Tetracationic phosphonium-bridged ladder stilbenes: redox states and electronic properties of highly charged P-heteropolycyclic materials
Senn, Sebastian; Konrad, Nele; Müller, Jens; Ballmann, Joachim; Gade, Lutz H.; Chemical Communications 62 (2026) 6391–6395; doi:10.1039/D6CC00544F

data_7135561
_publ_section_title
;
 Tetracationic phosphonium-bridged ladder stilbenes: redox states and
 electronic properties of highly charged P-heteropolycyclic materials
;
_journal_issue                   23
_journal_name_full               'Chemical Communications'
_journal_page_first              6391
_journal_page_last               6395
_journal_paper_doi               10.1039/D6CC00544F
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         '2(Br), C46 H66 P4, 1[C4H10O]'
_chemical_formula_sum            'C50 H76 Br2 O P4'
_chemical_formula_weight         976.80
_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             2025-02-16
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2026-01-22 deposited with the CCDC.	2026-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.625(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.5338(2)
_cell_length_b                   15.7508(2)
_cell_length_c                   14.4968(3)
_cell_measurement_reflns_used    19846
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      70.7530
_cell_measurement_theta_min      3.9180
_cell_volume                     2580.43(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (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    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_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    -25.00  71.00   1.00    5.00    --    0.00  77.00 150.00   96
  2  \w    -21.00  69.00   1.00    5.00    --    0.00  57.00 -90.00   90
  3  \w    -31.00  69.00   1.00    5.00    --    0.00  77.00  30.00  100
  4  \w    -38.00  -7.00   1.00    5.00    --   14.00 130.00  25.30   31
  5  \w    -16.00   9.00   1.00   18.00    --   30.00 105.00 -88.34   25
  6  \w     -2.00  25.00   1.00   18.00    --   38.00  94.00 -63.05   27
  7  \w      3.00  28.00   1.00   18.00    --   42.00  91.00  56.05   25
  8  \w     10.00  35.00   1.00   18.00    --   46.00  85.00 138.81   25
  9  \w     11.00  38.00   1.00   18.00    --   46.00  84.00 -73.01   27
 10  \w     17.00  42.00   1.00   18.00    --   50.00  80.00 -14.08   25
 11  \w     16.00  41.00   1.00   18.00    --   50.00  81.00-142.69   25
 12  \w     16.00  41.00   1.00   18.00    --   50.00  81.00  31.75   25
 13  \w     17.00  44.00   1.00   18.00    --   50.00  80.00 115.94   27
 14  \w     16.00  41.00   1.00   18.00    --   50.00  81.00 173.54   25
 15  \w     17.00  42.00   1.00   18.00    --   50.00  80.00  62.66   25
 16  \w    -10.00  86.00   1.00   18.00    --   54.47 -77.00  60.00   96
 17  \w     23.00 106.00   1.00   18.00    --   54.47-125.00 -60.00   83
 18  \w      1.00  58.00   1.00   18.00    --   54.47 -99.00-150.00   57
 19  \w    -15.00  75.00   1.00   18.00    --   54.47 -57.00 -60.00   90
 20  \w     71.00 126.00   1.00   18.00    --   62.00  74.00 -37.73   55
 21  \w     81.00 108.00   1.00   18.00    --   62.00  75.00 100.45   27
 22  \w     31.00  66.00   1.00   18.00    --   62.00  76.00-176.79   35
 23  \w     32.00  58.00   1.00   18.00    --   62.00  74.00 -37.73   26
 24  \w     31.00  60.00   1.00   18.00    --   62.00  77.00 -20.57   29
 25  \w     69.00 122.00   1.00   18.00    --   62.00  76.00-176.79   53
 26  \w     31.00 116.00   1.00   18.00    --   62.00  76.00 151.43   85
 27  \w     31.00  70.00   1.00   18.00    --   62.00  75.00 100.45   39
 28  \w     31.00  58.00   1.00   18.00    --   62.00  76.00-124.99   27
 29  \w     30.00  56.00   1.00   18.00    --   62.00  77.00  69.40   26
 30  \w     31.00 133.00   1.00   18.00    --   62.00  75.00  22.07  102
 31  \w     31.00 133.00   1.00   18.00    --   62.00  75.00 -73.91  102
 32  \w     66.00 125.00   1.00   18.00    --   62.00  77.00  69.40   59
 33  \w     30.00 132.00   1.00   18.00    --   62.00  77.00-113.17  102
 34  \w     77.00 103.00   1.00   30.00    --  108.94  77.00-180.00   26
 35  \w     84.00 160.00   1.00   30.00    --  108.94  64.00 150.00   76
 36  \w     84.00 169.00   1.00   30.00    --  108.94  64.00 120.00   85
 37  \w     77.00 103.00   1.00   30.00    --  108.94  77.00   0.00   26
 38  \w     84.00 166.00   1.00   30.00    --  108.94  64.00 -90.00   82
 39  \w     77.00 103.00   1.00   30.00    --  108.94  77.00 -60.00   26
 40  \w     84.00 177.00   1.00   30.00    --  108.94  64.00-150.00   93
 41  \w     82.00 145.00   1.00   30.00    --  108.94  38.00 -90.00   63
 42  \w     84.00 177.00   1.00   30.00    --  108.94  64.00  90.00   93
 43  \w     84.00 177.00   1.00   30.00    --  108.94  64.00  60.00   93
 44  \w     84.00 166.00   1.00   30.00    --  108.94  64.00   0.00   82
 45  \w     84.00 122.00   1.00   30.00    --  108.94  64.00-180.00   38
 46  \w     77.00 103.00   1.00   30.00    --  108.94  77.00 150.00   26
 47  \w    101.00 176.00   1.00   30.00    --  108.94 111.00 150.00   75
 48  \w     84.00 165.00   1.00   30.00    --  108.94  64.00 -60.00   81
 49  \w     36.00 102.00   1.00   30.00    --  108.94 -92.00  60.00   66
 50  \w     77.00 103.00   1.00   30.00    --  108.94  77.00  90.00   26
 51  \w     39.00 123.00   1.00   30.00    --  108.94 -50.00  60.00   84
 52  \w     59.00 112.00   1.00   30.00    --  108.94-111.00-150.00   53
 53  \w     77.00 103.00   1.00   30.00    --  108.94  77.00  30.00   26
 54  \w    136.00 163.00   1.00   30.00    --  108.94  77.00-120.00   27
 55  \w     77.00 103.00   1.00   30.00    --  108.94  77.00 120.00   26
 56  \w     84.00 110.00   1.00   30.00    --  108.94  64.00 -30.00   26
 57  \w     77.00 104.00   1.00   30.00    --  108.94  77.00  60.00   27
 58  \w     77.00 103.00   1.00   30.00    --  108.94  77.00-120.00   26
 59  \w     36.00 108.00   1.00   30.00    --  108.94 -92.00-120.00   72
 60  \w     78.00 105.00   1.00   30.00    --  108.94  77.00-150.00   27
 61  \w     84.00 171.00   1.00   30.00    --  108.94  64.00  30.00   87
 62  \w     77.00 178.00   1.00   30.00    --  108.94  77.00 -30.00  101
 63  \w     75.00 112.00   1.00   30.00    --  108.94-111.00   0.00   37
 64  \w     77.00 103.00   1.00   30.00    --  108.94  77.00 -90.00   26
 65  \w     41.00 133.00   1.00   30.00    --  108.94 -64.00-120.00   92
 66  \w    131.00 158.00   1.00   30.00    --  108.94  77.00-180.00   27
 67  \w     82.00 109.00   1.00   30.00    --  108.94 -92.00  90.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0161791000
_diffrn_orient_matrix_UB_12      -0.0970421000
_diffrn_orient_matrix_UB_13      -0.0106696000
_diffrn_orient_matrix_UB_21      -0.1350236000
_diffrn_orient_matrix_UB_22      0.0118539000
_diffrn_orient_matrix_UB_23      -0.0570926000
_diffrn_orient_matrix_UB_31      0.0091925000
_diffrn_orient_matrix_UB_32      0.0034656000
_diffrn_orient_matrix_UB_33      -0.1025238000
_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  0.0454
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            38166
_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         71.096
_diffrn_reflns_theta_min         3.912
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.408
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.625
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       plate
_exptl_crystal_F_000             1028
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.929
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     243
_refine_ls_number_reflns         4956
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0663P)^2^+1.9381P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1123
_refine_ls_wR_factor_ref         0.1157
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4507
_reflns_number_total             4956
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00544f2.cif
_cod_data_source_block           ba_ss24
_cod_depositor_comments
'Adding full bibliography for 7135561--7135563.cif.'
_cod_original_cell_volume        2580.43(8)
_cod_database_code               7135561
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C50H76Br2OP4
_chemical_oxdiff_usercomment     ss447
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.685
_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:
 C12(H12), C15(H15), C18(H18), C21(H21)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 74 electrons were 
found in a volume of 374\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C4H10O] per formula unit 
which account for 84 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.4
_smtbx_masks_void_truncation_radius 1.1
_shelx_res_checksum              32144
_shelx_hkl_checksum              70309
_shelx_fab_checksum              70729
_olex2_date_sample_data_collection 2025-02-14
_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
- Detector area scaling
;