Synthesis and sulfide oxidation catalytic activity of a copper monosubstituted Keggin-type polyoxometalate-based supramolecular compound
Zhang, Yixuan; Zhu, Maochun; Liu, Yifei; Bai, Xue; Zhang, Ange; Yang, Yanli; Li, Bin; Liu, Shuxia; New Journal of Chemistry 49 (2025) 4191–4197; doi:10.1039/D4NJ05286B

data_7063646
_publ_section_title
;
 Synthesis and sulfide oxidation catalytic activity of a copper
 monosubstituted Keggin-type polyoxometalate-based supramolecular compound
;
_journal_issue                   10
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              4191
_journal_page_last               4197
_journal_paper_doi               10.1039/D4NJ05286B
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety
'3(Cu0.996 O40.006 P W11.004), C48 H32 Cu2.996 N8 O40 P W11.004, 2(C24 H18 Cu N4 O), 2(C24 H16 Cu N4), 4(H2 O)'
_chemical_formula_sum            'C144 H108 Cu9.98 N24 O166 P4 W44.02'
_chemical_formula_weight         13681.62
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-07-24
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2024-11-03 deposited with the CCDC.	2025-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                94.292(5)
_cell_angle_beta                 96.418(5)
_cell_angle_gamma                98.299(5)
_cell_formula_units_Z            1
_cell_length_a                   11.7259(6)
_cell_length_b                   22.3057(12)
_cell_length_c                   23.4333(13)
_cell_measurement_reflns_used    6293
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.7110
_cell_measurement_theta_min      3.6980
_cell_volume                     6001.0(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_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_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2375
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.961
_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    -51.00  36.00   1.00   20.90    --   10.78 -71.00  25.00   87
  2  \w    -14.00  83.00   1.00   20.90    --   10.78  71.00 155.00   97
  3  \w    -42.00  37.00   1.00   20.90    --   -9.60  77.00 -90.00   79
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0509555000
_diffrn_orient_matrix_UB_12      0.0137060000
_diffrn_orient_matrix_UB_13      -0.0000452000
_diffrn_orient_matrix_UB_21      0.0259862000
_diffrn_orient_matrix_UB_22      0.0195116000
_diffrn_orient_matrix_UB_23      0.0247516000
_diffrn_orient_matrix_UB_31      0.0228849000
_diffrn_orient_matrix_UB_32      0.0217498000
_diffrn_orient_matrix_UB_33      -0.0179768000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0730
_diffrn_reflns_av_unetI/netI     0.1405
_diffrn_reflns_Laue_measured_fraction_full 0.961
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            36977
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         3.338
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    21.994
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57417
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    3.786
_exptl_crystal_description       block
_exptl_crystal_F_000             6075
_refine_diff_density_max         2.401
_refine_diff_density_min         -1.815
_refine_diff_density_rms         0.344
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.900
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1794
_refine_ls_number_reflns         20284
_refine_ls_number_restraints     2403
_refine_ls_restrained_S_all      2.727
_refine_ls_R_factor_all          0.1075
_refine_ls_R_factor_gt           0.0551
_refine_ls_shift/su_max          0.079
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     'w=1/[\s^2^(Fo^2^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0794
_refine_ls_wR_factor_ref         0.1011
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12419
_reflns_number_total             20284
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj05286b2.cif
_cod_data_source_block           20230531-3ml_auto
_cod_depositor_comments          'Adding full bibliography for 7063646.cif.'
_cod_database_code               7063646
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.46
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Shared sites
{Cu1A, W1}
{Cu2A, W2}
{Cu3A, W3}
{Cu4, W4}
{Cu5, W5}
{Cu6, W6}
{Cu7, W7}
{Cu8, W8}
{Cu9, W9}
{Cu10, W10}
{Cu11, W11}
{Cu12, W12}
{Cu13, W13}
{Cu14, W14}
{Cu15, W15}
{Cu16, W16}
{Cu17, W17}
{Cu18, W18}
{Cu19, W19}
{Cu20, W20}
{Cu21, W21}
{Cu22, W22}
{Cu23, W23}
{Cu24, W24}
2. Restrained distances
 O28-N8_$1
 3.2 with sigma of 0.002
 C68-C61 = C64-C61
 1.414 with sigma of 0.0001
 C75-C4 = C75-C54 = C7-C54 = C7-C6 = C9-C7 = C9-C78 = C78-C10 = C8-C10 = C8-C6
 = C76-C10 = C76-C72 = C72-C65 = N1-C65 = N1-C8 = N2-C6 = N2-C4 = N12-C1 = N12-
 C68 = C68-C61 = C64-C61 = C64-C43 = C43-C1 = C55-C43 = C60-C55 = C60-C59 = C59-
 C21 = C21-C1 = Cu2A-O41 = C59-C38 = C53-C38 = C53-C34 = N11-C34 = N11-C21 = N4-
 C77 = N4-C66 = C66-C28 = C58-C28 = C58-C50 = C77-C50 = C62-C28 = C62-C56 = C56-
 C36 = C80-C36 = C80-C66 = C36-C33 = C67-C33 = C67-C57 = N3-C57 = N3-C80 = N9-
 C23 = C31-C23 = C31-C25 = C27-C25 = C35-C27 = N9-C35 = C41-C35 = C73-C41 = C73-
 C46 = C51-C46 = C51-C27 = C73-C2 = C3-C2 = C40-C3 = N10-C40 = C18-C15 = C47-
 C18 = C47-C32 = C32-C22 = C37-C22 = C37-C15 = N5-C15 = N5-C17 = C63-C17 = C63-
 C16 = C18-C16 = N6-C37 = N6-C45 = C45-C24 = C26-C24 = C26-C22 = N7-C49 = C71-
 C49 = C71-C52 = C70-C52 = C70-C30 = N7-C30 = C70-C69 = C69-C14 = C14-C13 = C13-
 C12 = C30-C12 = N8-C12 = C19-C13 = C20-C19 = C48-C20 = N8-C48
 1.4 with sigma of 0.0001
3. Restrained planarity
 C12, C13, C19, C20, C48, N8
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C2 \\sim C3: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C61 \\sim C68: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(O50) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O88) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C21) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C47) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(W24) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O3) \\sim Ueq, Uanis(C32) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C8) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(N2) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O59) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O15) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O89) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cu1A) = Uanis(W1)
Uanis(Cu2A) = Uanis(W2)
Uanis(Cu3A) = Uanis(W3)
Uanis(Cu4) = Uanis(W4)
Uanis(Cu5) = Uanis(W5)
Uanis(Cu6) = Uanis(W6)
Uanis(Cu7) = Uanis(W7)
Uanis(Cu8) = Uanis(W8)
Uanis(Cu9) = Uanis(W9)
Uanis(Cu10) = Uanis(W10)
Uanis(Cu11) = Uanis(W11)
Uanis(Cu12) = Uanis(W12)
Uanis(Cu13) = Uanis(W13)
Uanis(Cu14) = Uanis(W14)
Uanis(Cu15) = Uanis(W15)
Uanis(Cu16) = Uanis(W16)
Uanis(Cu17) = Uanis(W17)
Uanis(Cu18) = Uanis(W18)
Uanis(Cu19) = Uanis(W19)
Uanis(Cu20) = Uanis(W20)
Uanis(Cu21) = Uanis(W21)
Uanis(Cu22) = Uanis(W22)
Uanis(Cu23) = Uanis(W23)
Uanis(Cu24) = Uanis(W24)
5. Rigid body (RIGU) restrains
 W1, O83, O21, O27, O33, O40, O56, W12, W2, W7, W4, P3, O41, O5, O84, O48, O13,
  O34, O31, O1, O22, O25, O29, O2, O26, O49, O52, O53, W19, W8, W5, W9, O36,
 W10, W11, W6, O32, O58, O19, O18, O37, O85, O30, O47, O20, O24, O16, O4, O28,
 O46, O51, C38, O45, C59, H38, C53, C21, C60, C34, H53, N11, C1, H60, C55, Cu1,
 N12, C43, H55, N10, N9, C68, C64, C40, C41, C23, C35, H68, C61, H64, C73, C31,
 H23, C27, H61, C46, C25, H31, C51, H46, H25, H51
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O12, W3, O35, O7, O9, O75, W15, W14, W20, W17, O72, O38, O76, O77, O80, O14,
 O8, O81, O6, O23, O10, O60, N5, O11, O74, P2, W18, Cu3, C15, C17, O82, O17,
 O73, N6, O43, N8, N7, C18, C37, H17, C63, C45, W13, C12, C48, C30, C49, C16,
 C47, C22, H63, C24, H45, O44, O57, O88, O69, O42, O39, C13, H48, C20, C70, H49,
  C71, H16, C32, H47, C26, H24, P1, O71, O78, W16, W22, C19, C14, H20, C69, C52,
  H71, H32, O79, O63, O64, O65, O70, O61, O54, O62, H19, H14, H69, H52, W24,
 W23, W21, O68, O66, O55, O59
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C28, C58, C62, C66, C50, H58, C56, H62, N4, C80, H50, C77, C36, H56, Cu2, N3,
 H77, C33, N2, O3, N1, C57, H33, C67, C4, C6, C8, C65, H57, H67, H4, C75, C7,
 C10, C72, H65, C54, H75, C9, C78, C76, H72, H54, H9, H78, H76
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 1*[Sof(O88)]+1*[Sof(O50)]=1 with esd of 0.0001
 1*[Sof(O41)]+1*[Sof(O89)]=1 with esd of 0.01
 Fixed Sof: W1(0.917) Cu1A(0.083) W2(0.917) Cu2A(0.083) W3(0.917) Cu3A(0.083)
 W4(0.917) Cu4(0.083) W5(0.917) Cu5(0.083) W6(0.917) Cu6(0.083) W7(0.917)
 Cu7(0.083) W8(0.917) Cu8(0.083) W9(0.917) Cu9(0.083) W10(0.917) Cu10(0.083)
 W11(0.917) Cu11(0.083) W12(0.917) Cu12(0.083) W13(0.917) Cu13(0.083)
 W14(0.917) Cu14(0.083) W15(0.917) Cu15(0.083) W16(0.917) Cu16(0.083)
 W17(0.917) Cu17(0.083) W18(0.917) Cu18(0.083) W19(0.917) Cu19(0.083)
 W20(0.917) Cu20(0.083) W21(0.917) Cu21(0.083) W22(0.917) Cu22(0.083)
 W23(0.917) Cu23(0.083) W24(0.917) Cu24(0.083) O57(0.5) O71(0.5) O72(0.5)
 O42(0.5) O81(0.5) O80(0.5) O82(0.5) O78(0.5)
7.a Riding coordinates:
 O87(H87A,H87B)
7.b Free rotating group:
 O67(H67A,H67B)
7.c Rotating group:
 O3(H3A,H3B)
7.d Aromatic/amide H refined with riding coordinates:
 C33(H33), C50(H50), C56(H56), C58(H58), C62(H62), C60(H60), C55(H55),
 C57(H57), C67(H67), C77(H77), C4(H4), C54(H54), C9(H9), C75(H75), C78(H78),
 C69(H69), C14(H14), C49(H49), C71(H71), C16(H16), C17(H17), C63(H63), C32(H32),
  C47(H47), C26(H26), C24(H24), C45(H45), C40(H40), C3(H3), C2(H2), C25(H25),
 C31(H31), C23(H23), C46(H46), C51(H51), C19(H19), C48(H48), C52(H52), C68(H68),
  C20(H20), C34(H34), C38(H38), C53(H53), C61(H61), C64(H64), C76(H76),
 C72(H72), C65(H65)
7.e Fitted hexagon refined as free rotating group:
 C12(C30,C70,C69,C14,C13), N10(C40,C3,C2,C73,C41), N1(C8,C10,C76,C72,C65)
;
_shelx_res_checksum              58151
_shelx_hkl_checksum              26278
_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 1.766
_oxdiff_exptl_absorpt_empirical_full_min 0.715