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_4133880
_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 Cl O18 V6, C8 H20 N'
_chemical_formula_sum            'C32 H80 Cl N O18 V6'
_chemical_formula_weight         1108.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-03-15
_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                 122.394(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.9220(4)
_cell_length_b                   11.57810(10)
_cell_length_c                   23.8929(4)
_cell_measurement_reflns_used    13912
_cell_measurement_temperature    100.0(4)
_cell_measurement_theta_max      77.1910
_cell_measurement_theta_min      4.3900
_cell_volume                     4887.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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      100.0(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.983
_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    -15.00  22.00   0.50    0.23    --  -49.62  86.00-133.00   74
  2  \w    -73.00 -17.00   0.50    0.23    --  -49.62  86.00-133.00  112
  3  \w    -85.00 -60.00   0.50    0.93    --  -84.25  86.00-133.00   50
  4  \w    -90.00 -15.00   0.50    0.23    --  -49.62 125.00 -90.00  150
  5  \w   -112.00 -87.00   0.50    0.23    --  -49.62 -57.00-150.00   50
  6  \w    -63.00 -37.00   0.50    0.23    --  -49.62 -57.00-150.00   52
  7  \w   -112.00 -77.00   0.50    0.23    --  -49.62-125.00-180.00   70
  8  \w     -6.00  38.00   0.50    0.23    --   49.62 -86.00 108.00   88
  9  \w     65.00  91.00   0.50    0.93    --  105.75 -86.00 108.00   52
 10  \w     36.00  62.00   0.50    0.93    --  105.75 -30.00  90.00   52
 11  \w     34.00  82.00   0.50    0.93    --  105.75 -15.00  90.00   96
 12  \w     38.00 119.00   0.50    0.93    --  105.75 -61.00  90.00  162
 13  \w    104.00 144.00   0.50    0.93    --  105.75   0.00   0.00   80
 14  \w     95.00 146.00   0.50    0.93    --  105.75  61.00  90.00  102
 15  \w     41.00  81.00   0.50    0.93    --  105.75 -45.00-120.00   80
 16  \w     39.00  64.00   0.50    0.93    --  105.75 -30.00 -90.00   50
 17  \w     37.00  64.00   0.50    0.93    --  105.75 -30.00 -60.00   54
 18  \w     34.00  64.00   0.50    0.93    --  105.75 -30.00 -30.00   60
 19  \w     34.00  66.00   0.50    0.93    --  105.75 -30.00  30.00   64
 20  \w     36.00  71.00   0.50    0.93    --  105.75 -30.00  60.00   70
 21  \w     39.00  91.00   0.50    0.93    --  105.75   0.00   0.00  104
 22  \w     36.00  80.00   0.50    0.93    --  105.75 -45.00 -90.00   88
 23  \w     35.00  67.00   0.50    0.93    --  105.75 -30.00-150.00   64
 24  \w     35.00  61.00   0.50    0.93    --  105.75 -30.00-180.00   52
 25  \w     38.00  65.00   0.50    0.93    --  105.75 -15.00-120.00   54
 26  \w     33.00  58.00   0.50    0.93    --  105.75 -15.00 -60.00   50
 27  \w    101.00 141.00   0.50    0.93    --  105.75  86.00-133.00   80
 28  \w     34.00  70.00   0.50    0.93    --  105.75 -30.00 120.00   72
 29  \w     36.00  82.00   0.50    0.93    --  105.75 -15.00 150.00   92
 30  \w     36.00  71.00   0.50    0.93    --  105.75 -30.00 150.00   70
 31  \w   -140.00-115.00   0.50    0.93    --  -84.25 -86.00 108.00   50
;
_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      -0.0103267000
_diffrn_orient_matrix_UB_12      0.0358426000
_diffrn_orient_matrix_UB_13      -0.0664375000
_diffrn_orient_matrix_UB_21      0.0671669000
_diffrn_orient_matrix_UB_22      -0.0773915000
_diffrn_orient_matrix_UB_23      0.0147874000
_diffrn_orient_matrix_UB_31      -0.0546999000
_diffrn_orient_matrix_UB_32      -0.1021403000
_diffrn_orient_matrix_UB_33      -0.0346300000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0410
_diffrn_reflns_av_unetI/netI     0.0289
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            21222
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.658
_diffrn_reflns_theta_min         4.383
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.298
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44179
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow-brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.506
_exptl_crystal_description       block
_exptl_crystal_F_000             2312
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.277
_exptl_crystal_size_min          0.149
_refine_diff_density_max         0.510
_refine_diff_density_min         -0.669
_refine_diff_density_rms         0.089
_refine_ls_extinction_coef       0.00019(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         5124
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0814P)^2^+6.8854P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1224
_refine_ls_wR_factor_ref         0.1249
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4702
_reflns_number_total             5124
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11874_si_002.cif
_cod_data_source_block           matrm17
_cod_original_cell_volume        4887.08(19)
_cod_database_code               4133880
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.309
_shelx_estimated_absorpt_t_min   0.148
_reflns_odcompleteness_completeness 99.54
_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. Restrained distances
 O8-C9 \\sim O8-C9'
 with sigma of 0.01
 O9-C11 \\sim O9-C11'
 with sigma of 0.01
 C9-C10 \\sim C9'-C10'
 with sigma of 0.01
 C11-C12 \\sim C11'-C12'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O8 \\sim C9' \\sim C10': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O9 \\sim C11 \\sim C12: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C12) = Uanis(C12')
Uanis(C13) = Uanis(C17)
Uanis(C14) = Uanis(C18)
Uanis(C15) = Uanis(C19)
Uanis(C16) = Uanis(C20)
4. Same fragment restrains
{N1, C17, C18} sigma for 1-2: 0.02, 1-3: 0.04
{N1, C15, C16} sigma for 1-2: 0.02, 1-3: 0.04
{N1, C19, C20} sigma for 1-2: 0.02, 1-3: 0.04
as
{N1, C13, C14}
5. Others
 1*[Sof(Cl1)]+1*[Sof(Cl2)]=0.5 with esd of 0.0001
 1*[Sof(O1)]+1*[Sof(O2)]=1.5 with esd of 0.0001
 1*[Sof(O1)]+1*[Sof(Cl1)]=1 with esd of 0.0001
 1*[Sof(O2)]+1*[Sof(Cl2)]=1 with esd of 0.0001
 Sof(C9')=Sof(H9'A)=Sof(H9'B)=Sof(C10')=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Sof(C11')=Sof(H11C)=Sof(H11D)=Sof(C12')=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(2)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(2)
 Fixed Sof: N1(0.5) C13(0.5) H13A(0.5) H13B(0.5) C14(0.5) H14A(0.5) H14B(0.5)
 H14C(0.5) C15(0.5) H15A(0.5) H15B(0.5) C16(0.5) H16A(0.5) H16B(0.5) H16C(0.5)
 C17(0.5) H17A(0.5) H17B(0.5) C18(0.5) H18A(0.5) H18B(0.5) H18C(0.5) C19(0.5)
 H19A(0.5) H19B(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5)
6.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), C9'(H9'A,H9'B), C11'(H11C,H11D), C13(H13A,H13B), C15(H15A,H15B),
 C17(H17A,H17B), C19(H19A,H19B)
6.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), C10'(H10D,H10E,H10F), C12'(H12D,H12E,H12F),
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C)
;
_shelx_res_checksum              65980
_shelx_hkl_checksum              9917
_olex2_submission_original_sample_id matrm17
_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 1.997
_oxdiff_exptl_absorpt_empirical_full_min 0.606