Proton Delocalization in Short Hydrogen Bonds Assembling HSeO4– Anions into Supramolecular Adducts
Beccaria, Roberta; Pizzi, Andrea; Chakalov, Edem R.; Resnati, Giuseppe; Tolstoy, Peter; Physical Chemistry Chemical Physics  (2025) –; doi:10.1039/D5CP01211B

data_7250519
_publ_section_title
;
 Proton Delocalization in Short Hydrogen Bonds Assembling HSeO4-- Anions
 into Supramolecular Adducts
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP01211B
_journal_year                    2025
_chemical_formula_moiety         'O4 Se, H O4 Se, H2 O, 3(C9 H8 N)'
_chemical_formula_sum            'C27 H27 N3 O9 Se2'
_chemical_formula_weight         695.43
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-01-17 deposited with the CCDC.	2025-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                76.9481(16)
_cell_angle_beta                 89.2209(14)
_cell_angle_gamma                71.1833(16)
_cell_formula_units_Z            2
_cell_length_a                   9.91309(16)
_cell_length_b                   10.3638(2)
_cell_length_c                   14.6046(3)
_cell_measurement_reflns_used    31454
_cell_measurement_temperature    298.4(2)
_cell_measurement_theta_max      76.0370
_cell_measurement_theta_min      3.0880
_cell_volume                     1380.70(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298.4(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.942
_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   -118.00 -51.00   0.50    0.12    --  -46.32-157.00 -81.00  134
  2  \w    -84.00  -9.00   0.50    0.12    --  -46.32 119.00 158.00  150
  3  \w     51.00 115.00   0.50    0.12    --   46.32-157.00 -81.00  128
  4  \w     30.00  91.00   0.50    0.12    --   46.32-119.00  73.00  122
  5  \w   -163.00 -77.00   0.50    0.49    --  -91.75-119.00  73.00  172
  6  \w   -143.00 -51.00   0.50    0.49    --  -91.75-157.00 -81.00  184
  7  \w    -84.00 -19.00   0.50    0.49    --  -91.75 119.00 158.00  130
  8  \w     51.00 134.00   0.50    0.49    --  105.25-157.00 -81.00  166
  9  \w     73.00 160.00   0.50    0.49    --  105.25 157.00 -46.00  174
 10  \w     99.00 178.00   0.50    0.49    --  105.25 119.00 158.00  158
 11  \w     33.00 110.00   0.50    0.49    --  105.25-119.00  73.00  154
 12  \w    -40.00 -11.00   0.50    0.12    --    6.00 123.00-129.75   58
 13  \w    -15.00  27.00   0.50    0.12    --   18.00  98.00 179.88   84
 14  \w     -6.00  29.00   0.50    0.12    --   26.00  96.00 -24.30   70
 15  \w      8.00  34.00   0.50    0.12    --   38.00  93.00 123.65   52
 16  \w      9.00  42.00   0.50    0.12    --   38.00  91.00-106.48   66
 17  \w     15.00  43.00   0.50    0.12    --   42.00  87.00  -1.50   56
 18  \w   -118.00 -24.00   0.50    0.12    --  -46.32 -77.00-150.00  188
 19  \w   -118.00 -24.00   0.50    0.12    --  -46.32 -77.00  30.00  188
 20  \w    -89.00 -61.00   0.50    0.12    --  -46.32 -77.00 150.00   56
 21  \w    -49.00 -24.00   0.50    0.12    --  -46.32 -77.00 150.00   50
 22  \w   -105.00 -32.00   0.50    0.12    --  -46.32 157.00 -46.00  146
 23  \w     36.00  83.00   0.50    0.12    --   46.32  38.00  90.00   94
 24  \w     50.00  78.00   0.50    0.12    --   46.32  19.00   0.00   56
 25  \w     42.00  72.00   0.50    0.12    --   46.32  38.00   0.00   60
 26  \w     26.00  52.00   0.50    0.12    --   46.32  77.00 -60.00   52
 27  \w     28.00  57.00   0.50    0.12    --   50.00  76.00 -38.05   58
 28  \w   -110.00 -82.00   0.50    0.12    --  -54.00 -77.00  99.89   56
 29  \w    -57.00 -31.00   0.50    0.12    --  -54.00 -77.00  99.89   52
 30  \w     83.00 111.00   0.50    0.12    --   54.00  77.00-160.51   56
 31  \w     72.00 103.00   0.50    0.12    --   54.00  76.00 138.72   62
 32  \w     31.00  58.00   0.50    0.12    --   54.00  77.00-160.51   54
 33  \w     32.00  64.00   0.50    0.12    --   54.00  76.00 138.72   64
 34  \w     34.00  61.00   0.50    0.12    --   54.00  71.00  49.73   54
 35  \w     35.00  62.00   0.50    0.12    --   54.00  73.00  21.47   54
 36  \w     33.00  59.00   0.50    0.12    --   54.00  74.00   0.25   52
 37  \w     39.00  66.00   0.50    0.12    --   58.00  71.00 123.82   54
 38  \w     37.00  63.00   0.50    0.12    --   58.00  74.00-120.64   52
 39  \w     98.00 128.00   0.50    0.12    --   58.00  74.00-120.64   60
 40  \w     41.00  75.00   0.50    0.12    --   62.00  75.00-103.17   68
 41  \w     40.00  66.00   0.50    0.12    --   62.00  76.00  67.01   52
 42  \w     41.00  68.00   0.50    0.12    --   62.00  72.00  87.70   54
 43  \w    -75.00 -48.00   0.50    0.12    --  -66.00 -65.00 -56.01   54
 44  \w    -82.00 -48.00   0.50    0.12    --  -66.00 -64.00  93.15   68
 45  \w   -134.00-107.00   0.50    0.12    --  -66.00 -66.00  63.56   54
 46  \w    -73.00 -47.00   0.50    0.12    --  -66.00 -67.00 136.49   52
 47  \w    -75.00 -48.00   0.50    0.12    --  -66.00 -66.00  63.56   54
 48  \w    -85.00 -50.00   0.50    0.12    --  -66.00 -63.00 107.40   70
 49  \w    -88.00 -49.00   0.50    0.12    --  -66.00 -74.00 -20.24   78
 50  \w    -84.00 -48.00   0.50    0.12    --  -66.00 -65.00 156.33   72
 51  \w     43.00  69.00   0.50    0.12    --   66.00  77.00  53.57   52
 52  \w     44.00  71.00   0.50    0.12    --   66.00  76.00 -72.40   54
 53  \w     49.00  75.00   0.50    0.12    --   70.00  74.00 -87.30   52
 54  \w    -80.00 -53.00   0.50    0.49    --  -70.00 -64.00  52.52   54
 55  \w    -77.00 -51.00   0.50    0.49    --  -70.00 -67.00 175.33   52
 56  \w    -84.00 -57.00   0.50    0.49    --  -74.00 -63.00 -87.73   54
 57  \w    -85.00 -58.00   0.50    0.49    --  -74.00 -63.00 -48.42   54
 58  \w    -78.00 -52.00   0.50    0.49    --  -74.00 -74.00   5.30   52
 59  \w    -83.00 -57.00   0.50    0.49    --  -78.00 -72.00  33.03   52
 60  \w    -82.00 -57.00   0.50    0.49    --  -78.00 -72.00  25.20   50
 61  \w    -82.00 -56.00   0.50    0.49    --  -78.00 -74.00 107.70   52
 62  \w    -88.00 -61.00   0.50    0.49    --  -78.00 -62.00 -93.34   54
 63  \w    -90.00 -64.00   0.50    0.49    --  -82.00 -65.00  39.49   52
 64  \w    -96.00 -67.00   0.50    0.49    --  -82.00 -62.00-172.72   58
 65  \w    -92.00 -65.00   0.50    0.49    --  -82.00 -63.00 -28.15   54
 66  \w    -87.00 -60.00   0.50    0.49    --  -82.00 -74.00-105.58   54
 67  \w    -87.00 -61.00   0.50    0.49    --  -82.00 -73.00-120.55   52
 68  \w    -89.00 -62.00   0.50    0.49    --  -82.00 -72.00 132.81   54
 69  \w    -91.00 -65.00   0.50    0.49    --  -82.00 -63.00-165.54   52
 70  \w    -90.00 -62.00   0.50    0.49    --  -82.00 -69.00  -6.59   56
 71  \w    -91.00 -65.00   0.50    0.49    --  -86.00 -73.00 160.24   52
 72  \w   -161.00 -72.00   0.50    0.49    --  -90.00 -64.00 -72.12  178
 73  \w   -107.00 -77.00   0.50    0.49    --  -91.75 -64.00-120.98   60
 74  \w   -162.00 -69.00   0.50    0.49    --  -91.75 -77.00 -30.00  186
 75  \w   -162.00-113.00   0.50    0.49    --  -91.75 -64.00-120.98   98
 76  \w    -69.00 -26.00   0.50    0.49    --  -91.75  61.00 -30.00   86
 77  \w   -160.00 -69.00   0.50    0.49    --  -91.75 -76.00-175.74  182
 78  \w   -100.00 -73.00   0.50    0.49    --  -91.75 -68.00 118.73   54
 79  \w   -116.00 -70.00   0.50    0.49    --  -91.75 -74.00  32.41   92
 80  \w   -144.00 -70.00   0.50    0.49    --  -91.75 -77.00  90.00  148
 81  \w   -148.00 -71.00   0.50    0.49    --  -91.75 -71.00 -49.05  154
 82  \w   -130.00 -73.00   0.50    0.49    --  -91.75 -68.00 154.46  114
 83  \w   -154.00 -77.00   0.50    0.49    --  -91.75 -63.00  57.88  154
 84  \w   -123.00 -96.00   0.50    0.49    --  -91.75 -15.00 -60.00   54
 85  \w   -101.00 -73.00   0.50    0.49    --  -91.75 -66.00-144.30   56
 86  \w   -153.00 -74.00   0.50    0.49    --  -91.75 -65.00-144.31  158
 87  \w   -110.00 -79.00   0.50    0.49    --  -91.75 -68.00 -92.14   62
 88  \w   -162.00 -74.00   0.50    0.49    --  -91.75 -63.00  52.36  176
 89  \w   -103.00 -70.00   0.50    0.49    --  -91.75 -76.00  52.17   66
 90  \w   -162.00-115.00   0.50    0.49    --  -91.75 -68.00 -92.14   94
 91  \w   -162.00-137.00   0.50    0.49    --  -91.75 -76.00  52.17   50
 92  \w    -46.00 -20.00   0.50    0.49    --  -91.75 125.00 120.00   52
 93  \w    -70.00 -25.00   0.50    0.49    --  -91.75  61.00  90.00   90
 94  \w    -99.00 -72.00   0.50    0.49    --  -91.75 -72.00 -59.28   54
 95  \w   -146.00 -70.00   0.50    0.49    --  -91.75 -77.00  30.00  152
 96  \w   -163.00 -70.00   0.50    0.49    --  -91.75 -77.00   0.00  186
 97  \w   -103.00 -70.00   0.50    0.49    --  -91.75 -74.00 -76.62   66
 98  \w    -99.00 -71.00   0.50    0.49    --  -91.75 -74.00  99.80   56
 99  \w   -161.00-127.00   0.50    0.49    --  -91.75 -74.00 -76.62   68
100  \w   -145.00-105.00   0.50    0.49    --  -91.75 -74.00  99.80   80
101  \w    -96.00 -71.00   0.50    0.49    --  -91.75 -71.00 -22.42   50
102  \w   -152.00-125.00   0.50    0.49    --  -91.75 -71.00 -22.42   54
103  \w   -108.00 -68.00   0.50    0.49    --  -91.75 157.00 -46.00   80
104  \w    -95.00 -69.00   0.50    0.49    --  -91.75 -77.00 120.00   52
105  \w   -129.00 -71.00   0.50    0.49    --  -91.75 -71.00-171.38  116
106  \w   -147.00-117.00   0.50    0.49    --  -91.75 -77.00 120.00   60
107  \w   -160.00 -71.00   0.50    0.49    --  -91.75 -73.00 152.20  178
108  \w   -162.00 -71.00   0.50    0.49    --  -91.75 -72.00 130.23  182
109  \w   -162.00 -69.00   0.50    0.49    --  -91.75 -77.00-150.00  186
110  \w    -97.00 -71.00   0.50    0.49    --  -91.75 -73.00-119.37   52
111  \w     34.00  70.00   0.50    0.49    --  105.25 -61.00 -60.00   72
112  \w     34.00  91.00   0.50    0.49    --  105.25-125.00 150.00  114
113  \w     33.00 104.00   0.50    0.49    --  105.25 -95.00 -90.00  142
114  \w     52.00 112.00   0.50    0.49    --  105.25-125.00 120.00  120
115  \w     36.00  69.00   0.50    0.49    --  105.25 -61.00 -30.00   66
116  \w     35.00 107.00   0.50    0.49    --  105.25-125.00-150.00  144
117  \w     75.00 105.00   0.50    0.49    --  105.25-125.00   0.00   60
118  \w     33.00  60.00   0.50    0.49    --  105.25 -61.00 120.00   54
119  \w     63.00 109.00   0.50    0.49    --  105.25-125.00  30.00   92
120  \w     47.00  74.00   0.50    0.49    --  105.25-125.00   0.00   54
121  \w     45.00 112.00   0.50    0.49    --  105.25-125.00-180.00  134
122  \w     34.00  67.00   0.50    0.49    --  105.25 -61.00-150.00   66
123  \w     35.00 112.00   0.50    0.49    --  105.25-125.00 -90.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1512813000
_diffrn_orient_matrix_UB_12      0.0448297000
_diffrn_orient_matrix_UB_13      -0.0471601000
_diffrn_orient_matrix_UB_21      -0.0636454000
_diffrn_orient_matrix_UB_22      0.0025324000
_diffrn_orient_matrix_UB_23      0.0966574000
_diffrn_orient_matrix_UB_31      -0.0114243000
_diffrn_orient_matrix_UB_32      0.1551584000
_diffrn_orient_matrix_UB_33      -0.0143809000
_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  0.0384
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            47717
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.037
_diffrn_reflns_theta_min         3.113
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.868
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64989
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.55a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.673
_exptl_crystal_description       plate
_exptl_crystal_F_000             700
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         5435
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0288
_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^)+(0.0441P)^2^+0.8023P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0745
_refine_ls_wR_factor_ref         0.0811
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4617
_reflns_number_total             5435
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp01211b2.cif
_cod_data_source_block           rb150_1_auto
_cod_database_code               7250519
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C9 H8 N Se O4'
_shelx_estimated_absorpt_t_max   0.830
_shelx_estimated_absorpt_t_min   0.512
_olex2_refinement_description
;
1.a Free rotating group:
 O9(H9A)
1.b Aromatic/amide H refined with riding coordinates:
 N3(H3), C10(H10), C12(H12), C24(H24), C15(H15), C27(H27), C21(H21), C18(H18),
 C19(H19), C26(H26), C25(H25), C11(H11), C20(H20), C17(H17), C16(H16), C1(H1A),
 C3(H3A), C2(H2A), C6(H6), C9(H9), C8(H8), C7(H7)
;
_shelx_res_checksum              15663
_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 1.634
_oxdiff_exptl_absorpt_empirical_full_min 0.701