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_7129996
_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
'C60 H87 O19 P V6, 0.584(C4 H10 O), 0.208(C4 H6 N2)'
_chemical_formula_sum            'C63.17 H94.09 N0.42 O19.59 P V6'
_chemical_formula_weight         1509.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-03-09
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2022-01-28 deposited with the CCDC.	2022-04-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.5148(4)
_cell_length_b                   20.0029(3)
_cell_length_c                   15.83572(19)
_cell_measurement_reflns_used    22024
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.0600
_cell_measurement_theta_min      3.3990
_cell_volume                     7131.80(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_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 0.999
_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   -120.00 -22.00   0.50    3.10    --  -47.20 -83.00 -93.00  196
  2  \w     93.00 178.00   0.50   12.38    --  107.75  58.00 -88.00  170
  3  \w     82.00 178.00   0.50   12.38    --  107.75  83.00  28.00  192
  4  \w     82.00 178.00   0.50   12.38    --  107.75  83.00 136.00  192
  5  \w   -120.00 -34.00   0.50    3.10    --  -47.20 -38.00-180.00  172
  6  \w    -30.00  26.00   0.50    3.10    --  -47.20  38.00  30.00  112
  7  \w    -27.00   5.00   0.50    3.10    --   47.20 -19.00 120.00   64
  8  \w     35.00  87.00   0.50   12.38    --  107.75 -61.00  60.00  104
  9  \w     35.00  87.00   0.50   12.38    --  107.75 -61.00 -30.00  104
 10  \w     35.00 109.00   0.50   12.38    --  107.75 -94.00-150.00  148
 11  \w     35.00  87.00   0.50   12.38    --  107.75 -61.00 150.00  104
 12  \w     35.00  87.00   0.50   12.38    --  107.75 -61.00   0.00  104
 13  \w     94.00 164.00   0.50   12.38    --  107.75  15.00  90.00  140
 14  \w     94.00 164.00   0.50   12.38    --  107.75  15.00-120.00  140
 15  \w     32.00  57.00   0.50    3.10    --   47.20  57.00  30.00   50
;
_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      0.0505007000
_diffrn_orient_matrix_UB_12      0.0491935000
_diffrn_orient_matrix_UB_13      -0.0210196000
_diffrn_orient_matrix_UB_21      -0.0320459000
_diffrn_orient_matrix_UB_22      0.0194643000
_diffrn_orient_matrix_UB_23      -0.0823268000
_diffrn_orient_matrix_UB_31      -0.0332470000
_diffrn_orient_matrix_UB_32      0.0559663000
_diffrn_orient_matrix_UB_33      0.0473732000
_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  0.0493
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            48193
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.779
_diffrn_reflns_theta_min         3.412
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.103
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52261
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow-brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       needle
_exptl_crystal_F_000             3143
_exptl_crystal_size_max          0.261
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.733
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     559
_refine_ls_number_reflns         7723
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0587
_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^)+(0.0504P)^2^+21.0480P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1453
_refine_ls_wR_factor_ref         0.1475
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7056
_reflns_number_total             7723
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01228f2.cif
_cod_data_source_block           matrm28
_cod_original_cell_volume        7131.78(17)
_cod_database_code               7129996
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.789
_shelx_estimated_absorpt_t_min   0.259
_reflns_odcompleteness_completeness 99.85
_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
 C10-C20 \\sim C10-C20'
 with sigma of 0.01
 C20-C21 \\sim C20-C22 \\sim C20-C23 \\sim C20'-C21' \\sim C20'-C22' \\sim
C20'-C23'
 with sigma of 0.01
 C21-C22 \\sim C22-C23 \\sim C23-C21 \\sim C21'-C22' \\sim C22'-C23' \\sim
C23'-C21'
 with sigma of 0.02
 P1-C35 \\sim P1-C36
 with sigma of 0.01
3. Restrained planarity
 C29, C31, C33, C30, C32, C34
 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
C35 \\sim C36: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C40 \\sim C42: within 2A with sigma of 0.008 and sigma for terminal atoms of
0.016 within 2A
Uanis(C37) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C20) = Uanis(C20')
5. Rigid body (RIGU) restrains
 C37, C38, O13, C39, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C41, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C29, C34, C33, C32, C31, C30} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C29, C30, C31, C32, C33, C34}
{C40, C39, O13, C38, C37} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C37, C38, O13, C39, C40}
7. Others
 Sof(C20')=Sof(C21')=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22')=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=Sof(C23')=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(1)
 Sof(C20)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(N1)=Sof(C41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=0.5*(1-FVAR(3))
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(O13)=
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=0.5*FVAR(3)
 Fixed Sof: H25A(0.5) H25B(0.5) H25C(0.5) H26A(0.5) H26B(0.5) H26C(0.5)
 P1(0.5) C29(0.5) C30(0.5) H30(0.5) C31(0.5) H31(0.5) C32(0.5) H32(0.5)
 C33(0.5) H33(0.5) C34(0.5) H34(0.5) C35(0.5) H35A(0.5) H35B(0.5) H35C(0.5)
 C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C38(H38A,H38B), C39(H39A,H39B)
8.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34)
8.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C21'(H21D,H21E,H21F),
 C22'(H22D,H22E,H22F), C23'(H23D,H23E,H23F), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C40(H40A,H40B,H40C),
 C42(H42A,H42B,H42C)
;
_shelx_res_checksum              40973
_olex2_submission_original_sample_id matrm28
_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 2.191
_oxdiff_exptl_absorpt_empirical_full_min 0.533