A diazadiphospholenium cation featuring a reactive PP bond: synthesis and reversible main-group bond activation.
Wieneke, Jan; Cirigliano, Francesco; Schorpp, Marcel; Chemical communications (Cambridge, England) 61 (2025) 17601–17604; doi:10.1039/d5cc04820f

data_7135032
_publ_section_title
;
 A diazadiphospholenium cation featuring a reactive P&#xe006;P bond:
 synthesis and reversible main-group bond activation.
;
_journal_issue                   90
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              17601
_journal_page_last               17604
_journal_paper_doi               10.1039/d5cc04820f
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C F3 O3 S, C32 H41 N2 P2'
_chemical_formula_sum            'C33 H41 F3 N2 O3 P2 S'
_chemical_formula_weight         664.714
_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_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-11
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-08-13 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.664(1)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1104(2)
_cell_length_b                   13.7238(2)
_cell_length_c                   20.3093(3)
_cell_measurement_reflns_used    10807
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.8230
_cell_measurement_theta_min      3.6650
_cell_volume                     3345.27(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.144a 64-bit (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.9992
_diffrn_measured_fraction_theta_max 0.9828
_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    -68.00 -43.00   0.50    0.63    --  -78.25  61.00  62.04   50
  2  \w    -74.00 -42.00   0.50    0.63    --  -63.77 -15.00 -60.00   64
  3  \w   -108.00 -79.00   0.50    0.63    --  -78.25 -85.00 -60.31   58
  4  \w   -104.00 -77.00   0.50    0.63    --  -63.77 -15.00 -60.00   54
  5  \w   -101.00 -70.00   0.50    0.63    --  -63.77   0.00-150.00   62
  6  \w    -60.00 -34.00   0.50    0.63    --  -63.77   0.00-150.00   52
  7  \w    -80.00 -44.00   0.50    0.63    --  -78.25  95.00-179.31   72
  8  \w    -86.00 -42.00   0.50    0.63    --  -78.25  97.00-156.34   88
  9  \w    -94.00 -46.00   0.50    0.63    --  -78.25 119.00-128.77   96
 10  \w    -83.00 -47.00   0.50    0.63    --  -78.25  97.00-124.44   72
 11  \w    -92.00 -46.00   0.50    0.63    --  -78.25 117.00 120.72   92
 12  \w     49.00 112.00   0.50    0.63    --   79.75  -3.00 -28.02  126
 13  \w     28.00  70.00   0.50    0.63    --   62.91 -95.00 150.00   84
 14  \w     29.00  63.00   0.50    0.63    --   62.91 -95.00  60.00   68
 15  \w     25.00  71.00   0.50    0.63    --   62.91 -95.00 -30.00   92
 16  \w     26.00  88.00   0.50    0.63    --   62.91-125.00 -90.00  124
 17  \w     46.00 121.00   0.50    0.63    --   79.75   8.00-138.00  150
 18  \w     64.00 126.00   0.50    0.63    --   79.75  22.00-116.70  124
 19  \w     65.00 124.00   0.50    0.63    --   79.75  21.00 -68.87  118
 20  \w     66.00 126.00   0.50    0.63    --   79.75  23.00 -28.57  120
 21  \w     77.00 114.00   0.50    0.63    --   79.75  20.00  71.85   74
 22  \w     64.00 115.00   0.50    0.63    --   79.75  22.00 146.24  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0924721000
_diffrn_orient_matrix_UB_12      0.0707257000
_diffrn_orient_matrix_UB_13      0.0146980000
_diffrn_orient_matrix_UB_21      0.0889611000
_diffrn_orient_matrix_UB_22      0.0710235000
_diffrn_orient_matrix_UB_23      0.0331942000
_diffrn_orient_matrix_UB_31      0.0041929000
_diffrn_orient_matrix_UB_32      0.0504685000
_diffrn_orient_matrix_UB_33      -0.0673897000
_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  0.0458
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 0.9992
_diffrn_reflns_Laue_measured_fraction_max 0.9828
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            28361
_diffrn_reflns_point_group_measured_fraction_full 0.9992
_diffrn_reflns_point_group_measured_fraction_max 0.9828
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         75.32
_diffrn_reflns_theta_min         3.68
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.211
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.912
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             1408.187
_exptl_crystal_recrystallization_method
'layered a solution of JW073 in ortho-difluorobenzene with Diethylether.'
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.3557
_refine_diff_density_min         -0.4170
_refine_diff_density_rms         0.0676
_refine_ls_d_res_high            0.7969
_refine_ls_d_res_low             12.0022
_refine_ls_goodness_of_fit_ref   1.0083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    64
_refine_ls_number_parameters     406
_refine_ls_number_reflns         6797
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0083
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0380
_refine_ls_shift/su_max          -0.0003
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0385P)^2^+2.0311P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0895
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              17
_reflns_limit_k_min              0
_reflns_limit_l_max              25
_reflns_limit_l_min              0
_reflns_number_gt                5617
_reflns_number_total             6797
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cc04820f2.cif
_cod_data_source_block           JW073_colorless_measurment_autored
_cod_depositor_comments
'Adding full bibliography for 7135028--7135034.cif.'
_cod_database_code               7135032
_chemical_oxdiff_formula         'C H N P O F'
_cell_oxdiff_angle_alpha         89.9789(19)
_cell_oxdiff_angle_beta          97.6680(18)
_cell_oxdiff_angle_gamma         89.9626(16)
_cell_oxdiff_length_a            12.1078(2)
_cell_oxdiff_length_b            13.7279(3)
_cell_oxdiff_length_c            20.3076(5)
_cell_oxdiff_measurement_reflns_used 10807
_cell_oxdiff_volume              3345.25(13)
_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.a Ternary CH refined with riding coordinates:
 C27(H27), C18(H18), C30(H30), C15(H15)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C25(H25), C11(H11), C23(H23), C4(H4), C24(H24), C6(H6),
 C13(H13), C12(H12)
2.c Idealised Me refined as rotating group:
 C28(H28a,H28b,H28c), C29(H29a,H29b,H29c), C19(H19a,H19b,H19c), C31(H31a,H31b,
 H31c), C32(H32a,H32b,H32c), C8(H8a,H8b,H8c), C16(H16a,H16b,H16c), C20(H20a,
 H20b,H20c), C17(H17a,H17b,H17c)
;
_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 2.361
_oxdiff_exptl_absorpt_empirical_full_min 0.546