Coordination-induced bond weakening of water at the surface of an oxygen-deficient polyoxovanadate cluster.
Cooney, Shannon E.; Fertig, Alex A.; Buisch, Madeleine R.; Brennessel, William W.; Matson, Ellen M.; Chemical science 13 (2022) 12726–12737; doi:10.1039/d2sc04843d

data_1567756
_publ_section_title
;
 Coordination-induced bond weakening of water at the surface of an
 oxygen-deficient polyoxovanadate cluster.
;
_journal_issue                   43
_journal_name_full               'Chemical science'
_journal_page_first              12726
_journal_page_last               12737
_journal_paper_doi               10.1039/d2sc04843d
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety
'C53.046 H80.523 N0.523 O18.477 V6, 3.477(C4 H8 O)'
_chemical_formula_sum            'C66.95 H108.34 N0.52 O21.95 V6'
_chemical_formula_weight         1577.57
_space_group_crystal_system      orthorhombic
_space_group_IT_number           57
_space_group_name_Hall           '-P 2c 2b'
_space_group_name_H-M_alt        'P b c m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-06-22
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-24 deposited with the CCDC.	2022-10-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4807(2)
_cell_length_b                   27.8595(5)
_cell_length_c                   18.7836(2)
_cell_measurement_reflns_used    17304
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      78.7590
_cell_measurement_theta_min      3.4540
_cell_volume                     7577.77(19)
_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 2019/2 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_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    -20.00  27.00   0.50    3.37    --  -47.29  23.00  77.00   94
  2  \w   -122.00 -35.00   0.50    3.37    --  -47.29 -23.00 -87.00  174
  3  \w    -80.00 -19.00   0.50   13.49    --  -91.75 101.00-123.00  122
  4  \w    -98.00 -21.00   0.50   13.49    --  -91.75 141.00 -58.00  154
  5  \w    101.00 178.00   0.50   13.49    --  113.25  23.00  77.00  154
  6  \w     43.00 123.00   0.50   13.49    --  113.25-141.00-115.00  160
  7  \w   -119.00 -73.00   0.50    3.37    --  -47.29-125.00-120.00   92
  8  \w    -16.00  28.00   0.50    3.37    --  -47.29  19.00-150.00   88
  9  \w    -27.00  30.00   0.50    3.37    --   47.29 -19.00-180.00  114
 10  \w    101.00 178.00   0.50   13.49    --  113.25  45.00  30.00  154
 11  \w     42.00 111.00   0.50   13.49    --  113.25-125.00 -30.00  138
 12  \w     42.00 106.00   0.50   13.49    --  113.25 -94.00  60.00  128
 13  \w     42.00 111.00   0.50   13.49    --  113.25-125.00 150.00  138
 14  \w     42.00  79.00   0.50   13.49    --  113.25 -61.00-180.00   74
 15  \w     32.00  95.00   0.50    3.37    --   47.29  57.00 120.00  126
;
_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      -0.0052944000
_diffrn_orient_matrix_UB_12      -0.0525993000
_diffrn_orient_matrix_UB_13      -0.0250601000
_diffrn_orient_matrix_UB_21      0.1061115000
_diffrn_orient_matrix_UB_22      -0.0034426000
_diffrn_orient_matrix_UB_23      0.0024668000
_diffrn_orient_matrix_UB_31      -0.0048748000
_diffrn_orient_matrix_UB_32      -0.0167682000
_diffrn_orient_matrix_UB_33      0.0780533000
_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  0.0397
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            48002
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.488
_diffrn_reflns_theta_min         3.440
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.538
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60932
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_description       block
_exptl_crystal_F_000             3309
_exptl_crystal_size_max          0.248
_exptl_crystal_size_mid          0.182
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.665
_refine_diff_density_min         -0.479
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     704
_refine_ls_number_reflns         8377
_refine_ls_number_restraints     566
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0843
_refine_ls_R_factor_gt           0.0644
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1040P)^2^+5.1446P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1861
_refine_ls_wR_factor_ref         0.2032
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5983
_reflns_number_total             8377
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04843d2.cif
_cod_data_source_block           matsec01
_cod_depositor_comments          'Adding full bibliography for 1567756.cif.'
_cod_original_cell_volume        7577.78(19)
_cod_database_code               1567756
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.461
_shelx_estimated_absorpt_t_min   0.294
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Shared sites
{N1, O1}
3. Restrained distances
 C24-C25 \\sim C24-C26 \\sim C24-C27
 with sigma of 0.01
 C25-C26 \\sim C26-C27 \\sim C27-C25
 with sigma of 0.02
 C28-C29 \\sim C28-C30 \\sim C28-C31 \\sim C28'-C29' \\sim C28'-C30' \\sim
C28'-C31'
 with sigma of 0.01
 C29-C30 \\sim C30-C31 \\sim C31-C29 \\sim C29'-C30' \\sim C30'-C31' \\sim
C31'-C29'
 with sigma of 0.02
 C32-C33 \\sim C32-C34 \\sim C32-C35
 with sigma of 0.01
 C33-C34 \\sim C34-C35 \\sim C35-C33
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 1.2A
Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(N1) = Uanis(O1)
5. 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
 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
 C32, C33, C34, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15, C36, C37, C38, C39
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O16, C40, C41, C42, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15', C36', C37', C38', C39'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17, C44, C45, C46, C47
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17', C44', C45', C46', C47'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{O15, C36, C37, C38, C39} sigma for 1-2: 0.02, 1-3: 0.04
{O16, C43, C42, C41, C40} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O16, C40, C41, C42, C43}
{O15, C39, C38, C37, C36} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O15, C36, C37, C38, C39}
{O15', C39', C38', C37', C36'} sigma for 1-2: 0.02, 1-3: 0.04
{O15, C36, C37, C38, C39} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O15', C36', C37', C38', C39'}
{O15, C36, C37, C38, C39} sigma for 1-2: 0.02, 1-3: 0.04
{O17, C47, C46, C45, C44} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O17, C44, C45, C46, C47}
{O17', C47', C46', C45', C44'} sigma for 1-2: 0.02, 1-3: 0.04
{O15, C36, C37, C38, C39} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O17', C44', C45', C46', C47'}
7. Others
 Sof(C28')=Sof(C29')=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30')=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=Sof(C31')=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(1)
 Sof(C28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=
 Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(1)
 Sof(O15')=Sof(C36')=Sof(H36C)=Sof(H36D)=Sof(C37')=Sof(H37C)=Sof(H37D)=
 Sof(C38')=Sof(H38C)=Sof(H38D)=Sof(C39')=Sof(H39C)=Sof(H39D)=1-FVAR(2)
 Sof(O15)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=
 Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=FVAR(2)
 Sof(O1)=Sof(H1A)=Sof(H1B)=Sof(O16)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=
 Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 0.5*(1-FVAR(4))
 Sof(N1)=Sof(C1)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=0.5*FVAR(4)
 Sof(O17')=Sof(C44')=Sof(H44C)=Sof(H44D)=Sof(C45')=Sof(H45C)=Sof(H45D)=
 Sof(C46')=Sof(H46C)=Sof(H46D)=Sof(C47')=Sof(H47C)=Sof(H47D)=0.5*(1-FVAR(5))
 Sof(O17)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=
 Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=0.5*FVAR(5)
 Fixed Sof: H5A(0.5) H5B(0.5) H5C(0.5) H7A(0.5) H7B(0.5) H7C(0.5) C24(0.5)
 C25(0.5) H25A(0.5) H25B(0.5) H25C(0.5) C26(0.5) H26A(0.5) H26B(0.5) H26C(0.5)
 C27(0.5) H27A(0.5) H27B(0.5) H27C(0.5) C33(0.5) H33A(0.5) H33B(0.5) H33C(0.5)
 C34(0.5) H34A(0.5) H34B(0.5) H34C(0.5) C35(0.5) H35A(0.5) H35B(0.5) H35C(0.5)
8.a Riding coordinates:
 C2(H2A,H2B,H2C), O1(H1A,H1B)
8.b Secondary CH2 refined with riding coordinates:
 C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C22(H22A,
 H22B), C23(H23A,H23B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B),
 C39(H39A,H39B), C36'(H36C,H36D), C37'(H37C,H37D), C38'(H38C,H38D), C39'(H39C,
 H39D), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B),
 C44'(H44C,H44D), C45'(H45C,H45D), C46'(H46C,H46D), C47'(H47C,H47D)
8.c Me refined with riding coordinates:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C26(H26A,H26B,H26C)
8.d Aromatic/amide H refined with riding coordinates:
 C10(H10), C14(H14), C16(H16), C20(H20)
8.e Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C25(H25A,H25B,H25C),
 C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C29'(H29D,H29E,H29F), C30'(H30D,H30E,H30F), C31'(H31D,H31E,H31F),
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              82440
_shelx_hkl_checksum              50833
_olex2_submission_original_sample_id matsec01
_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 1.345
_oxdiff_exptl_absorpt_empirical_full_min 0.785