Mechanistic Insight into Rapid Oxygen-Atom Transfer from a Calix-Functionalized Polyoxovanadate
Fertig, Alex A.; Cooney, Shannon E.; Meyer, Rachel L.; Brennessel, William W.; Matson, Ellen; Chemical Communications  (2022) –; doi:10.1039/D2CC01228F

data_7129997
_publ_section_title
;
 Mechanistic Insight into Rapid Oxygen-Atom Transfer from a
 Calix-Functionalized Polyoxovanadate
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01228F
_journal_year                    2022
_chemical_formula_moiety         'C52 H76 O19 V6, 5(C2 H3 N)'
_chemical_formula_sum            'C62 H91 N5 O19 V6'
_chemical_formula_weight         1516.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-12-07
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2022-01-28 deposited with the CCDC.	2022-04-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.8300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.2605(2)
_cell_length_b                   17.61780(10)
_cell_length_c                   20.1094(2)
_cell_measurement_reflns_used    31409
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      77.4470
_cell_measurement_theta_min      3.3250
_cell_volume                     7281.34(11)
_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      99.99(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 0.985
_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    -79.00  22.00   0.50    0.48    --  -49.75  96.00-167.00  202
  2  \w    -30.00  22.00   0.50    0.48    --  -49.75  38.00 -60.00  104
  3  \w    -42.00 -12.00   0.50    1.94    --  -84.25  45.00  60.00   60
  4  \w    -83.00 -12.00   0.50    1.94    --  -84.25  96.00-167.00  142
  5  \w    -23.00   5.00   0.50    0.48    --   49.75 -19.00 -90.00   56
  6  \w    -23.00   5.00   0.50    0.48    --   49.75 -19.00-150.00   56
  7  \w    -23.00   5.00   0.50    0.48    --   49.75 -19.00-180.00   56
  8  \w     34.00 109.00   0.50    1.94    --  105.75 -94.00 -90.00  150
  9  \w     34.00  87.00   0.50    1.94    --  105.75 -61.00-120.00  106
 10  \w     34.00 127.00   0.50    1.94    --  105.75 -77.00-120.00  186
 11  \w     98.00 164.00   0.50    1.94    --  105.75  15.00   0.00  132
 12  \w     97.00 178.00   0.50    1.94    --  105.75  45.00  60.00  162
 13  \w     98.00 164.00   0.50    1.94    --  105.75  15.00 -30.00  132
 14  \w    103.00 178.00   0.50    1.94    --  105.75  96.00-167.00  150
 15  \w     92.00 178.00   0.50    1.94    --  105.75 125.00 -30.00  172
 16  \w     98.00 139.00   0.50    1.94    --  105.75  15.00 120.00   82
 17  \w     34.00 109.00   0.50    1.94    --  105.75 -96.00  83.00  150
 18  \w     34.00  87.00   0.50    1.94    --  105.75 -61.00  90.00  106
 19  \w     34.00 109.00   0.50    1.94    --  105.75 -94.00 120.00  150
 20  \w     34.00 127.00   0.50    1.94    --  105.75 -77.00 120.00  186
 21  \w     34.00  87.00   0.50    1.94    --  105.75 -61.00 120.00  106
 22  \w     34.00 109.00   0.50    1.94    --  105.75 -94.00   0.00  150
 23  \w     34.00  87.00   0.50    1.94    --  105.75 -61.00 -30.00  106
 24  \w    -10.00  80.00   0.50    0.48    --   49.75 -96.00  83.00  180
 25  \w    -23.00   5.00   0.50    0.48    --   49.75 -19.00 120.00   56
 26  \w   -121.00 -70.00   0.50    0.48    --  -49.75-125.00-120.00  102
 27  \w   -156.00 -81.00   0.50    1.94    --  -84.25 -96.00  83.00  150
;
_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      0.0121332000
_diffrn_orient_matrix_UB_12      0.0608240000
_diffrn_orient_matrix_UB_13      -0.0503689000
_diffrn_orient_matrix_UB_21      -0.0256262000
_diffrn_orient_matrix_UB_22      -0.0547193000
_diffrn_orient_matrix_UB_23      -0.0606273000
_diffrn_orient_matrix_UB_31      -0.0693942000
_diffrn_orient_matrix_UB_32      0.0308415000
_diffrn_orient_matrix_UB_33      -0.0083901000
_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  0.0422
_diffrn_reflns_av_unetI/netI     0.0246
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            46057
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.870
_diffrn_reflns_theta_min         3.304
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.772
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48741
_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    1.383
_exptl_crystal_description       needle
_exptl_crystal_F_000             3152
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.094
_refine_diff_density_max         0.671
_refine_diff_density_min         -0.849
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     448
_refine_ls_number_reflns         7666
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0447
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0855P)^2^+8.4034P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1284
_refine_ls_wR_factor_ref         0.1302
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7171
_reflns_number_total             7666
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01228f2.cif
_cod_data_source_block           matrm24
_cod_database_code               7129997
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.569
_shelx_estimated_absorpt_t_min   0.255
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
2. Restrained distances
 C4-C15 \\sim C4-C15'
 with sigma of 0.02
 C15-C16 \\sim C15-C17 \\sim C15-C18 \\sim C15'-C16' \\sim C15'-C17' \\sim
C15'-C18'
 with sigma of 0.02
 C16-C17 \\sim C17-C18 \\sim C18-C16 \\sim C16'-C17' \\sim C17'-C18' \\sim
C18'-C16'
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C15) = Uanis(C15')
Uanis(C16) = Uanis(C16')
Uanis(C17) = Uanis(C17')
Uanis(C18) = Uanis(C18')
4. Others
 Sof(C15')=Sof(C16')=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17')=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=Sof(C18')=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(C15)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(1)
 Fixed Sof: H32A(0.5) H32B(0.5) H32C(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11)
5.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C16(H16A,
 H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C16'(H16D,H16E,H16F),
 C17'(H17D,H17E,H17F), C18'(H18D,H18E,H18F), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              83348
_olex2_submission_original_sample_id matrm24
_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 2.143
_oxdiff_exptl_absorpt_empirical_full_min 0.643