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_7135030
_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
'C38 H51 N2 P2, 1(C6 H4 F2), C F3 O3 S, 0.5[C6H4F2]'
_chemical_formula_sum            'C48 H57 F6 N2 O3 P2 S'
_chemical_formula_weight         917.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_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                 94.1461(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.14470(10)
_cell_length_b                   29.8408(3)
_cell_length_c                   13.06799(10)
_cell_measurement_reflns_used    25584
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.6910
_cell_measurement_theta_min      2.9330
_cell_volume                     4723.54(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 44.100a 64-bit (release 20-03-2025))'
_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  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip  (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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 0.998
_diffrn_measured_fraction_theta_max 0.976
_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     25.00  71.00   0.50    2.00    --   62.91 -95.00-120.00   92
  2  \w     31.00  65.00   0.50    2.00    --   62.91 -95.00   0.00   68
  3  \w     25.00  69.00   0.50    2.00    --   62.91 -95.00-180.00   88
  4  \w     27.00  60.00   0.50    2.00    --   62.91 -95.00  30.00   66
  5  \w    -99.00 -33.00   0.50    2.00    --  -63.46 -15.00 -90.00  132
  6  \w    -84.00 -31.00   0.50    2.00    --  -63.46 125.00  60.00  106
  7  \w   -108.00 -41.00   0.50    2.00    --  -63.46 -15.00-150.00  134
  8  \w     38.00  69.00   0.50    2.00    --   75.92 -95.00  90.00   62
  9  \w    -73.00 -42.00   0.50    2.00    --  -78.25  88.00  19.33   62
 10  \w    -74.00 -43.00   0.50    2.00    --  -78.25  87.00 -40.35   62
 11  \w    -88.00 -47.00   0.50    2.00    --  -78.25  98.00  34.92   82
 12  \w    -94.00 -53.00   0.50    2.00    --  -78.25 117.00 -28.88   82
 13  \w   -118.00 -88.00   0.50    2.00    --  -78.25 -36.00 -88.34   60
 14  \w    -81.00 -43.00   0.50    2.00    --  -78.25  88.00 -15.02   76
 15  \w     40.00  79.00   0.50    2.00    --   79.75  -4.00  66.10   78
 16  \w     46.00  78.00   0.50    2.00    --   79.75  -4.00  27.07   64
 17  \w     43.00  78.00   0.50    2.00    --   79.75  -4.00 111.08   70
 18  \w     66.00 123.00   0.50    2.00    --   79.75  22.00 117.27  114
 19  \w     54.00 110.00   0.50    2.00    --   79.75  19.00  35.41  112
 20  \w     46.00  81.00   0.50    2.00    --   79.75  -4.00 147.64   70
 21  \w     59.00 112.00   0.50    2.00    --   79.75  19.00  84.69  106
 22  \w     65.00 118.00   0.50    2.00    --   79.75  22.00-162.15  106
 23  \w     59.00 121.00   0.50    2.00    --   79.75  19.00-101.29  124
;
_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      -0.0374653000
_diffrn_orient_matrix_UB_12      0.0455830000
_diffrn_orient_matrix_UB_13      -0.0454889000
_diffrn_orient_matrix_UB_21      0.1168454000
_diffrn_orient_matrix_UB_22      0.0080687000
_diffrn_orient_matrix_UB_23      -0.0348743000
_diffrn_orient_matrix_UB_31      -0.0334023000
_diffrn_orient_matrix_UB_32      -0.0228453000
_diffrn_orient_matrix_UB_33      -0.1034097000
_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  0.0186
_diffrn_reflns_av_unetI/netI     0.0128
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            40351
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.387
_diffrn_reflns_theta_min         2.962
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.806
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79785
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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    1.291
_exptl_crystal_description       prism
_exptl_crystal_F_000             1932
_exptl_crystal_size_max          0.211
_exptl_crystal_size_mid          0.186
_exptl_crystal_size_min          0.127
_refine_diff_density_max         0.297
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     754
_refine_ls_number_reflns         9562
_refine_ls_number_restraints     842
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0496
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0573P)^2^+3.3093P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1323
_refine_ls_wR_factor_ref         0.1339
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8734
_reflns_number_total             9562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04820f2.cif
_cod_data_source_block           jw071_autored
_cod_depositor_comments
'Adding full bibliography for 7135028--7135034.cif.'
_cod_database_code               7135030
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N P O S F'
_cell_oxdiff_angle_alpha         90.0560(7)
_cell_oxdiff_angle_beta          94.1320(5)
_cell_oxdiff_angle_gamma         89.9807(7)
_cell_oxdiff_length_a            12.14591(8)
_cell_oxdiff_length_b            29.8469(3)
_cell_oxdiff_length_c            13.06379(9)
_cell_oxdiff_measurement_reflns_used 25578
_cell_oxdiff_volume              4723.54(7)
_shelx_estimated_absorpt_t_max   0.803
_shelx_estimated_absorpt_t_min   0.702
_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
 C1J-C1K = C1J-C1O = C1K-C1L
 1.39 with sigma of 0.02
 S1_3-O1_3 = S1_3-O2_3 = S1_3-O3_3
 1.33 with sigma of 0.02
 S1_3-C1_3
 1.82 with sigma of 0.02
 C1A-C1B = C1A-C1F = C1B-C1C
 1.39 with sigma of 0.02
 C1J-F3 = C1K-F4
 1.35 with sigma of 0.02
 C1_3-F1_3 = C1_3-F2_3 = C1_3-F3_3
 1.44 with sigma of 0.02
 C1L-C1M = C1M-C1N = C1N-C1O
 1.4 with sigma of 0.02
 C1A-F8 = C1B-F9
 1.35 with sigma of 0.02
 C1_4-F1_4 = C1_4-F2_4 = C1_4-F3_4
 1.33 with sigma of 0.02
 C1_4-S1_4
 1.82 with sigma of 0.02
 C1C-C1D = C1D-C1E = C1E-C1F
 1.4 with sigma of 0.02
 S1_4-O1_4 = S1_4-O2_4 = S1_4-O3_4
 1.44 with sigma of 0.02
 C5-C14 = C5-C1I = C14-C18
 1.39 with sigma of 0.02
 C5-F1 = C14-F2
 1.35 with sigma of 0.02
 C18-C1G = C1G-C1H = C1H-C1I
 1.4 with sigma of 0.02
 C1J-C1L = C1L-C1N = C1M-C1O
 2.42 with sigma of 0.04
 C1J-F4
 2.37 with sigma of 0.04
 S1_3-F1_3
 2.58 with sigma of 0.04
 C1A-C1C = C1C-C1E = C1D-C1F
 2.42 with sigma of 0.04
 C1J-C1N = C1K-C1M
 2.4 with sigma of 0.04
 S1_3-F2_3
 2.56 with sigma of 0.04
 S1_3-F3_3
 2.57 with sigma of 0.04
 C1A-F9
 2.37 with sigma of 0.04
 C1A-C1E = C1B-C1D
 2.4 with sigma of 0.04
 C1_4-O1_4
 2.58 with sigma of 0.04
 C1_4-O2_4
 2.56 with sigma of 0.04
 C1_4-O3_4
 2.57 with sigma of 0.04
 C5-C18 = C18-C1H = C1G-C1I
 2.42 with sigma of 0.04
 C5-F2
 2.37 with sigma of 0.04
 C5-C1H = C14-C1G
 2.4 with sigma of 0.04
 C2-C4
 2.4 with sigma of 0.04
 C1J-F3 \\sim C1K-F4
 with sigma of 0.02
 C1J-C1O \\sim C1N-C1O \\sim C1J-C1K \\sim C1M-C1N \\sim C1L-C1M \\sim C1K-C1L
 with sigma of 0.02
 C1J-F4 \\sim C1L-F4 \\sim C1K-F3 \\sim C1O-F3
 with sigma of 0.04
 C1M-C1O \\sim C1L-C1N \\sim C1K-C1M \\sim C1J-C1L \\sim C1K-C1O \\sim C1J-C1N
 with sigma of 0.04
 C1A-F8 \\sim C1B-F9
 with sigma of 0.02
 C1A-C1F \\sim C1E-C1F \\sim C1A-C1B \\sim C1D-C1E \\sim C1C-C1D \\sim C1B-C1C
 with sigma of 0.02
 C1A-F9 \\sim C1C-F9 \\sim C1B-F8 \\sim C1F-F8
 with sigma of 0.04
 C1D-C1F \\sim C1C-C1E \\sim C1B-C1D \\sim C1A-C1C \\sim C1B-C1F \\sim C1A-C1E
 with sigma of 0.04
 S1_3-O1_3 \\sim S1_3-O2_3 \\sim S1_3-O3_3
 S1_4-O1_4 \\sim S1_4-O2_4 \\sim S1_4-O3_4
 with sigma of 0.02
 O1_3-O2_3 \\sim O2_3-O3_3 \\sim O3_3-O1_3
 O1_4-O2_4 \\sim O2_4-O3_4 \\sim O3_4-O1_4
 with sigma of 0.04
 C1_3-O1_3 \\sim C1_3-O2_3 \\sim C1_3-O3_3
 C1_4-O1_4 \\sim C1_4-O2_4 \\sim C1_4-O3_4
 with sigma of 0.04
 C5-F1 \\sim C14-F2
 with sigma of 0.02
 C1_3-F1_3 \\sim C1_3-F2_3 \\sim C1_3-F3_3
 C1_4-F1_4 \\sim C1_4-F2_4 \\sim C1_4-F3_4
 with sigma of 0.02
 C5-C1I \\sim C1H-C1I \\sim C5-C14 \\sim C1G-C1H \\sim C18-C1G \\sim C14-C18
 with sigma of 0.02
 F1_3-F2_3 \\sim F2_3-F3_3 \\sim F1_3-F3_3
 F1_4-F2_4 \\sim F2_4-F3_4 \\sim F1_4-F3_4
 with sigma of 0.04
 C5-F2 \\sim C18-F2 \\sim C14-F1 \\sim C1I-F1
 with sigma of 0.04
 C1G-C1I \\sim C18-C1H \\sim C14-C1G \\sim C5-C18 \\sim C14-C1I \\sim C5-C1H
 with sigma of 0.04
 S1_3-F1_3 \\sim S1_3-F2_3 \\sim S1_3-F3_3
 S1_4-F1_4 \\sim S1_4-F2_4 \\sim S1_4-F3_4
 with sigma of 0.04
 S1_3-C1_3
 S1_4-C1_4
 with sigma of 0.02
3. Restrained planarity
 C1J, C1K, C1L, C1M, C1N, C1O, F3, F4
 with sigma of 0.1
 C1A, C1B, C1C, C1D, C1E, C1F, F8, F9
 with sigma of 0.1
 C5, C14, C18, C1G, C1H, C1I, F1, F2
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.02 and sigma
for terminal atoms of 0.01 within 1A
F4 \\sim C1A \\sim C1B \\sim C1F \\sim F8 \\sim C1C \\sim F9 \\sim C1E \\sim
H1F \\sim C1H \\sim H1H \\sim C1I \\sim C1M \\sim H1M \\sim C1N \\sim H1N \\sim
H1I \\sim C1L \\sim F1 \\sim H1L \\sim H1C \\sim C1D \\sim H1E \\sim C1G \\sim
C5 \\sim C1O \\sim C1K \\sim H1D \\sim C18 \\sim H1G \\sim C14 \\sim C1J \\sim
H1O \\sim H18 \\sim F3 \\sim F2: within 1A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1A
Uanis(F3) = Uanis(F2)
Uanis(F4) = Uanis(F3)
5. Rigid body (RIGU) restrains
 S1_3, O1_3, O2_3, O3_3, C1_3, F1_3, F2_3, F3_3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1J, C1K, C1L, C1M, C1N, C1O, F3, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1B, C1C, C1D, C1E, C1F, F8, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1_4, F1_4, F2_4, F3_4, S1_4, O1_4, O2_4, O3_4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5, C14, C18, C1G, C1H, C1I, F1, F2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(C1A)+Sof(C1B)+Sof(C1C)+Sof(H1C)+Sof(C1D)+Sof(H1D)+Sof(C1E)+Sof(H1E)+
 Sof(C1F)+Sof(H1F)+Sof(F8)+Sof(F9)]+1*[Sof(C5)+Sof(C14)+Sof(C18)+Sof(H18)+
 Sof(C1G)+Sof(H1G)+Sof(C1H)+Sof(H1H)+Sof(C1I)+Sof(H1I)+Sof(F1)+Sof(F2)]+1*
 [Sof(C1J)+Sof(C1K)+Sof(C1L)+Sof(H1L)+Sof(C1M)+Sof(H1M)+Sof(C1N)+Sof(H1N)+
 Sof(C1O)+Sof(H1O)+Sof(F3)+Sof(F4)]=1 with esd of 0.0001
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(C1)=Sof(F1)=Sof(F2)=Sof(F3)=1-FVAR(1)
 Sof(C1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(S1)=Sof(O1)=Sof(O2)=Sof(O3)=FVAR(1)
 Sof(C1A)=Sof(C1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=Sof(H1D)=Sof(C1E)=Sof(H1E)=
 Sof(C1F)=Sof(H1F)=Sof(F8)=Sof(F9)=FVAR(2)
 Sof(C5)=Sof(C14)=Sof(C18)=Sof(H18)=Sof(C1G)=Sof(H1G)=Sof(C1H)=Sof(H1H)=
 Sof(C1I)=Sof(H1I)=Sof(F1)=Sof(F2)=FVAR(3)
 Sof(C1J)=Sof(C1K)=Sof(C1L)=Sof(H1L)=Sof(C1M)=Sof(H1M)=Sof(C1N)=Sof(H1N)=
 Sof(C1O)=Sof(H1O)=Sof(F3)=Sof(F4)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C33(H33), C7(H7), C31(H31), C13(H13)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B)
7.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C30(H30), C43(H43), C55(H55), C75(H75), C85(H85), C20(H20),
 C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C18(H18), C1G(H1G), C1H(H1H), C1I(H1I),
  C1L(H1L), C1M(H1M), C1N(H1N), C1O(H1O)
7.d Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C71(H71A,H71B,H71C), C89(H89A,H89B,H89C), C91(H91A,H91B,
 H91C), C95(H95A,H95B,H95C), C34(H34A,H34B,H34C), C9(H9A,H9B,H9C), C11(H11A,
 H11B,H11C), C17(H17A,H17B,H17C), C15(H15A,H15B,H15C), C25(H25A,H25B,H25C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              89651
_shelx_fab_checksum              15195
_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 1.509
_oxdiff_exptl_absorpt_empirical_full_min 0.744