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_4126532
_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 P6, C2 F6 N O4 S2, 1.5(C7 H8)'
_chemical_formula_sum            'C70.5 H94 F6 Ga2 N5 O4 P6 S2'
_chemical_formula_weight         1578.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-06-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.9060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   49.1449(6)
_cell_length_b                   12.6868(2)
_cell_length_c                   24.6372(4)
_cell_measurement_reflns_used    26089
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.9110
_cell_measurement_theta_min      2.6180
_cell_volume                     15304.8(4)
_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 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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    -96.00  46.00   0.50    4.00    --  -38.16  19.00   0.00  284
  2  \w   -117.00  -7.00   0.50    4.00    --  -38.16 -38.00-180.00  220
  3  \w    -96.00  46.00   0.50    4.00    --  -38.16  19.00   0.00  284
  4  \w      2.00 122.00   0.50    4.00    --   38.16  77.00   0.00  240
  5  \w     23.00  97.00   0.50    4.00    --   38.16-125.00  60.00  148
  6  \w     23.00  97.00   0.50    4.00    --   38.16-125.00-180.00  148
  7  \w     34.00 116.00   0.50   16.00    --  115.00-111.00  60.00  164
  8  \w    100.00 178.00   0.50   16.00    --  115.00 111.00 -60.00  156
  9  \w     34.00 116.00   0.50   16.00    --  115.00-111.00 -90.00  164
 10  \w    100.00 178.00   0.50   16.00    --  115.00 111.00-120.00  156
 11  \w     84.00 178.00   0.50   16.00    --  115.00  45.00 -60.00  188
 12  \w     34.00 116.00   0.50   16.00    --  115.00-111.00   0.00  164
 13  \w    100.00 178.00   0.50   16.00    --  115.00 111.00-180.00  156
 14  \w     28.00 109.00   0.50   16.00    --  115.00 -94.00 -30.00  162
 15  \w     84.00 109.00   0.50   16.00    --  115.00 -94.00 -90.00   50
 16  \w     39.00  65.00   0.50   16.00    --  115.00 -94.00 -90.00   52
 17  \w     39.00  90.00   0.50   16.00    --  115.00-111.00 120.00  102
 18  \w     79.00 164.00   0.50   16.00    --  115.00  77.00   0.00  170
 19  \w     75.00 101.00   0.50   16.00    --  115.00-111.00-120.00   52
 20  \w     37.00  63.00   0.50   16.00    --  115.00-111.00-120.00   52
;
_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      -0.0152753000
_diffrn_orient_matrix_UB_12      -0.0878326000
_diffrn_orient_matrix_UB_13      0.0279892000
_diffrn_orient_matrix_UB_21      -0.0012111000
_diffrn_orient_matrix_UB_22      0.0702653000
_diffrn_orient_matrix_UB_23      0.0508119000
_diffrn_orient_matrix_UB_31      -0.0274764000
_diffrn_orient_matrix_UB_32      0.0457963000
_diffrn_orient_matrix_UB_33      -0.0239392000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       61
_diffrn_reflns_limit_h_min       -61
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            24026
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.413
_diffrn_reflns_theta_min         3.599
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.088
_exptl_absorpt_correction_T_max  0.813
_exptl_absorpt_correction_T_min  0.528
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.370
_exptl_crystal_description       block
_exptl_crystal_F_000             6576
_exptl_crystal_size_max          0.304
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.716
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.138
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1182
_refine_ls_number_reflns         24026
_refine_ls_number_restraints     681
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0631
_refine_ls_R_factor_gt           0.0601
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0666P)^2^+41.6862P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1596
_refine_ls_wR_factor_ref         0.1613
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22571
_reflns_number_total             24026
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07704_si_024.cif
_cod_data_source_block           11
_cod_original_formula_sum        'C70.50 H94 F6 Ga2 N5 O4 P6 S2'
_cod_database_code               4126532
_chemical_oxdiff_formula         C70.5H91F6Ga2N5O4P6S2
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5278(8) 0.4722(8)
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
S1 \\sim S2 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim O1
\\sim O2 \\sim O3 \\sim O4 \\sim N5 \\sim C73 \\sim C74: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
S3 \\sim S4 \\sim F7 \\sim F8 \\sim F9 \\sim F10 \\sim F11 \\sim F12 \\sim O5
\\sim O6 \\sim O7 \\sim O8 \\sim N6 \\sim C75 \\sim C76: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
N2A \\sim N2B \\sim C2A \\sim C2B \\sim C3A \\sim C3B \\sim C5A \\sim C5B \\sim
C18A \\sim C18B \\sim C19A \\sim C19B \\sim C20A \\sim C20B \\sim C21A \\sim
C21B \\sim C22A \\sim C22B \\sim C23A \\sim C23B \\sim C24A \\sim C24B \\sim
C25A \\sim C25B \\sim C26A \\sim C26B \\sim C27A \\sim C27B \\sim C28A \\sim
C28B \\sim C29A \\sim C29B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Same fragment restrains
{P1B, P2B, P3B, P4B, P5B, P6B} sigma for 1-2: 0.02, 1-3: 0.02
as
{P1A, P2A, P3A, P4A, P5A, P6A}
5. Others
 Sof(N2B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=
 Sof(C18B)=Sof(C19B)=Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(H21B)=Sof(C22B)=
 Sof(H22B)=Sof(C23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27B)=Sof(H27B)=
 Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29B)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=1-FVAR(1)
 Sof(N2A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=
 Sof(C18A)=Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=
 Sof(H22A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=Sof(H27A)=
 Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29A)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=FVAR(1)
 Sof(Ga1B)=Sof(P1B)=Sof(P2B)=Sof(P3B)=Sof(P4B)=Sof(P5B)=Sof(P6B)=1-FVAR(2)
 Sof(Ga1A)=Sof(P1A)=Sof(P2A)=Sof(P3A)=Sof(P4A)=Sof(P5A)=Sof(P6A)=FVAR(2)
 Fixed Sof: S3(0.5) S4(0.5) F7(0.5) F8(0.5) F9(0.5) F10(0.5) F11(0.5) F12(0.5)
 O5(0.5) O6(0.5) O7(0.5) O8(0.5) N6(0.5) C75(0.5) C76(0.5) S1(0.5) S2(0.5)
 F1(0.5) F2(0.5) F3(0.5) F4(0.5) F5(0.5) F6(0.5) O1(0.5) O2(0.5) O3(0.5)
 O4(0.5) N5(0.5) C73(0.5) C74(0.5) C66(0.5) C67(0.5) H67(0.5) C68(0.5) H68(0.5)
 C69(0.5) H69(0.5) C70(0.5) H70(0.5) C71(0.5) H71(0.5) C72(0.5) H72A(0.5)
 H72B(0.5) H72C(0.5)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24A(H24A), C24B(H24B), C27A(H27A), C27B(H27B), C41(H41),
 C44(H44), C53(H53), C56(H56)
6.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C2B(H2B), C8(H8), C9(H9), C10(H10), C20A(H20A), C20B(H20B),
 C21A(H21A), C21B(H21B), C22A(H22A), C22B(H22B), C31(H31), C37(H37), C38(H38),
 C39(H39), C49(H49), C50(H50), C51(H51), C60(H60), C61(H61), C62(H62), C63(H63),
  C64(H64), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71)
6.c Fitted hexagon refined as free rotating group:
 C66(C67,C68,C69,C70,C71)
6.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5A(H5AA,H5AB,H5AC), C5B(H5BA,H5BB,H5BC), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C25A(H25A,H25B,H25C), C25B(H25D,H25E,H25F), C26A(H26A,H26B,H26C), C26B(H26D,
 H26E,H26F), C28A(H28A,H28B,H28C), C28B(H28D,H28E,H28F), C29A(H29A,H29B,H29C),
 C29B(H29D,H29E,H29F), 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),
 C65(H65A,H65B,H65C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              5258
_shelx_hkl_checksum              44092
_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 1.591
_oxdiff_exptl_absorpt_empirical_full_min 0.637
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 179.9974\% 
 around [-0.17 -0.00 0.99] (reciprocal) or [0.00 0.00 1.00] (direct)
;