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_7251300
_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 O28 V8 Zn8, H2 O'
_chemical_formula_sum            'C80 H66 N32 O29 V8 Zn8'
_chemical_formula_weight         2870.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           41
_space_group_name_Hall           'A 2 -2ab'
_space_group_name_H-M_alt        'A e a 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-10-24
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_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
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.1731(10)
_cell_length_b                   20.1804(12)
_cell_length_c                   27.4319(16)
_cell_measurement_reflns_used    9875
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.042
_cell_measurement_theta_min      2.506
_cell_volume                     11167.6(11)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  bruker
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0647
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            50273
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.050
_diffrn_reflns_theta_max         25.050
_diffrn_reflns_theta_min         2.018
_diffrn_source_current           0.9
_diffrn_source_power             0.0405
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    2.400
_exptl_absorpt_correction_T_max  0.7174
_exptl_absorpt_correction_T_min  0.6500
_exptl_absorpt_correction_type   multi-scan
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.707
_exptl_crystal_description       block
_exptl_crystal_F_000             5704
_refine_diff_density_max         1.327
_refine_diff_density_min         -0.737
_refine_diff_density_rms         0.225
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.50(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     884
_refine_ls_number_reflns         9798
_refine_ls_number_restraints     368
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0772
_refine_ls_R_factor_gt           0.0674
_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^)+(0.1003P)^2^+31.8365P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1650
_refine_ls_wR_factor_ref         0.1719
_reflns_Friedel_coverage         0.950
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                8600
_reflns_number_total             9798
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc04571a3.cif
_cod_data_source_block           2
_cod_original_sg_symbol_Hall     'A 2 -2ac'
_cod_database_code               7251300
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.50(3)
 0.50(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
3. Restrained distances
 N5-C15A \\sim N5-C15B
 with sigma of 0.02
 C22A-C21A \\sim C22A-C23A \\sim C24A-C23A \\sim C25A-C24A
 with sigma of 0.02
 C12A-C11A \\sim C13A-C12A \\sim C14A-C13A \\sim C14A-C15A
 with sigma of 0.02
 N9-C21B \\sim N9-C25B
 with sigma of 0.02
 N5-C11B \\sim N5-C11A
 with sigma of 0.02
 N9-C21A \\sim N9-C25A
 with sigma of 0.02
 C22B-C21B \\sim C22B-C23B \\sim C24B-C23B \\sim C25B-C24B
 with sigma of 0.02
 C18B-C17B \\sim C18A-C17A
 with sigma of 0.02
 N7A-C18A \\sim N7B-C18B
 with sigma of 0.02
 C18B-C19B \\sim C18A-C19A
 with sigma of 0.02
 N8B-N7B \\sim N8A-N7A
 with sigma of 0.02
 N16B-N15B \\sim N16A-N15A
 with sigma of 0.02
 N15A-C28A \\sim N15B-C28B
 with sigma of 0.02
 C12B-C11B \\sim C14B-C15B \\sim C14B-C13B \\sim C12B-C13B
 with sigma of 0.02
4. Restrained planarity
 C27A, C26A, N14, C30A, C29A, C28A
 with sigma of 0.1
 N14, C26B, C27B, C28B, C29B, C30B
 with sigma of 0.1
 N5, C12B, C11B, C15B, C14B, C13B
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
O14 \\sim O12 \\sim O13: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(O6B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13A) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N7B) \\sim Ueq, Uanis(C18B) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C24B) \\sim Ueq, Uanis(C23B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C27A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N16B) \\sim Ueq, Uanis(N15A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C28B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O13) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
6. Rigid body (RIGU) restrains
 N9, C25A, C21A, C22A, C24A, C23A, C25B, C24B, C23B, C22B, C21B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C15A, N5, C11A, C12A, C13A, C14A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 N6, C20B, C19B, C18B, C17B, C16B, C18A, C17A, C19A, C20A, C16A, N7A, N8A, N7B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 N5, C12B, C11B, C15B, C14B, C13B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
7. Others
 Fixed Sof: O6B(0.565) V2B(0.435) O5A(0.565) V2A(0.565) O5B(0.435) C20B(0.5)
 H20B(0.5) C19B(0.5) H19B(0.5) C18B(0.5) C17B(0.5) H17B(0.5) C16B(0.5)
 H16B(0.5) C21A(0.5) H21A(0.5) C22A(0.5) H22A(0.5) C23A(0.5) C24A(0.5)
 H24A(0.5) C25A(0.5) H25A(0.5) C25B(0.5) H25B(0.5) C24B(0.5) H24B(0.5)
 C23B(0.5) C22B(0.5) H22B(0.5) C21B(0.5) H21B(0.5) C26B(0.5) H26B(0.5)
 C27B(0.5) H27B(0.5) C28B(0.5) C29B(0.5) H29B(0.5) C30B(0.5) H30B(0.5)
 C28A(0.5) N15A(0.5) C27A(0.5) H27A(0.5) C26A(0.5) H26A(0.5) C30A(0.5)
 H30A(0.5) C18A(0.5) C17A(0.5) H17A(0.5) C19A(0.5) H19A(0.5) C20A(0.5)
 H20A(0.5) C16A(0.5) H16A(0.5) N7A(0.5) N8A(0.5) N7B(0.5) N8B(0.5) C29A(0.5)
 H29A(0.5) N16A(0.5) N15B(0.5) N16B(0.5) C15A(0.5) H15A(0.5) C11A(0.5)
 H11A(0.5) C12A(0.5) H12A(0.5) C13A(0.5) C14A(0.5) H14A(0.5) C12B(0.5)
 H12B(0.5) C13B(0.5) C14B(0.5) H14B(0.5) C15B(0.5) H15B(0.5) C11B(0.5)
 H11B(0.5) O6A(0.435) O15(0.5) H15C(0.5) H15D(0.5)
8.a Riding coordinates:
 O15(H15C,H15D)
8.b Aromatic/amide H refined with riding coordinates:
 C40(H40), C4(H4), C39(H39), C1(H1), C5(H5), C10(H10), C9(H9), C8(H8), C7(H7),
 C2(H2), C37(H37), C35(H35), C34(H34), C32(H32), C31(H31), C38(H38), C20B(H20B),
  C19B(H19B), C17B(H17B), C16B(H16B), C21A(H21A), C22A(H22A), C24A(H24A),
 C25A(H25A), C25B(H25B), C24B(H24B), C22B(H22B), C21B(H21B), C26B(H26B),
 C27B(H27B), C29B(H29B), C30B(H30B), C27A(H27A), C26A(H26A), C30A(H30A),
 C17A(H17A), C19A(H19A), C20A(H20A), C16A(H16A), C29A(H29A), C15A(H15A),
 C11A(H11A), C12A(H12A), C14A(H14A), C12B(H12B), C14B(H14B), C15B(H15B),
 C11B(H11B)
8.c Fitted hexagon refined as free rotating group:
 C6(C10,C9,N4,C8,C7), C35(C34,C33,C32,C31,N10), N6(C20B,C19B,C18B,C17B,C16B),
 N9(C21A,C22A,C23A,C24A,C25A), N14(C26B,C27B,C28B,C29B,C30B), C12B(C13B,C14B,
 C15B,N5,C11B)
;
_shelx_res_checksum              41203
_olex2_submission_special_instructions 'No special instructions were received'