Selective Derivatization of a Hexaphosphane from Functionalization of White Phosphorus.
Hennersdorf, Felix; Frötschel, Julia; Weigand, Jan J.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b07704

data_4126528
_publ_section_title
;
 Selective Derivatization of a Hexaphosphane from Functionalization of
 White Phosphorus.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b07704
_journal_year                    2017
_chemical_formula_moiety
'C70 H92 Cl Ga2 N4 P7, 0.11(C6 H6), 0.39(C5 H12)'
_chemical_formula_sum            'C72.61 H97.32 Cl Ga2 N4 P7'
_chemical_formula_weight         1417.91
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                95.1054(10)
_cell_angle_beta                 91.9061(10)
_cell_angle_gamma                109.6612(13)
_cell_formula_units_Z            2
_cell_length_a                   12.29883(16)
_cell_length_b                   15.2753(2)
_cell_length_c                   21.4327(2)
_cell_measurement_reflns_used    22470
_cell_measurement_temperature    300.01(10)
_cell_measurement_theta_max      75.9290
_cell_measurement_theta_min      3.0510
_cell_volume                     3768.15(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      300.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -28.00  -1.00   0.50    0.50    --   42.75 -38.00  60.00   54
  2  \w     32.00 135.00   0.50    2.00    --  111.00 -15.00 -60.00  206
  3  \w    141.00 178.00   0.50    2.00    --  111.00  45.00-120.00   74
  4  \w    110.00 151.00   0.50    2.00    --  111.00 -15.00-180.00   82
  5  \w     83.00 115.00   0.50    2.00    --  111.00 -30.00-120.00   64
  6  \w     75.00 108.00   0.50    2.00    --  111.00 -94.00-120.00   66
  7  \w     77.00 121.00   0.50    2.00    --  111.00-125.00-180.00   88
  8  \w     77.00 120.00   0.50    2.00    --  111.00-125.00 -90.00   86
  9  \w     87.00 121.00   0.50    2.00    --  111.00-125.00 -60.00   68
 10  \w     64.00  97.00   0.50    2.00    --  111.00 -94.00-180.00   66
 11  \w     55.00  82.00   0.50    2.00    --  111.00-125.00 -60.00   54
 12  \w     50.00 121.00   0.50    2.00    --  111.00-125.00   0.00  142
 13  \w     94.00 121.00   0.50    2.00    --  111.00-125.00  60.00   54
 14  \w    101.00 140.00   0.50    2.00    --  111.00 -77.00  90.00   78
 15  \w     81.00 106.00   0.50    2.00    --  111.00 -94.00  90.00   50
 16  \w     79.00 121.00   0.50    2.00    --  111.00-125.00 120.00   84
 17  \w     63.00  90.00   0.50    2.00    --  111.00 -77.00  90.00   54
 18  \w     51.00  99.00   0.50    2.00    --  111.00-125.00  90.00   96
 19  \w     47.00  75.00   0.50    2.00    --  111.00-125.00  60.00   56
 20  \w     30.00  72.00   0.50    2.00    --  111.00 -94.00   0.00   84
 21  \w     40.00 102.00   0.50    2.00    --  111.00 -45.00  30.00  124
 22  \w     45.00  99.00   0.50    2.00    --  111.00 -45.00  90.00  108
 23  \w     42.00 111.00   0.50    2.00    --  111.00 -45.00 150.00  138
 24  \w     31.00 153.00   0.50    2.00    --  111.00 -15.00  60.00  244
 25  \w     39.00  68.00   0.50    2.00    --  111.00 -30.00-120.00   58
 26  \w     40.00 142.00   0.50    2.00    --  111.00 -77.00 -90.00  204
 27  \w     31.00  91.00   0.50    2.00    --  111.00 -15.00-180.00  120
 28  \w     30.00 107.00   0.50    0.50    --   42.75  38.00-120.00  154
 29  \w     14.00  82.00   0.50    0.50    --   42.75 -99.00 -90.00  136
 30  \w     25.00  76.00   0.50    0.50    --   42.75-125.00-180.00  102
 31  \w    -63.00  32.00   0.50    0.50    --  -38.50  57.00 120.00  190
 32  \w   -109.00 -15.00   0.50    0.50    --  -38.50 -57.00 -30.00  188
;
_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      -0.0821012000
_diffrn_orient_matrix_UB_12      -0.0554841000
_diffrn_orient_matrix_UB_13      0.0465163000
_diffrn_orient_matrix_UB_21      -0.0344392000
_diffrn_orient_matrix_UB_22      0.0860978000
_diffrn_orient_matrix_UB_23      0.0195568000
_diffrn_orient_matrix_UB_31      -0.0992334000
_diffrn_orient_matrix_UB_32      -0.0333139000
_diffrn_orient_matrix_UB_33      -0.0518205000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            39952
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.413
_diffrn_reflns_theta_min         3.090
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.923
_exptl_absorpt_correction_T_max  0.754
_exptl_absorpt_correction_T_min  0.638
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_description       block
_exptl_crystal_F_000             1490
_exptl_crystal_size_max          0.246
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.162
_refine_diff_density_max         0.434
_refine_diff_density_min         -0.309
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     924
_refine_ls_number_reflns         15595
_refine_ls_number_restraints     238
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0517P)^2^+0.9939P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0982
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13842
_reflns_number_total             15595
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_020.cif
_cod_data_source_block           8_2_300
_cod_original_cell_volume        3768.15(9)
_cod_database_code               4126528
_chemical_oxdiff_formula         'C72.65 H97.12 Cl Ga2 N4 P7'
_reflns_odcompleteness_completeness 99.96
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C75-C74 \\sim C74-C73 \\sim C72-C73 \\sim C72-C71
 with sigma of 0.001
 C75-C73 \\sim C73-C71 \\sim C74-C72
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C79 \\sim C80 \\sim C78 \\sim
C81 \\sim C77 \\sim C76: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C59B \\sim C60B \\sim C61B \\sim C62B \\sim C63B \\sim C64B \\sim C65B \\sim
C70B \\sim C69B \\sim C68B \\sim C67B \\sim C66B \\sim P7B \\sim P4B: within 3A
with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Same fragment restrains
{C59B, C60B, C61B, C62B, C63B, C64B, C65B, C70B, C69B, C68B, C67B, C66B, P4B,
P7B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C59A, C60A, C61A, C62A, C63A, C64A, C65A, C66A, C67A, C68A, C69A, C70A, P4A,
P7A}
5. Others
 Sof(C79)=Sof(H79)=Sof(C80)=Sof(H80)=Sof(C81)=Sof(H81)=Sof(C76)=Sof(H76)=
 Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78)=0.5*(1-FVAR(2))
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=
 Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75A)=Sof(H75B)=
 Sof(H75C)=0.5*FVAR(2)
 Sof(C59B)=Sof(C60B)=Sof(H60B)=Sof(C61B)=Sof(H61B)=Sof(C62B)=Sof(H62B)=
 Sof(C63B)=Sof(H63B)=Sof(C64B)=Sof(H64B)=Sof(C65B)=Sof(C70B)=Sof(H70B)=
 Sof(C69B)=Sof(H69B)=Sof(C68B)=Sof(H68B)=Sof(C67B)=Sof(H67B)=Sof(C66B)=
 Sof(H66B)=Sof(P4B)=Sof(P7B)=1-FVAR(2)
 Sof(C59A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62A)=
 Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(C66A)=Sof(H66A)=
 Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=Sof(C70A)=
 Sof(H70A)=Sof(P4A)=Sof(P7A)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C41(H41), C44(H44), C53(H53), C56(H56)
6.b Secondary CH2 refined with riding coordinates:
 C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C31(H31),
 C37(H37), C38(H38), C39(H39), C49(H49), C50(H50), C51(H51), C60A(H60A),
 C61A(H61A), C62A(H62A), C63A(H63A), C64A(H64A), C66A(H66A), C67A(H67A),
 C68A(H68A), C69A(H69A), C70A(H70A), C60B(H60B), C61B(H61B), C62B(H62B),
 C63B(H63B), C64B(H64B), C70B(H70B), C69B(H69B), C68B(H68B), C67B(H67B),
 C66B(H66B), C79(H79), C80(H80), C81(H81), C76(H76), C77(H77), C78(H78)
6.d Fitted hexagon refined as free rotating group:
 C79(C80,C81,C76,C77,C78)
6.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C71(H71A,H71B,H71C), C75(H75A,H75B,H75C)
;
_shelx_res_checksum              6606
_shelx_hkl_checksum              49400
_shelx_shelxl_version_number     2014/7
_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 1.375
_oxdiff_exptl_absorpt_empirical_full_min 0.758