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_4338448
_publ_section_title
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 Synthesis and characterization of multinuclear manganese-containing
 tungstosilicates.
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_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 H51.5 K3 Mn4 Na4.5 O65 Si W9'
_chemical_formula_weight         3323.26
_chemical_name_systematic
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 ? 
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_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 95.847(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   42.0007(14)
_cell_length_b                   12.3264(4)
_cell_length_c                   21.4071(9)
_cell_measurement_reflns_used    2341
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.15
_cell_measurement_theta_min      3.66
_cell_volume                     11025.2(7)
_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      100(2)
_diffrn_measured_fraction_theta_full 0.575
_diffrn_measured_fraction_theta_max 0.994
_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  0.1633
_diffrn_reflns_av_unetI/netI     0.0645
_diffrn_reflns_Laue_measured_fraction_full 0.575
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            88716
_diffrn_reflns_point_group_measured_fraction_full 0.575
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         20.815
_diffrn_reflns_theta_min         3.441
_exptl_absorpt_coefficient_mu    20.006
_exptl_absorpt_correction_T_max  0.753
_exptl_absorpt_correction_T_min  0.142
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    4.005
_exptl_crystal_description       plate
_exptl_crystal_F_000             12100
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.015
_exptl_transmission_factor_max   0.753
_exptl_transmission_factor_min   0.142
_refine_diff_density_max         3.019
_refine_diff_density_min         -1.534
_refine_diff_density_rms         0.389
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     419
_refine_ls_number_reflns         5738
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0829
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0600P)^2^+1250.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1145
_refine_ls_wR_factor_ref         0.1380
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4035
_reflns_number_total             5738
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic500425c_si_006.cif
_cod_data_source_block           try
_cod_depositor_comments
'Adding full bibliography for 4338445--4338449.cif.'
_cod_original_formula_sum        'C9 H51.5 K3 Mn4 Na4.50 O65 Si W9'
_cod_database_code               4338448
_shelx_estimated_absorpt_t_min   0.142
_shelx_estimated_absorpt_t_max   0.753
_shelxl_version_number           2013-4
_thetm01_alert_3_a
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PROBLEM: The value of sine(theta_max)/wavelength is less 
than 0.550
RESPONSE:
This is yet another common alert in polyoxotungstate 
crystallography. Tungsten is a strong absorber of X-rays, 
resulting rarely to diffraction up to large angles. 
Also, almost always a large degree of disorder of 
crystal waters and some counter cations is observed, 
which contributes to the problem.
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_plat015_alert_5_a
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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.
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_plat201_alert_2_a
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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.
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_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.
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_chemw03_alert_2_a
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PROBLEM: ALERT: The ratio of given/expected molecular weight as
calculated from the _atom_site* data lies outside
the range 0.90 <> 1.10
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_plat043_alert_1_a
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PROBLEM: Calculated and Reported Mol. Weight Differ by
RESPONSE: These two alerts are a direct result from the previous alert. 
When a large number of asymmetric units must be connected to 
build up the entire molecule, then the calculated Z decreases 
significantly. For example, in the case of 5a, the calculated Z is 2, 
whereas the reported Z is 8, meaning that four asymmetric units 
are linked. Therefore, the calculated molecular formula is four 
times the reported one, which gives the two alerts in checkcif. 
However, for overall consistency, we always follow the standard 
procedure of reporting in the cif file the same formula as in the 
manuscript, which is based on elemental analysis and TGA data, 
and hence reflects bulk composition (rather than single crystal).
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