Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO2.
Petel, Brittney E.; Meyer, Rachel L.; Maiola, Michela L.; Brennessel, William W.; Müller, Astrid M; Matson, Ellen M.; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b11874

data_4133879
_publ_section_title
;
 Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically
 Precise Models for Electronic Effects of Anion Doping in VO2.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b11874
_journal_year                    2019
_chemical_formula_moiety         'C24 H60 O19 V6, 2(C16 H36 N)'
_chemical_formula_sum            'C56 H132 N2 O19 V6'
_chemical_formula_weight         1443.27
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-09-18
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.0957(3)
_cell_length_b                   18.7627(3)
_cell_length_c                   20.0038(3)
_cell_measurement_reflns_used    20978
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.8860
_cell_measurement_theta_min      4.0390
_cell_volume                     7167.10(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.60a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.60a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.60a (Rigaku OD, 2019)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.980
_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     -5.00  20.00   0.50    1.25    --  -49.87  19.00-120.00   50
  2  \w    -88.00 -21.00   0.50    1.25    --  -49.87 132.00 -67.00  134
  3  \w   -118.00 -73.00   0.50    1.25    --  -49.87-125.00-120.00   90
  4  \w     -5.00  20.00   0.50    1.25    --  -49.87  19.00 150.00   50
  5  \w    -33.00  22.00   0.50    1.25    --  -49.87  38.00 150.00  110
  6  \w    -40.00 -15.00   0.50    4.99    --  -84.25  45.00-180.00   50
  7  \w   -121.00 -96.00   0.50    4.99    --  -84.25 -27.00 -90.00   50
  8  \w    118.00 177.00   0.50    4.99    --  105.75 132.00 -67.00  118
  9  \w    120.00 178.00   0.50    4.99    --  105.75  95.00-138.00  116
 10  \w    143.00 174.00   0.50    4.99    --  105.75  45.00-150.00   62
 11  \w    121.00 176.00   0.50    4.99    --  105.75 125.00 -30.00  110
 12  \w    109.00 165.00   0.50    4.99    --  105.75  30.00  30.00  112
 13  \w     82.00 123.00   0.50    4.99    --  105.75 -77.00 150.00   82
 14  \w     38.00  75.00   0.50    4.99    --  105.75 -61.00 -30.00   74
 15  \w     43.00  78.00   0.50    4.99    --  105.75 -61.00 -60.00   70
 16  \w     37.00  74.00   0.50    4.99    --  105.75 -94.00  60.00   74
 17  \w     40.00  79.00   0.50    4.99    --  105.75 -61.00  90.00   78
 18  \w    101.00 132.00   0.50    4.99    --  105.75  45.00-150.00   62
;
_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      0.0176121000
_diffrn_orient_matrix_UB_12      -0.0745432000
_diffrn_orient_matrix_UB_13      -0.0274259000
_diffrn_orient_matrix_UB_21      0.0786866000
_diffrn_orient_matrix_UB_22      0.0173691000
_diffrn_orient_matrix_UB_23      0.0045209000
_diffrn_orient_matrix_UB_31      0.0017194000
_diffrn_orient_matrix_UB_32      -0.0295766000
_diffrn_orient_matrix_UB_33      0.0718985000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            38510
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         78.129
_diffrn_reflns_theta_min         3.974
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.822
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68386
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.60a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            teal
_exptl_crystal_colour_primary    teal
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       block
_exptl_crystal_F_000             3088
_exptl_crystal_size_max          0.109
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.051
_refine_diff_density_max         0.586
_refine_diff_density_min         -0.491
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     386
_refine_ls_number_reflns         7516
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0352
_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^)+(0.0503P)^2^+4.6600P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.0961
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6683
_reflns_number_total             7516
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11874_si_003.cif
_cod_data_source_block           matbp42
_cod_database_code               4133879
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.722
_shelx_estimated_absorpt_t_min   0.523
_diffrn_oxdiff_digest_frames
;
01d8879157ae2f0821cfef672db9f2356f000309433
;
_diffrn_oxdiff_digest_hkl
;
01f532449eaca03a75f135023710b825ecddc3
;
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B), C7(H7A,H7B), C9(H9A,H9B), C11(H11A,
 H11B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B),
  C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B)
2.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C),
 C24(H24A,H24B,H24C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              59397
_shelx_hkl_checksum              5375
_olex2_submission_original_sample_id matbp42
_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 1.601
_oxdiff_exptl_absorpt_empirical_full_min 0.613