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_4126531
_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, C H2 Cl2'
_chemical_formula_sum            'C59 H84 Cl2 Ga2 N4 P14'
_chemical_formula_weight         1493.22
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-02-29
_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                   13.4877(8)
_cell_length_b                   20.2357(9)
_cell_length_c                   25.9673(19)
_cell_measurement_reflns_used    4689
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.5240
_cell_measurement_theta_min      3.7120
_cell_volume                     7087.3(7)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     31.00  99.00   1.00   40.00    --   43.69  77.00-180.00   68
  2  \w     37.00  92.00   1.00   40.00    --   43.69  77.00-120.00   55
  3  \w     12.00  60.00   1.00   40.00    --   43.69  77.00 -30.00   48
  4  \w    -65.00 -28.00   1.00   40.00    --  -38.50  57.00-120.00   37
  5  \w    -57.00 -24.00   1.00   40.00    --  -38.50  38.00-180.00   33
  6  \w     57.00  89.00   1.00  120.00    --  111.00 -94.00-120.00   32
  7  \w     94.00 121.00   1.00  120.00    --  111.00 125.00-180.00   27
  8  \w    146.00 172.00   1.00  120.00    --  111.00 125.00-180.00   26
  9  \w     52.00 102.00   1.00  120.00    --  111.00-125.00  30.00   50
 10  \w     39.00  65.00   1.00  120.00    --  111.00 -94.00-150.00   26
 11  \w     84.00 120.00   1.00  120.00    --  111.00  77.00 150.00   36
 12  \w     30.00  76.00   1.00  120.00    --  111.00 -94.00 -30.00   46
 13  \w     37.00 131.00   1.00  120.00    --  111.00 -30.00   0.00   94
 14  \w     94.00 138.00   1.00  120.00    --  111.00 125.00  90.00   44
 15  \w     83.00 105.00   1.00  120.00    --  111.00  77.00  30.00   22
 16  \w     16.00  63.00   1.00   40.00    --   42.75  57.00  90.00   47
 17  \w    139.00 164.00   1.00  120.00    --  111.00  45.00  90.00   25
 18  \w    -30.00  31.00   1.00   40.00    --   42.75 -38.00-120.00   61
;
_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      0.0437511000
_diffrn_orient_matrix_UB_12      0.0227977000
_diffrn_orient_matrix_UB_13      0.0519137000
_diffrn_orient_matrix_UB_21      0.1053621000
_diffrn_orient_matrix_UB_22      -0.0059713000
_diffrn_orient_matrix_UB_23      -0.0223128000
_diffrn_orient_matrix_UB_31      -0.0048537000
_diffrn_orient_matrix_UB_32      0.0723763000
_diffrn_orient_matrix_UB_33      -0.0181693000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1331
_diffrn_reflns_av_unetI/netI     0.1061
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            27780
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.394
_diffrn_reflns_theta_max         67.394
_diffrn_reflns_theta_min         2.768
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.923
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.794
_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    1.399
_exptl_crystal_description       plate
_exptl_crystal_F_000             3088
_exptl_crystal_size_max          0.072
_exptl_crystal_size_mid          0.044
_exptl_crystal_size_min          0.013
_refine_diff_density_max         1.251
_refine_diff_density_min         -0.866
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     519
_refine_ls_number_reflns         6559
_refine_ls_number_restraints     181
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1079
_refine_ls_R_factor_gt           0.0748
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0810P)^2^+17.5770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1805
_refine_ls_wR_factor_ref         0.2028
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4564
_reflns_number_total             6559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_011.cif
_cod_data_source_block           6_1
_cod_original_cell_volume        7087.3(8)
_cod_database_code               4126531
_chemical_oxdiff_formula         C59H84Cl2Ga2N4P14
_chemical_oxdiff_usercomment     DCM
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 Cl1-C45 \\sim Cl2-C45
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
N3 \\sim C18 \\sim C17 \\sim N2 \\sim C16 \\sim C19 \\sim C20: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C28 \\sim C21 \\sim C22 \\sim C26 \\sim C27 \\sim C23 \\sim C30 \\sim C25 \\sim
C29 \\sim C24 \\sim C31 \\sim C32 \\sim C44 \\sim C33 \\sim C34 \\sim C39 \\sim
C35 \\sim C43 \\sim C42 \\sim C41 \\sim C40 \\sim C38 \\sim C37 \\sim C36:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N3) = Uanis(N2)
Uanis(C18) = Uanis(C16)
4. Others
 Fixed Sof: N3(0.5) Cl1(0.5) C18(0.5) Cl2(0.5) C21(0.5) C17(0.5) H17(0.5)
 C22(0.5) C27(0.5) H27(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C23(0.5)
 H23(0.5) C31(0.5) H31A(0.5) H31B(0.5) H31C(0.5) C30(0.5) H30(0.5) C44(0.5)
 H44A(0.5) H44B(0.5) H44C(0.5) C29(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C45(0.5)
 H45A(0.5) H45B(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C26(0.5) C25(0.5)
 H25(0.5) C24(0.5) H24(0.5) C33(0.5) C34(0.5) C39(0.5) H39(0.5) C35(0.5)
 H35(0.5) C43(0.5) H43A(0.5) H43B(0.5) H43C(0.5) C42(0.5) H42(0.5) C32(0.5)
 H32A(0.5) H32B(0.5) H32C(0.5) C41(0.5) H41A(0.5) H41B(0.5) H41C(0.5) C40(0.5)
 H40A(0.5) H40B(0.5) H40C(0.5) C38(0.5) C37(0.5) H37(0.5) C36(0.5) H36(0.5)
 N2(0.5) C16(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C27(H27), C30(H30), C39(H39), C42(H42)
5.b Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B)
5.c Me refined with riding coordinates:
 C14(H14A,H14B,H14C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C15(H15A,H15B,
 H15C), C31(H31A,H31B,H31C), C44(H44A,H44B,H44C), C29(H29A,H29B,H29C), C28(H28A,
 H28B,H28C), C43(H43A,H43B,H43C), C32(H32A,H32B,H32C), C41(H41A,H41B,H41C),
 C40(H40A,H40B,H40C), C19(H19A,H19B,H19C)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C17(H17), C6(H6), C8(H8), C7(H7), C23(H23), C25(H25), C24(H24),
 C35(H35), C37(H37), C36(H36)
5.e Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              22895
_shelx_hkl_checksum              80454
_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 2.011
_oxdiff_exptl_absorpt_empirical_full_min 0.591