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_4126535
_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
'3(C58 H82 Ga2 N4 P16), 2(C6 H14), C7 H8, 2(P4)'
_chemical_formula_sum            'C193 H282 Ga6 N12 P56'
_chemical_formula_weight         4922.93
_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             2016-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                70.7664(16)
_cell_angle_beta                 81.2661(12)
_cell_angle_gamma                75.7253(14)
_cell_formula_units_Z            1
_cell_length_a                   16.4384(2)
_cell_length_b                   17.9501(4)
_cell_length_c                   22.3596(4)
_cell_measurement_reflns_used    26813
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      76.4650
_cell_measurement_theta_min      3.6030
_cell_volume                     6019.1(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      100.0(3)
_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    -64.00  31.00   0.50    3.50    --  -38.50  57.00-180.00  190
  2  \w   -109.00 -13.00   0.50    3.50    --  -38.50 -57.00  30.00  192
  3  \w     36.00  98.00   0.50    3.50    --   42.50-125.00 -60.00  124
  4  \w     26.00 109.00   0.50    3.50    --   42.50  38.00 -30.00  166
  5  \w     41.00 112.00   0.50    3.50    --   42.50  38.00-120.00  142
  6  \w     46.00  71.00   0.50    3.50    --   42.50-125.00  90.00   50
  7  \w    132.00 167.00   0.50   14.00    --  111.00  45.00  60.00   70
  8  \w     64.00 132.00   0.50   14.00    --  111.00 -45.00  30.00  136
  9  \w     89.00 172.00   0.50   14.00    --  111.00  45.00  90.00  166
 10  \w     32.00  59.00   0.50   14.00    --  111.00 -94.00  60.00   54
 11  \w     83.00 109.00   0.50   14.00    --  111.00 -94.00  60.00   52
 12  \w     87.00 130.00   0.50   14.00    --  111.00  45.00  60.00   86
 13  \w    133.00 178.00   0.50   14.00    --  111.00  45.00 -60.00   90
 14  \w     93.00 120.00   0.50   14.00    --  111.00-125.00-180.00   54
 15  \w     90.00 169.00   0.50   14.00    --  111.00  45.00 -30.00  158
 16  \w     80.00 151.00   0.50   14.00    --  111.00  77.00   0.00  142
 17  \w     85.00 119.00   0.50   14.00    --  111.00-125.00  30.00   68
 18  \w    128.00 155.00   0.50   14.00    --  111.00 125.00  30.00   54
 19  \w     91.00 130.00   0.50   14.00    --  111.00  30.00 150.00   78
 20  \w    101.00 149.00   0.50   14.00    --  111.00 125.00   0.00   96
 21  \w     89.00 133.00   0.50   14.00    --  111.00 -61.00  60.00   88
 22  \w     88.00 121.00   0.50   14.00    --  111.00-125.00  90.00   66
 23  \w     45.00  75.00   0.50   14.00    --  111.00-125.00  30.00   60
 24  \w     41.00  69.00   0.50   14.00    --  111.00 -30.00 120.00   56
 25  \w     81.00 134.00   0.50   14.00    --  111.00 -30.00 120.00  106
 26  \w    115.00 169.00   0.50   14.00    --  111.00  15.00  30.00  108
 27  \w     39.00  87.00   0.50   14.00    --  111.00-125.00-120.00   96
 28  \w     51.00  99.00   0.50   14.00    --  111.00 -77.00-150.00   96
 29  \w    100.00 133.00   0.50   14.00    --  111.00 -77.00-150.00   66
 30  \w     90.00 141.00   0.50   14.00    --  111.00 -77.00 -30.00  102
 31  \w     68.00 108.00   0.50   14.00    --  111.00 -94.00 120.00   80
 32  \w     75.00 107.00   0.50   14.00    --  111.00 -94.00-150.00   64
 33  \w     39.00  66.00   0.50   14.00    --  111.00 -94.00 -90.00   54
 34  \w     40.00 121.00   0.50   14.00    --  111.00-125.00 -30.00  162
 35  \w     48.00 139.00   0.50   14.00    --  111.00 -61.00 -60.00  182
 36  \w     81.00 121.00   0.50   14.00    --  111.00-123.00-135.88   80
;
_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      -0.0291337000
_diffrn_orient_matrix_UB_12      -0.0475081000
_diffrn_orient_matrix_UB_13      0.0675952000
_diffrn_orient_matrix_UB_21      0.0261859000
_diffrn_orient_matrix_UB_22      -0.0787361000
_diffrn_orient_matrix_UB_23      -0.0181788000
_diffrn_orient_matrix_UB_31      0.0887303000
_diffrn_orient_matrix_UB_32      -0.0137694000
_diffrn_orient_matrix_UB_33      0.0213844000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            68478
_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         76.706
_diffrn_reflns_theta_min         2.667
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.652
_exptl_absorpt_correction_T_max  0.926
_exptl_absorpt_correction_T_min  0.577
_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    1.358
_exptl_crystal_description       plate
_exptl_crystal_F_000             2550
_exptl_crystal_size_max          0.148
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.017
_refine_diff_density_max         1.495
_refine_diff_density_min         -1.212
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1220
_refine_ls_number_reflns         25054
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0659P)^2^+5.5267P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1208
_refine_ls_wR_factor_ref         0.1279
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21413
_reflns_number_total             25054
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_014.cif
_cod_data_source_block           7_2
_cod_original_cell_volume        6019.08(18)
_cod_database_code               4126535
_chemical_oxdiff_formula         'C174 H246 Ga6 N12 P56 '
_chemical_oxdiff_usercomment     Ga2P16
_reflns_odcompleteness_completeness 99.99
_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
 C36-C42
 1.5 with sigma of 0.02
3. Others
 Fixed Sof: C36(0.5) C41(0.5) H41(0.5) C40(0.5) H40(0.5) C39(0.5) H39(0.5)
 C38(0.5) H38(0.5) C37(0.5) H37(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5)
4.a Ternary CH refined with riding coordinates:
 C12A(H12A), C15A(H15A), C24A(H24A), C27A(H27A), C12C(H12C), C15C(H15C),
 C24C(H24C), C27C(H27C), C12B(H12B), C15B(H15B), C24B(H24B), C27B(H27B)
4.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B)
4.c Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C8A(H8A), C9A(H9A), C10A(H10A), C20A(H20A), C21A(H21A), C22A(H22A),
 C2C(H2C), C8C(H8C), C9C(H9C), C10C(H10C), C20C(H20C), C21C(H21C), C22C(H22C),
 C2B(H2B), C8B(H8B), C9B(H9B), C10B(H10B), C20B(H20B), C21B(H21B), C22B(H22B),
 C41(H41), C40(H40), C39(H39), C38(H38), C37(H37)
4.d Fitted hexagon refined as free rotating group:
 C36(C41,C40,C39,C38,C37)
4.e Idealised Me refined as rotating group:
 C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C13A(H13A,H13B,H13C), C14A(H14A,
 H14B,H14C), C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C25A(H25A,H25B,H25C),
 C26A(H26A,H26B,H26C), C28A(H28A,H28B,H28C), C29A(H29A,H29B,H29C), C4C(H4CA,
 H4CB,H4CC), C5C(H5CA,H5CB,H5CC), C13C(H13D,H13E,H13F), C14C(H14D,H14E,H14F),
 C16C(H16D,H16E,H16F), C17C(H17D,H17E,H17F), C25C(H25D,H25E,H25F), C26C(H26D,
 H26E,H26F), C28C(H28D,H28E,H28F), C29C(H29D,H29E,H29F), C4B(H4BA,H4BB,H4BC),
 C5B(H5BA,H5BB,H5BC), C13B(H13G,H13H,H13I), C14B(H14G,H14H,H14I), C16B(H16G,
 H16H,H16I), C17B(H17G,H17H,H17I), C25B(H25G,H25H,H25I), C26B(H26G,H26H,H26I),
 C28B(H28G,H28H,H28I), C29B(H29G,H29H,H29I), C30(H30A,H30B,H30C), C35(H35A,H35B,
 H35C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              61651
_shelx_hkl_checksum              30487
_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 0.762