Structural modifications of <i>M</i><sub>5</sub>O<sub>4</sub>I<sub>11</sub> (<i>M</i> = Nb, Ta) cluster networks from heterogeneous solid-state reactions.
Grahlow, Fabian; Beitlberger, Jan; Martin, Mario; Juriatti, Eric; Peisert, Heiko; Scheele, Marcus; Ströbele, Markus; Romao, Carl P.; Meyer, Hans-Jürgen; Dalton transactions (Cambridge, England : 2003) 54 (2025) 16593–16604; doi:10.1039/d5dt02097b

data_7719754
_publ_section_title
;
 Structural modifications of
 <i>M</i><sub>5</sub>O<sub>4</sub>I<sub>11</sub> (<i>M</i> = Nb, Ta)
 cluster networks from heterogeneous solid-state reactions.
;
_journal_issue                   44
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16593
_journal_page_last               16604
_journal_paper_doi               10.1039/d5dt02097b
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'I12 Li1 O2 Ta3'
_chemical_formula_sum            'I12 Li O2 Ta3'
_chemical_formula_weight         2104.59
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-11 deposited with the CCDC.	2025-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                82.9620(10)
_cell_angle_beta                 81.225(2)
_cell_angle_gamma                87.797(2)
_cell_formula_units_Z            2
_cell_length_a                   7.4370(2)
_cell_length_b                   11.1829(2)
_cell_length_c                   15.0653(3)
_cell_measurement_reflns_used    14829
_cell_measurement_temperature    249.99(10)
_cell_measurement_theta_max      45.5930
_cell_measurement_theta_min      2.4020
_cell_volume                     1228.69(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.121a 64-bit (release 24-04-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      249.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -29.00  -4.00   0.50   16.00    --  -38.33   7.00  81.00   50
  2  \w    -96.00 -71.00   0.50   16.00    --  -38.33  -7.00 -93.00   50
  3  \w    -29.00  -4.00   0.50   16.00    --   40.83  -7.00 -93.00   50
  4  \w     52.00  78.00   0.50   16.00    --   40.83   7.00  81.00   52
  5  \w    -63.00 -27.00   0.50   16.00    --  -38.33 -57.00 150.00   72
  6  \w    -77.00 -27.00   0.50   16.00    --  -38.33 -57.00  60.00  100
  7  \w    -75.00 -30.00   0.50   16.00    --  -38.33 -47.00 -52.69   90
  8  \w     23.00  70.00   0.50   16.00    --   40.83 -99.00-180.00   94
  9  \w    -11.00  70.00   0.50   16.00    --   40.83 -99.00 150.00  162
 10  \w     -5.00  21.00   0.50   16.00    --   40.83 -99.00 -90.00   52
 11  \w     -7.00  70.00   0.50   16.00    --   40.83 -99.00 -60.00  154
 12  \w    -22.00   4.00   0.50   16.00    --   40.83 -99.00  60.00   52
 13  \w     23.00  95.00   0.50   16.00    --   40.83-141.00 116.34  144
 14  \w     28.00  70.00   0.50   16.00    --   40.83 -99.00 -90.00   84
 15  \w     21.00  70.00   0.50   16.00    --   40.83 -99.00  60.00   98
 16  \w     45.00  70.00   0.50   16.00    --   40.83 -99.00   0.00   50
 17  \w      9.00  43.00   0.50   16.00    --   42.00 -57.00 -36.45   68
 18  \w     23.00 108.00   0.50   16.00    --   42.00  75.00 -15.80  170
 19  \w    -29.00   3.00   0.50   16.00    --   42.00 -57.00 -36.45   64
 20  \w    -28.00  30.00   0.50   16.00    --   42.00 -46.00 132.11  116
 21  \w     23.00 113.00   0.50   16.00    --   42.00  77.00-130.03  180
 22  \w     23.00 113.00   0.50   16.00    --   42.00  77.00  22.81  180
 23  \w    -17.00  24.00   0.50   16.00    --   42.00 -40.00 166.42   82
 24  \w     23.00 112.00   0.50   16.00    --   42.00  75.00 178.82  178
 25  \w    -28.00  25.00   0.50   16.00    --   42.00 -41.00-152.11  106
 26  \w    -28.00  25.00   0.50   16.00    --   42.00 -41.00  88.58  106
 27  \w     23.00  84.00   0.50   16.00    --   42.00  77.00  89.05  122
 28  \w    -29.00  51.00   0.50   16.00    --   42.00 -62.00  11.39  160
 29  \w    -28.00  21.00   0.50   16.00    --   42.00 -40.00 -79.74   98
 30  \w     38.00  97.00   0.50   16.00    --   42.00  33.00 138.40  118
 31  \w     23.00 113.00   0.50   16.00    --   42.00  77.00 -99.53  180
 32  \w     23.00  85.00   0.50   16.00    --   42.00  77.00 137.51  124
 33  \w     23.00  68.00   0.50   16.00    --   42.00  75.00 -56.07   90
 34  \w    -24.00  11.00   0.50   16.00    --   42.00 -28.00 -44.13   70
 35  \w    -96.00 -71.00   0.50   16.00    --  -38.33  -7.00 -93.00   50
 36  \w     42.00  79.00   0.50   16.00    --   42.00-115.00 103.51   74
 37  \w      7.00  39.00   0.50   16.00    --   42.00-115.00 103.51   64
;
_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      -0.0891634000
_diffrn_orient_matrix_UB_12      -0.0225861000
_diffrn_orient_matrix_UB_13      0.0044796000
_diffrn_orient_matrix_UB_21      -0.0363970000
_diffrn_orient_matrix_UB_22      0.0596035000
_diffrn_orient_matrix_UB_23      -0.0005141000
_diffrn_orient_matrix_UB_31      0.0064824000
_diffrn_orient_matrix_UB_32      0.0048249000
_diffrn_orient_matrix_UB_33      -0.0477627000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0120
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            38906
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         2.161
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    28.392
_exptl_absorpt_correction_T_max  0.447
_exptl_absorpt_correction_T_min  0.074
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    5.689
_exptl_crystal_description       block
_exptl_crystal_F_000             1748
_exptl_crystal_size_max          0.113
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.734
_refine_diff_density_min         -0.432
_refine_diff_density_rms         0.121
_refine_ls_extinction_coef       0.000638(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.305
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     183
_refine_ls_number_reflns         4499
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.303
_refine_ls_R_factor_all          0.0137
_refine_ls_R_factor_gt           0.0133
_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^)+(0.0026P)^2^+2.3573P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0290
_refine_ls_wR_factor_ref         0.0292
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4416
_reflns_number_total             4499
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02097b2.cif
_cod_data_source_block           fg180v1
_cod_depositor_comments
'Adding full bibliography for 7719753--7719758.cif.'
_cod_database_code               7719754
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'I12 Li O2 Ta3 '
_shelx_estimated_absorpt_t_max   0.368
_shelx_estimated_absorpt_t_min   0.142
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(Li3) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(Li2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
2. Others
 Sof(Li2)=0.73*(1-FVAR(2))
 Sof(Li3)=0.27*(1-FVAR(2))
 Sof(Li1)=FVAR(1)
;
_shelx_res_checksum              61674
_shelx_hkl_checksum              11775
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.606
_oxdiff_exptl_absorpt_empirical_full_min 0.716