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_4126516
_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 H84 Ga2 N4 O P6, 2(C7 H8)'
_chemical_formula_sum            'C72 H100 Ga2 N4 O P6'
_chemical_formula_weight         1362.81
_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   mixed
_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                89.6385(11)
_cell_angle_beta                 68.9491(14)
_cell_angle_gamma                88.0122(12)
_cell_formula_units_Z            2
_cell_length_a                   13.2249(2)
_cell_length_b                   15.7757(2)
_cell_length_c                   18.2072(3)
_cell_measurement_reflns_used    29551
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.5570
_cell_measurement_theta_min      3.5790
_cell_volume                     3542.88(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 0.988
_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    -26.00  59.00   0.50    1.00    --   42.75 -77.00-120.00  170
  2  \w     63.00 127.00   0.50    4.00    --  111.00 -61.00 -90.00  128
  3  \w     87.00 133.00   0.50    4.00    --  111.00 -30.00 -90.00   92
  4  \w     94.00 126.00   0.50    4.00    --  111.00 -45.00-180.00   64
  5  \w     60.00  86.00   0.50    4.00    --  111.00 -45.00 -30.00   52
  6  \w     88.00 134.00   0.50    4.00    --  111.00 -45.00 -30.00   92
  7  \w    104.00 134.00   0.50    4.00    --  111.00 -30.00  30.00   60
  8  \w    132.00 177.00   0.50    4.00    --  111.00   0.00  60.00   90
  9  \w    138.00 168.00   0.50    4.00    --  111.00  30.00  90.00   60
 10  \w    112.00 178.00   0.50    4.00    --  111.00  61.00  60.00  132
 11  \w    104.00 173.00   0.50    4.00    --  111.00 125.00 -60.00  138
 12  \w     88.00 168.00   0.50    4.00    --  111.00  45.00   0.00  160
 13  \w     77.00 103.00   0.50    4.00    --  111.00 -30.00  30.00   52
 14  \w     75.00 110.00   0.50    4.00    --  111.00 -45.00  60.00   70
 15  \w     64.00  98.00   0.50    4.00    --  111.00 -94.00  90.00   68
 16  \w     57.00  93.00   0.50    4.00    --  111.00 -94.00   0.00   72
 17  \w     41.00 121.00   0.50    4.00    --  111.00-125.00 -90.00  160
 18  \w     50.00  76.00   0.50    4.00    --  111.00 -94.00-150.00   52
 19  \w     41.00 111.00   0.50    4.00    --  111.00-125.00-120.00  140
 20  \w     40.00 120.00   0.50    4.00    --  111.00-125.00   0.00  160
 21  \w     50.00  83.00   0.50    1.00    --   42.75 -99.00 150.00   66
 22  \w     31.00  74.00   0.50    1.00    --   42.75-125.00  30.00   86
 23  \w     30.00  94.00   0.50    4.00    --  111.00 -94.00 -90.00  128
 24  \w     40.00  77.00   0.50    4.00    --  111.00 -45.00-180.00   74
 25  \w     40.00 121.00   0.50    4.00    --  111.00-125.00-180.00  162
 26  \w     28.00  81.00   0.50    4.00    --  111.00   0.00  60.00  106
 27  \w     68.00  95.00   0.50    1.00    --   42.75  77.00 -90.00   54
 28  \w     47.00 120.00   0.50    4.00    --  111.00-125.00  90.00  146
 29  \w     39.00  89.00   0.50    4.00    --  111.00-125.00 150.00  100
 30  \w    -63.00  30.00   0.50    1.00    --  -38.50  57.00 150.00  186
 31  \w   -109.00 -14.00   0.50    1.00    --  -38.50 -57.00   0.00  190
;
_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      -0.1145670000
_diffrn_orient_matrix_UB_12      -0.0067103000
_diffrn_orient_matrix_UB_13      -0.0026701000
_diffrn_orient_matrix_UB_21      0.0005994000
_diffrn_orient_matrix_UB_22      -0.0947704000
_diffrn_orient_matrix_UB_23      0.0208323000
_diffrn_orient_matrix_UB_31      -0.0497267000
_diffrn_orient_matrix_UB_32      0.0228434000
_diffrn_orient_matrix_UB_33      0.0881995000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0186
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            38427
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.733
_diffrn_reflns_theta_min         2.600
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.551
_exptl_absorpt_correction_T_max  0.840
_exptl_absorpt_correction_T_min  0.678
_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    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.079
_refine_diff_density_max         0.636
_refine_diff_density_min         -0.595
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.330
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     852
_refine_ls_number_reflns         14750
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.328
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0589
_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^)+11.6522P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1375
_refine_ls_wR_factor_ref         0.1375
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14630
_reflns_number_total             14750
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_025.cif
_cod_data_source_block           13_1
_cod_original_cell_volume        3542.88(9)
_cod_database_code               4126516
_chemical_oxdiff_formula         'C144 H200 Ga4 N8 O2 P12 '
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
C72B \\sim C71B \\sim C66B \\sim C70B \\sim C67B \\sim C69B \\sim C68B \\sim
C69C \\sim C66C \\sim C71C \\sim C67C \\sim C72C \\sim C70C \\sim C68C \\sim
C69A \\sim C72A \\sim C71A \\sim C67A \\sim C73A \\sim C70A \\sim C68A: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 1*[Sof(C72A)+Sof(C71A)+Sof(H71A)+Sof(C70A)+Sof(H70A)+Sof(C69A)+Sof(H69A)+
 Sof(C68A)+Sof(H68A)+Sof(C67A)+Sof(H67A)+Sof(C73A)+Sof(H73A)+Sof(H73B)+
 Sof(H73C)]+1*[Sof(C66C)+Sof(C71C)+Sof(H71C)+Sof(C70C)+Sof(H70C)+Sof(C69C)+
 Sof(H69C)+Sof(C68C)+Sof(H68C)+Sof(C67C)+Sof(H67C)+Sof(C72C)+Sof(H72D)+
 Sof(H72E)+Sof(H72F)]+1*[Sof(C71B)+Sof(H71B)+Sof(C66B)+Sof(C67B)+Sof(H67B)+
 Sof(C68B)+Sof(H68B)+Sof(C69B)+Sof(H69B)+Sof(C70B)+Sof(H70B)+Sof(C72B)+
 Sof(H72A)+Sof(H72B)+Sof(H72C)]=1 with esd of 0.0001
 Sof(P1B)=Sof(P2B)=Sof(P3B)=Sof(P4B)=Sof(H4B)=Sof(P5B)=Sof(P6B)=Sof(O1B)=
 Sof(H1B)=1-FVAR(1)
 Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(H4A)=Sof(P5A)=Sof(P6A)=Sof(O1A)=
 Sof(H1A)=FVAR(1)
 Sof(C72A)=Sof(C71A)=Sof(H71A)=Sof(C70A)=Sof(H70A)=Sof(C69A)=Sof(H69A)=
 Sof(C68A)=Sof(H68A)=Sof(C67A)=Sof(H67A)=Sof(C73A)=Sof(H73A)=Sof(H73B)=
 Sof(H73C)=FVAR(2)
 Sof(C66C)=Sof(C71C)=Sof(H71C)=Sof(C70C)=Sof(H70C)=Sof(C69C)=Sof(H69C)=
 Sof(C68C)=Sof(H68C)=Sof(C67C)=Sof(H67C)=Sof(C72C)=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=FVAR(3)
 Sof(C71B)=Sof(H71B)=Sof(C66B)=Sof(C67B)=Sof(H67B)=Sof(C68B)=Sof(H68B)=
 Sof(C69B)=Sof(H69B)=Sof(C70B)=Sof(H70B)=Sof(C72B)=Sof(H72A)=Sof(H72B)=
 Sof(H72C)=FVAR(4)
4.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C41(H41), C44(H44), C53(H53), C56(H56)
4.b 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), C71B(H71B),
 C67B(H67B), C68B(H68B), C69B(H69B), C70B(H70B), C71C(H71C), C70C(H70C),
 C69C(H69C), C68C(H68C), C67C(H67C), C60(H60), C61(H61), C62(H62), C63(H63),
 C64(H64), C71A(H71A), C70A(H70A), C69A(H69A), C68A(H68A), C67A(H67A)
4.c Fitted hexagon refined as free rotating group:
 C71B(C66B,C67B,C68B,C69B,C70B), C66C(C71C,C70C,C69C,C68C,C67C), C72A(C71A,
 C70A,C69A,C68A,C67A)
4.d Idealised Me refined as rotating group:
 C4(H4C,H4D,H4E), 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), C72B(H72A,H72B,H72C), C72C(H72D,H72E,H72F),
 C65(H65A,H65B,H65C), C73A(H73A,H73B,H73C)
4.e Idealised tetrahedral OH refined as rotating group:
 O1A(H1A), O1B(H1B)
;
_shelx_res_checksum              18700
_shelx_hkl_checksum              34365
_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 1.264
_oxdiff_exptl_absorpt_empirical_full_min 0.881