The stepwise construction of polyoxovanadate-based Zn-MOF nanoparticles with Lewis acid sites for the one-pot synthesis of N-heterocycles in air
Zhu, Maochun; Bai, Xue; Yang, Yanli; Zhang, Ange; Wang, Siyue; Sun, Chengyu; Lu, Ying; Li, Bin; Liu, Shuxia; Green Chemistry  (2025) –; doi:10.1039/D5GC04571A

data_7251299
_publ_section_title
;
 The stepwise construction of polyoxovanadate-based Zn-MOF nanoparticles
 with Lewis acid sites for the one-pot synthesis of N-heterocycles in air
;
_journal_name_full               'Green Chemistry'
_journal_paper_doi               10.1039/D5GC04571A
_journal_year                    2025
_chemical_formula_moiety         'C80 H64 N32 O24 V8 Zn4, 1.375[H2O]'
_chemical_formula_sum            'C80 H64 N32 O24 V8 Zn4'
_chemical_formula_weight         2526.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-12-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2024-12-10 deposited with the CCDC.	2025-11-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.43(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.10(2)
_cell_length_b                   18.388(17)
_cell_length_c                   13.743(15)
_cell_measurement_reflns_used    2132
_cell_measurement_temperature    268.76
_cell_measurement_theta_max      22.773
_cell_measurement_theta_min      3.333
_cell_volume                     4827(9)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      268.76
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1630
_diffrn_reflns_av_unetI/netI     0.1936
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21914
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.114
_diffrn_reflns_theta_max         25.114
_diffrn_reflns_theta_min         2.588
_diffrn_source_current           0.9
_diffrn_source_power             0.0405
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    1.799
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6096
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
 SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.738
_exptl_crystal_description       block
_exptl_crystal_F_000             2528
_refine_diff_density_max         1.261
_refine_diff_density_min         -0.583
_refine_diff_density_rms         0.150
_refine_ls_abs_structure_details
;
 Flack x determined using 1601 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.044(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     668
_refine_ls_number_reflns         8391
_refine_ls_number_restraints     667
_refine_ls_restrained_S_all      5.029
_refine_ls_R_factor_all          0.1457
_refine_ls_R_factor_gt           0.0767
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0762P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1494
_refine_ls_wR_factor_ref         0.1749
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    0.958
_reflns_Friedel_fraction_max     0.958
_reflns_number_gt                5100
_reflns_number_total             8391
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc04571a3.cif
_cod_data_source_block           1
_cod_database_code               7251299
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 N4-C9 = N4-C8 = C10-C9 = C10-C6 = C7-C6 = C7-C8 = C4-C5 = C5-C3 = C2-C3 = N1-
 C2 = C1-C4 = N1-C1 = N5-C15 = C14-C15 = C14-C13 = C12-C13 = C11-C12 = N5-C11 =
 N13-C31 = N13-C35 = C34-C35 = C34-C33 = C33-C32 = C32-C31 = C40-C36 = C37-C36 =
  C37-C38 = N16-C38 = N16-C39 = C40-C39 = C20-C19 = N7-C20 = N7-C16 = C16-C17 =
 C17-C18 = C19-C18 = N9-C21 = N9-C25 = C24-C25 = C24-C23 = C23-C22 = C21-C22 =
 C26-C30 = C30-C29 = C29-C28 = N12-C28 = N12-C27 = C26-C27
 1.41 with sigma of 0.00001
 C9-N4 = C9-H9 = C9-C10
 1.4 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Zn2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N16) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C16) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C8) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C20) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N12) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C3, Zn2, O8, N9, N7, V3, C21, C25, C20, C16, O7, O9, O10, C22, C24, C19, C17,
 V1, V4, C23, C18, O1, O2, O3, O12, O13, O11, N10, N8, Zn1, V2, N11, N13, N1,
 N5, O5, O6, O4, C30, C31, C35, C2, C1, C11, C15, C29, C26, C32, C34, C4, C12,
 C14, C28, C27, C33, C5, C13, N12, N14, N2, N6, N15, N3, C36, C40, C6, C37, C39,
  C10, C7, C38, N16, C9, C8, N4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5.a Aromatic/amide H refined with riding coordinates:
 C28(H28), C9(H9), C3(H3), C29(H29), C22(H22), C10(H10), C27(H27), C8(H8),
 C2(H2), C21(H21), C38(H38), C25(H25), C31(H31), C39(H39), C37(H37), C26(H26),
 C7(H7), C32(H32), C35(H35), C4(H4), C12(H12), C24(H24), C11(H11), C40(H40),
 C1(H1), C19(H19), C15(H15), C20(H20), C17(H17), C34(H34), C16(H16), C14(H14)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              20816
_shelx_fab_checksum              96750
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'