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_1552112
_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_formula_moiety         'C15 H45 O19 P V6'
_chemical_formula_sum            'C15 H45 O19 P V6'
_chemical_formula_weight         866.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-02-07
_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                 106.417(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.7527(3)
_cell_length_b                   20.6175(3)
_cell_length_c                   17.6285(3)
_cell_measurement_reflns_used    25165
_cell_measurement_temperature    192.99(10)
_cell_measurement_theta_max      75.8950
_cell_measurement_theta_min      3.0970
_cell_volume                     7235.2(2)
_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      192.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.975
_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     -4.00  39.00   0.50    1.67    --   49.87 -74.00  30.00   86
  2  \w     51.00  77.00   0.50    1.67    --   49.87  74.00 158.00   52
  3  \w    -69.00  16.00   0.50    1.67    --  -49.87  74.00 158.00  170
  4  \w   -112.00 -37.00   0.50    1.67    --  -49.87 -74.00  30.00  150
  5  \w   -109.00 -74.00   0.50    1.67    --  -49.87-125.00 -90.00   70
  6  \w   -115.00 -82.00   0.50    1.67    --  -49.87-125.00-180.00   66
  7  \w    -82.00 -57.00   0.50    6.70    --  -84.25  74.00 158.00   50
  8  \w    -49.00 -13.00   0.50    6.70    --  -84.25  30.00   0.00   72
  9  \w     63.00 120.00   0.50    6.70    --  105.75 -74.00  30.00  114
 10  \w     64.00  90.00   0.50    6.70    --  105.75 -45.00 -60.00   52
 11  \w     43.00  68.00   0.50    6.70    --  105.75 -30.00-120.00   50
 12  \w     44.00  80.00   0.50    6.70    --  105.75 -15.00-120.00   72
 13  \w     35.00  67.00   0.50    6.70    --  105.75 -30.00-150.00   64
 14  \w     34.00  59.00   0.50    6.70    --  105.75 -30.00 -90.00   50
 15  \w     35.00  65.00   0.50    6.70    --  105.75 -15.00-150.00   60
 16  \w     35.00  70.00   0.50    6.70    --  105.75 -30.00-180.00   70
 17  \w     34.00  72.00   0.50    6.70    --  105.75 -30.00   0.00   76
 18  \w     70.00 120.00   0.50    6.70    --  105.75 -61.00  60.00  100
 19  \w     40.00  67.00   0.50    6.70    --  105.75 -30.00 150.00   54
 20  \w     39.00  71.00   0.50    6.70    --  105.75 -30.00  90.00   64
 21  \w     40.00  69.00   0.50    6.70    --  105.75 -30.00  30.00   58
 22  \w     41.00 119.00   0.50    6.70    --  105.75 -61.00  30.00  156
 23  \w     40.00  82.00   0.50    6.70    --  105.75 -15.00 150.00   84
 24  \w     35.00  70.00   0.50    6.70    --  105.75 -30.00  60.00   70
 25  \w     34.00  81.00   0.50    6.70    --  105.75 -15.00  60.00   94
 26  \w     46.00  81.00   0.50    6.70    --  105.75 -15.00   0.00   70
 27  \w    132.00 166.00   0.50    6.70    --  105.75  77.00  60.00   68
 28  \w    102.00 173.00   0.50    6.70    --  105.75  74.00 158.00  142
 29  \w     35.00  61.00   0.50    6.70    --  105.75 -30.00 120.00   52
;
_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      -0.0041388000
_diffrn_orient_matrix_UB_12      0.0044003000
_diffrn_orient_matrix_UB_13      0.0857163000
_diffrn_orient_matrix_UB_21      0.0439253000
_diffrn_orient_matrix_UB_22      -0.0612029000
_diffrn_orient_matrix_UB_23      0.0215471000
_diffrn_orient_matrix_UB_31      0.0635477000
_diffrn_orient_matrix_UB_32      0.0427099000
_diffrn_orient_matrix_UB_33      0.0220645000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0864
_diffrn_reflns_av_unetI/netI     0.0439
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            62308
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         78.236
_diffrn_reflns_theta_min         3.086
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.493
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20142
_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    1.590
_exptl_crystal_description       plate
_exptl_crystal_F_000             3520
_exptl_crystal_size_max          0.362
_exptl_crystal_size_mid          0.259
_exptl_crystal_size_min          0.057
_refine_diff_density_max         1.087
_refine_diff_density_min         -0.977
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1011
_refine_ls_number_reflns         15129
_refine_ls_number_restraints     350
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.1242
_refine_ls_R_factor_gt           0.0967
_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^)+(0.1444P)^2^+20.1029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2638
_refine_ls_wR_factor_ref         0.2878
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10478
_reflns_number_total             15129
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02882j2.cif
_cod_data_source_block           matbp15
_cod_database_code               1552112
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.513
_shelx_estimated_absorpt_t_min   0.085
_reflns_odcompleteness_completeness 99.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O7-C4 \\sim O7-C4'
 with sigma of 0.01
 O8-C5 \\sim O8-C5'
 with sigma of 0.01
 O9-C6 \\sim O9-C6'
 with sigma of 0.01
 O11-C8 \\sim O11-C8'
 with sigma of 0.01
 O13-C10 \\sim O13-C10'
 with sigma of 0.01
 O14-C11 \\sim O14-C11'
 with sigma of 0.01
 O15-C12 \\sim O15-C12'
 with sigma of 0.01
 O16-C13 \\sim O16-C13'
 with sigma of 0.01
 O17-C14 \\sim O17-C14'
 with sigma of 0.01
 V8-O21 \\sim V8'-O21'
 with sigma of 0.01
 V9-O22 \\sim V9'-O22'
 with sigma of 0.01
 V10-O23 \\sim V10'-O23'
 with sigma of 0.01
 V11-O24 \\sim V11'-O24'
 with sigma of 0.01
 V12-O25 \\sim V12'-O25'
 with sigma of 0.01
 O26-C19 \\sim O26'-C19'
 with sigma of 0.01
 O27-C20 \\sim O27'-C20'
 with sigma of 0.01
 O28-C21 \\sim O28'-C21'
 with sigma of 0.01
 O29-C22 \\sim O29'-C22'
 with sigma of 0.01
 O30-C23 \\sim O30'-C23'
 with sigma of 0.01
 O31-C24 \\sim O31'-C24'
 with sigma of 0.01
 O32-C25 \\sim O32'-C25'
 with sigma of 0.01
 O33-C26 \\sim O33'-C26'
 with sigma of 0.01
 O34-C27 \\sim O34'-C27'
 with sigma of 0.01
 O35-C28 \\sim O35'-C28'
 with sigma of 0.01
 O36-C29 \\sim O36'-C29'
 with sigma of 0.01
 O37-C30 \\sim O37'-C30'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O7 \\sim C4 \\sim C4': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O8 \\sim C5 \\sim C5': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O9 \\sim C6 \\sim C6': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O11 \\sim C8 \\sim C8': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O13 \\sim C10 \\sim C10': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O14 \\sim C11 \\sim C11': within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
O15 \\sim C12 \\sim C12': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O16 \\sim C13 \\sim C13': within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O34 \\sim C27: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O34' \\sim C27': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O26 \\sim O26' \\sim C19 \\sim C19': within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O28 \\sim C21: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O28' \\sim C21': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O30 \\sim C23: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O30' \\sim C23': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O31 \\sim C24: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O31' \\sim C24': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O32 \\sim C25: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O32' \\sim C25': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O33 \\sim C26: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O33' \\sim C26': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O35 \\sim C28: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O35' \\sim C28': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O37 \\sim C30: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O37' \\sim C30': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
V8 \\sim O21: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
V8' \\sim O21': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
V8 \\sim V8': within 2A with sigma of 0.004 and sigma for terminal atoms of
0.008
O32 \\sim O32': within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
V10 \\sim V10' \\sim O32 \\sim O32': within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O34) = Uanis(O34')
Uanis(O31) = Uanis(O31')
Uanis(V9) = Uanis(V9')
Uanis(V11) = Uanis(V11')
Uanis(V12) = Uanis(V12')
Uanis(O22) = Uanis(O22')
Uanis(O23) = Uanis(O23')
Uanis(O24) = Uanis(O24')
Uanis(O25) = Uanis(O25')
Uanis(O26) = Uanis(O26')
Uanis(O27) = Uanis(O27')
Uanis(O28) = Uanis(O28')
Uanis(O29) = Uanis(O29')
Uanis(O30) = Uanis(O30')
Uanis(O33) = Uanis(O33')
Uanis(O35) = Uanis(O35')
Uanis(O36) = Uanis(O36')
Uanis(O37) = Uanis(O37')
Uanis(C20) = Uanis(C20')
Uanis(C22) = Uanis(C22')
Uanis(C24) = Uanis(C24')
Uanis(C29) = Uanis(C29')
Uanis(C14) = Uanis(C14')
4. Others
 Sof(C4')=Sof(H4'A)=Sof(H4'B)=Sof(H4'C)=1-FVAR(1)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(1)
 Sof(C5')=Sof(H5'A)=Sof(H5'B)=Sof(H5'C)=1-FVAR(2)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(2)
 Sof(C8')=Sof(H8'A)=Sof(H8'B)=Sof(H8'C)=1-FVAR(3)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(3)
 Sof(C10')=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(4)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(4)
 Sof(C13')=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(5)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(5)
 Sof(C6')=Sof(H6'A)=Sof(H6'B)=Sof(H6'C)=1-FVAR(6)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(6)
 Sof(C12')=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(7)
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(7)
 Sof(C14')=Sof(H14D)=Sof(H14E)=Sof(H14F)=1-FVAR(8)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(8)
 Fixed Sof: C11(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C11'(0.5) H11D(0.5)
 H11E(0.5) H11F(0.5) V8(0.5) V8'(0.5) V9(0.5) V9'(0.5) V10(0.5) V10'(0.5)
 V11(0.5) V11'(0.5) V12(0.5) V12'(0.5) O21(0.5) O21'(0.5) O22(0.5) O22'(0.5)
 O23(0.5) O23'(0.5) O24(0.5) O24'(0.5) O25(0.5) O25'(0.5) O26(0.5) O26'(0.5)
 O27(0.5) O27'(0.5) O28(0.5) O28'(0.5) O29(0.5) O29'(0.5) O30(0.5) O30'(0.5)
 O31(0.5) O31'(0.5) O32(0.5) O32'(0.5) O33(0.5) O33'(0.5) O34(0.5) O34'(0.5)
 O35(0.5) O35'(0.5) O36(0.5) O36'(0.5) O37(0.5) O37'(0.5) C19(0.5) H19A(0.5)
 H19B(0.5) H19C(0.5) C19'(0.5) H19D(0.5) H19E(0.5) H19F(0.5) C20(0.5) H20A(0.5)
 H20B(0.5) H20C(0.5) C20'(0.5) H20D(0.5) H20E(0.5) H20F(0.5) C21(0.5) H21A(0.5)
 H21B(0.5) H21C(0.5) C21'(0.5) H21D(0.5) H21E(0.5) H21F(0.5) C22(0.5) H22A(0.5)
 H22B(0.5) H22C(0.5) C22'(0.5) H22D(0.5) H22E(0.5) H22F(0.5) C23(0.5) H23A(0.5)
 H23B(0.5) H23C(0.5) C23'(0.5) H23D(0.5) H23E(0.5) H23F(0.5) C24(0.5) H24A(0.5)
 H24B(0.5) H24C(0.5) C24'(0.5) H24D(0.5) H24E(0.5) H24F(0.5) C25(0.5) H25A(0.5)
 H25B(0.5) H25C(0.5) C25'(0.5) H25D(0.5) H25E(0.5) H25F(0.5) C26(0.5) H26A(0.5)
 H26B(0.5) H26C(0.5) C26'(0.5) H26D(0.5) H26E(0.5) H26F(0.5) C27(0.5) H27A(0.5)
 H27B(0.5) H27C(0.5) C27'(0.5) H27D(0.5) H27E(0.5) H27F(0.5) C28(0.5) H28A(0.5)
 H28B(0.5) H28C(0.5) C28'(0.5) H28D(0.5) H28E(0.5) H28F(0.5) C29(0.5) H29A(0.5)
 H29B(0.5) H29C(0.5) C29'(0.5) H29D(0.5) H29E(0.5) H29F(0.5) C30(0.5) H30A(0.5)
 H30B(0.5) H30C(0.5) C30'(0.5) H30D(0.5) H30E(0.5) H30F(0.5)
5.a Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C4'(H4'A,H4'B,H4'C), C5(H5A,H5B,H5C), C5'(H5'A,H5'B,H5'C),
 C8(H8A,H8B,H8C), C8'(H8'A,H8'B,H8'C), C10(H10A,H10B,H10C), C10'(H10D,H10E,
 H10F), C11(H11A,H11B,H11C), C11'(H11D,H11E,H11F), C13(H13A,H13B,H13C),
 C13'(H13D,H13E,H13F), C19(H19A,H19B,H19C), C19'(H19D,H19E,H19F), C20(H20A,H20B,
 H20C), C20'(H20D,H20E,H20F), C21(H21A,H21B,H21C), C21'(H21D,H21E,H21F),
 C22(H22A,H22B,H22C), C22'(H22D,H22E,H22F), C23(H23A,H23B,H23C), C23'(H23D,H23E,
 H23F), C24(H24A,H24B,H24C), C24'(H24D,H24E,H24F), C25(H25A,H25B,H25C),
 C25'(H25D,H25E,H25F), C26(H26A,H26B,H26C), C26'(H26D,H26E,H26F), C27(H27A,H27B,
 H27C), C27'(H27D,H27E,H27F), C28(H28A,H28B,H28C), C28'(H28D,H28E,H28F),
 C29(H29A,H29B,H29C), C29'(H29D,H29E,H29F), C30(H30A,H30B,H30C), C30'(H30D,H30E,
 H30F)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C6(H6A,H6B,H6C), C6'(H6'A,
 H6'B,H6'C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C12'(H12D,
 H12E,H12F), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C14'(H14D,H14E,H14F)
;
_shelx_res_checksum              1892
_shelx_fab_checksum              82418
_olex2_submission_original_sample_id matbp15
_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 3.008
_oxdiff_exptl_absorpt_empirical_full_min 0.535