Oxygen-Atom Vacancy Formation at Polyoxovanadate Clusters: Homogeneous Models for Reducible Metal Oxides.
Petel, Brittney E.; Brennessel, William W.; Matson, Ellen M.; Journal of the American Chemical Society 140 (2018) 8424–8428; doi:10.1021/jacs.8b05298

data_4132642
_publ_section_title
;
 Oxygen-Atom Vacancy Formation at Polyoxovanadate Clusters: Homogeneous
 Models for Reducible Metal Oxides.
;
_journal_issue                   27
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8424
_journal_page_last               8428
_journal_paper_doi               10.1021/jacs.8b05298
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C13 H36 F3 O21 S1 V6'
_chemical_formula_sum            'C13 H36 F3 O21 S V6'
_chemical_formula_weight         923.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-04-01
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.702(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1551(4)
_cell_length_b                   15.5316(8)
_cell_length_c                   20.0248(11)
_cell_measurement_reflns_used    9518
_cell_measurement_temperature    192.99(10)
_cell_measurement_theta_max      75.4560
_cell_measurement_theta_min      3.6190
_cell_volume                     3158.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      192.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -40.00   3.00   0.50    1.59    --  -49.37  23.00  64.00   86
  2  \w    -46.00 -13.00   0.50    6.35    --  -84.25  23.00  64.00   66
  3  \w   -111.00 -83.00   0.50    1.59    --  -49.37 -23.00-100.00   56
  4  \w   -141.00-116.00   0.50    6.35    --  -84.25 -23.00-100.00   50
  5  \w   -113.00 -71.00   0.50    1.59    --  -49.37-125.00-180.00   84
  6  \w     -7.00  18.00   0.50    1.59    --   49.37 -23.00-100.00   50
  7  \w     32.00  69.00   0.50    6.35    --  105.75 -23.00-100.00   74
  8  \w     34.00  59.00   0.50    6.35    --  105.75 -30.00 -60.00   50
  9  \w     34.00  79.00   0.50    6.35    --  105.75 -15.00 -90.00   90
 10  \w     35.00  72.00   0.50    6.35    --  105.75 -30.00-150.00   74
 11  \w     46.00  71.00   0.50    6.35    --  105.75 -30.00   0.00   50
 12  \w     45.00  88.00   0.50    6.35    --  105.75 -45.00  60.00   86
 13  \w     44.00  72.00   0.50    6.35    --  105.75 -30.00  90.00   56
 14  \w     98.00 156.00   0.50    6.35    --  105.75  23.00  64.00  116
 15  \w    113.00 178.00   0.50    6.35    --  105.75 125.00 -60.00  130
 16  \w    121.00 169.00   0.50    6.35    --  105.75 125.00  90.00   96
 17  \w     42.00  89.00   0.50    1.59    --   49.37  23.00  64.00   94
 18  \w     37.00  83.00   0.50    6.35    --  105.75 -45.00  90.00   92
 19  \w     37.00  75.00   0.50    6.35    --  105.75 -15.00  60.00   76
 20  \w    153.00 178.00   0.50    6.35    --  105.75  23.00  64.00   50
 21  \w   -121.00 -96.00   0.50    1.59    --  -49.62-125.00  60.00   50
 22  \w    -58.00  13.00   0.50    1.59    --  -49.62  57.00  90.00  142
 23  \w     40.00  66.00   0.50    1.59    --   49.62-125.00-180.00   52
 24  \w     32.00  80.00   0.50    1.59    --   49.62 -99.00  30.00   96
 25  \w     68.00 112.00   0.50    6.35    --  105.75 -61.00   0.00   88
 26  \w     34.00  59.00   0.50    6.35    --  105.75 -30.00-120.00   50
 27  \w     44.00  70.00   0.50    6.35    --  105.75 -94.00 -60.00   52
 28  \w     83.00 108.00   0.50    6.35    --  105.75 -94.00 -30.00   50
 29  \w     95.00 120.00   0.50    6.35    --  105.75-125.00 150.00   50
 30  \w     84.00 120.00   0.50    6.35    --  105.75-125.00-180.00   72
 31  \w     43.00  70.00   0.50    6.35    --  105.75 -94.00 -30.00   54
 32  \w     39.00  65.00   0.50    6.35    --  105.75-125.00 -90.00   52
 33  \w     67.00  93.00   0.50    6.35    --  105.75 -94.00 150.00   52
 34  \w     34.00 103.00   0.50    6.35    --  105.75 -94.00 -90.00  138
 35  \w     34.00  61.00   0.50    6.35    --  105.75-125.00 150.00   54
 36  \w     91.00 118.00   0.50    6.35    --  105.75-125.00 -90.00   54
 37  \w     37.00  67.00   0.50    6.35    --  105.75-125.00   0.00   60
 38  \w     85.00 119.00   0.50    6.35    --  105.75-125.00   0.00   68
 39  \w    100.00 126.00   0.50    6.35    --  105.75 125.00 120.00   52
 40  \w    144.00 169.00   0.50    6.35    --  105.75 125.00 120.00   50
 41  \w     56.00 106.00   0.50    6.35    --  105.75 -94.00-120.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1381941000
_diffrn_orient_matrix_UB_12      0.0280291000
_diffrn_orient_matrix_UB_13      0.0221140000
_diffrn_orient_matrix_UB_21      0.0403173000
_diffrn_orient_matrix_UB_22      0.0951429000
_diffrn_orient_matrix_UB_23      -0.0070031000
_diffrn_orient_matrix_UB_31      -0.0474938000
_diffrn_orient_matrix_UB_32      -0.0006758000
_diffrn_orient_matrix_UB_33      -0.0734274000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10567
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.737
_diffrn_reflns_theta_min         3.602
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.837
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77295
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.941
_exptl_crystal_description       plate
_exptl_crystal_F_000             1852
_exptl_crystal_size_max          0.116
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.716
_refine_diff_density_min         -0.523
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     509
_refine_ls_number_reflns         10567
_refine_ls_number_restraints     145
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0684
_refine_ls_R_factor_gt           0.0568
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0841P)^2^+6.1065P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1498
_refine_ls_wR_factor_ref         0.1598
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8852
_reflns_number_total             10567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05298_si_002.cif
_cod_data_source_block           matbp10
_cod_database_code               4132642
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         V6SF3OC12H36CO6O12
_shelx_estimated_absorpt_t_max   0.570
_shelx_estimated_absorpt_t_min   0.261
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5725(12)
 0.4275(12)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 V1-O1 \\sim V1-O1' \\sim V1-O1"
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
O20 \\sim O20' \\sim O20": within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O21 \\sim O21' \\sim O21": within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
F2 \\sim F2' \\sim F2": within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
F3 \\sim F3' \\sim F3": within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O21' \\sim O20": within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
F3' \\sim F2": within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(F1) = Uanis(F1') = Uanis(F1")
Uanis(S1) = Uanis(S1') = Uanis(S1")
Uanis(C13) = Uanis(C13') = Uanis(C13")
Uanis(O1) = Uanis(O1') = Uanis(O1")
5. Same fragment restrains
{O1', O20', O21', S1', C13', F1', F2', F3'} sigma for 1-2: 0.02, 1-3: 0.04
{O1", O20", O21", S1", C13", F1", F2", F3"} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1, O20, O21, S1, C13, F1, F2, F3}
6. Others
 1*[Sof(O1)+Sof(O20)+Sof(O21)+Sof(S1)+Sof(C13)+Sof(F1)+Sof(F2)+Sof(F3)]+1*
 [Sof(O1')+Sof(O20')+Sof(O21')+Sof(S1')+Sof(C13')+Sof(F1')+Sof(F2')+Sof(F3')]+1*
 [Sof(O1")+Sof(O20")+Sof(O21")+Sof(S1")+Sof(C13")+Sof(F1")+Sof(F2")+Sof(F3")]=1
 with esd of 0.0001
 Sof(O1)=Sof(O20)=Sof(O21)=Sof(S1)=Sof(C13)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(O1')=Sof(O20')=Sof(O21')=Sof(S1')=Sof(C13')=Sof(F1')=Sof(F2')=Sof(F3')=
 FVAR(2)
 Sof(O1")=Sof(O20")=Sof(O21")=Sof(S1")=Sof(C13")=Sof(F1")=Sof(F2")=Sof(F3")=
 FVAR(3)
7.a Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              98748
_shelx_hkl_checksum              65064
_olex2_submission_original_sample_id matbp10
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.932
_oxdiff_exptl_absorpt_empirical_full_min 0.639