Oxygen atom transfer with organofunctionalized polyoxovanadium clusters: O-atom vacancy formation with tertiary phosphines and deoxygenation of styrene oxide
Petel, Brittney E.; Meyer, Rachel L.; Brennessel, William W.; Matson, Ellen; Chemical Science  (2019) –; doi:10.1039/C9SC02882J

data_1552108
_publ_section_title
;
 Oxygen atom transfer with organofunctionalized polyoxovanadium clusters:
 O-atom vacancy formation with tertiary phosphines and deoxygenation of
 styrene oxide
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02882J
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H71 O19 P V6'
_chemical_formula_sum            'C32 H71 O19 P V6'
_chemical_formula_weight         1096.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-01-29
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-05-06 deposited with the CCDC.    2019-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.7536(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.7441(3)
_cell_length_b                   10.74980(16)
_cell_length_c                   21.6524(3)
_cell_measurement_reflns_used    25219
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      77.5260
_cell_measurement_theta_min      4.1330
_cell_volume                     4727.14(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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     14.00  40.00   0.50    0.36    --   49.87 -97.00 -83.00   52
  2  \w     47.00  72.00   0.50    1.44    --  105.75 -97.00 -83.00   50
  3  \w     58.00 127.00   0.50    1.44    --  105.75 -77.00 -30.00  138
  4  \w     77.00 115.00   0.50    1.44    --  105.75-125.00   0.00   76
  5  \w     47.00  72.00   0.50    1.44    --  105.75 -45.00   0.00   50
  6  \w     45.00  70.00   0.50    1.44    --  105.75 -30.00 -30.00   50
  7  \w     40.00  87.00   0.50    1.44    --  105.75 -45.00 -30.00   94
  8  \w     44.00 120.00   0.50    0.36    --   49.87  19.00   0.00  152
  9  \w    106.00 158.00   0.50    1.44    --  105.75  97.00  25.00  104
 10  \w    152.00 178.00   0.50    1.44    --  105.75  77.00   0.00   52
 11  \w    142.00 168.00   0.50    1.44    --  105.75  77.00 -30.00   52
 12  \w    137.00 173.00   0.50    1.44    --  105.75  77.00 -60.00   72
 13  \w    139.00 178.00   0.50    1.44    --  105.75  61.00  30.00   78
 14  \w    148.00 175.00   0.50    1.44    --  105.75  61.00  90.00   54
 15  \w    107.00 163.00   0.50    1.44    --  105.75 125.00  90.00  112
 16  \w     93.00 169.00   0.50    1.44    --  105.75  61.00 -30.00  152
 17  \w    123.00 149.00   0.50    1.44    --  105.75  30.00 -60.00   52
 18  \w    115.00 176.00   0.50    1.44    --  105.75  77.00 -90.00  122
 19  \w     96.00 122.00   0.50    1.44    --  105.75  61.00  30.00   52
 20  \w     92.00 164.00   0.50    1.44    --  105.75  61.00  60.00  144
 21  \w     97.00 133.00   0.50    1.44    --  105.75  61.00  90.00   72
 22  \w     85.00 138.00   0.50    1.44    --  105.75  77.00  30.00  106
 23  \w     86.00 141.00   0.50    1.44    --  105.75  77.00 -30.00  110
 24  \w    100.00 163.00   0.50    1.44    --  105.75  45.00 -60.00  126
 25  \w     85.00 110.00   0.50    1.44    --  105.75  77.00 -60.00   50
 26  \w     92.00 118.00   0.50    1.44    --  105.75  61.00 -60.00   52
 27  \w     92.00 151.00   0.50    1.44    --  105.75  61.00   0.00  118
 28  \w     85.00 147.00   0.50    1.44    --  105.75  77.00   0.00  124
 29  \w     85.00 111.00   0.50    1.44    --  105.75  77.00 -90.00   52
 30  \w     34.00  72.00   0.50    1.44    --  105.75 -30.00-120.00   76
 31  \w     38.00  68.00   0.50    1.44    --  105.75 -30.00-180.00   60
 32  \w     38.00 118.00   0.50    1.44    --  105.75 -61.00 -90.00  160
 33  \w     40.00  78.00   0.50    1.44    --  105.75 -45.00 -60.00   76
 34  \w     39.00  65.00   0.50    1.44    --  105.75 -15.00 -90.00   52
 35  \w     33.00  81.00   0.50    1.44    --  105.75 -15.00 -60.00   96
 36  \w     33.00  75.00   0.50    1.44    --  105.75 -15.00  30.00   84
 37  \w     34.00  72.00   0.50    1.44    --  105.75 -30.00  90.00   76
 38  \w     59.00  86.00   0.50    1.44    --  105.75 -45.00 120.00   54
 39  \w     45.00  71.00   0.50    1.44    --  105.75 -30.00 150.00   52
 40  \w     36.00  66.00   0.50    1.44    --  105.75 -30.00 120.00   60
 41  \w     35.00  78.00   0.50    1.44    --  105.75 -45.00  60.00   86
 42  \w    -62.00 -37.00   0.50    0.36    --  -49.87 -57.00 -60.00   50
 43  \w    -63.00 -29.00   0.50    0.36    --  -49.87 -77.00   0.00   68
 44  \w    -88.00 -62.00   0.50    1.44    --  -84.25 -81.00 -69.34   52
 45  \w    -92.00 -66.00   0.50    1.44    --  -84.25 -72.00 -32.92   52
 46  \w    -86.00 -61.00   0.50    1.44    --  -84.25 -82.00  -7.39   50
 47  \w    -90.00 -64.00   0.50    1.44    --  -84.25 -76.00  43.49   52
 48  \w    -92.00 -66.00   0.50    1.44    --  -84.25 -71.00   9.32   52
 49  \w    -90.00 -64.00   0.50    1.44    --  -84.25 -76.00 -42.16   52
 50  \w    -86.00 -61.00   0.50    1.44    --  -84.25 -82.00   2.30   50
 51  \w    -88.00 -63.00   0.50    1.44    --  -84.25 -77.00  30.00   50
 52  \w    -86.00 -61.00   0.50    1.44    --  -84.25 -82.00  -3.13   50
 53  \w    -89.00 -62.00   0.50    1.44    --  -84.25 -82.00  33.24   54
 54  \w    -88.00 -63.00   0.50    1.44    --  -84.25 -79.00   6.55   50
 55  \w    -93.00 -68.00   0.50    1.44    --  -84.25 -66.00  -2.51   50
 56  \w    -86.00 -61.00   0.50    1.44    --  -84.25 -83.00 -36.82   50
 57  \w    -91.00 -65.00   0.50    1.44    --  -84.25 -77.00 -60.00   52
 58  \w    -93.00 -67.00   0.50    1.44    --  -84.25 -68.00 -68.97   52
 59  \w    -89.00 -64.00   0.50    1.44    --  -84.25 -77.00 -30.00   50
 60  \w    -86.00 -61.00   0.50    1.44    --  -84.25 -83.00  20.28   50
 61  \w   -102.00 -75.00   0.50    0.36    --  -49.87-125.00  30.00   54
 62  \w   -119.00 -29.00   0.50    0.36    --  -49.87 -77.00  60.00  180
 63  \w   -118.00 -68.00   0.50    0.36    --  -49.87 -77.00   0.00  100
 64  \w   -117.00 -77.00   0.50    0.36    --  -49.87 -57.00 -60.00   80
 65  \w   -143.00-118.00   0.50    1.44    --  -84.25 -97.00 -83.00   50
 66  \w   -139.00-113.00   0.50    1.44    --  -84.25 -82.00  -3.13   52
 67  \w   -120.00 -90.00   0.50    0.36    --  -49.87-125.00  90.00   60
 68  \w    -80.00   5.00   0.50    0.36    --  -49.87  97.00  25.00  170
 69  \w    -72.00 -47.00   0.50    1.44    --  -84.25  97.00  25.00   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      -0.0221189000
_diffrn_orient_matrix_UB_12      -0.0471171000
_diffrn_orient_matrix_UB_13      0.0595786000
_diffrn_orient_matrix_UB_21      -0.0725517000
_diffrn_orient_matrix_UB_22      0.0150584000
_diffrn_orient_matrix_UB_23      -0.0334874000
_diffrn_orient_matrix_UB_31      -0.0003649000
_diffrn_orient_matrix_UB_32      -0.1345218000
_diffrn_orient_matrix_UB_33      -0.0246749000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0875
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            45966
_diffrn_reflns_point_group_measured_fraction_full 0.922
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.900
_diffrn_reflns_theta_min         4.171
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.457
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.11898
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.541
_exptl_crystal_description       block
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.343
_exptl_crystal_size_mid          0.229
_exptl_crystal_size_min          0.098
_refine_diff_density_max         1.337
_refine_diff_density_min         -0.830
_refine_diff_density_rms         0.133
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.297(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         9141
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0568
_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^)+(0.1034P)^2^+15.0238P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1553
_refine_ls_wR_factor_ref         0.1568
_reflns_Friedel_coverage         0.828
_reflns_Friedel_fraction_full    0.845
_reflns_Friedel_fraction_max     0.819
_reflns_number_gt                8777
_reflns_number_total             9141
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02882j2.cif
_cod_data_source_block           matrm14
_cod_database_code               1552108
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.427
_shelx_estimated_absorpt_t_min   0.124
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.703(9)
 0.297(9)
2. 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
3. Restrained distances
 V1-O1' = V6-O6
 1.6 with sigma of 0.01
 V1-O1 \\sim V6-O6'
 with sigma of 0.01
4. Restrained planarity
 C3', C4', C5', C6', C7', C8', P1'
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(O1) = Uanis(O1')
Uanis(O6) = Uanis(O6')
Uanis(C1) = Uanis(C1')
Uanis(P1) = Uanis(P1')
Uanis(C2) = Uanis(C2')
Uanis(C3) = Uanis(C3')
Uanis(C4) = Uanis(C4')
Uanis(C5) = Uanis(C5')
Uanis(C6) = Uanis(C6')
Uanis(C7) = Uanis(C7')
Uanis(C8) = Uanis(C8')
6. Same fragment restrains
{O1, P1, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as
{O6', P1', C1', C2', C3', C4', C5', C6', C7', C8'}
7. Others
 Sof(O1')=Sof(O6')=Sof(P1')=Sof(C1')=Sof(H1'A)=Sof(H1'B)=Sof(H1'C)=Sof(C2')=
 Sof(H2'A)=Sof(H2'B)=Sof(H2'C)=Sof(C3')=Sof(C4')=Sof(H4')=Sof(C5')=Sof(H5')=
 Sof(C6')=Sof(H6')=Sof(C7')=Sof(H7')=Sof(C8')=Sof(H8')=1-FVAR(1)
 Sof(O6)=Sof(O1)=Sof(P1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(H2A)=
 Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=
 Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=FVAR(1)
8.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C13(H13A,H13B), C15(H15A,H15B), C17(H17A,H17B),
 C19(H19A,H19B), C21(H21A,H21B), C23(H23A,H23B), C25(H25A,H25B), C27(H27A,H27B),
  C29(H29A,H29B), C31(H31A,H31B)
8.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C4'(H4'), C5'(H5'), C6'(H6'),
 C7'(H7'), C8'(H8')
8.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C1'(H1'A,H1'B,H1'C), C2'(H2'A,H2'B,H2'C),
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C24(H24A,
 H24B,H24C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C),
 C32(H32A,H32B,H32C)
;
_shelx_res_checksum              23652
_olex2_submission_original_sample_id matrm14
_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 5.599
_oxdiff_exptl_absorpt_empirical_full_min 0.375