A neutral diphosphene radical: synthesis, electronic structure and white phosphorus activation.
Haberstroh, Jan; Taube, Clemens; Fidelius, Jannis; Schulz, Stephen; Israel, Noel; Dmitrieva, Evgenia; Gomila, Rosa M.; Frontera, Antonio; Wolf, Robert; Schwedtmann, Kai; Weigand, Jan J.; Chemical communications (Cambridge, England) 60 (2024) 8537–8540; doi:10.1039/d4cc02200a

data_7133305
_publ_section_title
;
 A neutral diphosphene radical: synthesis, electronic structure and white
 phosphorus activation.
;
_journal_issue                   65
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8537
_journal_page_last               8540
_journal_paper_doi               10.1039/d4cc02200a
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C78 H102 Cl4 N4 O2 P4, C10 H24'
_chemical_formula_sum            'C88 H126 Cl4 N4 O2 P4'
_chemical_formula_weight         1537.60
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-07
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2024-04-26 deposited with the CCDC.	2024-07-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.1670(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.63850(10)
_cell_length_b                   34.7552(3)
_cell_length_c                   18.1897(2)
_cell_measurement_reflns_used    25909
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.5040
_cell_measurement_theta_min      3.4290
_cell_volume                     8741.26(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.993
_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    -77.00  14.00   0.50    5.00    --  -38.50  99.00  29.00  182
  2  \w     15.00  73.00   0.50    5.00    --   42.50 -99.00 -76.00  116
  3  \w     67.00 107.00   0.50   20.00    --  111.00 -99.00 -76.00   80
  4  \w    121.00 151.00   0.50   20.00    --  111.00  99.00  29.00   60
  5  \w   -111.00 -22.00   0.50    5.00    --  -38.50 -38.00-120.00  178
  6  \w   -110.00 -27.00   0.50    5.00    --  -38.50 -38.00 -30.00  166
  7  \w     40.00  66.00   0.50    5.00    --   42.50  38.00 150.00   52
  8  \w     17.00 106.00   0.50    5.00    --   42.50  57.00-180.00  178
  9  \w     17.00  42.00   0.50    5.00    --   42.50 -99.00-150.00   50
 10  \w     97.00 148.00   0.50   20.00    --  111.00 125.00 120.00  102
 11  \w     30.00  70.00   0.50   20.00    --  111.00 -94.00 -30.00   80
 12  \w     98.00 144.00   0.50   20.00    --  111.00 125.00 -30.00   92
 13  \w     83.00 132.00   0.50   20.00    --  111.00  61.00 -90.00   98
 14  \w     31.00 107.00   0.50   20.00    --  111.00 -94.00-150.00  152
 15  \w     39.00 111.00   0.50   20.00    --  111.00-125.00  60.00  144
 16  \w     32.00 106.00   0.50   20.00    --  111.00 -94.00-180.00  148
 17  \w     81.00 107.00   0.50   20.00    --  111.00 -94.00-120.00   52
 18  \w     46.00 107.00   0.50   20.00    --  111.00 -94.00 -60.00  122
 19  \w     84.00 109.00   0.50   20.00    --  111.00-114.00   7.57   50
 20  \w     39.00  73.00   0.50   20.00    --  111.00-114.00   7.57   68
 21  \w     94.00 136.00   0.50   20.00    --  111.00  30.00 150.00   84
 22  \w    124.00 178.00   0.50   20.00    --  111.00  30.00-150.00  108
 23  \w    100.00 164.00   0.50   20.00    --  111.00 125.00   0.00  128
 24  \w     32.00  76.00   0.50   20.00    --  111.00 -94.00   0.00   88
 25  \w     44.00 110.00   0.50   20.00    --  111.00-125.00  90.00  132
 26  \w     31.00 107.00   0.50   20.00    --  111.00 -94.00  90.00  152
 27  \w     49.00  75.00   0.50   20.00    --  111.00   0.00-180.00   52
 28  \w     98.00 178.00   0.50   20.00    --  111.00   0.00-180.00  160
 29  \w     70.00 108.00   0.50   20.00    --  111.00-109.00  93.81   76
 30  \w     32.00  64.00   0.50   20.00    --  111.00 -94.00-120.00   64
 31  \w     61.00 107.00   0.50   20.00    --  111.00 -94.00 120.00   92
 32  \w     49.00  76.00   0.50   20.00    --  111.00 -45.00 -90.00   54
 33  \w     98.00 130.00   0.50   20.00    --  111.00 -45.00 -90.00   64
 34  \w     81.00 109.00   0.50   20.00    --  111.00-125.00-150.00   56
 35  \w     90.00 171.00   0.50   20.00    --  111.00  45.00  90.00  162
 36  \w     82.00 107.00   0.50   20.00    --  111.00 -94.00   0.00   50
 37  \w     41.00 103.00   0.50   20.00    --  111.00 -45.00  60.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0036508000
_diffrn_orient_matrix_UB_12      -0.0383492000
_diffrn_orient_matrix_UB_13      -0.0434361000
_diffrn_orient_matrix_UB_21      -0.0761896000
_diffrn_orient_matrix_UB_22      0.0170830000
_diffrn_orient_matrix_UB_23      -0.0726031000
_diffrn_orient_matrix_UB_31      0.0811812000
_diffrn_orient_matrix_UB_32      0.0142600000
_diffrn_orient_matrix_UB_33      -0.0296887000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            53294
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.797
_diffrn_reflns_theta_min         2.543
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.278
_exptl_absorpt_correction_T_max  0.894
_exptl_absorpt_correction_T_min  0.783
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.168
_exptl_crystal_description       plate
_exptl_crystal_F_000             3304
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.314
_refine_diff_density_min         -0.726
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     499
_refine_ls_number_reflns         9164
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0455
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0294P)^2^+12.5848P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0930
_refine_ls_wR_factor_ref         0.0954
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8388
_reflns_number_total             9164
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02200a2.cif
_cod_data_source_block           jjw1561
_cod_depositor_comments
'Adding full bibliography for 7133304--7133306.cif.'
_cod_original_cell_volume        8741.26(14)
_cod_database_code               7133305
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C88H126Cl4N4O2P4
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.712
_reflns_odcompleteness_completeness 99.98
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C42-C43B \\sim C42-C43A
 with sigma of 0.02
 C43B-C44B \\sim C43A-C44A
 with sigma of 0.02
 C42-C44B \\sim C42-C44A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C40 \\sim C41 \\sim C42 \\sim C43A \\sim C43B \\sim C44A \\sim C44B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C40, C41, C42, C43A, C43B, C44A, C44B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43A)=Sof(H43B)=Sof(C44A)=Sof(H44A)=
 Sof(H44B)=Sof(H44C)=1-FVAR(1)
 Sof(H42A)=Sof(H42B)=Sof(C43B)=Sof(H43C)=Sof(H43D)=Sof(C44B)=Sof(H44D)=
 Sof(H44E)=Sof(H44F)=FVAR(1)
 Fixed Sof: O1(0.5)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C13(H13), C18(H18), C25(H25), C30(H30), C37(H37)
6.b Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C42(H42A,H42B), C42(H42C,H42D), C43A(H43A,H43B), C43B(H43C,
 H43D)
6.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C21(H21), C22(H22), C23(H23), C33(H33), C34(H34),
 C35(H35)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C), C44A(H44A,H44B,H44C), C44B(H44D,H44E,H44F)
;
_shelx_res_checksum              86764
_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 1.755
_oxdiff_exptl_absorpt_empirical_full_min 0.876