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_4126542
_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 P14, 1.267(C7 H8), 0.733(P4)'
_chemical_formula_sum            'C66.87 H92.14 Ga2 N4 P16.93'
_chemical_formula_weight         1615.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.3813(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.63849(19)
_cell_length_b                   21.16817(16)
_cell_length_c                   20.1663(2)
_cell_measurement_reflns_used    20138
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2800
_cell_measurement_theta_min      3.0540
_cell_volume                     7771.42(13)
_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      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    -92.00 -56.00   0.50   10.00    --  -38.50 125.00-180.00   72
  2  \w    -32.00  -5.00   0.50   10.00    --  -38.50 125.00-180.00   54
  3  \w   -109.00 -20.00   0.50   10.00    --  -38.50 -38.00  90.00  178
  4  \w   -104.00 -18.00   0.50   10.00    --  -38.50 -38.00   0.00  172
  5  \w     72.00 175.00   0.50   40.00    --  111.00  15.00 -90.00  206
  6  \w     47.00 116.00   0.50   40.00    --  111.00-125.00-180.00  138
  7  \w     95.00 128.00   0.50   40.00    --  111.00 -30.00 -60.00   66
  8  \w     56.00  96.00   0.50   40.00    --  111.00 -94.00-120.00   80
  9  \w     61.00  88.00   0.50   40.00    --  111.00 -94.00-150.00   54
 10  \w     74.00 104.00   0.50   40.00    --  111.00  15.00   0.00   60
 11  \w    141.00 172.00   0.50   40.00    --  111.00  15.00   0.00   62
 12  \w     55.00 109.00   0.50   40.00    --  111.00 -94.00  60.00  108
 13  \w     31.00  62.00   0.50   40.00    --  111.00 -94.00   0.00   62
 14  \w     79.00  91.00   0.50   40.00    --  111.00 -94.00   0.00   24
 15  \w     41.00 124.00   0.50   40.00    --  111.00 -45.00  90.00  166
 16  \w     38.00  71.00   0.50   40.00    --  111.00 -94.00 -90.00   66
 17  \w     37.00  82.00   0.50   40.00    --  111.00 -30.00 -60.00   90
 18  \w     30.00  83.00   0.50   40.00    --  111.00 -94.00 120.00  106
 19  \w    106.00 171.00   0.50   40.00    --  111.00  45.00 120.00  130
;
_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      0.0080501000
_diffrn_orient_matrix_UB_12      -0.0060182000
_diffrn_orient_matrix_UB_13      0.0773905000
_diffrn_orient_matrix_UB_21      0.0834719000
_diffrn_orient_matrix_UB_22      0.0105022000
_diffrn_orient_matrix_UB_23      0.0102757000
_diffrn_orient_matrix_UB_31      -0.0115306000
_diffrn_orient_matrix_UB_32      0.0717436000
_diffrn_orient_matrix_UB_33      0.0048837000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            45077
_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         76.530
_diffrn_reflns_theta_min         2.931
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.470
_exptl_absorpt_correction_T_max  0.928
_exptl_absorpt_correction_T_min  0.661
_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    1.381
_exptl_crystal_description       plate
_exptl_crystal_F_000             3349
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.111
_exptl_crystal_size_min          0.016
_refine_diff_density_max         0.800
_refine_diff_density_min         -0.443
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     853
_refine_ls_number_reflns         16144
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0357
_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^)+(0.0495P)^2^+4.8174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.0948
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13926
_reflns_number_total             16144
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_012.cif
_cod_data_source_block           6_2
_cod_original_cell_volume        7771.43(13)
_cod_database_code               4126542
_chemical_oxdiff_formula         C65H90Ga2N4P18
_reflns_odcompleteness_completeness 99.92
_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. Uiso/Uaniso restraints and constraints
C72 \\sim C66 \\sim C67 \\sim C71 \\sim C68 \\sim C70 \\sim C69: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
3. Same fragment restrains
{C72, C66, C67, C68, C69, C70, C71} sigma for 1-2: 0.02, 1-3: 0.02
as
{C65, C59, C60, C61, C62, C63, C64}
4. Others
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C66)=Sof(C67)=Sof(H67)=Sof(C68)=
 Sof(H68)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71)=1-FVAR(1)
 Sof(P15)=Sof(P18)=Sof(P16)=Sof(P17)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C12(H12), C41(H41), C24(H24), C53(H53), C15(H15), C44(H44), C56(H56)
5.b Aromatic/amide H refined with riding coordinates:
 C31(H31), C2(H2), C20(H20), C22(H22), C21(H21), C8(H8), C10(H10), C49(H49),
 C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C37(H37), C9(H9), C50(H50),
 C51(H51), C39(H39), C38(H38), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71)
5.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C5(H5A,H5B,H5C), C28(H28A,H28B,H28C), C34(H34A,H34B,
 H34C), C29(H29A,H29B,H29C), C25(H25A,H25B,H25C), C4(H4A,H4B,H4C), C14(H14A,
 H14B,H14C), C65(H65A,H65B,H65C), C13(H13A,H13B,H13C), C54(H54A,H54B,H54C),
 C16(H16A,H16B,H16C), C26(H26A,H26B,H26C), C43(H43A,H43B,H43C), C55(H55A,H55B,
 H55C), C42(H42A,H42B,H42C), C57(H57A,H57B,H57C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C17(H17A,H17B,H17C), C58(H58A,H58B,H58C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              40560
_shelx_hkl_checksum              90475
_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 1.858
_oxdiff_exptl_absorpt_empirical_full_min 0.824