Modelling local structural and electronic consequences of proton and hydrogen-atom uptake in VO2 with polyoxovanadate clusters
Chakraborty, Sourav; Schreiber, Eric; Sanchez-Lievanos, Karla R.; Tariq, Mehrin; Brennessel, William W.; Knowles, Kathryn E.; Matson, Ellen M.; Chemical Science  (2021) –; doi:10.1039/D1SC02809J

data_1564547
_publ_section_title
;
 Modelling local structural and electronic consequences of proton and
 hydrogen-atom uptake in VO2 with polyoxovanadate clusters
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02809J
_journal_year                    2021
_chemical_formula_moiety         'C15 H45 O19 Si V6, C16 H36 N'
_chemical_formula_sum            'C31 H81 N O19 Si V6'
_chemical_formula_weight         1105.69
_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             2020-12-02
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-01-23 deposited with the CCDC.	2021-08-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.6012(3)
_cell_length_b                   18.2780(3)
_cell_length_c                   29.0427(6)
_cell_measurement_reflns_used    27111
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.9700
_cell_measurement_theta_min      3.0290
_cell_volume                     9874.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (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 0.981
_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   -121.00 -52.00   0.50    3.40    --  -49.87-152.00 -63.00  138
  2  \w   -121.00 -42.00   0.50    3.40    --  -49.87-171.00  41.00  158
  3  \w   -156.00 -73.00   0.50   13.61    --  -84.25-121.00  96.00  166
  4  \w    -30.00  22.00   0.50    3.40    --  -49.87  38.00 -60.00  104
  5  \w    -30.00  12.00   0.50    3.40    --  -49.87  38.00-150.00   84
  6  \w    -30.00  22.00   0.50    3.40    --  -49.87  38.00-180.00  104
  7  \w    -21.00   5.00   0.50    3.40    --   49.87 -19.00-180.00   52
  8  \w     38.00  73.00   0.50   13.61    --  105.75 -61.00-180.00   70
  9  \w     76.00 107.00   0.50   13.61    --  105.75-125.00-180.00   62
 10  \w     88.00 116.00   0.50   13.61    --  105.75-125.00 -90.00   56
 11  \w     52.00  81.00   0.50   13.61    --  105.75 -61.00 -60.00   58
 12  \w     41.00  66.00   0.50   13.61    --  105.75-125.00-180.00   50
 13  \w     41.00 108.00   0.50   13.61    --  105.75 -94.00  60.00  134
 14  \w     38.00  65.00   0.50   13.61    --  105.75 -94.00 120.00   54
 15  \w     35.00  81.00   0.50   13.61    --  105.75 -61.00 150.00   92
 16  \w     98.00 164.00   0.50   13.61    --  105.75  15.00 100.00  132
 17  \w     98.00 178.00   0.50   13.61    --  105.75 115.00 -86.00  160
 18  \w     99.00 175.00   0.50   13.61    --  105.75  45.00 -90.00  152
 19  \w    -22.00   5.00   0.50    3.40    --   49.87 -19.00 120.00   54
;
_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      -0.0608792000
_diffrn_orient_matrix_UB_12      0.0164090000
_diffrn_orient_matrix_UB_13      -0.0344524000
_diffrn_orient_matrix_UB_21      0.0554860000
_diffrn_orient_matrix_UB_22      0.0045071000
_diffrn_orient_matrix_UB_23      -0.0392954000
_diffrn_orient_matrix_UB_31      -0.0089527000
_diffrn_orient_matrix_UB_32      -0.0825208000
_diffrn_orient_matrix_UB_33      -0.0090603000
_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  0.0661
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            65851
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.968
_diffrn_reflns_theta_min         3.043
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.946
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43657
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.488
_exptl_crystal_description       plate
_exptl_crystal_F_000             4624
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.042
_refine_diff_density_max         1.063
_refine_diff_density_min         -0.810
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     734
_refine_ls_number_reflns         10356
_refine_ls_number_restraints     274
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0619
_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^)+(0.1083P)^2^+13.1967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1761
_refine_ls_wR_factor_ref         0.2044
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7853
_reflns_number_total             10356
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02809j2.cif
_cod_data_source_block           matsc04
_cod_database_code               1564547
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.680
_shelx_estimated_absorpt_t_min   0.169
_reflns_odcompleteness_completeness 99.67
_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-C5 \\sim O8-C5'
 with sigma of 0.01
 O9-C6 \\sim O9-C6'
 with sigma of 0.01
 O12-C9 \\sim O12-C9'
 with sigma of 0.01
 O14-C11 \\sim O14-C11'
 with sigma of 0.01
 O15-C12 \\sim O15-C12'
 with sigma of 0.01
 O16-C13 \\sim O16-C13'
 with sigma of 0.01
 O17-C14 \\sim O17-C14'
 with sigma of 0.01
 O18-C15 \\sim O18-C15'
 with sigma of 0.01
 N1-C24 \\sim N1-C24' \\sim N1-C28 \\sim N1-C28'
 with sigma of 0.01
 O1-Si1 \\sim O1-Si1'
 with sigma of 0.01
 Si1-C1 \\sim Si1-C2 \\sim Si1-C3 \\sim Si1'-C1' \\sim Si1'-C2' \\sim Si1'-C3'
 with sigma of 0.01
 C1-C2 \\sim C2-C3 \\sim C3-C1 \\sim C1'-C2' \\sim C2'-C3' \\sim C3'-C1'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Si1 \\sim Si1': within 2A with sigma of 0.008 and sigma for terminal atoms of
0.016 within 2A
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.2A
Uanis(C11) = Uanis(C11')
4. Rigid body (RIGU) restrains
 C24, C25, C26, C27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24', C25', C26', C27'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28, C29, C30, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C28', C29', C30', C31'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8, C5'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O9, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O9, C6'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O12, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O12, C9'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15, C12'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O16, C13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O16, C13'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17, C14'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O18, C15
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O18, C15'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Si1', C1', C2', C3'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C24, C25, C26, C27} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C24', C25', C26', C27'}
{C28, C29, C30, C31} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C28', C29', C30', C31'}
6. Others
 Sof(C5')=Sof(H5'A)=Sof(H5'B)=Sof(H5'C)=1-FVAR(1)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(1)
 Sof(C6')=Sof(H6'A)=Sof(H6'B)=Sof(H6'C)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(2)
 Sof(C9')=Sof(H9'A)=Sof(H9'B)=Sof(H9'C)=1-FVAR(3)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(3)
 Sof(C11')=Sof(H11D)=Sof(H11E)=Sof(H11F)=1-FVAR(4)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(4)
 Sof(C12')=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13')=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14')=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15')=Sof(H15D)=
 Sof(H15E)=Sof(H15F)=1-FVAR(5)
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 FVAR(5)
 Sof(C24')=Sof(H24C)=Sof(H24D)=Sof(C25')=Sof(H25C)=Sof(H25D)=Sof(C26')=
 Sof(H26C)=Sof(H26D)=Sof(C27')=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(6)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=
 Sof(H26B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(6)
 Sof(C28')=Sof(H28C)=Sof(H28D)=Sof(C29')=Sof(H29C)=Sof(H29D)=Sof(C30')=
 Sof(H30C)=Sof(H30D)=Sof(C31')=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(7)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(7)
 Sof(Si1')=Sof(C1')=Sof(H1'A)=Sof(H1'B)=Sof(H1'C)=Sof(C2')=Sof(H2'A)=Sof(H2'B)=
 Sof(H2'C)=Sof(C3')=Sof(H3'A)=Sof(H3'B)=Sof(H3'C)=1-FVAR(8)
 Sof(Si1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(H2A)=Sof(H2B)=
 Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(8)
7.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B), C21(H21A,
 H21B), C22(H22A,H22B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B),
 C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C24'(H24C,H24D), C25'(H25C,
 H25D), C26'(H26C,H26D), C28'(H28C,H28D), C29'(H29C,H29D), C30'(H30C,H30D)
7.b Me refined with riding coordinates:
 C1'(H1'A,H1'B,H1'C), C2'(H2'A,H2'B,H2'C), C3'(H3'A,H3'B,H3'C)
7.c 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), C5'(H5'A,H5'B,H5'C), C6(H6A,H6B,H6C), C6'(H6'A,H6'B,H6'C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C9'(H9'A,H9'B,H9'C), C10(H10A,H10B,
 H10C), C11(H11A,H11B,H11C), C11'(H11D,H11E,H11F), C12(H12A,H12B,H12C),
 C12'(H12D,H12E,H12F), C13(H13A,H13B,H13C), C13'(H13D,H13E,H13F), C14(H14A,H14B,
 H14C), C14'(H14D,H14E,H14F), C15(H15A,H15B,H15C), C15'(H15D,H15E,H15F),
 C19(H19A,H19B,H19C), C23(H23A,H23B,H23C), C27(H27A,H27B,H27C), C31(H31A,H31B,
 H31C), C27'(H27D,H27E,H27F), C31'(H31D,H31E,H31F)
;
_shelx_res_checksum              84313
_shelx_hkl_checksum              62420
_olex2_submission_original_sample_id matsc04
_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 3.525
_oxdiff_exptl_absorpt_empirical_full_min 0.571