Synthesis and characterization of multinuclear manganese-containing tungstosilicates.
Al-Oweini, Rami; Bassil, Bassem S.; Friedl, Jochen; Kottisch, Veronika; Ibrahim, Masooma; Asano, Marie; Keita, Bineta; Novitchi, Ghenadie; Lan, Yanhua; Powell, Annie; Stimming, Ulrich; Kortz, Ulrich; Inorganic chemistry 53 (2014) 5663–5673; doi:10.1021/ic500425c

data_4338446
_publ_section_title
;
 Synthesis and characterization of multinuclear manganese-containing
 tungstosilicates.
;
_journal_issue                   11
_journal_name_full               'Inorganic chemistry'
_journal_page_first              5663
_journal_page_last               5673
_journal_paper_doi               10.1021/ic500425c
_journal_volume                  53
_journal_year                    2014
_chemical_formula_sum            'C9 H53.5 K3 Mn4 Na4.5 O66 Si W9'
_chemical_formula_weight         3341.27
_chemical_name_systematic
; 
 ? 
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                81.702(5)
_cell_angle_beta                 87.042(5)
_cell_angle_gamma                78.853(5)
_cell_formula_units_Z            2
_cell_length_a                   12.1739(11)
_cell_length_b                   13.1095(11)
_cell_length_c                   18.4657(17)
_cell_measurement_reflns_used    7459
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.19
_cell_measurement_theta_min      2.55
_cell_volume                     2860.3(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.779
_diffrn_measured_fraction_theta_max 0.980
_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  0.0782
_diffrn_reflns_av_unetI/netI     0.0566
_diffrn_reflns_Laue_measured_fraction_full 0.779
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            47971
_diffrn_reflns_point_group_measured_fraction_full 0.779
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         23.256
_diffrn_reflns_theta_min         3.412
_exptl_absorpt_coefficient_mu    19.281
_exptl_absorpt_correction_T_max  0.1130
_exptl_absorpt_correction_T_min  0.0540
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    3.880
_exptl_crystal_description       block
_exptl_crystal_F_000             3045
_exptl_crystal_size_max          0.142
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.041
_exptl_transmission_factor_max   0.1130
_exptl_transmission_factor_min   0.0540
_refine_diff_density_max         4.691
_refine_diff_density_min         -3.257
_refine_diff_density_rms         0.441
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     424
_refine_ls_number_reflns         8065
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0826
_refine_ls_R_factor_gt           0.0694
_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^)+(0.0010P)^2^+650.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1569
_refine_ls_wR_factor_ref         0.1632
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6767
_reflns_number_total             8065
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic500425c_si_005.cif
_cod_data_source_block           try
_cod_depositor_comments
'Adding full bibliography for 4338445--4338449.cif.'
_cod_original_formula_sum        'C9 H53.5 K3 Mn4 Na4.50 O66 Si W9'
_cod_database_code               4338446
_shelx_estimated_absorpt_t_min   0.0540
_shelx_estimated_absorpt_t_max   0.1130
_shelxl_version_number           2013-4
_plat015_alert_5_a
;
PROBLEM: No _shelx_hkl_file record in SHELXL20xy CIF 
RESPONSE: The new SHELX package (2011 and after) includes
the hkl file in the cif file. For our compounds however, 
due to the very large number of reflections, 
the size of the cif file would become too large. 
Therefore, we usually delete the hkl part.
;
_plat201_alert_2_a
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s)
RESPONSE: This is a common alert in polyoxotungstate 
crystallography, and should be ignored. All C, N, O 
atoms as well as disordered counter cations are usually 
refined isotropically. Most of the electron density is 
located at the heavy tungsten atoms and fully occupied 
counter-cations (e.g. K), and anisotropic refinement of 
light atoms (e.g. O, C, H) does not lead to any significant 
improvement in the refinement parameters (e.g. esds of 
bond lengths/angles, R factor, residuals in electron 
density map). To the opposite, it contributes to a decrease 
of the ratio reflections/parameters, which is counterproductive 
as it lowers the quality of the structure refinement 
and may even render it unstable. In summary, isotropic 
refinement for light atoms is very justified.
;
_plat780_alert_1_a
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PROBLEM: Coordinates do not Form a Properly Connected Set
RESPONSE: This alert occurs when the molecule(s) 
in the asymmetric unit is (are) fragmented, which is 
almost always the case in POM crystallography. Then one
must generate the symmetry-related atoms to form a 
connected set. This can be done either by hand or by means 
of XP in SHELXTL etc.
;