Adducts of Donor-Functionalized Ar3P with the Soft Lewis Acid I2: Probing Simultaneous Lewis Acidity and Basicity at Internally Solvated P(III) Centers.
Borys, Andryj M.; Clark, Ewan R.; Inorganic chemistry  (2017) –; doi:10.1021/acs.inorgchem.7b00278

data_4345971
_publ_section_title
;
 Adducts of Donor-Functionalized Ar3P with the Soft Lewis Acid I2: Probing
 Simultaneous Lewis Acidity and Basicity at Internally Solvated P(III)
 Centers.
;
_journal_name_full               'Inorganic chemistry'
_journal_paper_doi               10.1021/acs.inorgchem.7b00278
_journal_year                    2017
_chemical_formula_moiety         'C18 H15 I P, C32 H12 B F24, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C50.5 H28 B Cl F24 I P'
_chemical_formula_weight         1294.86
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-01-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5289)
;
_cell_angle_alpha                90.8265(10)
_cell_angle_beta                 110.2111(11)
_cell_angle_gamma                109.0350(11)
_cell_formula_units_Z            2
_cell_length_a                   12.47595(15)
_cell_length_b                   13.15500(16)
_cell_length_c                   17.7202(2)
_cell_measurement_reflns_used    42240
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3870
_cell_measurement_theta_min      3.5590
_cell_volume                     2553.34(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2887
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   -115.00 -17.00   1.00    3.00    --  -41.14 -38.00 150.00   98
  2  \w   -113.00 -65.00   1.00    3.00    --  -41.14-138.00 146.00   48
  3  \w   -117.00  -9.00   1.00    3.00    --  -41.14 -77.00  90.00  108
  4  \w    -31.00  69.00   1.00    3.00    --   41.14 -57.00 -30.00  100
  5  \w      1.00  82.00   1.00    3.00    --   41.14 -99.00-150.00   81
  6  \w     13.00 113.00   1.00    3.00    --   41.14  57.00 120.00  100
  7  \w     23.00  97.00   1.00    3.00    --   41.14-125.00   0.00   74
  8  \w     29.00 109.00   1.00   12.00    --  112.00 -94.00  90.00   80
  9  \w     29.00 109.00   1.00   12.00    --  112.00 -94.00-120.00   80
 10  \w     83.00 178.00   1.00   12.00    --  112.00  61.00  30.00   95
 11  \w     36.00 116.00   1.00   12.00    --  112.00-111.00  90.00   80
 12  \w     84.00 178.00   1.00   12.00    --  112.00  30.00-150.00   94
 13  \w    100.00 178.00   1.00   12.00    --  112.00 111.00 -90.00   78
 14  \w     39.00 138.00   1.00   12.00    --  112.00 -45.00 150.00   99
 15  \w     36.00 116.00   1.00   12.00    --  112.00-111.00 -30.00   80
 16  \w     36.00 116.00   1.00   12.00    --  112.00-111.00-150.00   80
 17  \w     91.00 178.00   1.00   12.00    --  112.00 131.00  32.00   87
 18  \w     29.00 109.00   1.00   12.00    --  112.00 -94.00  30.00   80
 19  \w     40.00 141.00   1.00   12.00    --  112.00 -61.00 -60.00  101
 20  \w    100.00 178.00   1.00   12.00    --  112.00 111.00 -60.00   78
 21  \w     36.00 140.00   1.00   12.00    --  112.00 -30.00-120.00  104
 22  \w     29.00 109.00   1.00   12.00    --  112.00 -94.00 -30.00   80
 23  \w     57.00 151.00   1.00   12.00    --  112.00 178.00 -90.00   94
 24  \w     36.00 140.00   1.00   12.00    --  112.00 -30.00  30.00  104
 25  \w     84.00 178.00   1.00   12.00    --  112.00  30.00 -90.00   94
 26  \w     40.00 128.00   1.00   12.00    --  112.00-138.00 146.00   88
 27  \w     29.00 109.00   1.00   12.00    --  112.00 -94.00 120.00   80
 28  \w     36.00 116.00   1.00   12.00    --  112.00-111.00-120.00   80
 29  \w   -113.00 -13.00   1.00    3.00    --  -41.14 -57.00 -60.00  100
 30  \w   -115.00 -17.00   1.00    3.00    --  -41.14 -38.00 -30.00   98
 31  \w     13.00 113.00   1.00    3.00    --   41.14  57.00-150.00  100
 32  \w      9.00 117.00   1.00    3.00    --   41.14  77.00 -30.00  108
 33  \w      1.00  82.00   1.00    3.00    --   41.14 -99.00 120.00   81
 34  \w      9.00 117.00   1.00    3.00    --   41.14  77.00-120.00  108
 35  \w     84.00 178.00   1.00   12.00    --  112.00  30.00 120.00   94
 36  \w     79.00 178.00   1.00   12.00    --  112.00  77.00 -90.00   99
 37  \w     86.00 178.00   1.00   12.00    --  112.00  45.00 150.00   92
 38  \w     83.00 137.00   1.00   12.00    --  112.00  61.00  60.00   54
 39  \w     83.00 178.00   1.00   12.00    --  112.00  61.00 -30.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0446577000
_diffrn_orient_matrix_UB_12      -0.0124832000
_diffrn_orient_matrix_UB_13      -0.0934267000
_diffrn_orient_matrix_UB_21      0.0837227000
_diffrn_orient_matrix_UB_22      0.1177746000
_diffrn_orient_matrix_UB_23      0.0052356000
_diffrn_orient_matrix_UB_31      0.1037964000
_diffrn_orient_matrix_UB_32      -0.0405191000
_diffrn_orient_matrix_UB_33      0.0025683000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            50646
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.905
_diffrn_reflns_theta_min         2.685
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.847
_exptl_absorpt_correction_T_max  0.585
_exptl_absorpt_correction_T_min  0.233
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.684
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1274
_exptl_crystal_size_max          0.349
_exptl_crystal_size_mid          0.258
_exptl_crystal_size_min          0.088
_refine_diff_density_max         1.126
_refine_diff_density_min         -2.000
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     752
_refine_ls_number_reflns         10020
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0387
_refine_ls_R_factor_gt           0.0385
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0447P)^2^+5.2572P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0950
_refine_ls_wR_factor_ref         0.0951
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9940
_reflns_number_total             10020
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00278_si_002.cif
_cod_data_source_block           '[3g]BArF'
_cod_original_cell_volume        2553.33(5)
_cod_original_formula_sum        'C50.50 H28 B Cl F24 I P'
_cod_database_code               4345971
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C50.5 P1 B1 I1 F24 H28 Cl1'
_chemical_oxdiff_usercomment     'ABS-128/131 BArF Salt'
_cell_oxdiff_angle_alpha         90.8265(10)
_cell_oxdiff_angle_beta          110.2111(11)
_cell_oxdiff_angle_gamma         109.0350(11)
_cell_oxdiff_length_a            12.47595(15)
_cell_oxdiff_length_b            13.15500(16)
_cell_oxdiff_length_c            17.7202(2)
_cell_oxdiff_measurement_reflns_used 42240
_cell_oxdiff_volume              2553.33(5)
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F33-F31 \\sim F31-F32 \\sim F32-F33
 with sigma of 0.02
 F32-C51 \\sim F31-C51 \\sim F33-C51
 with sigma of 0.02
 F7-F8 \\sim F8-F9 \\sim F9-F7
 with sigma of 0.02
 F7-C42 \\sim F9-C42 \\sim F8-C42
 with sigma of 0.02
 F13-F14 \\sim F14-F15 \\sim F15-F13 \\sim F16-F17 \\sim F17-F18 \\sim F18-F16
 with sigma of 0.02
 F15-C27 \\sim F17-C27 \\sim F14-C27 \\sim F16-C27 \\sim F13-C27 \\sim F18-C27
 with sigma of 0.02
 F19-F20 \\sim F20-F21 \\sim F21-F19
 with sigma of 0.02
 F20-C35 \\sim F21-C35 \\sim F19-C35
 with sigma of 0.02
 F25-F26 \\sim F26-F27 \\sim F27-F25 \\sim F28-F29 \\sim F29-F30 \\sim F30-F28
 with sigma of 0.02
 F25-C26 \\sim F26-C26 \\sim F28-C26 \\sim F29-C26 \\sim F27-C26 \\sim F30-C26
 with sigma of 0.02
 F31-F32 \\sim F32-F33 \\sim F33-F31 \\sim F34-F35 \\sim F35-F36 \\sim F36-F34
 with sigma of 0.02
 F33-C51 \\sim F35-C51 \\sim F32-C51 \\sim F34-C51 \\sim F31-C51 \\sim F36-C51
 with sigma of 0.02
 Cl1-C19 \\sim Cl1_$1-C19_$1
 with sigma of 0.02
 Cl1-C19 \\sim Cl2-C19 \\sim Cl2_$1-C19_$1 \\sim Cl1_$1-C19_$1
 with sigma of 0.02
 Cl2-C19 \\sim Cl1-C19
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F17) = Uanis(F13)
Uanis(F18) = Uanis(F14)
Uanis(F15) = Uanis(F16)
Uanis(F30) = Uanis(F26)
Uanis(F27) = Uanis(F28)
Uanis(F25) = Uanis(F29)
Uanis(F35) = Uanis(F31)
Uanis(F36) = Uanis(F32)
Uanis(F33) = Uanis(F34)
Uiso(Cl1) = Uiso(Cl2)
4. Others
 Sof(F15)=Sof(F13)=Sof(F14)=1-FVAR(1)
 Sof(F18)=Sof(F17)=Sof(F16)=FVAR(1)
 Sof(F27)=Sof(F25)=Sof(F26)=1-FVAR(2)
 Sof(F30)=Sof(F28)=Sof(F29)=FVAR(2)
 Sof(F36)=Sof(F35)=Sof(F34)=1-FVAR(3)
 Sof(F33)=Sof(F32)=Sof(F31)=FVAR(3)
 Fixed Sof: Cl1(0.5) C19(0.5) H19A(0.5) H19B(0.5) Cl2(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B)
5.b Aromatic/amide H refined with riding coordinates:
 C33(H33), C29(H29), C37(H37), C25(H25), C49(H49), C23(H23), C31(H31),
 C21(H21), C41(H41), C6(H6), C14(H14), C8(H8), C39(H39), C5(H5), C9(H9),
 C18(H18), C12(H12), C2(H2), C10(H10), C17(H17), C16(H16), C3(H3), C11(H11),
 C15(H15)
;
_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 2.824
_oxdiff_exptl_absorpt_empirical_full_min 0.633