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_7720457
_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 Ni0.5 O2 P S2), C16 H36 N'
_chemical_formula_sum            'C30 H50 N Ni O4 P2 S4'
_chemical_formula_weight         737.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_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                 111.905(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   36.3137(10)
_cell_length_b                   9.4106(2)
_cell_length_c                   22.9791(6)
_cell_measurement_reflns_used    9679
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9730
_cell_measurement_theta_min      2.6190
_cell_volume                     7285.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.44.123a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.123a 64-bit (release 06-10-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.123a (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      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 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.952
_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    -54.00  16.00   0.50    0.10    --  -54.87  63.00 143.00  140
  2  \w    -54.00 -22.00   0.50    0.10    --  -92.65  63.00 143.00   64
  3  \w    -51.00 -21.00   0.50    0.10    --  -92.65  61.00 120.00   60
  4  \w    -51.00 -21.00   0.50    0.10    --  -92.65  61.00  90.00   60
  5  \w    -51.00 -21.00   0.50    0.10    --  -92.65  61.00   0.00   60
  6  \w    -51.00 -24.00   0.50    0.10    --  -92.65  61.00  30.00   54
  7  \w    -51.00 -26.00   0.50    0.10    --  -92.65  61.00  60.00   50
  8  \w    -51.00 -21.00   0.50    0.10    --  -92.65  61.00 -30.00   60
  9  \w    -22.00  20.00   0.50    0.10    --  -54.87  38.00 -90.00   84
 10  \w    -22.00  20.00   0.50    0.10    --  -54.87  38.00-120.00   84
 11  \w    -51.00 -21.00   0.50    0.10    --  -92.65  61.00-120.00   60
 12  \w    -51.00 -21.00   0.50    0.10    --  -92.65  61.00 -90.00   60
 13  \w   -162.00 -97.00   0.50    0.10    --  -92.65 -95.00 150.00  130
 14  \w   -124.00 -98.00   0.50    0.10    --  -92.65 -15.00  60.00   52
 15  \w   -127.00 -79.00   0.50    0.10    --  -54.87 -57.00  30.00   96
 16  \w   -150.00 -92.00   0.50    0.10    --  -92.65 -15.00-120.00  116
 17  \w   -150.00 -92.00   0.50    0.10    --  -92.65 -15.00-180.00  116
 18  \w   -164.00 -83.00   0.50    0.10    --  -92.65 -63.00   6.00  162
 19  \w   -159.00-123.00   0.50    0.10    --  -92.65 -63.00   6.00   72
 20  \w    -23.00  22.00   0.50    0.10    --   51.62 -38.00 -90.00   90
 21  \w     40.00  66.00   0.50    0.10    --  103.98 -77.00 -90.00   52
 22  \w     37.00  62.00   0.50    0.10    --  103.98 -77.00-150.00   50
 23  \w    -19.00  54.00   0.50    0.10    --   51.62 -63.00   6.00  146
 24  \w     37.00  62.00   0.50    0.10    --  103.98 -77.00  30.00   50
 25  \w    -19.00  54.00   0.50    0.10    --   51.62 -63.00   6.00  146
 26  \w     37.00  62.00   0.50    0.10    --  103.98 -77.00 120.00   50
 27  \w     37.00  63.00   0.50    0.10    --  103.98 -77.00  90.00   52
 28  \w     41.00  66.00   0.50    0.10    --  103.98 -77.00  60.00   50
 29  \w    103.00 148.00   0.50    0.10    --  103.98  15.00 -30.00   90
 30  \w     79.00 124.00   0.50    0.10    --   51.62  57.00-120.00   90
 31  \w    106.00 156.00   0.50    0.10    --  103.98  30.00  60.00  100
 32  \w     94.00 175.00   0.50    0.10    --  103.98  63.00 143.00  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      0.0122280360
_diffrn_orient_matrix_UB_12      0.0311912684
_diffrn_orient_matrix_UB_13      0.0705562850
_diffrn_orient_matrix_UB_21      -0.0320056639
_diffrn_orient_matrix_UB_22      0.1164706953
_diffrn_orient_matrix_UB_23      -0.0151977443
_diffrn_orient_matrix_UB_31      -0.0302490394
_diffrn_orient_matrix_UB_32      -0.1107924473
_diffrn_orient_matrix_UB_33      0.0038464096
_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  0.0742
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            37450
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.954
_diffrn_reflns_theta_min         2.623
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.010
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.604
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.123a (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            purple
_exptl_crystal_density_diffrn    1.345
_exptl_crystal_description       block
_exptl_crystal_F_000             3128
_exptl_crystal_size_max          0.242
_exptl_crystal_size_mid          0.136
_exptl_crystal_size_min          0.087
_refine_diff_density_max         1.292
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     438
_refine_ls_number_reflns         7409
_refine_ls_number_restraints     237
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0756
_refine_ls_R_factor_gt           0.0620
_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^)+(0.0965P)^2^+11.7095P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1667
_refine_ls_wR_factor_ref         0.1784
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5880
_reflns_number_total             7409
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02816g2.cif
_cod_data_source_block           1TBA
_cod_original_cell_volume        7285.8(3)
_cod_database_code               7720457
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C30 H50 N1 O4 P2 S4 Ni1 '
_diffrn_oxdiff_digest_hkl
;
435daa855cc6ad5e6d068e03b877105c894b70
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name 251015d_NiS2P(O)R.par
_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
 C00Y-C011 \\sim C00Y-C4
 with sigma of 0.02
 C00Y-C017 \\sim C00Y-C0
 with sigma of 0.02
 C011-C015 \\sim C4-C3
 with sigma of 0.02
 O013-C014 \\sim O0-C2
 with sigma of 0.02
 O013-C016 \\sim O0-C5
 with sigma of 0.02
 C014-C015 \\sim C2-C3
 with sigma of 0.02
 C014-C019 \\sim C2-C1
 with sigma of 0.02
 C017-C019 \\sim C0-C1
 with sigma of 0.02
 C00Y-C015 \\sim C00Y-C3
 with sigma of 0.04
 C00Y-C019 \\sim C00Y-C1
 with sigma of 0.04
 C011-C014 \\sim C4-C2
 with sigma of 0.04
 O013-C015 \\sim O0-C3
 with sigma of 0.04
 O013-C019 \\sim O0-C1
 with sigma of 0.04
 C014-C016 \\sim C2-C5
 with sigma of 0.04
 C014-C017 \\sim C2-C0
 with sigma of 0.04
 C015-C019 \\sim C3-C1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C00Y) \\sim Ueq, Uanis(C01Y) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C00D, C00E, C00F, C00G, C00H, C00I, C00J, C00K, C00L, C00M, C00N, C00O, C00P,
 C00Q, C00R, C00S, C00T, C00U, C00V, C00W, C00X, C00Z, C010, C00Y, C011, C015,
 C014, C019, C017, C016, C01Y, C0, C1, C2, C3, C4, C5, O009, O00A, O00C, O013,
 O0
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C01Y)=Sof(C0)=Sof(H0)=Sof(C1)=Sof(H1A)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(H4)=Sof(O0)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=1-FVAR(1)
 Sof(C00Y)=Sof(C011)=Sof(H011)=Sof(C015)=Sof(H015)=Sof(C014)=Sof(C019)=
 Sof(H019)=Sof(C017)=Sof(H017)=Sof(O013)=Sof(C016)=Sof(H01D)=Sof(H01E)=
 Sof(H01F)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00B), C00E(H00C,H00D), C00F(H00E,H00F), C00G(H00G,H00H), C00H(H00I,
 H00J), C00I(H00K,H00L), C00J(H00M,H00N), C00K(H00O,H00P), C00L(H00Q,H00R),
 C00R(H00S,H00T), C00T(H00U,H00V), C00W(H00,HB)
6.b Aromatic/amide H refined with riding coordinates:
 C00M(H2), C00P(H5), C00Q(H6), C00S(H7), C011(H011), C015(H015), C019(H019),
 C017(H017), C0(H0), C1(H1A), C3(H3), C4(H4)
6.c Fitted hexagon refined as free rotating group:
 C00Y(C011,C015,C014,C019,C017), C01Y(C0,C1,C2,C3,C4)
6.d Idealised Me refined as rotating group:
 C00U(H00W,H00X,H00Y), C00V(H00Z,H,HA), C00X(H1,HC,HD), C00Z(H8,HE,HF),
 C010(H01A,H01B,H01C), C016(H01D,H01E,H01F), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              41645
_shelx_hkl_checksum              91922
_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 2.096
_oxdiff_exptl_absorpt_empirical_full_min 0.625