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_4126522
_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 H106 Ga2 N4 Na O3 P7, C4 H8 O'
_chemical_formula_sum            'C74 H114 Ga2 N4 Na O4 P7'
_chemical_formula_weight         1502.91
_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             2017-07-03
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                76.660(3)
_cell_angle_beta                 88.072(2)
_cell_angle_gamma                69.876(3)
_cell_formula_units_Z            2
_cell_length_a                   13.0457(3)
_cell_length_b                   14.2179(5)
_cell_length_c                   23.0315(6)
_cell_measurement_reflns_used    18163
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2650
_cell_measurement_theta_min      4.0180
_cell_volume                     3898.0(2)
_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 0.987
_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    -65.00  32.00   0.50    2.00    --  -38.50  57.00  30.00  194
  2  \w     25.00 115.00   0.50    2.00    --   42.25  38.00 150.00  180
  3  \w     42.00 135.00   0.50    8.00    --  111.00 -45.00  30.00  186
  4  \w    117.00 145.00   0.50    8.00    --  111.00 -15.00 -30.00   56
  5  \w    116.00 142.00   0.50    8.00    --  111.00 -77.00 -30.00   52
  6  \w     88.00 142.00   0.50    8.00    --  111.00 -77.00  30.00  108
  7  \w     83.00 119.00   0.50    8.00    --  111.00-125.00  90.00   72
  8  \w     78.00 121.00   0.50    8.00    --  111.00-125.00 150.00   86
  9  \w     51.00 121.00   0.50    8.00    --  111.00-125.00  60.00  140
 10  \w     61.00  90.00   0.50    8.00    --  111.00-125.00   0.00   58
 11  \w     56.00  85.00   0.50    8.00    --  111.00 -77.00 -30.00   58
 12  \w     50.00  78.00   0.50    8.00    --  111.00-125.00 -90.00   56
 13  \w     79.00 121.00   0.50    8.00    --  111.00-125.00 -90.00   84
 14  \w     90.00 121.00   0.50    8.00    --  111.00-125.00-180.00   62
 15  \w     70.00 102.00   0.50    8.00    --  111.00 -94.00-120.00   64
 16  \w     58.00 129.00   0.50    8.00    --  111.00 -30.00-120.00  142
 17  \w     39.00  79.00   0.50    8.00    --  111.00 -77.00  30.00   80
 18  \w     53.00  81.00   0.50    8.00    --  111.00-125.00  90.00   56
 19  \w     42.00  91.00   0.50    8.00    --  111.00 -61.00 150.00   98
 20  \w     49.00 105.00   0.50    8.00    --  111.00 -45.00 150.00  112
 21  \w     90.00 144.00   0.50    8.00    --  111.00  45.00 120.00  108
 22  \w     94.00 121.00   0.50    8.00    --  111.00 125.00  30.00   54
 23  \w    153.00 178.00   0.50    8.00    --  111.00 125.00 -60.00   50
 24  \w     31.00  98.00   0.50    8.00    --  111.00 -15.00 -30.00  134
 25  \w     40.00 108.00   0.50    8.00    --  111.00 -94.00 -60.00  136
 26  \w     31.00  95.00   0.50    2.00    --   42.25-122.00-134.00  128
 27  \w     32.00  99.00   0.50    8.00    --  111.00 -94.00 -90.00  134
 28  \w     33.00 154.00   0.50    8.00    --  111.00 -15.00-150.00  242
 29  \w     32.00 153.00   0.50    8.00    --  111.00 -15.00  90.00  242
 30  \w      7.00  63.00   0.50    2.00    --   42.25 -99.00  60.00  112
 31  \w    -98.00 -63.00   0.50    2.00    --  -38.50-152.00  64.00   70
 32  \w   -109.00 -14.00   0.50    2.00    --  -38.50 -57.00-120.00  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      -0.1245310000
_diffrn_orient_matrix_UB_12      0.0479677000
_diffrn_orient_matrix_UB_13      0.0044210000
_diffrn_orient_matrix_UB_21      0.0130436000
_diffrn_orient_matrix_UB_22      -0.0412525000
_diffrn_orient_matrix_UB_23      0.0683348000
_diffrn_orient_matrix_UB_31      0.0133806000
_diffrn_orient_matrix_UB_32      0.1004105000
_diffrn_orient_matrix_UB_33      0.0069629000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0388
_diffrn_reflns_av_unetI/netI     0.0414
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            42672
_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         76.886
_diffrn_reflns_theta_min         3.405
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.633
_exptl_absorpt_correction_T_max  0.927
_exptl_absorpt_correction_T_min  0.635
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             1592
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.848
_refine_diff_density_min         -1.436
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     859
_refine_ls_number_reflns         16236
_refine_ls_number_restraints     48
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0727
_refine_ls_R_factor_gt           0.0669
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1024P)^2^+8.6969P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1836
_refine_ls_wR_factor_ref         0.1901
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14512
_reflns_number_total             16236
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_029.cif
_cod_data_source_block           16
_cod_database_code               4126522
_chemical_oxdiff_formula         C70H101Ga2N4NaO3P7
_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, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
O4 \\sim C71 \\sim C72 \\sim C73A \\sim C73B \\sim C74: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
3. Others
 Sof(H72C)=Sof(H72D)=Sof(C73B)=Sof(H73C)=Sof(H73D)=Sof(H74C)=Sof(H74D)=1-FVAR(1)
 Sof(H72A)=Sof(H72B)=Sof(C73A)=Sof(H73A)=Sof(H73B)=Sof(H74A)=Sof(H74B)=FVAR(1)
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 Secondary CH2 refined with riding coordinates:
 C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,
 H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B),
 C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B), C72(H72C,H72D),
  C72(H72A,H72B), C73A(H73A,H73B), C73B(H73C,H73D), C74(H74C,H74D), C74(H74A,
 H74B)
4.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)
4.d 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)
;
_shelx_res_checksum              63696
_shelx_hkl_checksum              29094
_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 1.643
_oxdiff_exptl_absorpt_empirical_full_min 0.619