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_4345968
_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         '2(C20 H19 I O2 P), C H2 Cl2, 2(C32 H12 B F24)'
_chemical_formula_sum            'C105 H64 B2 Cl2 F48 I2 O4 P2'
_chemical_formula_weight         2709.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-01-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5289)
;
_cell_angle_alpha                90.0
_cell_angle_beta                 110.6112(13)
_cell_angle_gamma                90.0
_cell_formula_units_Z            2
_cell_length_a                   12.46086(15)
_cell_length_b                   34.0625(3)
_cell_length_c                   13.54015(16)
_cell_measurement_reflns_used    79014
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      30.0930
_cell_measurement_theta_min      2.5340
_cell_volume                     5379.22(11)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -12.00  87.00   1.00   57.50    --   12.34  38.00  60.00   99
  2  \w    -62.00  37.00   1.00   57.50    --   12.34 -38.00 -90.00   99
  3  \w    -64.00  45.00   1.00   57.50    --   12.34 -77.00-150.00  109
  4  \w     35.00 101.00   1.00   57.50    --   12.34 178.00-150.00   66
  5  \w    -61.00  40.00   1.00   57.50    --   12.34 -57.00  60.00  101
  6  \w    -20.00  28.00   1.00   57.50    --  -12.80 -99.00-120.00   48
  7  \w    -20.00  28.00   1.00   57.50    --  -12.80 -99.00  90.00   48
  8  \w   -100.00 -55.00   1.00   57.50    --  -12.80 178.00-120.00   45
  9  \w    -87.00  12.00   1.00   57.50    --  -12.80 -38.00-120.00   99
 10  \w    -20.00   5.00   1.00   57.50    --  -12.80 -99.00  30.00   25
 11  \w    -87.00  12.00   1.00   57.50    --  -12.80 -38.00 150.00   99
;
_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      -0.0339458000
_diffrn_orient_matrix_UB_12      -0.0020156000
_diffrn_orient_matrix_UB_13      0.0321687000
_diffrn_orient_matrix_UB_21      0.0500133000
_diffrn_orient_matrix_UB_22      0.0014325000
_diffrn_orient_matrix_UB_23      0.0457973000
_diffrn_orient_matrix_UB_31      -0.0067784000
_diffrn_orient_matrix_UB_32      0.0206745000
_diffrn_orient_matrix_UB_33      -0.0000333000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            114233
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.003
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.799
_exptl_absorpt_correction_T_max  0.960
_exptl_absorpt_correction_T_min  0.810
_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    1.673
_exptl_crystal_description       plate
_exptl_crystal_F_000             2676
_exptl_crystal_size_max          0.288
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.068
_refine_diff_density_max         1.227
_refine_diff_density_min         -0.742
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.296(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1574
_refine_ls_number_reflns         21933
_refine_ls_number_restraints     230
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0354
_refine_ls_shift/su_max          0.111
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0527P)^2^+5.8085P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0887
_refine_ls_wR_factor_ref         0.0894
_reflns_Friedel_coverage         0.966
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                21416
_reflns_number_total             21933
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic7b00278_si_002.cif
_cod_data_source_block           '[3d]BArF'
_cod_database_code               4345968
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C105 P2 I2 B2 O4 F48 H64 Cl2'
_chemical_oxdiff_usercomment
'ABS-195 iodo-bismethoxyphenyl-phenylphopshonium BArF'
_cell_oxdiff_angle_alpha         90.0014(9)
_cell_oxdiff_angle_beta          110.6180(13)
_cell_oxdiff_angle_gamma         89.9963(9)
_cell_oxdiff_length_a            12.45950(16)
_cell_oxdiff_length_b            34.0655(3)
_cell_oxdiff_length_c            13.5410(2)
_cell_oxdiff_measurement_reflns_used 79017
_cell_oxdiff_volume              5379.22(11)
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.704(11) 0.296(11)
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
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F4-F5 \\sim F5-F6 \\sim F6-F4
 with sigma of 0.02
 F6-C03H \\sim F3-C03H \\sim F4-C03H \\sim F1-C03H \\sim F5-C03H \\sim F2-C03H
 with sigma of 0.02
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F10-F11 \\sim F11-F12 \\sim F12-F10
 with sigma of 0.02
 F11-C036 \\sim F8-C036 \\sim F12-C036 \\sim F9-C036 \\sim F10-C036 \\sim
F7-C036
 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
 F17-C030 \\sim F14-C030 \\sim F18-C030 \\sim F15-C030 \\sim F16-C030 \\sim
F13-C030
 with sigma of 0.02
 F19-F20 \\sim F20-F21 \\sim F21-F19 \\sim F22-F23 \\sim F23-F24 \\sim F24-F22
 with sigma of 0.02
 F21-C02O \\sim F24-C02O \\sim F19-C02O \\sim F22-C02O \\sim F20-C02O \\sim
F23-C02O
 with sigma of 0.02
 F25-F26 \\sim F26-F27 \\sim F27-F25
 with sigma of 0.02
 F25-C04I \\sim F26-C04I \\sim F27-C04I
 with sigma of 0.02
 F31-F32 \\sim F32-F33 \\sim F33-F31 \\sim F34-F35 \\sim F35-F36 \\sim F36-F33
 with sigma of 0.02
 F35-C02J \\sim F32-C02J \\sim F33-C02J \\sim F36-C02J \\sim F31-C02J \\sim
F34-C02J
 with sigma of 0.02
 F37-F38 \\sim F38-F39 \\sim F39-F37
 with sigma of 0.02
 F39-C01N \\sim F37-C01N \\sim F38-C01N
 with sigma of 0.02
 F43-F44 \\sim F44-F45 \\sim F45-F43 \\sim F46-F47 \\sim F47-F48 \\sim F48-F46
 with sigma of 0.02
 F48-C03D \\sim F44-C03D \\sim F47-C03D \\sim F43-C03D \\sim F46-C03D \\sim
F45-C03D
 with sigma of 0.02
 F49-F50 \\sim F50-F51 \\sim F51-F49
 with sigma of 0.02
 F50-C03E \\sim F49-C03E \\sim F51-C03E
 with sigma of 0.02
 F55-F56 \\sim F56-F57 \\sim F57-F55 \\sim F58-F59 \\sim F59-F60 \\sim F60-F58
 with sigma of 0.02
 F56-C049 \\sim F59-C049 \\sim F57-C049 \\sim F60-C049 \\sim F55-C049 \\sim
F58-C049
 with sigma of 0.02
 F61-F62 \\sim F62-F63 \\sim F63-F61
 with sigma of 0.02
 F63-C048 \\sim F61-C048 \\sim F62-C048
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(F2) = Uanis(F4)
Uanis(F5) = Uanis(F3)
Uanis(F57) = Uanis(F58)
Uanis(F60) = Uanis(F56)
Uanis(F55) = Uanis(F59)
Uanis(F47) = Uanis(F45)
Uanis(F48) = Uanis(F43)
Uanis(F44) = Uanis(F46)
Uanis(F18) = Uanis(F13)
Uanis(F13) = Uanis(F14)
Uanis(F15) = Uanis(F17)
Uanis(F3) = Uanis(F5)
Uanis(F1) = Uanis(F6)
Uanis(F4) = Uanis(F2)
Uanis(F20) = Uanis(F24)
Uanis(F7) = Uanis(F12)
Uanis(F8) = Uanis(F10)
Uanis(F11) = Uanis(F9)
Uanis(F24) = Uanis(F20)
Uanis(F22) = Uanis(F21)
Uanis(F23) = Uanis(F19)
5. Others
 Sof(F5)=Sof(F6)=Sof(F4)=1-FVAR(1)
 Sof(F2)=Sof(F1)=Sof(F3)=FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=1-FVAR(2)
 Sof(F9)=Sof(F8)=Sof(F7)=FVAR(2)
 Sof(F18)=Sof(F17)=Sof(F16)=1-FVAR(3)
 Sof(F15)=Sof(F14)=Sof(F13)=FVAR(3)
 Sof(F22)=Sof(F24)=Sof(F23)=1-FVAR(4)
 Sof(F21)=Sof(F19)=Sof(F20)=FVAR(4)
 Sof(F35)=Sof(F36)=Sof(F34)=1-FVAR(5)
 Sof(F32)=Sof(F33)=Sof(F31)=FVAR(5)
 Sof(F48)=Sof(F47)=Sof(F46)=1-FVAR(6)
 Sof(F43)=Sof(F44)=Sof(F45)=FVAR(6)
 Sof(F56)=Sof(F57)=Sof(F55)=1-FVAR(7)
 Sof(F60)=Sof(F58)=Sof(F59)=FVAR(7)
6.a Secondary CH2 refined with riding coordinates:
 C04N(H04E,H04F)
6.b Aromatic/amide H refined with riding coordinates:
 C017(H017), C01A(H01A), C01B(H01B), C01D(H01D), C01E(H01E), C01G(H01G),
 C01J(H01J), C01M(H01M), C01P(H01P), C01R(H01R), C01T(H01T), C01V(H01V),
 C020(H020), C021(H021), C023(H023), C024(H024), C026(H026), C029(H029),
 C02C(H02C), C02H(H02H), C02I(H02I), C02L(H02L), C02N(H02N), C02R(H02R),
 C02S(H02S), C02T(H02T), C02W(H02W), C02Y(H02Y), C034(H034), C037(H037),
 C038(H038), C03A(H03A), C03C(H03C), C03F(H03I), C03K(H03K), C03N(H03N),
 C03O(H03O), C03Q(H03Q), C03R(H03R), C03S(H03S), C03U(H03U), C03X(H03X),
 C03Y(H03Y), C040(H040), C043(H043), C046(H046), C04B(H04B), C04G(H04G),
 C04K(H04K), C04L(H04L)
6.c Idealised Me refined as rotating group:
 C02M(H02A,H02B,H02D), C035(H03F,H03G,H03H), C03T(H03B,H03D,H03E), C041(H04A,
 H04C,H04D)
;
_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 1.444
_oxdiff_exptl_absorpt_empirical_full_min 0.484