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_4126524
_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         'C58 H82 Ga2 N4 P8'
_chemical_formula_sum            'C58 H82 Ga2 N4 P8'
_chemical_formula_weight         1222.47
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3'
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-03-16
_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                120
_cell_formula_units_Z            18
_cell_length_a                   39.4235(14)
_cell_length_b                   39.4235(14)
_cell_length_c                   31.1940(6)
_cell_measurement_reflns_used    6057
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.2240
_cell_measurement_theta_min      3.6700
_cell_volume                     41987(2)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.964
_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    -61.00  -8.00   0.50   25.00    --  -38.50 125.00  60.00  106
  2  \w      5.00  67.00   0.50   25.00    --   42.75 -99.00  30.00  124
  3  \w     60.00  88.50   0.50  100.00    --  111.00 -97.00 -85.00   57
  4  \w    103.00 129.00   0.50  100.00    --  111.00 125.00 -90.00   52
  5  \w    132.00 162.00   0.50  100.00    --  111.00 117.00  52.00   60
  6  \w     94.00 175.00   0.50  100.00    --  111.00 125.00   0.00  162
  7  \w     51.00  82.00   0.50  100.00    --  111.00 -45.00  90.00   62
  8  \w    105.00 132.00   0.50  100.00    --  111.00 -45.00  90.00   54
  9  \w     92.00 178.00   0.50  100.00    --  111.00  45.00 -90.00  172
;
_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      0.0440951000
_diffrn_orient_matrix_UB_12      0.0256091000
_diffrn_orient_matrix_UB_13      -0.0094712000
_diffrn_orient_matrix_UB_21      0.0068522000
_diffrn_orient_matrix_UB_22      -0.0330763000
_diffrn_orient_matrix_UB_23      0.0160150000
_diffrn_orient_matrix_UB_31      -0.0067299000
_diffrn_orient_matrix_UB_32      -0.0169066000
_diffrn_orient_matrix_UB_33      -0.0457122000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0597
_diffrn_reflns_av_unetI/netI     0.0819
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            37541
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.840
_diffrn_reflns_theta_min         2.951
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.203
_exptl_absorpt_correction_T_max  0.930
_exptl_absorpt_correction_T_min  0.833
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.870
_exptl_crystal_description       block
_exptl_crystal_F_000             11520
_exptl_crystal_size_max          0.126
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.042
_refine_diff_density_max         1.178
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     895
_refine_ls_number_reflns         18980
_refine_ls_number_restraints     965
_refine_ls_restrained_S_all      0.978
_refine_ls_R_factor_all          0.0973
_refine_ls_R_factor_gt           0.0564
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0699P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1418
_refine_ls_wR_factor_ref         0.1614
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11182
_reflns_number_total             18980
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_007.cif
_cod_data_source_block           4
_cod_original_cell_volume        41987(3)
_cod_database_code               4126524
_chemical_oxdiff_formula         C58H82Ga2N4P8
_chemical_oxdiff_usercomment     'from Hexane'
_reflns_odcompleteness_completeness 99.42
_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
 C44B-C45B \\sim C44A-C45A \\sim C46B-C44B \\sim C44A-C46A \\sim C58A-C56A
\\sim C58B-C56B \\sim C57B-
 C56B \\sim C57A-C56A \\sim C55B-C53B \\sim C54B-C53B \\sim C42B-C41B \\sim
C42A-C41A \\sim C43B-C41B ~
 C43A-C41A \\sim C54A-C53A \\sim C53A-C55A
 with sigma of 0.01
 N4-C47B \\sim N4-C47A \\sim N3-C35A \\sim N3-C35B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C47B \\sim C52B \\sim C51B \\sim C50B \\sim C49B \\sim C48B \\sim C56B \\sim
C53B \\sim C54A \\sim C55B \\sim C57B \\sim C58B \\sim C47A \\sim C52A \\sim
C51A \\sim C50A \\sim C49A \\sim C48A \\sim C56A \\sim C53A \\sim C54B \\sim
C55A \\sim C57A \\sim C58A: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04
C35A \\sim C40A \\sim C39A \\sim C38A \\sim C37A \\sim C36A \\sim C44A \\sim
C41A \\sim C43A \\sim C45B \\sim C46A \\sim C42A \\sim C35B \\sim C40B \\sim
C39B \\sim C38B \\sim C37B \\sim C36B \\sim C44B \\sim C41B \\sim C43B \\sim
C45A \\sim C46B \\sim C42B: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04
4. Same fragment restrains
{C47B, C52B, C51B, C50B, C49B, C48B, C56B, C53B} sigma for 1-2: 0.02, 1-3: 0.02
{C47A, C52A, C51A, C50A, C49A, C48A, C56A, C53A} sigma for 1-2: 0.02, 1-3: 0.02
{C35B, C40B, C39B, C38B, C37B, C36B, C44B, C41B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C35A, C40A, C39A, C38A, C37A, C36A, C44A, C41A}
5. Others
 Sof(C47B)=Sof(C52B)=Sof(C51B)=Sof(H51B)=Sof(C50B)=Sof(H50B)=Sof(C49B)=
 Sof(H49B)=Sof(C48B)=Sof(C56B)=Sof(H56B)=Sof(C53B)=Sof(H53B)=Sof(C55B)=
 Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C57B)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C58B)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C54B)=Sof(H54D)=Sof(H54E)=
 Sof(H54F)=1-FVAR(1)
 Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C47A)=Sof(C52A)=Sof(C51A)=
 Sof(H51A)=Sof(C50A)=Sof(H50A)=Sof(C49A)=Sof(H49A)=Sof(C48A)=Sof(C56A)=
 Sof(H56A)=Sof(C53A)=Sof(H53A)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=
 Sof(C57A)=Sof(H57D)=Sof(H57E)=Sof(H57F)=Sof(C58A)=Sof(H58D)=Sof(H58E)=
 Sof(H58F)=FVAR(1)
 Sof(C45B)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C35B)=Sof(C40B)=Sof(C39B)=
 Sof(H39B)=Sof(C38B)=Sof(H38B)=Sof(C37B)=Sof(H37B)=Sof(C36B)=Sof(C44B)=
 Sof(H44B)=Sof(C41B)=Sof(H41B)=Sof(C43B)=Sof(H43D)=Sof(H43E)=Sof(H43F)=
 Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C42B)=Sof(H42D)=Sof(H42E)=
 Sof(H42F)=1-FVAR(2)
 Sof(C35A)=Sof(C40A)=Sof(C39A)=Sof(H39A)=Sof(C38A)=Sof(H38A)=Sof(C37A)=
 Sof(H37A)=Sof(C36A)=Sof(C44A)=Sof(H44A)=Sof(C41A)=Sof(H41A)=Sof(C43A)=
 Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C45A)=Sof(H45D)=Sof(H45E)=
 Sof(H45F)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C44A(H44A), C41A(H41A), C56B(H56B), C53B(H53B), C27(H27), C15(H15), C12(H12),
 C24(H24), C56A(H56A), C53A(H53A), C44B(H44B), C41B(H41B)
6.b Aromatic/amide H refined with riding coordinates:
 C31(H31), C2(H2), C39A(H39A), C38A(H38A), C37A(H37A), C9(H9), C51B(H51B),
 C50B(H50B), C49B(H49B), C8(H8), C22(H22), C10(H10), C20(H20), C21(H21),
 C51A(H51A), C50A(H50A), C49A(H49A), C39B(H39B), C38B(H38B), C37B(H37B)
6.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C5(H5A,H5B,H5C), C4(H4A,H4B,H4C), C17(H17A,H17B,H17C),
 C34(H34A,H34B,H34C), C13(H13A,H13B,H13C), C28(H28A,H28B,H28C), C16(H16A,H16B,
 H16C), C29(H29A,H29B,H29C), C25(H25A,H25B,H25C), C43A(H43A,H43B,H43C),
 C45B(H45A,H45B,H45C), C14(H14A,H14B,H14C), C54A(H54A,H54B,H54C), C55B(H55A,
 H55B,H55C), C26(H26A,H26B,H26C), C46A(H46A,H46B,H46C), C42A(H42A,H42B,H42C),
 C57B(H57A,H57B,H57C), C58B(H58A,H58B,H58C), C54B(H54D,H54E,H54F), C55A(H55D,
 H55E,H55F), C57A(H57D,H57E,H57F), C58A(H58D,H58E,H58F), C43B(H43D,H43E,H43F),
 C45A(H45D,H45E,H45F), C46B(H46D,H46E,H46F), C42B(H42D,H42E,H42F)
;
_shelx_res_checksum              81714
_shelx_hkl_checksum              42654
_shelx_fab_checksum              21014
_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 2.550
_oxdiff_exptl_absorpt_empirical_full_min 0.610