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_7135563
_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_absolute_configuration ad
_chemical_formula_moiety         '4(Br), C46 H66 P4, 8[H2O]'
_chemical_formula_sum            'C46 H82 Br4 O8 P4'
_chemical_formula_weight         1206.63
_space_group_crystal_system      trigonal
_space_group_IT_number           154
_space_group_name_Hall           'P 32 2"'
_space_group_name_H-M_alt        'P 32 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-13
_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                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   12.4139(3)
_cell_length_b                   12.4139(3)
_cell_length_c                   32.4727(5)
_cell_measurement_reflns_used    9492
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      69.6180
_cell_measurement_theta_min      4.0760
_cell_volume                     4333.77(16)
_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 0.999
_diffrn_measured_fraction_theta_max 0.997
_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    -29.00  12.00   1.00   10.00    --    0.00  77.00  90.00   41
  2  \w     34.00  70.00   1.00   10.00    --    0.00  77.00  90.00   36
  3  \w    -22.00   7.00   1.00   10.00    --   14.00 104.00 159.61   29
  4  \w    -25.00  17.00   1.00   10.00    --   14.00 102.00  18.08   42
  5  \w    -27.00  -2.00   1.00   10.00    --   18.00 109.00-124.46   25
  6  \w    -26.00   2.00   1.00   10.00    --   22.00 118.00-173.91   28
  7  \w      2.00  28.00   1.00   34.00    --   38.00  92.00-121.62   26
  8  \w     -1.00  27.00   1.00   34.00    --   38.00  93.00 120.36   28
  9  \w      0.00  26.00   1.00   34.00    --   38.00  92.00 -15.11   26
 10  \w     -1.00  26.00   1.00   34.00    --   38.00  93.00  74.94   27
 11  \w     29.00 124.00   1.00   34.00    --   54.34  38.00-180.00   95
 12  \w     27.00 124.00   1.00   34.00    --   54.34  77.00-120.00   97
 13  \w     40.00 123.00   1.00   34.00    --   54.34  57.00  30.00   83
 14  \w     40.00 112.00   1.00   34.00    --   54.34  57.00 -60.00   72
 15  \w    108.00 134.00   1.00   34.00    --   74.00 122.00 -36.87   26
 16  \w    102.00 151.00   1.00   54.00    --   82.00 118.00  96.41   49
 17  \w    102.00 130.00   1.00   54.00    --   82.00 119.00-149.98   28
 18  \w    116.00 155.00   1.00   54.00    --   90.00 137.00-106.58   39
 19  \w    100.00 139.00   1.00   54.00    --  102.00 116.00  -8.65   39
 20  \w    136.00 162.00   1.00   54.00    --  102.00 120.00  16.46   26
 21  \w     98.00 163.00   1.00   54.00    --  106.00 119.00-171.56   65
 22  \w    110.00 173.00   1.00   54.00    --  106.00 114.00  74.13   63
 23  \w    110.00 170.00   1.00   54.00    --  106.00 109.00 129.44   60
 24  \w     99.00 153.00   1.00   54.00    --  108.67 139.00-112.95   54
 25  \w    108.00 178.00   1.00   54.00    --  108.67  38.00-180.00   70
 26  \w    104.00 143.00   1.00   54.00    --  108.67 149.00 -59.41   39
 27  \w    108.00 177.00   1.00   54.00    --  108.67 143.00 -26.73   69
 28  \w    114.00 178.00   1.00   54.00    --  108.67 140.00 157.34   64
 29  \w    104.00 177.00   1.00   54.00    --  108.67 143.00  97.44   73
 30  \w    103.00 177.00   1.00   54.00    --  108.67 138.00-145.78   74
 31  \w    124.00 177.00   1.00   54.00    --  108.67 143.00 -87.30   53
 32  \w     83.00 162.00   1.00   54.00    --  108.67  38.00 -90.00   79
 33  \w    105.00 177.00   1.00   54.00    --  108.67 143.00  27.80   72
 34  \w     89.00 170.00   1.00   54.00    --  108.67  64.00 -60.00   81
;
_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      -0.0231353000
_diffrn_orient_matrix_UB_12      -0.1157125000
_diffrn_orient_matrix_UB_13      -0.0246465000
_diffrn_orient_matrix_UB_21      0.1391321000
_diffrn_orient_matrix_UB_22      0.0410114000
_diffrn_orient_matrix_UB_23      0.0032687000
_diffrn_orient_matrix_UB_31      -0.0254349000
_diffrn_orient_matrix_UB_32      -0.0738897000
_diffrn_orient_matrix_UB_33      0.0403917000
_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  0.0811
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            33705
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.199
_diffrn_reflns_theta_min         4.084
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.800
_exptl_absorpt_correction_T_max  0.986
_exptl_absorpt_correction_T_min  0.728
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1866
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.358
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.087
_refine_ls_abs_structure_details
;
 Flack x determined using 1855 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         5564
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0499
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0763P)^2^+3.9971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1299
_refine_ls_wR_factor_ref         0.1368
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                4892
_reflns_number_total             5564
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00544f2.cif
_cod_data_source_block           ba_ss23
_cod_depositor_comments
'Adding full bibliography for 7135561--7135563.cif.'
_cod_original_cell_volume        4333.8(2)
_cod_database_code               7135563
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C46H80Br4O7P4
_chemical_oxdiff_usercomment     ss438
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.620
_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. Others
 Fixed Sof: Br1(0.5)
3.a Ternary CH refined with riding coordinates:
 C18(H18), C15(H15), C12(H12), C21(H21)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C5(H5), C2(H2), C4(H4), C3(H3)
3.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C14(H14A,H14B,H14C), C20(H20A,H20B,H20C), C17(H17A,H17B,
 H17C), C22(H22A,H22B,H22C), C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C23(H23A,
 H23B,H23C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 231 electrons were 
found in a volume of 1039\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
8[H2O] per formula unit 
which account for 240 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.4
_shelx_res_checksum              71156
_shelx_hkl_checksum              38024
_shelx_fab_checksum              75601
_olex2_date_sample_data_collection 2025-02-11
_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
;