Zirconium-Substituted Isopolytungstates: Structural Models for Zirconia-Supported Tungsten Catalysts
Carabineiro, Hugo; Villanneau, Richard; Carrier, Xavier; Herson, Patrick; Lemos, Francisco; Ramôa Ribeiro, Fernando; Proust, Anna; Che, Michel; Inorganic Chemistry 45 (2006) 1915–1923; doi:10.1021/ic051941l

data_4331969
_publ_section_title
;
 Zirconium-Substituted Isopolytungstates:&#x00A0; Structural Models for
 Zirconia-Supported Tungsten Catalysts
;
_journal_issue                   5
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              1915
_journal_page_last               1923
_journal_paper_doi               10.1021/ic051941l
_journal_volume                  45
_journal_year                    2006
_chemical_formula_moiety
'2(N C4 H12)+, (C2 H10 O21 S W5 Zr)2-, (C2 H6 O S), (H2O)'
_chemical_formula_sum            'C12 H42 N2 O23 S2 W5 Zr'
_chemical_formula_weight         1657.07
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             05-10-18
_audit_creation_method           CRYSTALS_ver_12.82
_cell_angle_alpha                90
_cell_angle_beta                 101.337(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.8962(14)
_cell_length_b                   10.8357(6)
_cell_length_c                   21.9071(17)
_cell_measurement_reflns_used    291
_cell_measurement_temperature    295
_cell_measurement_theta_max      22
_cell_measurement_theta_min      4
_cell_volume                     3467.0(5)
_computing_cell_refinement
'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)'
_computing_data_collection       'COLLECT. Nonius (1997-2001).'
_computing_data_reduction        'EvalCCD (Duisenberg & Schreurs 1990-2000)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SHELXS 86 (Sheldrick, 1986)'
_diffrn_ambient_temperature      295
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.965
_diffrn_measurement_device_type  'Nonius Kappa CCD'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.030
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            22279
_diffrn_reflns_theta_full        25.200
_diffrn_reflns_theta_max         30.000
_diffrn_reflns_theta_min         2.121
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    17.016
_exptl_absorpt_correction_T_max  0.248
_exptl_absorpt_correction_T_min  0.190
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Siemens, 1996)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    3.17
_exptl_crystal_description       block
_exptl_crystal_F_000             3016
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.99
_refine_diff_density_min         -1.38
_refine_ls_extinction_coef       18.507
_refine_ls_extinction_method
'Larson 1970 Crystallographic Computing eq 22'
_refine_ls_goodness_of_fit_ref   1.0657
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     406
_refine_ls_number_reflns         6065
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0592
_refine_ls_R_factor_gt           0.0274
_refine_ls_shift/su_max          0.000563
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details
;
Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
[weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
Method = Robust Weighting (Prince, 1982) 
W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
A~i~ are: 
0.956 -0.281 0.724 -0.612E-01 0.127 

'Because the data were collected with molybdenum radiation, there were no 
measurable anomalous differences, as a consequence of which it was 
admissible to merge Friedel pairs of reflections. 

All hydrogen atoms were found in difference density syntheses. 

Hydrogen atoms were placed geometrically after each cycle. 

Hydrogen atoms were placed geometrically after each cycle, the preferred 
orientations of those groups whose conformations could not be assigned 
unambiguously having been previously identified by examination of a 
difference Fourier map. 

Hydrogen atoms were seen in a difference density synthesis. Those 
attached to carbon atoms were repositioned geometrically. 

Hydrogen were initially refined with soft restraints on the 
bonds to regularise their geometry (bond lengths to accepted values, 
angles either set by symmetry or to accepted values, and 
U[iso] dependent upon the adjacent bonded atom), 
after which they were refined with riding constraints only. 

donated by Bill Clegg: 

The H atoms were all located in a difference map, but those 
attached to carbon atoms were repositioned geometrically. 
The H atoms were initially refined with soft restraints on the 
bond lengths and angles to regularise their geometry (C---H in the range 
0.93-98, O---N in the range 0.86-0.89 and O---H = 0.82 \%A) and isotropic adps 
(U(H) in the range 1.2-1.5 times U~equiv~ of the adjacent atom), 
after which they were refined with riding constraints. ' 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0428
_refine_ls_wR_factor_gt          0.0285
_refine_ls_wR_factor_ref         0.0285
_reflns_limit_h_max              20
_reflns_limit_h_min              -20
_reflns_limit_k_max              15
_reflns_limit_k_min              0
_reflns_limit_l_max              30
_reflns_limit_l_min              0
_reflns_number_gt                6065
_reflns_number_total             6065
_reflns_threshold_expression     I>3.00u(I)
_cod_data_source_file            ic051941lsup1.cif
_cod_data_source_block           1b_cif
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Monoclinic' changed to 'monoclinic'
according to /home/saulius/struct/CIF-dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 1891 2012-01-12 08:04:46Z andrius 
;
_cod_original_cell_volume        3467.1(5)
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_original_formula_sum        'C12 H42 N2 O23 S2 W5 Zr1'
_cod_database_code               4331969