Solving the P-O/P-OH riddle: direct synthesis and neutron diffraction characterization of dianionic dithiophosphonates.
Pillay, Michael N.; Li, Min-Chi; Ni, Yu-Rong; Yen, Wei-Jung; Chiu, Tzu-Hao; Wang, Xiaoping; Saillard, Jean-Yves; Liu, C. W.; Dalton transactions (Cambridge, England : 2003) 55 (2026) 1637–1641; doi:10.1039/d5dt02816g

data_7720453
_publ_section_title
;
 Solving the P-O/P-OH riddle: direct synthesis and neutron diffraction
 characterization of dianionic dithiophosphonates.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1637
_journal_page_last               1641
_journal_paper_doi               10.1039/d5dt02816g
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         '2(C7 H7 O2 P S2), H2 O, 4(H4 N)'
_chemical_formula_sum            'C14 H32 N4 O5 P2 S4'
_chemical_formula_weight         526.61
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-12-15
_audit_creation_method
;
Olex2 1.5-ac7-013
(compiled 2025.01.02 svn.rf662f148 for Rigaku Oxford Diffraction, GUI svn.r7109)
;
_audit_update_record
;
2025-12-16 deposited with the CCDC.	2025-12-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.586(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.1011(2)
_cell_length_b                   10.9171(2)
_cell_length_c                   9.21900(10)
_cell_measurement_reflns_used    27373
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      77.1900
_cell_measurement_theta_min      3.6400
_cell_volume                     1207.25(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.120a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.120a 64-bit (release 22-08-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.120a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5-ac7-013 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-013 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.974
_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    -51.00 -21.00   0.50    0.10    --  -92.62  61.00 150.00   60
  2  \w    -51.00 -21.00   0.50    0.10    --  -92.62  61.00   0.00   60
  3  \w    -51.00 -21.00   0.50    0.10    --  -92.62  61.00 -30.00   60
  4  \w    -51.00 -21.00   0.50    0.10    --  -92.62  61.00 -60.00   60
  5  \w    -51.00 -21.00   0.50    0.10    --  -92.62  61.00-150.00   60
  6  \w    -73.00 -25.00   0.50    0.10    --  -92.62  77.00-150.00   96
  7  \w    -22.00  20.00   0.50    0.10    --  -54.85  38.00 -30.00   84
  8  \w    -22.00  20.00   0.50    0.10    --  -54.85  38.00 120.00   84
  9  \w     28.00  54.00   0.50    0.10    --   38.00  64.00 114.95   52
 10  \w     28.00  56.00   0.50    0.10    --   38.00  63.00  41.82   56
 11  \w     28.00  56.00   0.50    0.10    --   38.00  63.00 -62.25   56
 12  \w     28.00  56.00   0.50    0.10    --   38.00  63.00-163.67   56
 13  \w     28.00  56.00   0.50    0.10    --   38.00  63.00-101.06   56
 14  \w     -5.00  21.00   0.50    0.10    --   14.00  82.00  36.76   52
 15  \w     79.00 124.00   0.50    0.10    --   51.60  57.00  30.00   90
 16  \w     79.00 124.00   0.50    0.10    --   51.60  57.00  90.00   90
 17  \w     82.00 163.00   0.50    0.10    --  103.97 135.00   1.00  162
 18  \w     82.00 163.00   0.50    0.10    --  103.97 135.00-178.00  162
 19  \w     79.00 124.00   0.50    0.10    --   51.60  57.00 -90.00   90
 20  \w    103.00 150.00   0.50    0.10    --  103.97  15.00 -60.00   94
 21  \w    103.00 150.00   0.50    0.10    --  103.97  15.00  30.00   94
 22  \w    103.00 150.00   0.50    0.10    --  103.97  15.00 120.00   94
 23  \w     37.00  73.00   0.50    0.10    --  103.97 -77.00  90.00   72
 24  \w     16.00 103.00   0.50    0.10    --   51.60-135.00 115.00  174
 25  \w     33.00 106.00   0.50    0.10    --  103.97-135.00 115.00  146
 26  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00 150.00  114
 27  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00  60.00  114
 28  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00  90.00  114
 29  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00  30.00  114
 30  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00 -30.00  114
 31  \w     33.00 106.00   0.50    0.10    --  103.97-135.00 -64.00  146
 32  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00 -90.00  114
 33  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00-150.00  114
 34  \w     35.00  92.00   0.50    0.10    --  103.97 -95.00-180.00  114
 35  \w   -105.00 -16.00   0.50    0.10    --  -54.85 135.00-178.00  178
 36  \w   -105.00 -21.00   0.50    0.10    --  -92.62 135.00-178.00  168
 37  \w    -97.00 -29.00   0.50    0.10    --  -99.00 115.00 -90.48  136
 38  \w    -92.00 -30.00   0.50    0.10    --  -99.00 100.00 -77.86  124
 39  \w   -105.00 -21.00   0.50    0.10    --  -92.62 135.00   1.00  168
 40  \w    -92.00 -30.00   0.50    0.10    --  -99.00  94.00  13.11  124
 41  \w    -92.00 -31.00   0.50    0.10    --  -99.00  91.00  46.46  122
 42  \w    -92.00 -30.00   0.50    0.10    --  -99.00  94.00 106.38  124
 43  \w   -150.00 -92.00   0.50    0.10    --  -92.62 -15.00 -60.00  116
 44  \w   -164.00 -83.00   0.50    0.10    --  -94.00 -65.00-114.19  162
 45  \w   -164.00 -84.00   0.50    0.10    --  -94.00 -66.00-163.49  160
 46  \w   -160.00 -99.00   0.50    0.10    --  -92.62 -77.00-120.00  122
 47  \w   -160.00 -99.00   0.50    0.10    --  -92.62 -77.00 -60.00  122
 48  \w   -165.00 -84.00   0.50    0.10    --  -94.00 -63.00 -90.36  162
 49  \w   -165.00 -84.00   0.50    0.10    --  -94.00 -63.00  -5.53  162
 50  \w   -164.00 -84.00   0.50    0.10    --  -92.62 -61.00 -30.00  160
 51  \w   -165.00 -84.00   0.50    0.10    --  -94.00 -63.00-151.84  162
 52  \w   -164.00 -84.00   0.50    0.10    --  -92.62 -61.00 -60.00  160
 53  \w   -165.00 -84.00   0.50    0.10    --  -94.00 -64.00  44.36  162
 54  \w   -164.00 -83.00   0.50    0.10    --  -94.00 -65.00  73.21  162
 55  \w   -169.00 -87.00   0.50    0.10    --  -99.00 -67.00 167.04  164
 56  \w   -164.00 -84.00   0.50    0.10    --  -92.62 -61.00 120.00  160
 57  \w   -162.00 -83.00   0.50    0.10    --  -90.00 -57.00  19.15  158
 58  \w   -158.00 -79.00   0.50    0.10    --  -86.00 -57.00  94.28  158
 59  \w   -158.00 -79.00   0.50    0.10    --  -86.00 -57.00   3.16  158
 60  \w   -159.00 -79.00   0.50    0.10    --  -86.00 -56.00  73.67  160
 61  \w   -147.00 -68.00   0.50    0.10    --  -74.00 -55.00  21.73  158
 62  \w   -127.00 -79.00   0.50    0.10    --  -54.85 -57.00 -30.00   96
 63  \w   -158.00 -79.00   0.50    0.10    --  -86.00 -59.00-154.53  158
 64  \w   -158.00 -79.00   0.50    0.10    --  -86.00 -57.00 -86.56  158
 65  \w   -151.00 -72.00   0.50    0.10    --  -78.00 -54.00 -62.50  158
 66  \w   -151.00 -73.00   0.50    0.10    --  -78.00 -53.00-150.99  156
 67  \w   -151.00 -72.00   0.50    0.10    --  -78.00 -55.00 -23.42  158
 68  \w   -151.00-111.00   0.50    0.10    --  -78.00 -50.00 -39.68   80
 69  \w   -155.00 -78.00   0.50    0.10    --  -82.00 -51.00  41.85  154
 70  \w   -151.00 -74.00   0.50    0.10    --  -78.00 -50.00 121.04  154
 71  \w   -151.00 -72.00   0.50    0.10    --  -78.00 -55.00 170.31  158
 72  \w   -152.00 -75.00   0.50    0.10    --  -78.00 -48.00 143.35  154
 73  \w   -159.00 -80.00   0.50    0.10    --  -86.00 -55.00 122.14  158
 74  \w   -150.00 -92.00   0.50    0.10    --  -92.62 -15.00 120.00  116
 75  \w   -140.00 -64.00   0.50    0.10    --  -66.00 -47.00-135.14  152
 76  \w   -163.00 -82.00   0.50    0.10    --  -92.62-135.00 -64.00  162
 77  \w   -163.00 -82.00   0.50    0.10    --  -92.62-135.00 115.00  162
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0377208000
_diffrn_orient_matrix_UB_12      -0.1207149000
_diffrn_orient_matrix_UB_13      0.0779515000
_diffrn_orient_matrix_UB_21      0.0620853000
_diffrn_orient_matrix_UB_22      0.0731971000
_diffrn_orient_matrix_UB_23      0.1286283000
_diffrn_orient_matrix_UB_31      -0.1058867000
_diffrn_orient_matrix_UB_32      -0.0000912000
_diffrn_orient_matrix_UB_33      0.0760829000
_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  0.0474
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            46159
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.161
_diffrn_reflns_theta_min         3.685
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.157
_exptl_absorpt_correction_T_max  0.973
_exptl_absorpt_correction_T_min  0.756
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.120a (Rigaku Oxford Diffraction, 2025)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_description       block
_exptl_crystal_F_000             556
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.417
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2489
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0337
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0438P)^2^+1.4527P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0877
_refine_ls_wR_factor_ref         0.0882
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2443
_reflns_number_total             2489
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02816g2.cif
_cod_data_source_block           LPO
_cod_database_code               7720453
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C7 H16 N2 O2.500 P1 S2 '
_shelx_estimated_absorpt_t_max   0.601
_shelx_estimated_absorpt_t_min   0.512
_diffrn_oxdiff_digest_hkl
;
43162d00b4cb0a724ae9e966d11a76a759e311
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name 251008a_S2P(O)R.par
_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, All O(H,H) groups
2. Others
 Fixed Sof: O3(0.5) H3A(0.5) H3B(0.5)
3.a Free rotating group:
 O3(H3A,H3B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6)
3.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              16808
_shelx_hkl_checksum              37203
_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 2.041
_oxdiff_exptl_absorpt_empirical_full_min 0.701