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_4126523
_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
'0.883(C58 H82 Ga2 N4 P4), 0.117(C58 H82 Ga2 N4 P6), C7 H8'
_chemical_formula_sum            'C65 H90 Ga2 N4 P4.23'
_chemical_formula_weight         1197.93
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-02-11
_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            4
_cell_length_a                   13.64428(9)
_cell_length_b                   14.83342(10)
_cell_length_c                   31.5549(2)
_cell_measurement_reflns_used    39966
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.3690
_cell_measurement_theta_min      2.9690
_cell_volume                     6386.44(7)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_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   -125.00  48.00   0.50    3.00    --  -38.50   0.00  60.00  346
  2  \w     39.00 121.00   0.50   12.00    --  111.00-125.00 120.00  164
  3  \w     36.00 135.00   0.50   12.00    --  111.00 -30.00 120.00  198
  4  \w     94.00 178.00   0.50   12.00    --  111.00 125.00 120.00  168
  5  \w      6.00 121.00   0.50    3.00    --   42.75  19.00   0.00  230
  6  \w     23.00  98.00   0.50    3.00    --   42.75-125.00-180.00  150
  7  \w     66.00 178.00   0.50   12.00    --  111.00  15.00 -90.00  224
  8  \w     66.00 178.00   0.50   12.00    --  111.00  15.00  30.00  224
  9  \w     30.00 109.00   0.50   12.00    --  111.00 -94.00 150.00  158
 10  \w     81.00 178.00   0.50   12.00    --  111.00  73.00  83.00  194
 11  \w     11.00 117.00   0.50    3.00    --   42.75  77.00-150.00  212
 12  \w     11.00 117.00   0.50    3.00    --   42.75  77.00  30.00  212
 13  \w     80.00 162.00   0.50   12.00    --  111.00  77.00 150.00  164
;
_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      -0.0093178000
_diffrn_orient_matrix_UB_12      -0.0795678000
_diffrn_orient_matrix_UB_13      -0.0311358000
_diffrn_orient_matrix_UB_21      -0.0972417000
_diffrn_orient_matrix_UB_22      -0.0277372000
_diffrn_orient_matrix_UB_23      0.0211364000
_diffrn_orient_matrix_UB_31      -0.0567191000
_diffrn_orient_matrix_UB_32      0.0607499000
_diffrn_orient_matrix_UB_33      -0.0310523000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            51453
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.491
_diffrn_reflns_theta_min         3.292
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.342
_exptl_absorpt_correction_T_max  0.866
_exptl_absorpt_correction_T_min  0.619
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_description       block
_exptl_crystal_F_000             2534
_exptl_crystal_size_max          0.275
_exptl_crystal_size_mid          0.151
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.510
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.038(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     741
_refine_ls_number_reflns         13044
_refine_ls_number_restraints     22
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0319
_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^)+(0.0287P)^2^+5.0353P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0780
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                12988
_reflns_number_total             13044
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_003.cif
_cod_data_source_block           2_1
_cod_original_cell_volume        6386.43(7)
_cod_database_code               4126523
_chemical_oxdiff_formula         'C256 H360 Ga8 N20 P16 '
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.962(18) 0.038(18)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
C59B \\sim C60B \\sim C61B \\sim C62B \\sim C63B \\sim C64B \\sim C65B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Same fragment restrains
{C59B, C60B, C61B, C62B, C63B, C64B, C65B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C59A, C60A, C61A, C62A, C63A, C64A, C65A}
5. Others
 Sof(C59B)=Sof(C60B)=Sof(H60B)=Sof(C61B)=Sof(H61B)=Sof(C62B)=Sof(H62B)=
 Sof(C63B)=Sof(H63B)=Sof(C64B)=Sof(H64B)=Sof(C65B)=Sof(H65D)=Sof(H65E)=
 Sof(H65F)=1-FVAR(1)
 Sof(C59A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62A)=
 Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(H65B)=
 Sof(H65C)=FVAR(1)
 Sof(P5)=Sof(P6)=Sof(P7)=1-FVAR(2)
 Sof(P1)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C41(H41), C44(H44), C53(H53), C56(H56)
6.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), C60A(H60A),
 C61A(H61A), C62A(H62A), C63A(H63A), C64A(H64A), C60B(H60B), C61B(H61B),
 C62B(H62B), C63B(H63B), C64B(H64B)
6.c 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), C65A(H65A,H65B,H65C), C65B(H65D,H65E,H65F)
;
_shelx_res_checksum              41042
_shelx_hkl_checksum              42168
_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 1.254
_oxdiff_exptl_absorpt_empirical_full_min 0.760