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_4126517
_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_absolute_configuration ad
_chemical_formula_moiety         'C29 H41 Ga N2 P4, C7 H8'
_chemical_formula_sum            'C36 H49 Ga N2 P4'
_chemical_formula_weight         703.37
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_symmetry_space_group_name_Hall  'P 4abw 2nw'
_symmetry_space_group_name_H-M   'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-04-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.95431(13)
_cell_length_b                   19.95431(13)
_cell_length_c                   18.5098(2)
_cell_measurement_reflns_used    14476
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3410
_cell_measurement_theta_min      3.2430
_cell_volume                     7370.13(10)
_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      N~2~
_diffrn_ambient_temperature      100.00(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 0.992
_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     11.00  38.00   0.50    1.00    --  -38.50   0.00-150.00   54
  2  \w     28.00  85.00   0.50    1.00    --   42.75-125.00 -30.00  114
  3  \w     36.00 135.00   0.50    4.00    --  111.00 -30.00  30.00  198
  4  \w     92.00 125.00   0.50    4.00    --  111.00  45.00  90.00   66
  5  \w    141.00 168.00   0.50    4.00    --  111.00  45.00  90.00   54
  6  \w    108.00 175.00   0.50    4.00    --  111.00  77.00 120.00  134
  7  \w    108.00 177.00   0.50    4.00    --  111.00 125.00 -60.00  138
  8  \w     71.00 107.00   0.50    4.00    --  111.00 -94.00 150.00   72
  9  \w   -124.00 -40.00   0.50    1.00    --  -38.50   0.00-150.00  168
;
_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      0.0136035000
_diffrn_orient_matrix_UB_12      0.0273597000
_diffrn_orient_matrix_UB_13      -0.0765047000
_diffrn_orient_matrix_UB_21      0.0746506000
_diffrn_orient_matrix_UB_22      -0.0180004000
_diffrn_orient_matrix_UB_23      0.0080185000
_diffrn_orient_matrix_UB_31      -0.0137579000
_diffrn_orient_matrix_UB_32      -0.0699774000
_diffrn_orient_matrix_UB_33      -0.0318618000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0276
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            22939
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.613
_diffrn_reflns_theta_min         3.132
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.857
_exptl_absorpt_correction_T_max  0.826
_exptl_absorpt_correction_T_min  0.584
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             2960
_exptl_crystal_size_max          0.343
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.079
_refine_diff_density_max         0.488
_refine_diff_density_min         -0.337
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 3092 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         7665
_refine_ls_number_restraints     351
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0301
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0444P)^2^+2.1453P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0789
_refine_ls_wR_factor_ref         0.0800
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                7382
_reflns_number_total             7665
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_002.cif
_cod_data_source_block           1
_cod_original_cell_volume        7370.15(12)
_cod_database_code               4126517
_chemical_oxdiff_formula         'C260 H328 Ga8 N16 P32 '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37A-C43A \\sim C37B-C43B \\sim C30-C36
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C43A \\sim C37A \\sim C42A \\sim C38A \\sim C41A \\sim C39A \\sim C40A \\sim
C40B \\sim C43B \\sim C37B \\sim C42B \\sim C38B \\sim C41B \\sim C39B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C36 \\sim C30 \\sim C35 \\sim C31 \\sim C34 \\sim C32 \\sim C33: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C43A) \\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(C42A) \\sim Ueq,
Uanis(C38A) \\sim Ueq, Uanis(C41A) \\sim Ueq, Uanis(C39A) \\sim Ueq,
Uanis(C40A) \\sim Ueq, Uanis(C43B) \\sim Ueq, Uanis(C37B) \\sim Ueq,
Uanis(C42B) \\sim Ueq, Uanis(C38B) \\sim Ueq, Uanis(C41B) \\sim Ueq,
Uanis(C39B) \\sim Ueq, Uanis(C40B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: C43A(0.25) H43A(0.25) H43B(0.25) H43C(0.25) C37A(0.25) C38A(0.25)
 H38A(0.25) C39A(0.25) H39A(0.25) C40A(0.25) H40A(0.25) C41A(0.25) H41A(0.25)
 C42A(0.25) H42A(0.25) C43B(0.25) H43D(0.25) H43E(0.25) H43F(0.25) C37B(0.25)
 C42B(0.25) H42B(0.25) C41B(0.25) H41B(0.25) C40B(0.25) H40B(0.25) C39B(0.25)
 H39B(0.25) C38B(0.25) H38B(0.25) C36(0.5) H36A(0.5) H36B(0.5) H36C(0.5)
 C30(0.5) C31(0.5) H31(0.5) C32(0.5) H32(0.5) C33(0.5) H33(0.5) C34(0.5)
 H34(0.5) C35(0.5) H35(0.5)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C24(H24), C15(H15), C27(H27)
5.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C2(H2), C20(H20), C21(H21), C22(H22), C38A(H38A),
 C39A(H39A), C40A(H40A), C41A(H41A), C42A(H42A), C42B(H42B), C41B(H41B),
 C40B(H40B), C39B(H39B), C38B(H38B), C31(H31), C32(H32), C33(H33), C34(H34),
 C35(H35)
5.c Fitted hexagon refined as free rotating group:
 C37A(C38A,C39A,C40A,C41A,C42A), C37B(C42B,C41B,C40B,C39B,C38B), C30(C31,C32,
 C33,C34,C35)
5.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C4(H4A,H4B,H4C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C),
 C13(H13A,H13B,H13C), C17(H17A,H17B,H17C), C26(H26A,H26B,H26C), C25(H25A,H25B,
 H25C), C29(H29A,H29B,H29C), C28(H28A,H28B,H28C), C43A(H43A,H43B,H43C),
 C43B(H43D,H43E,H43F), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              28768
_shelx_hkl_checksum              38223
_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 1.294
_oxdiff_exptl_absorpt_empirical_full_min 0.678