Inorganic-organic hybrids of the phosphotungstate Keggin anion and a Schiff base cation.
Mishra, Neeraj Kumar; Panday, Rishukumar; Supriya, Sabbani; Dalton transactions (Cambridge, England : 2003) 54 (2025) 7062–7070; doi:10.1039/d4dt03480e

data_7718327
_publ_section_title
;
 Inorganic-organic hybrids of the phosphotungstate Keggin anion and a
 Schiff base cation.
;
_journal_issue                   17
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7062
_journal_page_last               7070
_journal_paper_doi               10.1039/d4dt03480e
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'O44 P W12, C3.236 H2.157 N0.36 O44.36 P W12, 2(C9 H18 N O), 3.64(C9 H15 N O)'
_chemical_formula_sum            'C54 H108 N6 O94 P2 W24'
_chemical_formula_weight         6819.80
_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   geom
_audit_creation_date             2025-02-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-25 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                88.234(4)
_cell_angle_beta                 88.248(4)
_cell_angle_gamma                76.672(4)
_cell_formula_units_Z            1
_cell_length_a                   13.8413(17)
_cell_length_b                   13.8866(17)
_cell_length_c                   15.6107(15)
_cell_measurement_reflns_used    9778
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.27
_cell_measurement_theta_min      2.28
_cell_volume                     2917.5(6)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0948
_diffrn_reflns_av_unetI/netI     0.0750
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            79588
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.432
_diffrn_reflns_theta_min         2.242
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    23.688
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.4810
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1157 before and 0.0611 after correction.
The Ratio of minimum to maximum transmission is 0.6450.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'metallic dark orange'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    3.882
_exptl_crystal_description       block
_exptl_crystal_F_000             3032
_exptl_crystal_size_max          0.432
_exptl_crystal_size_mid          0.381
_exptl_crystal_size_min          0.315
_refine_diff_density_max         3.034
_refine_diff_density_min         -2.574
_refine_diff_density_rms         0.355
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     933
_refine_ls_number_reflns         14599
_refine_ls_number_restraints     1905
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.1476
_refine_ls_R_factor_gt           0.0833
_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^)+(0.0568P)^2^+180.6079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1921
_refine_ls_wR_factor_ref         0.2285
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7983
_reflns_number_total             14599
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03480e2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7718325--7718327.cif.'
_cod_database_code               7718327
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.050
_shelx_estimated_absorpt_t_min   0.035
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C20-N3 \\sim C20A-N3A
 with sigma of 0.02
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 C20-C19 \\sim C20A-C19A
 with sigma of 0.02
 C20-C27 \\sim C20A-C27A
 with sigma of 0.02
 N3-C16 \\sim N3A-C16A
 with sigma of 0.02
 N3-O3 \\sim N3A-O3A
 with sigma of 0.02
 C16-C17 \\sim C16A-C17A
 with sigma of 0.02
 C16-C22 \\sim C16A-C22A
 with sigma of 0.02
 C16-C26 \\sim C16A-C26A
 with sigma of 0.02
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 C19-C18 \\sim C19A-C18A
 with sigma of 0.02
 C20-C16 \\sim C20A-C16A
 with sigma of 0.04
 C20-C18 \\sim C20A-C18A
 with sigma of 0.04
 C20-O3 \\sim C20A-O3A
 with sigma of 0.04
 N3-C21 \\sim N3A-C21A
 with sigma of 0.04
 N3-C17 \\sim N3A-C17A
 with sigma of 0.04
 N3-C19 \\sim N3A-C19A
 with sigma of 0.04
 N3-C22 \\sim N3A-C22A
 with sigma of 0.04
 N3-C27 \\sim N3A-C27A
 with sigma of 0.04
 N3-C26 \\sim N3A-C26A
 with sigma of 0.04
 C21-C19 \\sim C21A-C19A
 with sigma of 0.04
 C21-C27 \\sim C21A-C27A
 with sigma of 0.04
 C16-C18 \\sim C16A-C18A
 with sigma of 0.04
 C16-O3 \\sim C16A-O3A
 with sigma of 0.04
 C17-C19 \\sim C17A-C19A
 with sigma of 0.04
 C17-C22 \\sim C17A-C22A
 with sigma of 0.04
 C17-C26 \\sim C17A-C26A
 with sigma of 0.04
 C19-C27 \\sim C19A-C27A
 with sigma of 0.04
 C22-C26 \\sim C22A-C26A
 with sigma of 0.04
 N1-O2 \\sim N1A-O2A
 with sigma of 0.02
 N1-C3 \\sim N1A-C3A
 with sigma of 0.02
 N1-C7 \\sim N1A-C7A
 with sigma of 0.02
 C8-C7 \\sim C8A-C7A
 with sigma of 0.02
 C3-C1 \\sim C3A-C1A
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
 C3-C4 \\sim C3A-C4A
 with sigma of 0.02
 C7-C6 \\sim C7A-C6A
 with sigma of 0.02
 C7-C9 \\sim C7A-C9A
 with sigma of 0.02
 C6-C5 \\sim C6A-C5A
 with sigma of 0.02
 C4-C5 \\sim C4A-C5A
 with sigma of 0.02
 N1-C8 \\sim N1A-C8A
 with sigma of 0.04
 N1-C1 \\sim N1A-C1A
 with sigma of 0.04
 N1-C6 \\sim N1A-C6A
 with sigma of 0.04
 N1-C9 \\sim N1A-C9A
 with sigma of 0.04
 N1-C2 \\sim N1A-C2A
 with sigma of 0.04
 N1-C4 \\sim N1A-C4A
 with sigma of 0.04
 C8-C6 \\sim C8A-C6A
 with sigma of 0.04
 C8-C9 \\sim C8A-C9A
 with sigma of 0.04
 O2-C3 \\sim O2A-C3A
 with sigma of 0.04
 O2-C7 \\sim O2A-C7A
 with sigma of 0.04
 C3-C7 \\sim C3A-C7A
 with sigma of 0.04
 C3-C5 \\sim C3A-C5A
 with sigma of 0.04
 C7-C5 \\sim C7A-C5A
 with sigma of 0.04
 C1-C2 \\sim C1A-C2A
 with sigma of 0.04
 C1-C4 \\sim C1A-C4A
 with sigma of 0.04
 C6-C9 \\sim C6A-C9A
 with sigma of 0.04
 C6-C4 \\sim C6A-C4A
 with sigma of 0.04
 C2-C4 \\sim C2A-C4A
 with sigma of 0.04
 N2-O1 \\sim N2A-O1A
 with sigma of 0.02
 N2-C10 \\sim N2A-C10A
 with sigma of 0.02
 N2-C13 \\sim N2A-C13A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C10-C23 \\sim C10A-C23A
 with sigma of 0.02
 C10-C24 \\sim C10A-C24A
 with sigma of 0.02
 C13-C14 \\sim C13A-C14A
 with sigma of 0.02
 C13-C12 \\sim C13A-C12A
 with sigma of 0.02
 C13-C25 \\sim C13A-C25A
 with sigma of 0.02
 C11-C80 \\sim C11A-C80A
 with sigma of 0.02
 C12-C80 \\sim C12A-C80A
 with sigma of 0.02
 N2-C14 \\sim N2A-C14A
 with sigma of 0.04
 N2-C11 \\sim N2A-C11A
 with sigma of 0.04
 N2-C12 \\sim N2A-C12A
 with sigma of 0.04
 N2-C23 \\sim N2A-C23A
 with sigma of 0.04
 N2-C24 \\sim N2A-C24A
 with sigma of 0.04
 N2-C25 \\sim N2A-C25A
 with sigma of 0.04
 O1-C10 \\sim O1A-C10A
 with sigma of 0.04
 O1-C13 \\sim O1A-C13A
 with sigma of 0.04
 C10-C13 \\sim C10A-C13A
 with sigma of 0.04
 C10-C80 \\sim C10A-C80A
 with sigma of 0.04
 C13-C80 \\sim C13A-C80A
 with sigma of 0.04
 C14-C12 \\sim C14A-C12A
 with sigma of 0.04
 C14-C25 \\sim C14A-C25A
 with sigma of 0.04
 C11-C12 \\sim C11A-C12A
 with sigma of 0.04
 C11-C23 \\sim C11A-C23A
 with sigma of 0.04
 C11-C24 \\sim C11A-C24A
 with sigma of 0.04
 C12-C25 \\sim C12A-C25A
 with sigma of 0.04
 C23-C24 \\sim C23A-C24A
 with sigma of 0.04
3. Rigid bond restraints
 O72
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
P2 \\sim P1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(N1) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C7) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(N1A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(C3A)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C6A) \\sim Ueq,
Uanis(C9A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C5A)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C26) \\sim Ueq, Uanis(O3A) \\sim Ueq, Uanis(N3A) \\sim Ueq, Uanis(C21A)
\\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(C18A) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C16A) \\sim Ueq,
Uanis(C22A) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(O1)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(N2A) \\sim Ueq,
Uanis(O1A) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C14A)
\\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C23A) \\sim Ueq,
Uanis(C24A) \\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C80A) \\sim Ueq, Uanis(O38)
\\sim Ueq, Uanis(O76) \\sim Ueq, Uanis(O77) \\sim Ueq, Uanis(O74) \\sim Ueq,
Uanis(O14) \\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(O73) \\sim Ueq, Uanis(O71)
\\sim Ueq, Uanis(O37) \\sim Ueq, Uanis(O70) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C22A) = Uanis(C22)
Uanis(C16A) = Uanis(C16)
Uanis(N3A) = Uanis(N3)
Uanis(O3A) = Uanis(O3)
Uanis(C17) = Uanis(C17A)
Uanis(C18) = Uanis(C18A)
Uanis(C19) = Uanis(C19A)
Uanis(C21) = Uanis(C21A)
Uanis(C20) = Uanis(C20A)
Uanis(C27A) = Uanis(C27)
Uanis(C26A) = Uanis(C26)
Uanis(C9) = Uanis(C9A)
Uanis(C7A) = Uanis(C7)
Uanis(C8A) = Uanis(C8)
Uanis(C6A) = Uanis(C6)
Uanis(C5A) = Uanis(C5)
Uanis(C4A) = Uanis(C4)
Uanis(C3) = Uanis(C3A)
Uanis(C2) = Uanis(C2A)
Uanis(C1) = Uanis(C1A)
Uanis(N1) = Uanis(N1A)
Uanis(O2) = Uanis(O2A)
Uanis(O1) = Uanis(O1A)
Uanis(N2) = Uanis(N2A)
Uanis(C24A) = Uanis(C24)
Uanis(C10A) = Uanis(C10)
Uanis(C23A) = Uanis(C23)
Uanis(C11A) = Uanis(C11)
Uanis(C80A) = Uanis(C80)
Uanis(C12A) = Uanis(C12)
Uanis(C13) = Uanis(C13A)
Uanis(C25) = Uanis(C25A)
Uanis(C14) = Uanis(C14A)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O3A)=Sof(N3A)=Sof(C21A)=Sof(C20A)=Sof(C27A)=Sof(C19A)=Sof(H19C)=Sof(H19D)=
 Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(C17A)=Sof(H17C)=Sof(H17D)=Sof(C16A)=
 Sof(C22A)=Sof(C26A)=1-FVAR(1)
 Sof(C20)=Sof(N3)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C16)=Sof(C17)=
 Sof(H17A)=Sof(H17B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(C22)=Sof(O3)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C26)=Sof(H26A)=
 Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(N1A)=Sof(C8A)=Sof(O2A)=Sof(C3A)=Sof(C7A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C5A)=
 Sof(H5AA)=Sof(H5AB)=1-FVAR(2)
 Sof(N1)=Sof(C8)=Sof(O2)=Sof(C3)=Sof(C7)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C2)=Sof(H2A)=
 Sof(H2B)=Sof(H2C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=FVAR(2)
 Sof(N2A)=Sof(O1A)=Sof(C10A)=Sof(C13A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C23A)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=
 Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C80A)=Sof(H80C)=Sof(H80D)=1-FVAR(3)
 Sof(N2)=Sof(O1)=Sof(C10)=Sof(C13)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(H25C)=Sof(C80)=Sof(H80A)=Sof(H80B)=FVAR(3)
7.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C4(H4A,H4B), C11(H11A,H11B), C12(H12A,H12B), C5(H5A,H5B),
 C17(H17A,H17B), C19(H19A,H19B), C18(H18A,H18B), C80(H80A,H80B), C19A(H19C,
 H19D), C18A(H18C,H18D), C17A(H17C,H17D), C6A(H6AA,H6AB), C4A(H4AA,H4AB),
 C5A(H5AA,H5AB), C11A(H11C,H11D), C12A(H12C,H12D), C80A(H80C,H80D)
7.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C14(H14A,H14B,H14C), C9(H9A,H9B,H9C), C2(H2A,H2B,H2C),
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C27(H27A,H27B,H27C), C26(H26A,H26B,H26C), C1A(H1AA,H1AB,H1AC), C9A(H9AA,
 H9AB,H9AC), C2A(H2AA,H2AB,H2AC), C14A(H14D,H14E,H14F), C23A(H23D,H23E,H23F),
 C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F)
;
_shelx_res_checksum              37579
_shelx_hkl_checksum              18453
_olex2_submission_special_instructions 'No special instructions were received'