Isolation of arylhalodiphosphenes: periodic trends in R–PP–X bonding (X = Cl, Br, I)
Wenger, John S.; Gaschik, Nina; Rowe, William J.; Crumpton, Agamemnon E.; van IJzendoorn, Bono; Mehta, Meera; Chemical Science  (2026) –; doi:10.1039/D6SC00723F

data_1576674
_publ_section_title
;
 Isolation of arylhalodiphosphenes: periodic trends in R-P[double bond,
 length as m-dash]P-X bonding (X = Cl, Br, I).
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              7475
_journal_page_last               7485
_journal_paper_doi               10.1039/d6sc00723f
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C72 H89 I P2, 2(C4 H10 O)'
_chemical_formula_sum            'C80 H109 I O2 P2'
_chemical_formula_weight         1291.51
_space_group_crystal_system      tetragonal
_space_group_IT_number           113
_space_group_name_Hall           'P -4 2ab'
_space_group_name_H-M_alt        'P -4 21 m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2026-01-14
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2026-01-15 deposited with the CCDC.	2026-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.63400(10)
_cell_length_b                   17.63400(10)
_cell_length_c                   11.51880(10)
_cell_measurement_reflns_used    39870
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      75.0290
_cell_measurement_theta_min      3.5290
_cell_volume                     3581.86(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     26.00  74.00   0.50    2.13    --   60.11-100.00 -38.00   96
  2  \w     35.00  61.00   0.50    2.13    --   73.66-100.00 -38.00   52
  3  \w     63.00  89.00   0.50    2.13    --   79.84-100.00 -38.00   52
  4  \w     62.00 106.00   0.50    2.13    --   60.11  30.00-150.00   88
  5  \w     11.00  36.00   0.50    2.13    --   60.11 -30.00  60.00   50
  6  \w     12.00  37.00   0.50    2.13    --   60.11 -30.00 150.00   50
  7  \w     37.00  63.00   0.50    2.13    --   60.11 -95.00   0.00   52
  8  \w     25.00  62.00   0.50    2.13    --   60.11 -95.00 -90.00   74
  9  \w     11.00  37.00   0.50    2.13    --   60.11 -30.00-180.00   52
 10  \w     77.00 103.00   0.50    2.13    --   60.11  30.00 120.00   52
 11  \w     11.00  37.00   0.50    2.13    --   60.11 -30.00-150.00   52
 12  \w     63.00 102.00   0.50    2.13    --   60.11  30.00  90.00   78
 13  \w     76.00 109.00   0.50    2.13    --   60.11  30.00   0.00   66
 14  \w     49.00  83.00   0.50    2.13    --   73.66 -95.00  90.00   68
 15  \w     44.00  72.00   0.50    2.13    --   73.66 -95.00  60.00   56
 16  \w     35.00  80.00   0.50    2.13    --   73.66 -95.00-150.00   90
 17  \w     34.00  75.00   0.50    2.13    --   73.66 -95.00 150.00   82
 18  \w     89.00 122.00   0.50    2.13    --   73.66  30.00 -60.00   66
 19  \w     76.00 111.00   0.50    2.13    --   73.66   0.00 -60.00   70
 20  \w     39.00  64.00   0.50    2.13    --   73.66   0.00 -60.00   50
 21  \w     42.00  67.00   0.50    2.13    --   73.66-125.00  90.00   50
 22  \w     32.00  63.00   0.50    2.13    --   73.66-125.00  30.00   62
 23  \w     68.00 101.00   0.50    2.13    --   73.66-125.00  30.00   66
 24  \w     89.00 120.00   0.50    2.13    --   73.66  30.00  30.00   62
 25  \w     78.00 122.00   0.50    2.13    --   73.66  30.00-180.00   88
 26  \w     78.00 103.00   0.50    2.13    --   73.66-125.00  90.00   50
 27  \w     76.00 117.00   0.50    2.13    --   73.66  30.00 150.00   82
 28  \w     42.00  67.00   0.50    2.13    --   79.84-125.00  60.00   50
 29  \w     62.00  88.00   0.50    2.13    --   79.84 -95.00-180.00   52
 30  \w     52.00 102.00   0.50    2.13    --   79.84-125.00   0.00  100
 31  \w     81.00 107.00   0.50    2.13    --   79.84-125.00  60.00   52
 32  \w     65.00  91.00   0.50    2.13    --   79.84 -95.00-120.00   52
 33  \w     67.00  92.00   0.50    2.13    --   79.84-125.00 -90.00   50
 34  \w     84.00 109.00   0.50    2.13    --   79.84-125.00  90.00   50
 35  \w     84.00 109.00   0.50    2.13    --   79.84-125.00-120.00   50
 36  \w     81.00 107.00   0.50    2.13    --   79.84  30.00-120.00   52
 37  \w     84.00 109.00   0.50    2.13    --   79.84-125.00 120.00   50
 38  \w     74.00 100.00   0.50    2.13    --   82.00-108.00 -50.06   52
 39  \w     42.00  96.00   0.50    2.13    --   83.00-102.00  96.51  108
 40  \w     49.00 127.00   0.50    2.13    --   83.00   9.00  33.66  156
 41  \w     73.00 109.00   0.50    2.13    --   83.00  21.00 -22.14   72
 42  \w     41.00 103.00   0.50    2.13    --   83.00-110.00-169.48  124
 43  \w     41.00 106.00   0.50    2.13    --   83.00-115.00 168.93  130
 44  \w     50.00  97.00   0.50    2.13    --   83.00-105.00-104.95   94
 45  \w     69.00 110.00   0.50    2.13    --   83.00  23.00 153.51   82
 46  \w     47.00  74.00   0.50    2.13    --   83.00 -78.00 -77.51   54
 47  \w     47.00  99.00   0.50    2.13    --   83.00-105.00  76.17  104
 48  \w    102.00 127.00   0.50    2.13    --   83.00   6.00-174.35   50
 49  \w     43.00  93.00   0.50    2.13    --   83.00 -94.00   0.71  100
 50  \w     85.00 111.00   0.50    2.13    --   83.00   0.00 -58.75   52
 51  \w     44.00  71.00   0.50    2.13    --   83.00   0.00 -58.75   54
 52  \w     48.00  73.00   0.50    2.13    --   83.00   6.00-174.35   50
 53  \w     44.00  93.00   0.50    2.13    --   83.00 -94.00  19.91   98
 54  \w     41.00  89.00   0.50    2.13    --   83.00-114.00-177.14   96
 55  \w     50.00  77.00   0.50    2.13    --   83.00-114.00 -66.21   54
 56  \w     63.00  90.00   0.50    2.13    --   83.00  22.00-108.06   54
 57  \w    107.00 132.00   0.50    2.13    --   83.00  22.00-108.06   50
 58  \w     59.00 128.00   0.50    2.13    --   83.00  21.00 -75.70  138
 59  \w     49.00  98.00   0.50    2.13    --   83.00-109.00 132.23   98
 60  \w     65.00 115.00   0.50    2.13    --   83.00  23.00 115.04  100
 61  \w     94.00 120.00   0.50    2.13    --   83.00  52.00  30.31   52
 62  \w     92.00 117.00   0.50    2.13    --   83.00  44.00-126.49   50
 63  \w     81.00 106.00   0.50    2.13    --   83.00-114.00   5.26   50
 64  \w     62.00  89.00   0.50    2.13    --   83.00   2.00-161.13   54
 65  \w     76.00 104.00   0.50    2.13    --   83.00  20.00  58.56   56
 66  \w     86.00 122.00   0.50    2.13    --   83.00   7.00  83.03   72
 67  \w     43.00 103.00   0.50    2.13    --   83.00-111.00  58.43  120
 68  \w     69.00  94.00   0.50    2.13    --   83.00  23.00 169.47   50
 69  \w     54.00  80.00   0.50    2.13    --   83.00-115.00 -82.38   52
 70  \w     47.00  89.00   0.50    2.13    --   83.00-103.00  -9.33   84
 71  \w     93.00 118.50   0.50    2.13    --   83.00  45.00 -40.05   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            73101
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.941
_diffrn_reflns_theta_min         3.545
_exptl_absorpt_coefficient_mu    4.262
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.727
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
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_density_diffrn    1.197
_exptl_crystal_description       block
_exptl_crystal_F_000             1376
_exptl_crystal_size_max          0.091
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.496
_refine_diff_density_min         -0.686
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1556 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         3923
_refine_ls_number_restraints     267
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0568
_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^)+(0.1054P)^2^+1.5833P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1635
_refine_ls_wR_factor_ref         0.1647
_reflns_Friedel_coverage         0.794
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3788
_reflns_number_total             3923
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00723f3.cif
_cod_data_source_block           compound_10
_cod_depositor_comments
'Adding full bibliography for 1576673--1576682.cif.'
_cod_original_cell_volume        3581.86(5)
_cod_database_code               1576674
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.825
_shelx_estimated_absorpt_t_min   0.698
_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
 C26A-C25A
 1.48 with sigma of 0.02
 C24A-C23A
 1.5 with sigma of 0.02
 O1A-C25A
 1.41 with sigma of 0.02
 C26B-C25B
 1.48 with sigma of 0.02
 O1A-C24A
 1.42 with sigma of 0.02
 C24B-C23B
 1.5 with sigma of 0.02
 O1B-C25B
 1.41 with sigma of 0.02
 O1B-C24B
 1.42 with sigma of 0.02
 O1A-C26A = O1A-C23A
 2.37 with sigma of 0.04
 O1B-C26B = O1B-C23B
 2.37 with sigma of 0.04
 P1A-P2A \\sim P1B-P2B
 with sigma of 0.02
 P1A-C1 \\sim P1B-C1
 with sigma of 0.02
 P2A-C1 \\sim P2B-C1
 with sigma of 0.04
 P2A-I1A \\sim P2B-I1B
 with sigma of 0.02
 C26A-C25A \\sim C24A-C23A
 with sigma of 0.02
 C5-C8A \\sim C5-C8B
 with sigma of 0.02
 C26A-O1A \\sim O1A-C23A
 with sigma of 0.04
 C26B-C25B \\sim C24B-C23B
 with sigma of 0.02
 C26B-O1B \\sim O1B-C23B
 with sigma of 0.04
 O1A-C25A \\sim O1A-C24A
 with sigma of 0.02
 O1A-C23A \\sim O1B-C23B
 with sigma of 0.02
 O1B-C25B \\sim O1B-C24B
 with sigma of 0.02
 C24A-C25A \\sim C24B-C25B
 with sigma of 0.02
 O1A-C25A \\sim O1B-C25B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1A \\sim C26A \\sim C25A \\sim C24A \\sim C23A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C1 \\sim P1B \\sim P1A \\sim P2B \\sim P2A \\sim I1B \\sim I1A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O1B \\sim C26B \\sim C25B \\sim C24B \\sim C23B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C23A \\sim C24A \\sim O1A \\sim C25A \\sim C26A \\sim C23B \\sim C24B \\sim O1B
\\sim C25B \\sim C26B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C26B \\sim C26A \\sim C25A \\sim C25B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C1, P1B, P1A, P2B, P2A, I1B, I1A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1A, C26A, C25A, C24A, C23A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1B, C26B, C25B, C24B, C23B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23A, C24A, O1A, C25A, C26A, C23B, C24B, O1B, C25B, C26B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(I1A)=Sof(P1A)=Sof(P2A)=0.25*(1-FVAR(2))
 Sof(P1B)=Sof(P2B)=Sof(I1B)=0.25*FVAR(2)
 Sof(O1B)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C25B)=Sof(H25C)=
 Sof(H25D)=Sof(C24B)=Sof(H24C)=Sof(H24D)=Sof(C23B)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=0.5*(1-FVAR(3))
 Sof(O1A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C25A)=Sof(H25A)=
 Sof(H25B)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(C23A)=Sof(H23A)=Sof(H23B)=
 Sof(H23C)=0.5*FVAR(3)
 Fixed Sof: H4A(0.5) H4B(0.5) C5(0.5) C8A(0.5) H8AA(0.5) H8AB(0.5) H8AC(0.5)
 C8B(0.5) H8BA(0.5) H8BB(0.5) H8BC(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C13(H13A,H13B), C14(H14A,H14B), C25A(H25A,H25B), C24A(H24A,H24B),
  C25B(H25C,H25D), C24B(H24C,H24D)
6.b Me refined with riding coordinates:
 C26A(H26A,H26B,H26C), C23A(H23A,H23B,H23C), C26B(H26D,H26E,H26F), C23B(H23D,
 H23E,H23F)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C10(H10), C17(H17)
6.d Fitted hexagon refined as free rotating group:
 C9(C10,C11,C16,C17,C18)
6.e Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C8A(H8AA,H8AB,H8AC), C8B(H8BA,H8BB,H8BC)
;
_shelx_res_checksum              41544
_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
;