journal_paper_doi               10.1039/D4RA03563A
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety
'C28 H25 Mo10 N6 O36, C14 H12 Mo N3 O5, C2 N, C2 H3 N, H2 O'
_chemical_formula_sum            'C46 H42 Mo11 N11 O42'
_chemical_formula_weight         2476.24
_chemical_name_systematic
'[(?2-oxo)[4-methoxy-2-oxidophenyl)methylidene]pyridin-1-ium-4-carbohydrazone-O,O',N)oxomolybdenum(VI)] {bis-[(?2-oxo)((4-methoxy-2-oxidophenyl)methylidene)pyridin-1-ium-4-carbohydrazidato-O,O',N)oxomolybdenum(VI)] dodecakis(?-oxido)-tetradecaoxooctamolybdenum(VI)}'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-02-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-27 deposited with the CCDC.	2024-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                88.5840(10)
_cell_angle_beta                 84.1140(10)
_cell_angle_gamma                88.5150(10)
_cell_formula_units_Z            2
_cell_length_a                   10.83910(10)
_cell_length_b                   17.04750(10)
_cell_length_c                   18.70750(10)
_cell_measurement_reflns_used    62611
_cell_measurement_temperature    170.15
_cell_measurement_theta_max      79.1970
_cell_measurement_theta_min      3.4700
_cell_volume                     3436.54(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.92a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.92a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.92a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0499
_diffrn_reflns_av_unetI/netI     0.0242
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            136522
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.395
_diffrn_reflns_theta_min         3.478
_diffrn_source                   'micro-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    16.844
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39513
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.92a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.393
_exptl_crystal_description       plate
_exptl_crystal_F_000             2386
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.083
_exptl_crystal_size_min          0.073
_refine_diff_density_max         1.508
_refine_diff_density_min         -1.809
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1024
_refine_ls_number_reflns         14751
_refine_ls_number_restraints     58
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0524P)^2^+16.9348P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1058
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13529
_reflns_number_total             14751
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra03563a2.cif
_cod_data_source_block           2O-CH3CN-H2O
_cod_database_code               7248866
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.373
_shelx_estimated_absorpt_t_min   0.231
_olex2_refinement_description
;
1. Restrained distances
 N10A-C44A
 1.14 with sigma of 0.02
 C44A-N10A
 1.137 with sigma of 0.01
 C44A-C43
 1.456 with sigma of 0.01
 C43-N10A
 2.593 with sigma of 0.02
 C46B-N11B
 1.137 with sigma of 0.01
 N11B-C46B
 1.14 with sigma of 0.02
 C46B-C45B
 1.456 with sigma of 0.01
 C45B-N11B
 2.593 with sigma of 0.02
 N10A-C43
 2.59 with sigma of 0.04
 N11B-C45B
 2.59 with sigma of 0.04
 N10A-C44A \\sim N10B-C44B
 with sigma of 0.02
 N10A-C43 \\sim N10B-C43
 with sigma of 0.04
 C44A-C43 \\sim C44B-C43
 with sigma of 0.02
 N11B-C46B \\sim N11A-C46A
 with sigma of 0.02
 N11B-C45B \\sim N11A-C45A
 with sigma of 0.04
 C46B-C45B \\sim C46A-C45A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
N10A \\sim C44A \\sim C43: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N11B \\sim C46B \\sim C45B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C43) = Uanis(C44B) = Uanis(N10B)
Uanis(C46B) = Uanis(C45B) = Uanis(N11B)
Uanis(C46B) = Uanis(C46A) = Uanis(C45A) = Uanis(N11A)
3. Rigid body (RIGU) restrains
 N10A, C44A, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N11B, C46B, C45B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C14B)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(O5A)=1-FVAR(1)
 Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(O5B)=FVAR(1)
 Sof(C44B)=Sof(N10B)=1-FVAR(2)
 Sof(N10A)=Sof(C44A)=FVAR(2)
 Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C46A)=Sof(N11A)=1-FVAR(3)
 Sof(N11B)=Sof(C46B)=Sof(C45B)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(3)
5.a Free rotating group:
 O42(H42D,H42E)
5.b Aromatic/amide H refined with riding coordinates:
 N9(H9), N6(H6), N2(H2), N3(H3), C38(H38), C27(H27), C35(H35), C24(H24),
 C26(H26), C34(H34), C39(H39), C21(H21), C13(H13), C33(H33), C11(H11), C10(H10),
  C31(H31), C17(H17), C25(H25), C12(H12), C41(H41), C40(H40), C19(H19), C7(H7),
 C20(H20), C6(H6A), C5(H5), C3(H3A)
5.c Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C28(H28A,H28B,H28C), C14A(H14A,H14B,H14C), C14B(H14D,
 H14E,H14F), C45B(H45A,H45B,H45C), C45A(H45D,H45E,H45F)
;
_shelx_res_checksum              44300
_shelx_hkl_checksum              12031
_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 3.231
_oxdiff_exptl_absorpt_empirical_full_min 0.597