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_1576677
_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_absolute_configuration unk
_chemical_formula_moiety         'C72 H89 Br P2, 2(C4 H10 O)'
_chemical_formula_sum            'C80 H109 Br O2 P2'
_chemical_formula_weight         1244.52
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-12-01
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-04 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                   17.64070(10)
_cell_length_b                   17.64070(10)
_cell_length_c                   11.47390(10)
_cell_measurement_reflns_used    43684
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.3730
_cell_measurement_theta_min      3.5230
_cell_volume                     3570.61(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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     11.00  36.00   0.50    2.01    --   60.11 -30.00-150.00   50
  2  \w     67.00 108.00   0.50    2.01    --   60.11  30.00   0.00   82
  3  \w     61.00 108.00   0.50    2.01    --   60.11  30.00  60.00   94
  4  \w     11.00  37.00   0.50    2.01    --   60.11 -30.00-180.00   52
  5  \w     32.00  61.00   0.50    2.01    --   60.11-125.00  60.00   58
  6  \w     11.00  36.00   0.50    2.01    --   60.11 -30.00 -60.00   50
  7  \w     68.00 109.00   0.50    2.01    --   60.11  30.00  90.00   82
  8  \w     65.00 101.00   0.50    2.01    --   60.11  30.00 150.00   72
  9  \w     11.00  36.00   0.50    2.01    --   60.11 -30.00 120.00   50
 10  \w     76.00 102.00   0.50    2.01    --   73.66-125.00-180.00   52
 11  \w     76.00 115.00   0.50    2.01    --   73.66  30.00-150.00   78
 12  \w     42.00  67.00   0.50    2.01    --   73.66   0.00-180.00   50
 13  \w     78.00 104.00   0.50    2.01    --   73.66   0.00 -60.00   52
 14  \w     34.00  65.00   0.50    2.01    --   73.66   0.00 -60.00   62
 15  \w     35.00  80.00   0.50    2.01    --   73.66 -95.00  90.00   90
 16  \w     34.00  59.00   0.50    2.01    --   73.66 -95.00 -90.00   50
 17  \w     35.00  84.00   0.50    2.01    --   73.66 -95.00 -60.00   98
 18  \w     35.00  84.00   0.50    2.01    --   73.66 -95.00-120.00   98
 19  \w     49.00  80.00   0.50    2.01    --   73.66 -95.00-180.00   62
 20  \w     43.00  84.00   0.50    2.01    --   73.66 -95.00   0.00   82
 21  \w     78.00 112.00   0.50    2.01    --   73.66  30.00 -60.00   68
 22  \w     70.00 112.00   0.50    2.01    --   73.66   0.00-180.00   84
 23  \w     38.00  71.00   0.50    2.01    --   73.66-125.00-180.00   66
 24  \w     44.00  70.00   0.50    2.01    --   79.84 -95.00 150.00   52
 25  \w     62.00  88.00   0.50    2.01    --   79.84 -95.00   0.00   52
 26  \w     84.00 109.00   0.50    2.01    --   79.84-125.00  90.00   50
 27  \w     48.00  80.00   0.50    2.01    --   79.84 -95.00 -90.00   64
 28  \w     72.00  98.00   0.50    2.01    --   79.84-125.00-180.00   52
 29  \w     64.00 109.00   0.50    2.01    --   79.84-125.00 150.00   90
 30  \w     56.00  82.00   0.50    2.01    --   79.84 -95.00  60.00   52
 31  \w     46.00  81.00   0.50    2.01    --   79.84 -95.00 -30.00   70
 32  \w     42.00  68.00   0.50    2.01    --   79.84 -95.00-180.00   52
 33  \w     51.00  83.00   0.50    2.01    --   79.84 -95.00  30.00   64
 34  \w     76.00 108.00   0.50    2.01    --   79.84-125.00 120.00   64
 35  \w     49.00  75.00   0.50    2.01    --   79.84 -95.00 -60.00   52
 36  \w     58.00  84.00   0.50    2.01    --   79.84-125.00   0.00   52
 37  \w     70.00  95.00   0.50    2.01    --   79.84-125.00  60.00   50
 38  \w     39.00  93.00   0.50    2.01    --   83.00-121.00 -94.31  108
 39  \w     50.00 114.00   0.50    2.01    --   83.00  13.00 117.39  128
 40  \w     43.00  71.00   0.50    2.01    --   83.00 -62.00 -27.14   56
 41  \w     40.00 109.00   0.50    2.01    --   83.00-122.00 -28.97  138
 42  \w     84.00 111.00   0.50    2.01    --   83.00  22.00 142.43   54
 43  \w     44.00  69.00   0.50    2.01    --   83.00 -59.00  35.71   50
 44  \w     65.00  90.00   0.50    2.01    --   83.00  23.00 -83.55   50
 45  \w     43.00  73.00   0.50    2.01    --   83.00 -71.00-162.28   60
 46  \w     39.00  64.00   0.50    2.01    --   83.00 -57.00  16.99   50
 47  \w     40.00 110.00   0.50    2.01    --   83.00-123.00-127.93  140
 48  \w    101.00 131.00   0.50    2.01    --   83.00  21.00  29.99   60
 49  \w     47.00 121.00   0.50    2.01    --   83.00  -1.00-145.58  148
 50  \w     61.00  87.00   0.50    2.01    --   83.00  21.00  29.99   52
 51  \w     74.00 105.00   0.50    2.01    --   83.00  21.00  71.85   62
 52  \w     69.00 105.00   0.50    2.01    --   83.00  23.00-176.05   72
 53  \w     72.00 125.00   0.50    2.01    --   83.00  19.00 122.25  106
 54  \w     47.00  85.00   0.50    2.01    --   83.00 -82.00  94.19   76
 55  \w     69.00 117.00   0.50    2.01    --   83.00-133.00 -64.37   96
 56  \w     65.00  90.00   0.50    2.01    --   83.00  22.00 179.99   50
 57  \w     81.00 106.00   0.50    2.01    --   83.00-121.00 -74.98   50
 58  \w     40.00  65.00   0.50    2.01    --   83.00 -62.00 -42.55   50
 59  \w     47.00  88.00   0.50    2.01    --   83.00   7.00 -67.86   82
 60  \w     56.00 128.00   0.50    2.01    --   83.00  20.00 -22.07  144
 61  \w     90.00 132.00   0.50    2.01    --   83.00  20.00 -76.97   84
 62  \w     89.00 117.00   0.50    2.01    --   83.00  23.00-158.82   56
 63  \w     42.00  99.00   0.50    2.01    --   83.00-106.00 174.01  114
 64  \w     39.00  65.00   0.50    2.01    --   83.00-133.00 -64.37   52
 65  \w     78.00 110.00   0.50    2.01    --   83.00-120.00  19.90   64
 66  \w     42.00  67.00   0.50    2.01    --   83.00-120.00  19.90   50
 67  \w    -15.00  11.00   0.50    2.01    --   -3.00-100.00  55.84   52
 68  \w    -39.00 -12.00   0.50    2.01    --   -3.00 -50.00 -10.35   54
 69  \w    -40.00 -14.00   0.50    2.01    --   -3.00 -50.00 133.91   52
 70  \w    -22.00   9.00   0.50    2.01    --   -3.00 -97.00-150.48   62
 71  \w     -8.00  17.00   0.50    2.01    --    6.00 101.00-125.38   50
 72  \w      3.00  28.00   0.50    2.01    --   14.00  95.00  21.42   50
 73  \w     13.00  38.00   0.50    2.01    --   22.00  92.00  13.09   50
 74  \w     16.00  41.00   0.50    2.01    --   22.00  88.00 106.90   50
 75  \w     17.00  32.00   0.50    2.01    --   22.00  87.00-106.22   30
;
_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      0.0068259000
_diffrn_orient_matrix_UB_12      -0.0202426000
_diffrn_orient_matrix_UB_13      0.1302170000
_diffrn_orient_matrix_UB_21      -0.0588926000
_diffrn_orient_matrix_UB_22      0.0614553000
_diffrn_orient_matrix_UB_23      0.0299010000
_diffrn_orient_matrix_UB_31      -0.0639741000
_diffrn_orient_matrix_UB_32      -0.0587695000
_diffrn_orient_matrix_UB_33      -0.0137506000
_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  0.0435
_diffrn_reflns_av_unetI/netI     0.0123
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            80005
_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         74.474
_diffrn_reflns_theta_min         3.543
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.537
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.666
_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    1.158
_exptl_crystal_description       block
_exptl_crystal_F_000             1340
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.342
_refine_diff_density_min         -0.287
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1601 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.004(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         3831
_refine_ls_number_restraints     274
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0462
_refine_ls_R_factor_gt           0.0453
_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^)+(0.0820P)^2^+1.1129P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1278
_refine_ls_wR_factor_ref         0.1286
_reflns_Friedel_coverage         0.790
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3718
_reflns_number_total             3831
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00723f3.cif
_cod_data_source_block           Compound_9
_cod_depositor_comments
'Adding full bibliography for 1576673--1576682.cif.'
_cod_original_cell_volume        3570.61(5)
_cod_database_code               1576677
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C80 H109 P2 Br O'
_cell_oxdiff_angle_alpha         90.0475(12)
_cell_oxdiff_angle_beta          90.0374(12)
_cell_oxdiff_angle_gamma         90.0160(13)
_cell_oxdiff_length_a            17.6625(3)
_cell_oxdiff_length_b            17.6249(3)
_cell_oxdiff_length_c            11.47002(14)
_cell_oxdiff_measurement_reflns_used 43684
_cell_oxdiff_volume              3570.61(9)
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.802
_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
 C1-P1A \\sim C1-P1B
 with sigma of 0.01
 C1-P1B \\sim C1-P1C
 with sigma of 0.01
 P1A-P2A \\sim P1B-P2B
 with sigma of 0.01
 P1B-P2B \\sim P1C-P2C
 with sigma of 0.01
 P2A-Br1A \\sim P2B-Br1B
 with sigma of 0.02
 P2B-Br1B \\sim P2C-Br1C
 with sigma of 0.02
 C1-P2A \\sim C1-P2B
 with sigma of 0.04
 C1-P2B \\sim C1-P2C
 with sigma of 0.04
 P1A-Br1A \\sim P1B-Br1B
 with sigma of 0.04
 P1B-Br1B \\sim P1C-Br1C
 with sigma of 0.04
 C5-C8A \\sim C5-C8B
 with sigma of 0.02
 O1-C23 \\sim O1-C26
 with sigma of 0.02
 O1-C24 \\sim O1-C25
 with sigma of 0.02
 O1-C24 \\sim O1A-C24A
 with sigma of 0.02
 O1-C25 \\sim O1A_$1-C25A_$2
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C26-C25 \\sim C26A_$1-C25A_$2
 with sigma of 0.02
 O1-C23 \\sim O1A-C23A
 with sigma of 0.04
 O1-C26 \\sim O1A-C26A
 with sigma of 0.04
 C24-C25 \\sim C24A_$1-C25A_$2
 with sigma of 0.04
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C7-C6_$3 \\sim C7-C6
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Br1A \\sim Br1B \\sim Br1C \\sim P1A \\sim P1B \\sim P1C \\sim P2A \\sim P2B
\\sim P2C \\sim C1: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
O1A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim O1 \\sim C23 \\sim C24
\\sim C25 \\sim C26: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
C25A \\sim C26A \\sim C25 \\sim C26: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O1A \\sim C23A \\sim C24A \\sim C25A \\sim C26A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
O1 \\sim C23 \\sim C24 \\sim C25 \\sim C26: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 Br1A, Br1B, Br1C, P1A, P1B, P1C, P2A, P2B, P2C, C1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1, C23, C24, C25, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1A, C23A, C24A, C25A, C26A, O1, C23, C24, C25, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(Br1C)+Sof(P1C)+Sof(P2C)]+1*[Sof(Br1B)+Sof(P1B)+Sof(P2B)]+1*[Sof(Br1A)+
 Sof(P1A)+Sof(P2A)]=1 with esd of 0.0001
 Sof(O1A)=Sof(C23A)=Sof(H23C)=Sof(H23A)=Sof(H23B)=Sof(C24A)=Sof(H24A)=
 Sof(H24B)=Sof(C25A)=Sof(H25B)=Sof(H25A)=Sof(C26A)=Sof(H26C)=Sof(H26B)=
 Sof(H26A)=0.5*(1-FVAR(2))
 Sof(O1)=Sof(C23)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24)=Sof(H24C)=Sof(H24D)=
 Sof(C25)=Sof(H25C)=Sof(H25D)=Sof(C26)=Sof(H26D)=Sof(H26E)=Sof(H26F)=0.5*FVAR(2)
 Sof(Br1A)=Sof(P1A)=Sof(P2A)=0.25*FVAR(3)
 Sof(Br1B)=Sof(P1B)=Sof(P2B)=0.25*FVAR(4)
 Sof(Br1C)=Sof(P1C)=Sof(P2C)=0.25*FVAR(5)
 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) H8BB(0.5) H8BC(0.5) H8BA(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C16(H16A,H16B), C17(H17B,H17A), C24A(H24A,H24B), C25A(H25B,H25A),
  C24(H24C,H24D), C25(H25C,H25D)
6.b Me refined with riding coordinates:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23A(H23C,H23A,H23B), C26A(H26C,H26B,H26A), C23(H23D,H23E,H23F),
 C26(H26D,H26E,H26F)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C13(H13), C10(H10)
6.d Fitted hexagon refined as free rotating group:
 C14(C13,C12,C11,C10,C9)
6.e Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C8B(H8BB,H8BC,H8BA)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.354
_oxdiff_exptl_absorpt_empirical_full_min 0.723