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_7720454
_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 Ni O4 P2 S4, H2 O, 2(H4 N)'
_chemical_formula_sum            'C14 H24 N2 Ni O5 P2 S4'
_chemical_formula_weight         549.24
_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                 112.818(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4408(3)
_cell_length_b                   10.4823(2)
_cell_length_c                   14.5603(3)
_cell_measurement_reflns_used    10186
_cell_measurement_temperature    293.15(10)
_cell_measurement_theta_max      77.5510
_cell_measurement_theta_min      2.9230
_cell_volume                     2312.91(8)
_computing_cell_refinement       'CrysAlisPro 1.171.44.120a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.116a 64-bit (release 30-06-2025))'
_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  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_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 0.990
_diffrn_measured_fraction_theta_max 0.929
_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    -20.00   5.00   0.50    3.02    --   51.62 -36.00  98.00   50
  2  \w     58.00  91.00   0.50    3.02    --   51.62  36.00-105.00   66
  3  \w   -119.00 -58.00   0.50    3.02    --  -54.87 -36.00  98.00  122
  4  \w     -7.00  18.00   0.50    3.02    --  -54.87  36.00-105.00   50
  5  \w   -143.00 -97.00   0.50    3.02    --  -92.65 -36.00  98.00   92
  6  \w    110.00 159.00   0.50    3.02    --  103.98  36.00-105.00   98
  7  \w    -23.00  22.00   0.50    3.02    --   51.62 -38.00 -60.00   90
  8  \w   -127.00 -79.00   0.50    3.02    --  -54.87 -57.00  60.00   96
  9  \w    -18.00  20.00   0.50    3.02    --  -54.87  38.00-150.00   76
 10  \w    -13.00  12.00   0.50    3.02    --  -54.87  38.00   0.00   50
 11  \w    -46.00 -21.00   0.50    3.02    --  -92.65  61.00   0.00   50
 12  \w    -51.00 -26.00   0.50    3.02    --  -92.65  61.00 -90.00   50
 13  \w    -48.00 -23.00   0.50    3.02    --  -92.65  61.00  30.00   50
 14  \w    -47.00 -22.00   0.50    3.02    --  -92.65  61.00  90.00   50
 15  \w    -51.00 -26.00   0.50    3.02    --  -92.65  61.00  60.00   50
 16  \w    -51.00 -23.00   0.50    3.02    --  -92.65  61.00 -30.00   56
 17  \w    -66.00 -40.00   0.50    3.02    --  -92.65  77.00-150.00   52
 18  \w   -157.00-105.00   0.50    3.02    --  -92.65 -77.00   0.00  104
 19  \w    -51.00 -26.00   0.50    3.02    --  -92.65  61.00 120.00   50
 20  \w    111.00 142.00   0.50    3.02    --  103.98  15.00-120.00   62
 21  \w    108.00 143.00   0.50    3.02    --  103.98  15.00-150.00   70
 22  \w     46.00  71.00   0.50    3.02    --  103.98 -77.00 -30.00   50
 23  \w     43.00  68.00   0.50    3.02    --  103.98 -77.00-120.00   50
 24  \w     35.00  76.00   0.50    3.02    --  103.98 -95.00 -30.00   82
 25  \w     39.00  69.00   0.50    3.02    --  103.98 -77.00 150.00   60
 26  \w     39.00  64.00   0.50    3.02    --  103.98 -77.00 120.00   50
;
_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      0.0264493000
_diffrn_orient_matrix_UB_12      -0.0668518000
_diffrn_orient_matrix_UB_13      -0.0785524000
_diffrn_orient_matrix_UB_21      0.0975998000
_diffrn_orient_matrix_UB_22      0.0037920000
_diffrn_orient_matrix_UB_23      0.0721775000
_diffrn_orient_matrix_UB_31      -0.0106321000
_diffrn_orient_matrix_UB_32      -0.1307958000
_diffrn_orient_matrix_UB_33      0.0422934000
_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  0.0185
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            14790
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.729
_diffrn_reflns_theta_min         2.916
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.146
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.697
_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            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.577
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.249
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     295
_refine_ls_number_reflns         4594
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0270
_refine_ls_R_factor_gt           0.0236
_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^)+(0.0335P)^2^+0.5178P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0637
_refine_ls_wR_factor_ref         0.0655
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4097
_reflns_number_total             4594
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02816g2.cif
_cod_data_source_block           1xray
_cod_database_code               7720454
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C14 H24 N2 O5 P2 S4 Ni1 '
_shelx_estimated_absorpt_t_max   0.837
_shelx_estimated_absorpt_t_min   0.459
_diffrn_oxdiff_digest_hkl
;
4370698c629ae0da224433b660b9ff373ace8b
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name 250809a.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
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C9(H9), C13(H13), C5(H5), C3(H3), C12(H12), C10(H10)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              22652
_shelx_hkl_checksum              54439
_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 1.435
_oxdiff_exptl_absorpt_empirical_full_min 0.817