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_1561005
_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         'C12 H24 O19 V6, 2(C16 H36 N), C2 H3 N'
_chemical_formula_sum            'C46 H99 N3 O19 V6'
_chemical_formula_weight         1303.92
_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             2020-12-21
_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                 100.8308(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.13612(16)
_cell_length_b                   16.90558(16)
_cell_length_c                   19.59064(19)
_cell_measurement_reflns_used    35039
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      76.3000
_cell_measurement_theta_min      3.0230
_cell_volume                     5899.52(10)
_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(11)
_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 0.984
_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    -21.00  71.00   0.50    2.22    --   49.75 -78.00  56.00  184
  2  \w     34.00 127.00   0.50    8.87    --  105.75 -78.00  56.00  186
  3  \w     98.00 164.00   0.50    8.87    --  105.75  15.00 120.00  132
  4  \w    129.00 163.00   0.50    8.87    --  105.75  15.00 150.00   68
  5  \w     98.00 164.00   0.50    8.87    --  105.75  15.00  90.00  132
  6  \w     98.00 164.00   0.50    8.87    --  105.75  15.00  30.00  132
  7  \w    105.00 135.00   0.50    8.87    --  105.75  30.00 150.00   60
  8  \w     92.00 178.00   0.50    8.87    --  105.75  61.00 150.00  172
  9  \w     90.00 137.00   0.50    8.87    --  105.75  77.00 -90.00   94
 10  \w    135.00 160.00   0.50    8.87    --  105.75  15.00-150.00   50
 11  \w     85.00 178.00   0.50    8.87    --  105.75  78.00-177.00  186
 12  \w     51.00  85.00   0.50    8.87    --  105.75 -61.00  60.00   68
 13  \w     34.00  87.00   0.50    8.87    --  105.75 -61.00 -30.00  106
 14  \w     34.00  87.00   0.50    8.87    --  105.75 -61.00 -90.00  106
 15  \w     34.00  87.00   0.50    8.87    --  105.75 -61.00-120.00  106
 16  \w     34.00  87.00   0.50    8.87    --  105.75 -61.00-150.00  106
 17  \w     51.00 115.00   0.50    8.87    --  105.75-125.00-150.00  128
 18  \w     36.00  86.00   0.50    8.87    --  105.75 -61.00   0.00  100
 19  \w     34.00  87.00   0.50    8.87    --  105.75 -61.00  90.00  106
 20  \w     38.00 101.00   0.50    8.87    --  105.75 -94.00  30.00  126
 21  \w    -23.00   5.00   0.50    2.22    --   49.75 -19.00-120.00   56
 22  \w     29.00 121.00   0.50    2.22    --   49.75  78.00-177.00  184
 23  \w    -23.00   5.00   0.50    2.22    --   49.75 -19.00  60.00   56
 24  \w    -71.00  22.00   0.50    2.22    --  -49.75  78.00-177.00  186
 25  \w    -42.00 -12.00   0.50    8.87    --  -84.25  45.00  30.00   60
 26  \w    -42.00 -12.00   0.50    8.87    --  -84.25  45.00   0.00   60
 27  \w   -105.00 -12.00   0.50    8.87    --  -84.25  78.00-177.00  186
 28  \w   -121.00 -29.00   0.50    2.22    --  -49.75 -78.00  56.00  184
 29  \w   -121.00 -70.00   0.50    2.22    --  -49.75-125.00 -60.00  102
;
_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      -0.0427906000
_diffrn_orient_matrix_UB_12      0.0377257000
_diffrn_orient_matrix_UB_13      -0.0675359000
_diffrn_orient_matrix_UB_21      -0.0583857000
_diffrn_orient_matrix_UB_22      -0.0670915000
_diffrn_orient_matrix_UB_23      -0.0070797000
_diffrn_orient_matrix_UB_31      -0.0472791000
_diffrn_orient_matrix_UB_32      0.0488115000
_diffrn_orient_matrix_UB_33      0.0424200000
_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  0.0457
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            76396
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.886
_diffrn_reflns_theta_min         3.048
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.238
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59084
_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            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       block
_exptl_crystal_F_000             2744
_exptl_crystal_size_max          0.154
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.049
_refine_diff_density_max         0.890
_refine_diff_density_min         -0.630
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     796
_refine_ls_number_reflns         12405
_refine_ls_number_restraints     216
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0636
_refine_ls_R_factor_gt           0.0544
_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^)+(0.0761P)^2^+7.5303P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1471
_refine_ls_wR_factor_ref         0.1542
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10455
_reflns_number_total             12405
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nr09201k2.cif
_cod_data_source_block           mataf29
_cod_depositor_comments
'Adding full bibliography for 1561002--1561005.cif.'
_cod_original_cell_volume        5899.53(10)
_cod_database_code               1561005
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.688
_shelx_estimated_absorpt_t_min   0.364
_reflns_odcompleteness_completeness 99.84
_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
 C34-C35 \\sim C34-C35' \\sim C35-C36 \\sim C35'-C36'
 with sigma of 0.01
 C38-C39 \\sim C38-C39' \\sim C39-C40 \\sim C39'-C40'
 with sigma of 0.01
 N2-C41 \\sim N2-C41'
 with sigma of 0.01
 N1-C25 \\sim N1-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 0.02 and sigma
for terminal atoms of 0.04 within 1.2A
C28 \\sim C28': within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
4. Rigid body (RIGU) restrains
 C34, C35, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, C35', C36'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38, C39, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38, C39', C40'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, C42, C43, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41', C42', C43', C44'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25, C26, C27, C28
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25', C26', C27', C28'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C25, C26, C27, C28} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C25', C26', C27', C28'}
{C41, C42, C43, C44} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C41', C42', C43', C44'}
6. Others
 Sof(C25')=Sof(H25C)=Sof(H25D)=Sof(C26')=Sof(H26C)=Sof(H26D)=Sof(C27')=
 Sof(H27C)=Sof(H27D)=Sof(C28')=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=
 Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(H34C)=Sof(H34D)=Sof(C35')=Sof(H35C)=Sof(H35D)=Sof(C36')=Sof(H36D)=
 Sof(H36E)=Sof(H36F)=1-FVAR(2)
 Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=FVAR(2)
 Sof(H38C)=Sof(H38D)=Sof(C39')=Sof(H39C)=Sof(H39D)=Sof(C40')=Sof(H40D)=
 Sof(H40E)=Sof(H40F)=1-FVAR(3)
 Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(H40C)=FVAR(3)
 Sof(C41')=Sof(H41C)=Sof(H41D)=Sof(C42')=Sof(H42C)=Sof(H42D)=Sof(C43')=
 Sof(H43C)=Sof(H43D)=Sof(C44')=Sof(H44D)=Sof(H44E)=Sof(H44F)=1-FVAR(4)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=
 Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B),
  C19(H19A,H19B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C25(H25A,
 H25B), C26(H26A,H26B), C27(H27A,H27B), C25'(H25C,H25D), C26'(H26C,H26D),
 C27'(H27C,H27D), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C33(H33A,
 H33B), C34(H34A,H34B), C34(H34C,H34D), C37(H37A,H37B), C38(H38A,H38B),
 C38(H38C,H38D), C35(H35A,H35B), C39(H39A,H39B), C41(H41A,H41B), C42(H42A,H42B),
  C43(H43A,H43B), C35'(H35C,H35D), C39'(H39C,H39D), C41'(H41C,H41D), C42'(H42C,
 H42D), C43'(H43C,H43D)
7.b Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C28(H28A,
 H28B,H28C), C28'(H28D,H28E,H28F), C32(H32A,H32B,H32C), C36(H36A,H36B,H36C),
 C40(H40A,H40B,H40C), C44(H44A,H44B,H44C), C36'(H36D,H36E,H36F), C40'(H40D,H40E,
 H40F), C44'(H44D,H44E,H44F), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              51941
_shelx_hkl_checksum              10154
_olex2_submission_original_sample_id mataf29
_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 1.510
_oxdiff_exptl_absorpt_empirical_full_min 0.720