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_4126544
_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 H92 As Cl Ga2 N4 P6, 3(C H2 Cl2)'
_chemical_formula_sum            'C73 H98 As Cl7 Ga2 N4 P6'
_chemical_formula_weight         1679.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-06-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.2849(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.42003(12)
_cell_length_b                   19.14839(14)
_cell_length_c                   31.4694(2)
_cell_measurement_reflns_used    41906
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4980
_cell_measurement_theta_min      2.3090
_cell_volume                     8073.47(11)
_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 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -63.00  32.00   0.50    2.00    --  -38.50  49.00  -8.00  190
  2  \w   -111.00 -16.00   0.50    2.00    --  -38.50 -38.00-180.00  190
  3  \w     23.00  98.00   0.50    2.00    --   42.75-125.00 150.00  150
  4  \w     23.00  98.00   0.50    2.00    --   42.75-125.00-120.00  150
  5  \w     23.00  98.00   0.50    2.00    --   42.75-125.00  30.00  150
  6  \w     41.00 139.00   0.50    8.00    --  111.00 -61.00 150.00  196
  7  \w     39.00 141.00   0.50    8.00    --  111.00 -73.00  15.00  204
  8  \w     31.00 156.00   0.50    8.00    --  111.00 -15.00 -30.00  250
  9  \w     80.00 178.00   0.50    8.00    --  111.00  77.00 150.00  196
 10  \w     87.00 178.00   0.50    8.00    --  111.00  45.00  90.00  182
 11  \w     40.00 135.00   0.50    8.00    --  111.00 -45.00 150.00  190
 12  \w     40.00 135.00   0.50    8.00    --  111.00 -45.00   0.00  190
 13  \w     87.00 178.00   0.50    8.00    --  111.00  45.00 -90.00  182
 14  \w     31.00 156.00   0.50    8.00    --  111.00 -15.00 120.00  250
 15  \w     11.00  44.00   0.50    2.00    --   42.75  77.00   0.00   66
;
_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      0.1129448000
_diffrn_orient_matrix_UB_12      0.0106982000
_diffrn_orient_matrix_UB_13      -0.0038700000
_diffrn_orient_matrix_UB_21      -0.0029101000
_diffrn_orient_matrix_UB_22      0.0643277000
_diffrn_orient_matrix_UB_23      0.0293478000
_diffrn_orient_matrix_UB_31      0.0215478000
_diffrn_orient_matrix_UB_32      -0.0471309000
_diffrn_orient_matrix_UB_33      0.0390663000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            68891
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.719
_diffrn_reflns_theta_min         2.702
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.853
_exptl_absorpt_correction_T_max  0.698
_exptl_absorpt_correction_T_min  0.489
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_description       block
_exptl_crystal_F_000             3472
_exptl_crystal_size_max          0.186
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.086
_refine_diff_density_max         0.804
_refine_diff_density_min         -1.536
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1039
_refine_ls_number_reflns         16824
_refine_ls_number_restraints     294
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0560
_refine_ls_R_factor_gt           0.0546
_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^)+(0.0641P)^2^+21.6976P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1463
_refine_ls_wR_factor_ref         0.1474
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16199
_reflns_number_total             16824
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_021.cif
_cod_data_source_block           9
_cod_original_cell_volume        8073.46(11)
_cod_database_code               4126544
_chemical_oxdiff_formula         'C292 H392 As4 Cl28 Ga8 N16 P24 '
_reflns_odcompleteness_completeness 99.89
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Cl6A \\sim Cl7A \\sim C73A \\sim Cl4A \\sim Cl5A \\sim C72A \\sim Cl4C \\sim
Cl5B \\sim Cl5C \\sim Cl4B \\sim Cl6B \\sim Cl6C \\sim Cl7B \\sim Cl7C \\sim
C72B \\sim C72C \\sim C73B \\sim C73C: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
C53A \\sim C53B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
3. Same fragment restrains
{As1B, C59B, C60B, C61B, C62B, C63B, C64B, C65B, C66B, C67B, C68B, C69B, C70B}
sigma for 1-2: 0.01, 1-3: 0.01
as
{As1A, C59A, C60A, C61A, C62A, C63A, C64A, C65A, C66A, C67A, C68A, C69A, C70A}
{Cl5B, Cl4B, C72B} sigma for 1-2: 0.02, 1-3: 0.02
{Cl5A, Cl4A, C72A} sigma for 1-2: 0.02, 1-3: 0.02
{Cl5C, Cl4C, C72C} sigma for 1-2: 0.02, 1-3: 0.02
{Cl7A, Cl6A, C73A} sigma for 1-2: 0.02, 1-3: 0.02
{Cl7B, Cl6B, C73B} sigma for 1-2: 0.02, 1-3: 0.02
{Cl7C, Cl6C, C73C} sigma for 1-2: 0.02, 1-3: 0.02
as
{Cl2, Cl3, C71}
4. Others
 1*[Sof(Cl5A)+Sof(Cl4A)+Sof(C72A)+Sof(H72A)+Sof(H72B)]+1*[Sof(Cl5B)+Sof(Cl4B)+
 Sof(C72B)+Sof(H72E)+Sof(H72F)]+1*[Sof(Cl5C)+Sof(Cl4C)+Sof(C72C)+Sof(H72C)+
 Sof(H72D)]+1*[Sof(Cl7A)+Sof(Cl6A)+Sof(C73A)+Sof(H73A)+Sof(H73B)]+1*[Sof(Cl7B)+
 Sof(Cl6B)+Sof(C73B)+Sof(H73C)+Sof(H73D)]+1*[Sof(Cl7C)+Sof(Cl6C)+Sof(C73C)+
 Sof(H73E)+Sof(H73F)]=2 with esd of 0.0001
 Sof(As1B)=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(C66B)=
 Sof(H66B)=Sof(C67B)=Sof(H67B)=Sof(C68B)=Sof(H68B)=Sof(C69B)=Sof(H69B)=
 Sof(C70B)=Sof(H70B)=Sof(P4B)=1-FVAR(1)
 Sof(As1A)=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(C66A)=
 Sof(H66A)=Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=
 Sof(C70A)=Sof(H70A)=Sof(P4A)=FVAR(1)
 Sof(C56B)=Sof(H56B)=Sof(C57B)=Sof(H57D)=Sof(H57E)=Sof(H57F)=Sof(C58B)=
 Sof(H58D)=Sof(H58E)=Sof(H58F)=1-FVAR(2)
 Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C58A)=
 Sof(H58A)=Sof(H58B)=Sof(H58C)=FVAR(2)
 Sof(C53B)=Sof(H53B)=Sof(C54B)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55B)=
 Sof(H55A)=Sof(H55B)=Sof(H55C)=1-FVAR(3)
 Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55A)=
 Sof(H55D)=Sof(H55E)=Sof(H55F)=FVAR(3)
 Sof(Cl5A)=Sof(Cl4A)=Sof(C72A)=Sof(H72A)=Sof(H72B)=FVAR(4)
 Sof(Cl5B)=Sof(Cl4B)=Sof(C72B)=Sof(H72E)=Sof(H72F)=FVAR(5)
 Sof(Cl5C)=Sof(Cl4C)=Sof(C72C)=Sof(H72C)=Sof(H72D)=FVAR(6)
 Sof(Cl7A)=Sof(Cl6A)=Sof(C73A)=Sof(H73A)=Sof(H73B)=FVAR(7)
 Sof(Cl7B)=Sof(Cl6B)=Sof(C73B)=Sof(H73C)=Sof(H73D)=FVAR(8)
 Sof(Cl7C)=Sof(Cl6C)=Sof(C73C)=Sof(H73E)=Sof(H73F)=FVAR(9)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C41(H41), C44(H44), C53A(H53A),
 C56A(H56A), C53B(H53B), C56B(H56B)
5.b Secondary CH2 refined with riding coordinates:
 C73A(H73A,H73B), C71(H71A,H71B), C72A(H72A,H72B), C72C(H72C,H72D), C72B(H72E,
 H72F), C73B(H73C,H73D), C73C(H73E,H73F)
5.c Aromatic/amide H refined with riding coordinates:
 C60A(H60A), C61A(H61A), C62A(H62A), C63A(H63A), C64A(H64A), C66A(H66A),
 C67A(H67A), C68A(H68A), C69A(H69A), C70A(H70A), 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), C60B(H60B), C61B(H61B), C62B(H62B), C63B(H63B),
 C64B(H64B), C66B(H66B), C67B(H67B), C68B(H68B), C69B(H69B), C70B(H70B)
5.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), C54A(H54D,H54E,H54F), C55A(H55D,H55E,H55F), C57A(H57A,
 H57B,H57C), C58A(H58A,H58B,H58C), C54B(H54A,H54B,H54C), C55B(H55A,H55B,H55C),
 C57B(H57D,H57E,H57F), C58B(H58D,H58E,H58F)
;
_shelx_res_checksum              96264
_shelx_hkl_checksum              8512
_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 2.601
_oxdiff_exptl_absorpt_empirical_full_min 0.780