Isolation of a Metastable Geometrical Isomer of a Hexacoordinated Dihydrophosphate: Elucidation of Its Enhanced Reactivity in Umpolung of a Hydrogen Atom of Water
Hideaki Miyake; Naokazu Kano; Takayuki Kawashima; Inorganic Chemistry 50 (2011) 9083–9089; doi:10.1021/ic2012765

data_4326278
_publ_contact_author_address
;
Department of Chemistry, Graduate School of Science,
The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan
;
_publ_contact_author_email       takayuki@chem.s.u-tokyo.ac.jp
_publ_contact_author_fax         +81-5800-6899
_publ_contact_author_name        'Takayuki Kawashima'
_publ_contact_author_phone       +81-5841-4338
_publ_section_title
;
 Isolation of a Metastable Geometrical Isomer of a Hexacoordinated
 Dihydrophosphate: Elucidation of Its Enhanced Reactivity in Umpolung of a
 Hydrogen Atom of Water
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              9083
_journal_page_last               9089
_journal_paper_doi               10.1021/ic2012765
_journal_volume                  50
_journal_year                    2011
_chemical_formula_moiety         'C24 H20 P, C18 H10 F12 O2 P'
_chemical_formula_sum            'C42 H30 F12 O2 P2'
_chemical_formula_weight         856.60
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           13
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yac'
_symmetry_space_group_name_H-M   'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 98.415(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   13.8932(17)
_cell_length_b                   7.3216(9)
_cell_length_c                   18.572(3)
_cell_measurement_reflns_used    5591
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      27.4835
_cell_measurement_theta_min      3.0088
_cell_volume                     1868.8(4)
_computing_cell_refinement       'CrystalClear (Rigaku Corp., 2000)'
_computing_data_collection       'CrystalClear (Rigaku Corp., 2000)'
_computing_data_reduction        'CrystalClear (Rigaku Corp., 2000)'
_computing_molecular_graphics
'ORTEP-3 for Windows ver 1.08 (Farrugia, 1997-2005)'
_computing_publication_material  Yadokaari-XG
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 14.5666
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
scan:
    Number of images: 600
               Slice: -70.0000 - 110.0000
         Image width: 0.3000
            Exp time: 20.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 45.0793
              2theta: 19.7407
scan:
    Number of images: 600
               Slice: -70.0000 - 110.0000
         Image width: 0.3000
            Exp time: 20.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 90.0000
                 XTD: 45.0793
              2theta: 19.7407

;
_diffrn_measurement_device
;
Mercury CCD (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC8: Eulerian 3-circle
;
_diffrn_measurement_method       dtprofit.ref
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0332
_diffrn_orient_matrix_UB_12      0.0644
_diffrn_orient_matrix_UB_13      -0.0070
_diffrn_orient_matrix_UB_21      -0.0895
_diffrn_orient_matrix_UB_22      -0.0556
_diffrn_orient_matrix_UB_23      -0.0869
_diffrn_orient_matrix_UB_31      -0.0361
_diffrn_orient_matrix_UB_32      -0.0052
_diffrn_orient_matrix_UB_33      0.0404
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71070
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_sigmaI/netI    0.0377
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            11729
_diffrn_reflns_reduction_process 'Lp corrections applied'
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         3.15
_exptl_absorpt_coefficient_mu    0.215
_exptl_absorpt_correction_T_max  0.9830
_exptl_absorpt_correction_T_min  0.9583
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
Jacobson, R. (1998) Private communication
;
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_description       Block
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.411
_refine_diff_density_min         -0.325
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    riding
_refine_ls_matrix_type           full
_refine_ls_number_parameters     267
_refine_ls_number_reflns         3248
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0377
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0526P)^2^+0.5610P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.1047
_reflns_number_gt                2698
_reflns_number_total             3248
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic2012765_si_001_1.cif
_cod_data_source_block           ph20415
_cod_database_code               4326278