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_1568297
_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 H34 O19 V6, 2(C16 H36 N)'
_chemical_formula_sum            'C43 H106 N2 O19 V6'
_chemical_formula_weight         1260.93
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-02-22
_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                95.1060(10)
_cell_angle_beta                 115.5700(10)
_cell_angle_gamma                113.8640(10)
_cell_formula_units_Z            1
_cell_length_a                   11.98260(10)
_cell_length_b                   11.99650(10)
_cell_length_c                   13.43130(10)
_cell_measurement_reflns_used    33917
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.6000
_cell_measurement_theta_min      3.8440
_cell_volume                     1509.23(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      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     25.00 119.00   0.50    0.09    --   47.30  77.00   0.00  188
  2  \w     25.00 119.00   0.50    0.09    --   47.30  77.00  30.00  188
  3  \w     25.00 119.00   0.50    0.09    --   47.30  77.00 120.00  188
  4  \w     25.00 119.00   0.50    0.09    --   47.30  77.00 -30.00  188
  5  \w     25.00 119.00   0.50    0.09    --   47.30  77.00-120.00  188
  6  \w     25.00 119.00   0.50    0.09    --   47.30  77.00-150.00  188
  7  \w     32.00 119.00   0.50    0.09    --   47.30  57.00-150.00  174
  8  \w     32.00 119.00   0.50    0.09    --   47.30  57.00 -30.00  174
  9  \w     32.00 119.00   0.50    0.09    --   47.30  57.00  90.00  174
 10  \w    -16.00  28.00   0.50    0.09    --  -47.30  19.00  60.00   88
 11  \w    -16.00  28.00   0.50    0.09    --  -47.30  19.00  90.00   88
 12  \w    -16.00  28.00   0.50    0.09    --  -47.30  19.00 150.00   88
 13  \w    -16.00  28.00   0.50    0.09    --  -47.30  19.00   0.00   88
 14  \w    -16.00  28.00   0.50    0.09    --  -47.30  19.00 -60.00   88
 15  \w    -16.00  28.00   0.50    0.09    --  -47.30  19.00-150.00   88
 16  \w     91.00 178.00   0.50    0.37    --  113.25  77.00  60.00  174
 17  \w    101.00 178.00   0.50    0.37    --  113.25  45.00  30.00  154
 18  \w    101.00 178.00   0.50    0.37    --  113.25  45.00 -60.00  154
 19  \w     91.00 178.00   0.50    0.37    --  113.25  77.00 -30.00  174
 20  \w    101.00 178.00   0.50    0.37    --  113.25  30.00   0.00  154
 21  \w    100.00 178.00   0.50    0.37    --  113.25  15.00  90.00  156
 22  \w    101.00 178.00   0.50    0.37    --  113.25  45.00 -90.00  154
 23  \w    101.00 178.00   0.50    0.37    --  113.25  30.00-150.00  154
 24  \w    101.00 178.00   0.50    0.37    --  113.25  30.00-180.00  154
 25  \w    100.00 178.00   0.50    0.37    --  113.25  15.00 -90.00  156
 26  \w    100.00 178.00   0.50    0.37    --  113.25  15.00 150.00  156
 27  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00  60.00   74
 28  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00  30.00   74
 29  \w    -24.00  70.00   0.50    0.09    --   47.30 -77.00  30.00  188
 30  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00   0.00   74
 31  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00 -30.00   74
 32  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00-120.00   74
 33  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00-180.00   74
 34  \w     95.00 178.00   0.50    0.37    --  113.25 125.00  90.00  166
 35  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00  90.00   74
 36  \w     42.00  79.00   0.50    0.37    --  113.25 -61.00 120.00   74
 37  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00 150.00  128
 38  \w     42.00 111.00   0.50    0.37    --  113.25-125.00 120.00  138
 39  \w     42.00 111.00   0.50    0.37    --  113.25-125.00 150.00  138
 40  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00  90.00  128
 41  \w     42.00 111.00   0.50    0.37    --  113.25-125.00   0.00  138
 42  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00 -90.00  128
 43  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00-120.00  128
 44  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00-150.00  128
 45  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00-180.00  128
 46  \w     34.00  95.00   0.50    0.09    --   47.30-125.00-150.00  122
 47  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00   0.00  128
 48  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00  30.00  128
 49  \w     42.00 106.00   0.50    0.37    --  113.25 -94.00 120.00  128
 50  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00-132.24  188
 51  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00 -95.96  188
 52  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00  30.00  188
 53  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00 -30.00  188
 54  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00  60.00  188
 55  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00 120.00  188
 56  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00 163.51  188
 57  \w   -163.00 -69.00   0.50    0.37    --  -91.75 -77.00 150.00  188
 58  \w   -163.00 -71.00   0.50    0.37    --  -91.75 -71.00  88.83  184
 59  \w   -163.00 -72.00   0.50    0.37    --  -91.75 -69.00  69.88  182
 60  \w   -163.00 -70.00   0.50    0.37    --  -91.75 -74.00 -17.11  186
 61  \w   -163.00 -77.00   0.50    0.37    --  -91.75 -57.00 -74.24  172
 62  \w    -65.00 -19.00   0.50    0.37    --  -91.75  61.00-150.00   92
 63  \w   -163.00 -75.00   0.50    0.37    --  -91.75 -61.00-180.00  176
 64  \w   -163.00 -73.00   0.50    0.37    --  -91.75-125.00-150.00  180
 65  \w   -119.00 -73.00   0.50    0.09    --  -47.30-125.00-180.00   92
 66  \w   -119.00 -73.00   0.50    0.09    --  -47.30-125.00-150.00   92
 67  \w   -119.00 -73.00   0.50    0.09    --  -47.30-125.00  60.00   92
;
_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      -0.1058053000
_diffrn_orient_matrix_UB_12      -0.0020559000
_diffrn_orient_matrix_UB_13      0.0369147000
_diffrn_orient_matrix_UB_21      0.0415540000
_diffrn_orient_matrix_UB_22      0.1392875000
_diffrn_orient_matrix_UB_23      -0.0006596000
_diffrn_orient_matrix_UB_31      -0.1179641000
_diffrn_orient_matrix_UB_32      -0.0505576000
_diffrn_orient_matrix_UB_33      -0.1290093000
_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  0.0426
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            51188
_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         80.300
_diffrn_reflns_theta_min         3.850
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.021
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78086
_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            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             668
_exptl_crystal_size_max          0.149
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.097
_refine_diff_density_max         1.082
_refine_diff_density_min         -1.015
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         6475
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0410P)^2^+1.5174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0935
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6129
_reflns_number_total             6475
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05928b2.cif
_cod_data_source_block           mates20
_cod_depositor_comments
'Adding full bibliography for 1568296--1568297.cif.'
_cod_database_code               1568297
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O7-C4 \\sim O7-C4'
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C4') \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 1*[Sof(H4)+Sof(C1)+Sof(H1A)+Sof(H1B)+Sof(H1C)]+1*[Sof(H5)+Sof(C2)+Sof(H2A)+
 Sof(H2B)+Sof(H2C)]+1*[Sof(H6)+Sof(C3)+Sof(H3A)+Sof(H3B)+Sof(H3C)]+1*[Sof(C4)+
 Sof(H4A)+Sof(H4B)+Sof(H4C)]+1*[Sof(C4')+Sof(H4'A)+Sof(H4'B)+Sof(H4'C)]+1*
 [Sof(H8)+Sof(C5)+Sof(H5A)+Sof(H5B)+Sof(H5C)]=4.5 with esd of 0.0001
 1*[Sof(C4)+Sof(H4A)+Sof(H4B)+Sof(H4C)]+1*[Sof(C4')+Sof(H4'A)+Sof(H4'B)+
 Sof(H4'C)]-1*[Sof(H7)]=0 with esd of 0.0001
 Sof(H4)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(1)
 Sof(H5)=1-FVAR(2)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=FVAR(2)
 Sof(H6)=1-FVAR(3)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(3)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(4)
 Sof(C4')=Sof(H4'A)=Sof(H4'B)=Sof(H4'C)=FVAR(5)
 Sof(H8)=1-FVAR(6)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(6)
5.a Riding coordinates:
 O4(H4), O5(H5), O6(H6), O7(H7), O8(H8)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C19(H19A,H19B),
  C20(H20A,H20B), C21(H21A,H21B)
5.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C4'(H4'A,
 H4'B,H4'C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C14(H14A,
 H14B,H14C), C18(H18A,H18B,H18C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              63809
_olex2_submission_original_sample_id mates20
_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 1.353
_oxdiff_exptl_absorpt_empirical_full_min 0.821