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_4126525
_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 P16, P4, C7 H8'
_chemical_formula_sum            'C65 H90 Ga2 N4 P20'
_chemical_formula_weight         1686.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.9681(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.29945(15)
_cell_length_b                   19.43507(12)
_cell_length_c                   21.56961(15)
_cell_measurement_reflns_used    13533
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      76.3630
_cell_measurement_theta_min      3.0670
_cell_volume                     8012.35(10)
_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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_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     25.00  51.00   0.50    1.00    --   42.75  57.00 120.00   52
  2  \w     81.00 106.00   0.50    1.00    --   42.75  57.00 120.00   50
  3  \w    102.00 172.00   0.50    3.00    --  111.00  30.00   0.00  140
  4  \w    111.00 168.00   0.50    3.00    --  111.00  45.00-150.00  114
  5  \w     94.00 133.00   0.50    3.00    --  111.00  45.00-180.00   78
  6  \w     51.00 129.00   0.50    3.00    --  111.00 -45.00-180.00  156
  7  \w     65.00  96.00   0.50    3.00    --  111.00 -94.00 -60.00   62
  8  \w     52.00 107.00   0.50    3.00    --  111.00 -94.00 -30.00  110
  9  \w     48.00 139.00   0.50    3.00    --  111.00 -15.00   0.00  182
 10  \w     52.00  83.00   0.50    1.00    --   42.75 -99.00-120.00   62
 11  \w     41.00  94.00   0.50    3.00    --  111.00 -61.00 -30.00  106
 12  \w     37.00  96.00   0.50    3.00    --  111.00 -94.00  30.00  118
 13  \w     45.00  72.00   0.50    3.00    --  111.00 -94.00  90.00   54
 14  \w     40.00 105.00   0.50    3.00    --  111.00 -94.00 120.00  130
 15  \w    -65.00  31.00   0.50    1.00    --  -38.50  57.00-120.00  192
 16  \w   -111.00 -35.00   0.50    1.00    --  -38.50 -38.00 -90.00  152
;
_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      0.0637863000
_diffrn_orient_matrix_UB_12      -0.0216228000
_diffrn_orient_matrix_UB_13      -0.0311832000
_diffrn_orient_matrix_UB_21      0.0482242000
_diffrn_orient_matrix_UB_22      0.0129224000
_diffrn_orient_matrix_UB_23      0.0620102000
_diffrn_orient_matrix_UB_31      -0.0100514000
_diffrn_orient_matrix_UB_32      -0.0751556000
_diffrn_orient_matrix_UB_33      0.0196106000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0176
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            22147
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.653
_diffrn_reflns_theta_min         3.074
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.921
_exptl_absorpt_correction_T_max  0.656
_exptl_absorpt_correction_T_min  0.473
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_description       block
_exptl_crystal_F_000             3480
_exptl_crystal_size_max          0.313
_exptl_crystal_size_mid          0.171
_exptl_crystal_size_min          0.157
_refine_diff_density_max         0.889
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         8294
_refine_ls_number_restraints     228
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0477P)^2^+22.0773P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1003
_refine_ls_wR_factor_ref         0.1018
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7857
_reflns_number_total             8294
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_013.cif
_cod_data_source_block           7_1
_cod_database_code               4126525
_chemical_oxdiff_formula         'C256 H328 Ga8 N16 P80 '
_chemical_oxdiff_usercomment     '+ P4 + Toluene'
_reflns_odcompleteness_completeness 99.91
_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
 C34A-C35A \\sim C33A-C34A \\sim C33A-C32A \\sim C31A-C32A \\sim C30A-C31A
\\sim C30A-C35A
 with sigma of 0.01
 P9B-P10B \\sim P9A-P10A \\sim P9A_$1-P10A \\sim P9B_$1-P10B \\sim P9A-P9A_$1
\\sim P9B-P9B_$1 ~
 P10B-P10B_$1 \\sim P10A-P10A_$1
 with sigma of 0.01
3. Restrained planarity
 C29B, C30B, C31B, C32B, C33B, C34B, C35B
 with sigma of 0.05
4. Uiso/Uaniso restraints and constraints
C29A \\sim C30A \\sim C31A \\sim C32A \\sim C33A \\sim C34A \\sim C35A \\sim
C29B \\sim C30B \\sim C31B \\sim C32B \\sim C33B \\sim C34B \\sim C35B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C19, C20, C21, C22
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Same fragment restrains
{C29B, C30B, C31B, C32B, C33B, C34B, C35B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C29A, C30A, C31A, C32A, C33A, C34A, C35A}
7. Others
 Sof(P10B)=Sof(P9B)=1-FVAR(1)
 Sof(P10A)=Sof(P9A)=FVAR(1)
 Sof(C29B)=Sof(C30B)=Sof(C31B)=Sof(C32B)=Sof(C33B)=Sof(C34B)=Sof(C35B)=0.5*(1-
 FVAR(3))
 Sof(C29A)=Sof(C30A)=Sof(C31A)=Sof(C32A)=Sof(C33A)=Sof(C34A)=Sof(C35A)=0.5*
 FVAR(3)
 Fixed Sof: H29A(0.5) H29B(0.5) H29C(0.5) H31A(0.5) H32A(0.5) H33A(0.5)
 H34A(0.5) H35A(0.5)
8.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C26(H26), C24(H24)
8.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C10(H10), C8(H8), C9(H9), C22(H22), C20(H20), C21(H21), C31A(H31A),
 C32A(H32A), C33A(H33A), C34A(H34A), C35A(H35A)
8.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C16(H16A,H16B,H16C), C13(H13A,H13B,H13C),
 C17(H17A,H17B,H17C), C28(H28A,H28B,H28C), C14(H14A,H14B,H14C), C27(H27A,H27B,
 H27C), C015(H01A,H01B,H01C), C25(H25A,H25B,H25C), C29A(H29A,H29B,H29C)
;
_shelx_res_checksum              76467
_shelx_hkl_checksum              16673
_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 1.184
_oxdiff_exptl_absorpt_empirical_full_min 0.839