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_1564546
_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, 2(C16 H36 N)'
_chemical_formula_sum            'C47 H117 N2 O19 Si V6'
_chemical_formula_weight         1348.15
_chemical_name_systematic        matsc01
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-08-26
_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                 96.0925(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.77236(17)
_cell_length_b                   34.8563(7)
_cell_length_c                   16.6545(3)
_cell_measurement_reflns_used    21443
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4440
_cell_measurement_theta_min      2.9620
_cell_volume                     6795.4(2)
_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 0.996
_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    -55.00   2.00   0.50    4.58    --  -49.87  82.00 -47.00  114
  2  \w    -45.00 -19.00   0.50   18.31    --  -84.25  82.00 -47.00   52
  3  \w     -5.00  23.00   0.50    4.58    --  -49.87  19.00 -60.00   56
  4  \w     -4.00  24.00   0.50    4.58    --  -49.87  19.00  60.00   56
  5  \w    -43.00 -13.00   0.50   18.31    --  -84.25  45.00 150.00   60
  6  \w     50.00  75.00   0.50    4.58    --   49.87  82.00 -47.00   50
  7  \w     83.00 137.00   0.50   18.31    --  105.75  82.00 -47.00  108
  8  \w    112.00 138.00   0.50   18.31    --  105.75 125.00 -90.00   52
  9  \w    124.00 169.00   0.50   18.31    --  105.75  30.00 -90.00   90
 10  \w    112.00 175.00   0.50   18.31    --  105.75  15.00-120.00  126
 11  \w     95.00 121.00   0.50   18.31    --  105.75 -82.00-169.00   52
 12  \w     58.00 115.00   0.50   18.31    --  105.75-125.00 -30.00  114
 13  \w     45.00  71.00   0.50   18.31    --  105.75 -82.00-169.00   52
 14  \w     38.00  79.00   0.50   18.31    --  105.75 -61.00-150.00   82
 15  \w     35.00 109.00   0.50   18.31    --  105.75 -94.00-180.00  148
 16  \w     39.00  65.00   0.50   18.31    --  105.75 -61.00 -30.00   52
 17  \w     38.00  77.00   0.50   18.31    --  105.75 -61.00   0.00   78
 18  \w     48.00  75.00   0.50   18.31    --  105.75 -61.00  30.00   54
 19  \w     41.00  78.00   0.50   18.31    --  105.75 -61.00  60.00   74
 20  \w     38.00  63.00   0.50   18.31    --  105.75 -61.00  90.00   50
 21  \w    100.00 178.00   0.50   18.31    --  105.75  30.00  90.00  156
 22  \w    100.00 174.00   0.50   18.31    --  105.75  15.00-150.00  148
 23  \w     35.00 116.00   0.50   18.31    --  105.75-125.00-180.00  162
 24  \w     34.00  74.00   0.50   18.31    --  105.75 -94.00 -60.00   80
 25  \w     36.00  79.00   0.50   18.31    --  105.75 -61.00 -60.00   86
 26  \w     34.00  63.00   0.50   18.31    --  105.75 -61.00-120.00   58
 27  \w     15.00  67.00   0.50    4.58    --   49.87 -82.00-169.00  104
 28  \w    -21.00  12.00   0.50    4.58    --   49.87 -82.00-169.00   66
 29  \w    -22.00  13.00   0.50    4.58    --   49.87 -19.00 -60.00   70
 30  \w    -22.00   7.00   0.50    4.58    --   49.87 -19.00-180.00   58
 31  \w   -121.00 -55.00   0.50    4.58    --  -49.87 -82.00-169.00  132
 32  \w   -133.00-108.00   0.50   18.31    --  -84.25 -82.00-169.00   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      0.0955341000
_diffrn_orient_matrix_UB_12      -0.0122809000
_diffrn_orient_matrix_UB_13      -0.0509705000
_diffrn_orient_matrix_UB_21      0.0199237000
_diffrn_orient_matrix_UB_22      -0.0365514000
_diffrn_orient_matrix_UB_23      0.0515818000
_diffrn_orient_matrix_UB_31      -0.0882916000
_diffrn_orient_matrix_UB_32      -0.0216161000
_diffrn_orient_matrix_UB_33      -0.0582516000
_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  0.0627
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            67275
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.853
_diffrn_reflns_theta_min         2.535
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.322
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40557
_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    1.318
_exptl_crystal_description       needle
_exptl_crystal_F_000             2868
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.156
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     990
_refine_ls_number_reflns         14212
_refine_ls_number_restraints     506
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.1125
_refine_ls_R_factor_gt           0.0840
_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^)+(0.1423P)^2^+8.6946P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2377
_refine_ls_wR_factor_ref         0.2650
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9746
_reflns_number_total             14212
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02809j2.cif
_cod_data_source_block           matsc01
_cod_database_code               1564546
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.644
_shelx_estimated_absorpt_t_min   0.235
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C32-C33 = C33-C34 = C34-C35 = C32'-C33' = C33'-C34' = C34'-C35'
 1.52 with sigma of 0.03
 C28-C29 = C29-C30 = C30-C31 = C28-C29' = C29'-C30' = C30'-C31'
 1.52 with sigma of 0.02
 O1-Si1 \\sim O1-Si1'
 with sigma of 0.01
 Si1-C1 \\sim Si1-C2 \\sim Si1-C3 \\sim Si1'-C1' \\sim Si1'-C2'
 with sigma of 0.01
 O7-C4 \\sim O7-C4'
 with sigma of 0.01
 O8-C5 \\sim O8-C5'
 with sigma of 0.01
 O9-C6 \\sim O9-C6'
 with sigma of 0.01
 O10-C7 \\sim O10-C7'
 with sigma of 0.01
 O11-C8 \\sim O11-C8'
 with sigma of 0.01
 O12-C9 \\sim O12-C9'
 with sigma of 0.01
 O16-C13 \\sim O16-C13'
 with sigma of 0.01
 N2-C32 \\sim N2-C36 \\sim N2-C40 \\sim N2-C44 \\sim N2'-C32' \\sim N2'-C36'
\\sim N2'-C40' \\sim N2'-C44'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
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(C35') \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 C3, Si1, C1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3, Si1', C1', C2'
 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
 O11, C8'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32, C33, C34, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C36, C37, C38, C39
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, C41, C42, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44, C45, C46, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C32', C33', C34', C35'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C36', C37', C38', C39'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40', C41', C42', C43'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44', C45', C46', C47'
 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
5. Same fragment restrains
{C28, C29', C30', C31'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C28, C29, C30, C31}
{C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C32', C33', C34', C35'}
{C36, C37, C38, C39} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C36', C37', C38', C39'}
{C40, C41, C42, C43} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C40', C41', C42', C43'}
{C44, C45, C46, C47} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C44', C45', C46', C47'}
6. Others
 Sof(H3BD)=Sof(H3BE)=Sof(H3BF)=Sof(Si1')=Sof(C1')=Sof(H1'A)=Sof(H1'B)=
 Sof(H1'C)=Sof(C2')=Sof(H2'A)=Sof(H2'B)=Sof(H2'C)=1-FVAR(1)
 Sof(Si1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(H2A)=Sof(H2B)=
 Sof(H2C)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=FVAR(1)
 Sof(C4')=Sof(H4'A)=Sof(H4'B)=Sof(H4'C)=1-FVAR(2)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(2)
 Sof(C5')=Sof(H5'A)=Sof(H5'B)=Sof(H5'C)=1-FVAR(3)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(3)
 Sof(C6')=Sof(H6'A)=Sof(H6'B)=Sof(H6'C)=1-FVAR(4)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(4)
 Sof(C7')=Sof(H7'A)=Sof(H7'B)=Sof(H7'C)=1-FVAR(5)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(5)
 Sof(C8')=Sof(H8'A)=Sof(H8'B)=Sof(H8'C)=1-FVAR(6)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(6)
 Sof(C9')=Sof(H9'A)=Sof(H9'B)=Sof(H9'C)=1-FVAR(7)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(7)
 Sof(C13')=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(8)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(8)
 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(9)
 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(9)
 Sof(N2')=Sof(C32')=Sof(H32C)=Sof(H32D)=Sof(C33')=Sof(H33C)=Sof(H33D)=
 Sof(C34')=Sof(H34C)=Sof(H34D)=Sof(C35')=Sof(H35D)=Sof(H35E)=Sof(H35F)=
 Sof(C36')=Sof(H36C)=Sof(H36D)=Sof(C37')=Sof(H37C)=Sof(H37D)=Sof(C38')=
 Sof(H38C)=Sof(H38D)=Sof(C39')=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40')=
 Sof(H40C)=Sof(H40D)=Sof(C41')=Sof(H41C)=Sof(H41D)=Sof(C42')=Sof(H42C)=
 Sof(H42D)=Sof(C43')=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(C44')=Sof(H44C)=
 Sof(H44D)=Sof(C45')=Sof(H45C)=Sof(H45D)=Sof(C46')=Sof(H46C)=Sof(H46D)=
 Sof(C47')=Sof(H47D)=Sof(H47E)=Sof(H47F)=1-FVAR(10)
 Sof(N2)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=
 Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=
 Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(10)
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), C28(H28C,H28D), C29(H29A,H29B), C30(H30A,H30B), C29'(H29C,
 H29D), C30'(H30C,H30D), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B),
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C40(H40A,H40B), C41(H41A,H41B),
  C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C32'(H32C,
 H32D), C33'(H33C,H33D), C34'(H34C,H34D), C36'(H36C,H36D), C37'(H37C,H37D),
 C38'(H38C,H38D), C40'(H40C,H40D), C41'(H41C,H41D), C42'(H42C,H42D), C44'(H44C,
 H44D), C45'(H45C,H45D), C46'(H46C,H46D)
7.b Me refined with riding coordinates:
 C3(H3AA,H3AB,H3AC), C3(H3BD,H3BE,H3BF), C35'(H35D,H35E,H35F), C47'(H47D,H47E,
 H47F)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C1'(H1'A,H1'B,H1'C), C2'(H2'A,H2'B,H2'C),
 C4(H4A,H4B,H4C), C4'(H4'A,H4'B,H4'C), 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), C7'(H7'A,H7'B,H7'C),
 C8(H8A,H8B,H8C), C8'(H8'A,H8'B,H8'C), C9(H9A,H9B,H9C), C9'(H9'A,H9'B,H9'C),
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C13'(H13D,H13E,H13F), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C19(H19A,H19B,H19C), C23(H23A,H23B,H23C), C27(H27A,H27B,H27C), C31(H31A,H31B,
 H31C), C31'(H31D,H31E,H31F), C35(H35A,H35B,H35C), C39(H39A,H39B,H39C),
 C43(H43A,H43B,H43C), C47(H47A,H47B,H47C), C39'(H39D,H39E,H39F), C43'(H43D,H43E,
 H43F)
;
_shelx_res_checksum              11879
_shelx_hkl_checksum              80129
_olex2_submission_original_sample_id matsc01
_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 1.861
_oxdiff_exptl_absorpt_empirical_full_min 0.577