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_7720455
_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         'C14 H14 O4 P2 Pd S4, 2(H4 N), H2 O'
_chemical_formula_sum            'C14 H24 N2 O5 P2 Pd S4'
_chemical_formula_weight         596.93
_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                 112.913(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.5343(2)
_cell_length_b                   10.61910(10)
_cell_length_c                   14.4834(2)
_cell_measurement_reflns_used    12645
_cell_measurement_temperature    293.15(10)
_cell_measurement_theta_max      77.5490
_cell_measurement_theta_min      2.9340
_cell_volume                     2342.34(6)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.15(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 1.000
_diffrn_measured_fraction_theta_max 0.956
_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     37.00  73.00   0.50    0.07    --  103.98 -77.00-180.00   72
  2  \w     37.00  73.00   0.50    0.07    --  103.98 -77.00 -60.00   72
  3  \w    -17.00  66.00   0.50    0.07    --   51.62 -73.00 147.00  166
  4  \w     37.00  73.00   0.50    0.07    --  103.98 -77.00 120.00   72
  5  \w     36.00  67.00   0.50    0.07    --  103.98 -73.00 147.00   62
  6  \w    103.00 150.00   0.50    0.07    --  103.98  15.00  90.00   94
  7  \w    103.00 150.00   0.50    0.07    --  103.98  15.00  60.00   94
  8  \w    103.00 150.00   0.50    0.07    --  103.98  15.00   0.00   94
  9  \w     99.00 172.00   0.50    0.07    --  103.98  73.00 -83.00  146
 10  \w    104.00 171.00   0.50    0.07    --  103.98  30.00-150.00  134
 11  \w     79.00 124.00   0.50    0.07    --   51.62  57.00-120.00   90
 12  \w    -22.00  20.00   0.50    0.07    --  -54.87  38.00 -90.00   84
 13  \w    -67.00  14.00   0.50    0.07    --  -54.87  73.00 -83.00  162
 14  \w    -73.00 -26.00   0.50    0.07    --  -92.65  77.00-120.00   94
 15  \w    -67.00 -24.00   0.50    0.07    --  -92.65  73.00 -83.00   86
 16  \w    -51.00 -21.00   0.50    0.07    --  -92.65  61.00  30.00   60
 17  \w    -51.00 -21.00   0.50    0.07    --  -92.65  61.00 -30.00   60
 18  \w    -51.00 -21.00   0.50    0.07    --  -92.65  61.00  90.00   60
 19  \w    -22.00  20.00   0.50    0.07    --  -54.87  38.00  30.00   84
 20  \w    -51.00 -21.00   0.50    0.07    --  -92.65  61.00-120.00   60
 21  \w    -51.00 -21.00   0.50    0.07    --  -92.65  61.00-150.00   60
 22  \w     35.00  92.00   0.50    0.07    --  103.98 -95.00-150.00  114
 23  \w   -130.00 -74.00   0.50    0.07    --  -54.87 -38.00 -90.00  112
 24  \w   -164.00 -87.00   0.50    0.07    --  -92.65-125.00-120.00  154
 25  \w   -164.00 -84.00   0.50    0.07    --  -92.65 -61.00-180.00  160
 26  \w   -127.00 -79.00   0.50    0.07    --  -54.87 -57.00   0.00   96
 27  \w   -161.00 -98.00   0.50    0.07    --  -92.65 -73.00 147.00  126
;
_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      -0.0133595000
_diffrn_orient_matrix_UB_12      0.0992593000
_diffrn_orient_matrix_UB_13      -0.0822223000
_diffrn_orient_matrix_UB_21      -0.0727896000
_diffrn_orient_matrix_UB_22      0.0626031000
_diffrn_orient_matrix_UB_23      0.0255362000
_diffrn_orient_matrix_UB_31      0.0689643000
_diffrn_orient_matrix_UB_32      0.0852990000
_diffrn_orient_matrix_UB_33      0.0769412000
_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  0.0682
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23412
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.878
_diffrn_reflns_theta_min         2.902
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.267
_exptl_absorpt_correction_T_max  0.154
_exptl_absorpt_correction_T_min  0.007
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.693
_exptl_crystal_description       prism
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.139
_refine_diff_density_min         -1.078
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     285
_refine_ls_number_reflns         4782
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0510
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0946P)^2^+0.0431P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1280
_refine_ls_wR_factor_ref         0.1302
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4470
_reflns_number_total             4782
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02816g2.cif
_cod_data_source_block           2
_cod_database_code               7720455
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'Pd S P O C H'
_shelx_estimated_absorpt_t_max   0.399
_shelx_estimated_absorpt_t_min   0.165
_diffrn_oxdiff_digest_hkl
;
43c22e9b326ffbaf7f33b6bd947f0840ebc70b
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name 250825d.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, H1A of C2, All N(H,H,H,H) groups, All O(H,H) groups
 At 1.2 times of:
  H13 of C13, H12 of C12, H9 of C9, H10 of C10, H2 of C2, H6 of C6, H3 of C3,
  H5 of C5
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              89694
_shelx_hkl_checksum              1194
_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 1.774
_oxdiff_exptl_absorpt_empirical_full_min 0.530