Regioselectivity of concerted proton-electron transfer at the surface of a polyoxovanadate cluster.
Schreiber, Eric; Brennessel, William W.; Matson, Ellen M.; Chemical science 14 (2023) 1386–1396; doi:10.1039/d2sc05928b

data_1568296
_publ_section_title
;
 Regioselectivity of concerted proton-electron transfer at the surface of
 a polyoxovanadate cluster.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              1386
_journal_page_last               1396
_journal_paper_doi               10.1039/d2sc05928b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C11 H33 O19 V6, 2(C10 H10 Co)'
_chemical_formula_sum            'C31 H53 Co2 O19 V6'
_chemical_formula_weight         1153.23
_space_group_crystal_system      orthorhombic
_space_group_IT_number           52
_space_group_name_Hall           '-P 2a 2bc'
_space_group_name_H-M_alt        'P n n a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-03-10
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-10-25 deposited with the CCDC.	2023-01-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.8845(2)
_cell_length_b                   41.3260(6)
_cell_length_c                   14.1744(3)
_cell_measurement_reflns_used    21249
_cell_measurement_temperature    223.00(10)
_cell_measurement_theta_max      79.2940
_cell_measurement_theta_min      3.2760
_cell_volume                     9890.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      223.00(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 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   -120.00 -64.00   0.50    5.38    --  -47.27-139.00-117.00  112
  2  \w    -70.00  25.00   0.50    5.38    --  -47.27  76.00-112.00  190
  3  \w    101.00 178.00   0.50   21.53    --  113.25  44.00  76.00  154
  4  \w     42.00 136.00   0.50   21.53    --  113.25 -76.00 121.00  188
  5  \w     91.00 178.00   0.50   21.53    --  113.25 131.00 128.00  174
  6  \w   -120.00 -73.00   0.50    5.38    --  -47.27-125.00  90.00   94
  7  \w     -3.00  28.00   0.50    5.38    --  -47.27  19.00 150.00   62
  8  \w     -3.00  28.00   0.50    5.38    --  -47.27  19.00 -60.00   62
  9  \w     42.00 106.00   0.50   21.53    --  113.25 -94.00  60.00  128
 10  \w     42.00  80.00   0.50   21.53    --  113.25 -61.00   0.00   76
 11  \w     42.00 106.00   0.50   21.53    --  113.25 -94.00 -90.00  128
 12  \w     42.00 111.00   0.50   21.53    --  113.25-125.00 150.00  138
 13  \w     42.00  80.00   0.50   21.53    --  113.25 -61.00  60.00   76
 14  \w    101.00 178.00   0.50   21.53    --  113.25  45.00-150.00  154
 15  \w     42.00  80.00   0.50   21.53    --  113.25 -61.00-150.00   76
 16  \w     42.00 122.00   0.50   21.53    --  113.25-139.00-117.00  160
 17  \w     25.00 103.00   0.50    5.38    --   47.27  77.00 -30.00  156
;
_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      -0.0504438000
_diffrn_orient_matrix_UB_12      -0.0021262000
_diffrn_orient_matrix_UB_13      -0.0903236000
_diffrn_orient_matrix_UB_21      -0.0007227000
_diffrn_orient_matrix_UB_22      0.0371963000
_diffrn_orient_matrix_UB_23      -0.0069025000
_diffrn_orient_matrix_UB_31      0.0760416000
_diffrn_orient_matrix_UB_32      -0.0010721000
_diffrn_orient_matrix_UB_33      -0.0600641000
_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  0.0904
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       52
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            67691
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.473
_diffrn_reflns_theta_min         3.296
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.753
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.08671
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark blue'
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       plate
_exptl_crystal_F_000             4664
_exptl_crystal_size_max          0.374
_exptl_crystal_size_mid          0.159
_exptl_crystal_size_min          0.097
_refine_diff_density_max         2.392
_refine_diff_density_min         -1.301
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     645
_refine_ls_number_reflns         10664
_refine_ls_number_restraints     999
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1086
_refine_ls_R_factor_gt           0.0854
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1734P)^2^+15.1708P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2566
_refine_ls_wR_factor_ref         0.2815
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7616
_reflns_number_total             10664
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05928b2.cif
_cod_data_source_block           mates15
_cod_depositor_comments
'Adding full bibliography for 1568296--1568297.cif.'
_cod_database_code               1568296
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.329
_shelx_estimated_absorpt_t_min   0.073
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Co2-C22 \\sim Co2-C23 \\sim Co2-C24 \\sim Co2-C25 \\sim Co2-C26 \\sim Co2-C27
\\sim Co2-C28 \\sim Co2-C29
 \\sim Co2-C30 \\sim Co2-C31 \\sim Co2'-C22' \\sim Co2'-C23' \\sim Co2'-C24'
\\sim Co2'-C25' \\sim Co2'-
 C26' \\sim Co2'-C27' \\sim Co2'-C28' \\sim Co2'-C29' \\sim Co2'-C30' \\sim
Co2'-C31'
 with sigma of 0.01
 C22-C27 \\sim C23-C28 \\sim C24-C29 \\sim C25-C30 \\sim C26-C31
 with sigma of 0.04
 C22'-C27' \\sim C23'-C28' \\sim C24'-C29' \\sim C25'-C30' \\sim C26'-C31'
 with sigma of 0.04
 O8-C1 \\sim O8-C1'
 with sigma of 0.01
3. Restrained planarity
 C22, C23, C24, C25, C26
 with sigma of 0.04
 C22', C23', C24', C25', C26'
 with sigma of 0.04
 C27, C28, C29, C30, C31
 with sigma of 0.04
 C27', C28', C29', C30', C31'
 with sigma of 0.04
4. 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
5. Rigid body (RIGU) restrains
 Co2, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Co2', C22', C23', C24', C25', C26', C27', C28', C29', C30', C31'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8, C1, C1'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C23, C24, C25, C26, C22} sigma for 1-2: 0.02, 1-3: 0.04
{C26, C25, C24, C23, C22} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C22, C23, C24, C25, C26}
{C22, C23, C24, C25, C26} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C27, C28, C29, C30, C31}
{C22, C23, C24, C25, C26} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C22', C23', C24', C25', C26'}
{C22, C23, C24, C25, C26} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C27', C28', C29', C30', C31'}
7. Others
 Sof(Co2')=Sof(C22')=Sof(H22')=Sof(C23')=Sof(H23')=Sof(C24')=Sof(H24')=
 Sof(C25')=Sof(H25')=Sof(C26')=Sof(H26')=Sof(C27')=Sof(H27')=Sof(C28')=
 Sof(H28')=Sof(C29')=Sof(H29')=Sof(C30')=Sof(H30')=Sof(C31')=Sof(H31')=1-FVAR(1)
 Sof(Co2)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=
 Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=
 Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=FVAR(1)
 Sof(C1')=Sof(H1'A)=Sof(H1'B)=Sof(H1'C)=1-FVAR(2)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(2)
8.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C22'(H22'), C23'(H23'),
 C24'(H24'), C25'(H25'), C26'(H26'), C27'(H27'), C28'(H28'), C29'(H29'),
 C30'(H30'), C31'(H31')
8.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C1'(H1'A,H1'B,H1'C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C),
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,
 H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              53327
_shelx_fab_checksum              33547
_olex2_submission_original_sample_id mates15
_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 4.456
_oxdiff_exptl_absorpt_empirical_full_min 0.372