Physicochemical implications of surface alkylation of high-valent, Lindqvist-type polyoxovanadate-alkoxide clusters.
Fertig, Alex A.; Rabbani, S. M. Gulam; Koch, Melissa D.; Brennessel, William W.; Miró, Pere; Matson, Ellen M.; Nanoscale 13 (2021) 6162–6173; doi:10.1039/d0nr09201k

data_1561003
_publ_section_title
;
 Physicochemical implications of surface alkylation of high-valent,
 Lindqvist-type polyoxovanadate-alkoxide clusters.
;
_journal_issue                   12
_journal_name_full               Nanoscale
_journal_page_first              6162
_journal_page_last               6173
_journal_paper_doi               10.1039/d0nr09201k
_journal_volume                  13
_journal_year                    2021
_chemical_formula_moiety         'C9 H15 N2 O23 V6, C16 H36 N'
_chemical_formula_sum            'C25 H51 N3 O23 V6'
_chemical_formula_weight         1067.32
_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             2020-09-01
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2020-12-30 deposited with the CCDC.	2021-03-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.6180(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.85930(10)
_cell_length_b                   17.31290(10)
_cell_length_c                   17.69540(10)
_cell_measurement_reflns_used    39776
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.3150
_cell_measurement_theta_min      3.5960
_cell_volume                     4173.22(5)
_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 0.998
_diffrn_measured_fraction_theta_max 0.987
_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     -5.00  24.00   0.50    0.20    --  -49.75  19.00 -90.00   58
  2  \w     -5.00  24.00   0.50    0.20    --  -49.75  19.00 -30.00   58
  3  \w     -5.00  24.00   0.50    0.20    --  -49.75  19.00  60.00   58
  4  \w     22.00  89.00   0.50    0.20    --   49.75-112.00  47.00  134
  5  \w     34.00 112.00   0.50    0.81    --  105.75-112.00  47.00  156
  6  \w     34.00 127.00   0.50    0.81    --  105.75 -77.00  60.00  186
  7  \w     98.00 178.00   0.50    0.81    --  105.75  30.00  60.00  160
  8  \w    100.00 178.00   0.50    0.81    --  105.75 112.00 140.00  156
  9  \w     92.00 178.00   0.50    0.81    --  105.75 125.00 120.00  172
 10  \w     98.00 175.00   0.50    0.81    --  105.75  15.00 -90.00  154
 11  \w     98.00 175.00   0.50    0.81    --  105.75  15.00-150.00  154
 12  \w     98.00 175.00   0.50    0.81    --  105.75  15.00-120.00  154
 13  \w     42.00 121.00   0.50    0.20    --   49.75  38.00  30.00  158
 14  \w     34.00  80.00   0.50    0.81    --  105.75 -61.00  60.00   92
 15  \w     34.00 109.00   0.50    0.81    --  105.75 -94.00  60.00  150
 16  \w     34.00 127.00   0.50    0.81    --  105.75 -77.00 150.00  186
 17  \w     34.00  80.00   0.50    0.81    --  105.75 -61.00  30.00   92
 18  \w     34.00 116.00   0.50    0.81    --  105.75-125.00 120.00  164
 19  \w     34.00 109.00   0.50    0.81    --  105.75 -94.00 120.00  150
 20  \w     34.00  80.00   0.50    0.81    --  105.75 -61.00-120.00   92
 21  \w     34.00 109.00   0.50    0.81    --  105.75 -94.00-180.00  150
 22  \w     34.00  80.00   0.50    0.81    --  105.75 -61.00-180.00   92
 23  \w     34.00  80.00   0.50    0.81    --  105.75 -61.00-150.00   92
 24  \w     29.00 121.00   0.50    0.20    --   49.75  77.00  60.00  184
 25  \w     29.00 121.00   0.50    0.20    --   49.75  77.00 150.00  184
 26  \w    -86.00   0.00   0.50    0.20    --  -49.75 112.00 140.00  172
 27  \w    -86.00 -12.00   0.50    0.81    --  -84.25 112.00 140.00  148
 28  \w   -121.00 -68.00   0.50    0.20    --  -49.75 -77.00-150.00  106
 29  \w   -121.00 -70.00   0.50    0.20    --  -49.75-125.00-150.00  102
 30  \w   -121.00 -70.00   0.50    0.20    --  -49.75-125.00-180.00  102
 31  \w   -121.00 -29.00   0.50    0.20    --  -49.75 -77.00 -90.00  184
 32  \w   -121.00 -29.00   0.50    0.20    --  -49.75 -77.00   0.00  184
 33  \w   -121.00 -70.00   0.50    0.20    --  -49.75-125.00 120.00  102
 34  \w   -156.00 -78.00   0.50    0.81    --  -84.25-112.00  47.00  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      0.1046485000
_diffrn_orient_matrix_UB_12      -0.0063475000
_diffrn_orient_matrix_UB_13      0.0475378000
_diffrn_orient_matrix_UB_21      -0.0007952000
_diffrn_orient_matrix_UB_22      0.0870808000
_diffrn_orient_matrix_UB_23      0.0177260000
_diffrn_orient_matrix_UB_31      -0.0429139000
_diffrn_orient_matrix_UB_32      -0.0170468000
_diffrn_orient_matrix_UB_33      0.0726172000
_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  0.0856
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            71313
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.910
_diffrn_reflns_theta_min         3.602
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.578
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17550
_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            red-orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.699
_exptl_crystal_description       block
_exptl_crystal_F_000             2176
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.047
_refine_diff_density_min         -1.006
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     648
_refine_ls_number_reflns         8801
_refine_ls_number_restraints     218
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.0668
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0530P)^2^+21.2508P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1586
_refine_ls_wR_factor_ref         0.1600
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8373
_reflns_number_total             8801
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nr09201k2.cif
_cod_data_source_block           mataf22
_cod_depositor_comments
'Adding full bibliography for 1561002--1561005.cif.'
_cod_database_code               1561003
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.314
_shelx_estimated_absorpt_t_min   0.141
_reflns_odcompleteness_completeness 99.83
_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
2. Restrained distances
 C8-N2 \\sim C8-N2'
 with sigma of 0.01
 N2-O22 \\sim N2-O23 \\sim N2'-O22' \\sim N2'-O23'
 with sigma of 0.01
 O22-O23 \\sim O22'-O23'
 with sigma of 0.02
 O16-C25 \\sim O10-C25' \\sim O9-C25"
 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
O22' \\sim N2' \\sim O23': within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 2A
O10 \\sim C25': within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
O9 \\sim C25": within 2A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 2A
4. Rigid body (RIGU) restrains
 C8, N2, O22, O23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O16, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C14, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C14', C15', C16'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C18, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C18, C19', C20'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22, C23, C24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22', C23', C24'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C13, C14', C15', C16'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C13, C14, C15, C16}
{C18, C19', C20'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C18, C19, C20}
{C21, C22', C23', C24'} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C21, C22, C23, C24}
6. Others
 1*[Sof(C25)+Sof(H25A)+Sof(H25B)+Sof(H25C)]+1*[Sof(C25')+Sof(H25D)+Sof(H25E)+
 Sof(H25F)]+1*[Sof(C25")+Sof(H25G)+Sof(H25H)+Sof(H25I)]=1 with esd of 0.0001
 1*[Sof(C25")+Sof(H25G)+Sof(H25H)+Sof(H25I)]+1*[Sof(H13A)+Sof(H13B)+Sof(H13C)+
 Sof(H13D)+Sof(C14)+Sof(H14A)+Sof(H14B)+Sof(C15)+Sof(H15A)+Sof(H15B)+Sof(C16)+
 Sof(H16A)+Sof(H16B)+Sof(H16C)+Sof(C14')+Sof(H14C)+Sof(H14D)+Sof(C15')+
 Sof(H15C)+Sof(H15D)+Sof(C16')+Sof(H16D)+Sof(H16E)+Sof(H16F)]=1 with esd of
 0.0001
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(1)
 Sof(C25')=Sof(H25D)=Sof(H25E)=Sof(H25F)=FVAR(2)
 Sof(C25")=Sof(H25G)=Sof(H25H)=Sof(H25I)=FVAR(3)
 Sof(N2')=Sof(O22')=Sof(O23')=1-FVAR(4)
 Sof(N2)=Sof(O22)=Sof(O23)=FVAR(4)
 Sof(H13C)=Sof(H13D)=Sof(C14')=Sof(H14C)=Sof(H14D)=Sof(C15')=Sof(H15C)=
 Sof(H15D)=Sof(C16')=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(5)
 Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(5)
 Sof(H18C)=Sof(H18D)=Sof(C19')=Sof(H19C)=Sof(H19D)=Sof(C20')=Sof(H20D)=
 Sof(H20E)=Sof(H20F)=1-FVAR(6)
 Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=FVAR(6)
 Sof(H21C)=Sof(H21D)=Sof(C22')=Sof(H22C)=Sof(H22D)=Sof(C23')=Sof(H23C)=
 Sof(H23D)=Sof(C24')=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(7)
 Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(7)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C13(H13C,H13D),
 C14(H14A,H14B), C15(H15A,H15B), C14'(H14C,H14D), C15'(H15C,H15D), C17(H17A,
 H17B), C18(H18A,H18B), C18(H18C,H18D), C19(H19A,H19B), C19'(H19C,H19D),
 C21(H21A,H21B), C21(H21C,H21D), C22(H22A,H22B), C23(H23A,H23B), C22'(H22C,
 H22D), C23'(H23C,H23D)
7.b Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C25'(H25D,H25E,H25F), C25"(H25G,H25H,H25I), C12(H12A,
 H12B,H12C), C16(H16A,H16B,H16C), C16'(H16D,H16E,H16F), C20(H20A,H20B,H20C),
 C20'(H20D,H20E,H20F), C24(H24A,H24B,H24C), C24'(H24D,H24E,H24F)
;
_shelx_res_checksum              14394
_shelx_hkl_checksum              99814
_shelx_fab_checksum              24675
_olex2_submission_original_sample_id mataf22
_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 3.942
_oxdiff_exptl_absorpt_empirical_full_min 0.556