Rearrangement of a Krebs-Type Polyoxometalate upon Coordination of N,O-Bis(bidentate) Ligands.
Artetxe, Beñat; Reinoso, Santiago; San Felices, Leire; Lezama, Luis; Pache, Aroa; Vicent, Cristian; Gutiérrez-Zorrilla, Juan M; Inorganic chemistry 54 (2015) 409–411; doi:10.1021/ic5026729

data_4342038
_publ_section_title
;
 Rearrangement of a Krebs-Type Polyoxometalate upon Coordination of
 N,O-Bis(bidentate) Ligands.
;
_journal_issue                   2
_journal_name_full               'Inorganic chemistry'
_journal_page_first              409
_journal_page_last               411
_journal_paper_doi               10.1021/ic5026729
_journal_volume                  54
_journal_year                    2015
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C12 H190 N4 Na24 Ni4 O241 Sb4 W40'
_chemical_formula_sum            'C12 H190 N4 Na24 Ni4 O241 Sb4 W40'
_chemical_formula_weight         12875.28
_chemical_name_systematic
;
 ?
;
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      15
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-01-28T22:02:38-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 94.788(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   43.6689(7)
_cell_length_b                   19.2964(3)
_cell_length_c                   26.5627(4)
_cell_measurement_reflns_used    32512
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.206
_cell_measurement_theta_min      3.013
_cell_measurement_wavelength     1.5418
_cell_volume                     22305.0(6)
_computing_cell_refinement
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
        (compiled Jan 23 2012,18:06:46)
;
_computing_data_collection
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
        (compiled Jan 23 2012,18:06:46)
;
_computing_data_reduction
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
        (compiled Jan 23 2012,18:06:46)
;
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'OLEX2 (Dolomanov, 2009)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0103365
_diffrn_orient_matrix_UB_12      0.0727109
_diffrn_orient_matrix_UB_13      0.0156127
_diffrn_orient_matrix_UB_21      0.0063972
_diffrn_orient_matrix_UB_22      -0.0198664
_diffrn_orient_matrix_UB_23      0.0560613
_diffrn_orient_matrix_UB_31      0.0332358
_diffrn_orient_matrix_UB_32      0.0264292
_diffrn_orient_matrix_UB_33      -0.0006931
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0718
_diffrn_reflns_av_unetI/netI     0.0477
_diffrn_reflns_limit_h_max       52
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            80184
_diffrn_reflns_theta_full        67
_diffrn_reflns_theta_max         67
_diffrn_reflns_theta_min         2.5
_exptl_absorpt_coefficient_mu    42.745
_exptl_absorpt_correction_T_max  0.328
_exptl_absorpt_correction_T_min  0.015
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
        (compiled Dec  3 2012,18:21:49)
Analytical numeric absorption correction using a multifaceted crystal
                        model based on expressions derived by R.C. Clark & J.S.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    3.834
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             23032
_exptl_crystal_size_max          0.496
_exptl_crystal_size_mid          0.0395
_exptl_crystal_size_min          0.0391
_platon_squeeze_details
;
The final structural solution contained large solvent accesible voids 
that have been analyzed using the SQUEEZE tool as shown above. These voids 
can host the number of Na ions and water molecules determined by elemental 
and thermal analyses and included in the formula that have not
been located in the structure and that are responsible for the large
disagreement between the formula and the atom count. The hkl 
reflection file generated with SQUEEZE contained only 6936 reflections, 
5807 of which observed. Refinement of the structural model using this file 
lead to a significant improvement of the final agreement factors, but also 
resulted in the following issues among others. a. the Ni1 atom could not be 
refined anisotropically unless using ISOR restraints tighter than the 
standard. b. the precision of the metal-ligand bonds decreased remarkably 
with the standard deviation values becoming associated with the second 
decimal instead of being associated with the third decimal as in the 
original solution. c. the C(sp2)-C(sp2) bonds lengthened considerably 
generating new alerts of type A and B when validating the corresponding 
CIF file, which would require the use of additional restraints in the 
refinement. Taking these issues into account, we decided to report the 
results obtained upon refinement of our structural model using the original 
hkl file that contains all 19886 reflections.
;
_refine_diff_density_max         2.675
_refine_diff_density_min         -1.674
_refine_diff_density_rms         0.394
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     693
_refine_ls_number_reflns         19886
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0763
_refine_ls_R_factor_gt           0.0635
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0784P)^2^+1625.1554P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1649
_refine_ls_wR_factor_ref         0.1789
_reflns_number_gt                16628
_reflns_number_total             19886
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic5026729_si_002.cif
_cod_data_source_block           NaNi4
_cod_depositor_comments          'Adding full bibliography for 4342038.cif.'
_cod_database_code               4342038