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_7133306
_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 P8, C6 H5 F'
_chemical_formula_sum            'C84 H107 Cl4 F N4 P8'
_chemical_formula_weight         1581.29
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-10
_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                 96.9330(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.39630(10)
_cell_length_b                   24.84720(10)
_cell_length_c                   15.60040(10)
_cell_measurement_reflns_used    37223
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3290
_cell_measurement_theta_min      2.6560
_cell_volume                     8617.92(8)
_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      100.00(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 0.990
_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    -80.00   7.00   0.50    6.00    --  -38.50 102.00-102.00  174
  2  \w     22.00  47.00   0.50    6.00    --   42.50-102.00 154.00   50
  3  \w     73.00 108.00   0.50   24.00    --  111.00-102.00 154.00   70
  4  \w    121.00 176.00   0.50   24.00    --  111.00 102.00-102.00  110
  5  \w   -108.00 -25.00   0.50    6.00    --  -38.50 -38.00-180.00  166
  6  \w   -111.00 -18.00   0.50    6.00    --  -38.50 -38.00  90.00  186
  7  \w     40.00  97.00   0.50    6.00    --   42.50-125.00  90.00  114
  8  \w     24.00 112.00   0.50    6.00    --   42.50  57.00  30.00  176
  9  \w     31.00 107.00   0.50   24.00    --  111.00 -94.00  60.00  152
 10  \w     82.00 174.00   0.50   24.00    --  111.00  15.00 -90.00  184
 11  \w     64.00  91.00   0.50   24.00    --  111.00 -77.00 -60.00   54
 12  \w     33.00 107.00   0.50   24.00    --  111.00 -94.00 -90.00  148
 13  \w    130.00 157.00   0.50   24.00    --  111.00  77.00-150.00   54
 14  \w    115.00 174.00   0.50   24.00    --  111.00  45.00-180.00  118
 15  \w     79.00 112.00   0.50   24.00    --  111.00-125.00 -90.00   66
 16  \w    102.00 147.00   0.50   24.00    --  111.00 125.00-150.00   90
 17  \w     48.00 108.00   0.50   24.00    --  111.00-125.00 150.00  120
 18  \w     97.00 173.00   0.50   24.00    --  111.00 125.00 -60.00  152
 19  \w     41.00 111.00   0.50   24.00    --  111.00-125.00  60.00  140
 20  \w     72.00 107.00   0.50   24.00    --  111.00 -94.00-150.00   70
 21  \w     39.00  66.00   0.50   24.00    --  111.00 -94.00   0.00   54
 22  \w     82.00 107.00   0.50   24.00    --  111.00 -94.00   0.00   50
 23  \w     30.00  71.00   0.50   24.00    --  111.00 -94.00  90.00   82
 24  \w    114.00 154.00   0.50   24.00    --  111.00 125.00 -90.00   80
 25  \w     87.00 159.00   0.50   24.00    --  111.00  30.00 -30.00  144
 26  \w     51.00 104.00   0.50   24.00    --  111.00 -94.00 -60.00  106
 27  \w     42.00 135.00   0.50   24.00    --  111.00 -45.00 150.00  186
 28  \w     61.00  88.00   0.50   24.00    --  111.00-125.00   0.00   54
 29  \w     43.00  91.00   0.50   24.00    --  111.00 -30.00 -90.00   96
;
_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      0.0269709000
_diffrn_orient_matrix_UB_12      -0.0533878000
_diffrn_orient_matrix_UB_13      -0.0276881000
_diffrn_orient_matrix_UB_21      -0.0112141000
_diffrn_orient_matrix_UB_22      -0.0256973000
_diffrn_orient_matrix_UB_23      0.0864900000
_diffrn_orient_matrix_UB_31      -0.0628263000
_diffrn_orient_matrix_UB_32      -0.0183117000
_diffrn_orient_matrix_UB_33      -0.0405889000
_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  0.0386
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            89080
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.872
_diffrn_reflns_theta_min         2.667
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.008
_exptl_absorpt_correction_T_max  0.917
_exptl_absorpt_correction_T_min  0.704
_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    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             3344
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.821
_refine_diff_density_min         -0.834
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1030
_refine_ls_number_reflns         18007
_refine_ls_number_restraints     547
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0474
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0642P)^2^+8.2239P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1241
_refine_ls_wR_factor_ref         0.1290
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15764
_reflns_number_total             18007
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02200a2.cif
_cod_data_source_block           jjw1573
_cod_depositor_comments
'Adding full bibliography for 7133304--7133306.cif.'
_cod_database_code               7133306
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C84H102Cl4FN4P8
_shelx_estimated_absorpt_t_max   0.915
_shelx_estimated_absorpt_t_min   0.584
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C80A-C79A \\sim C79A-C84A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1A \\sim F1B \\sim F1C \\sim C79C \\sim C80C \\sim C81C \\sim C82C \\sim C83C
\\sim C84C \\sim C79A \\sim C79B \\sim C80A \\sim C80B \\sim C81A \\sim C81B
\\sim C82A \\sim C82B \\sim C83A \\sim C83B \\sim C84A \\sim C84B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01 within 2A
4. Others
 Fixed Sof: F1A(0.33) F1B(0.33) C79B(0.33) C80B(0.33) H2A(0.33) C81B(0.33)
 H9A(0.33) C82B(0.33) H10A(0.33) C83B(0.33) H11A(0.33) C84B(0.33) H12A(0.33)
 F1C(0.34) C79C(0.34) C80C(0.34) H18(0.34) C81C(0.34) H17(0.34) C82C(0.34)
 H16(0.34) C83C(0.34) H15(0.34) C84C(0.34) H14(0.34) C79A(0.33) C80A(0.33)
 H4A(0.33) C81A(0.33) H5A(0.33) C82A(0.33) H6A(0.33) C83A(0.33) H7A(0.33)
 C84A(0.33) H8A(0.33)
5.a Free rotating group:
 F1B(C79B,C80B,C81B,C82B,C83B,C84B), F1C(C79C,C80C,C81C,C82C,C83C,C84C)
5.b Ternary CH refined with riding coordinates:
 C4(H00X), C11(H3), C18(H2), C25(H01K), C30(H01F), C37(H01G), C42(H012),
 C49(H01B), C55(H016), C62(H020), C69(H014), C76(H1)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H01P), C8(H5), C9(H01R), C21(H01W), C22(H022), C23(H01L), C33(H01Z),
 C34(H01), C35(H01Q), C45(H01X), C46(H024), C47(H01S), C58(H023), C59(H027),
 C60(H021), C72(H013), C73(H01A), C74(H00Z), C80B(H2A), C81B(H9A), C82B(H10A),
 C83B(H11A), C84B(H12A), C80C(H18), C81C(H17), C82C(H16), C83C(H15), C84C(H14),
 C80A(H4A), C81A(H5A), C82A(H6A), C83A(H7A), C84A(H8A)
5.d Idealised Me refined as rotating group:
 C5(H01C,H01D,H01E), C6(H02D,H02E,H02F), C12(H02S,H02T,H02U), C13(H12,HV,HW),
 C19(H7,HL,HM), C20(H02P,H02Q,H02R), C26(H11,HT,HU), C27(H02J,H02K,H02L),
 C31(H4,HB,HC), C32(H6,HD,HE), C38(H02Z,HH,HI), C39(H02,HJ,HK), C43(H01T,H01U,
 H01V), C44(H01H,H01I,H01J), C50(H02A,H02B,H02C), C51(H02V,H02W,H02X), C56(H02G,
 H02H,H02I), C57(H02Y,HF,HG), C63(H10,HR,HS), C64(H9,HP,HQ), C70(H,H01Y,HA),
 C71(H01M,H01N,H01O), C77(H8,HN,HO), C78(H02M,H02N,H02O)
;
_shelx_res_checksum              22161
_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 1.395
_oxdiff_exptl_absorpt_empirical_full_min 0.785