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_7250523
_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         '2(H O4 Se), H2 O, 2(C9 H20 N)'
_chemical_formula_sum            'C18 H44 N2 O9 Se2'
_chemical_formula_weight         590.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                90
_cell_angle_beta                 102.7673(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.50150(10)
_cell_length_b                   10.08722(6)
_cell_length_c                   16.80632(11)
_cell_measurement_reflns_used    25500
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4080
_cell_measurement_theta_min      4.3830
_cell_volume                     2562.98(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_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      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
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.969
_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     83.00 178.00   0.50    0.05    --  105.82  77.00-180.00  190
  2  \w    101.00 178.00   0.50    0.05    --  105.82  78.00 -98.00  154
  3  \w    108.00 165.00   0.50    0.05    --  105.82  77.00  30.00  114
  4  \w     35.00 120.00   0.50    0.05    --   47.37  38.00 -30.00  170
  5  \w     35.00  70.00   0.50    0.05    --  105.82 -61.00-180.00   70
  6  \w     33.00 103.00   0.50    0.05    --  105.82 -77.00 -90.00  140
  7  \w     34.00  65.00   0.50    0.05    --  105.82 -77.00  30.00   62
  8  \w     33.00 110.00   0.50    0.05    --  105.82 -78.00 136.00  154
  9  \w     34.00 105.00   0.50    0.05    --  105.82 -77.00  90.00  142
 10  \w     34.00  69.00   0.50    0.05    --  105.82 -61.00 150.00   70
 11  \w     69.00 100.00   0.50    0.05    --  105.82 -77.00  30.00   62
 12  \w     33.00  71.00   0.50    0.05    --  105.82 -61.00 -30.00   76
 13  \w     39.00  65.00   0.50    0.05    --  105.82 -61.00 -90.00   52
 14  \w     49.00 100.00   0.50    0.05    --  105.82 -95.00-120.00  102
 15  \w    -27.00  27.00   0.50    0.05    --   47.37 -19.00  60.00  108
 16  \w    -21.00  71.00   0.50    0.05    --   47.37 -78.00 136.00  184
 17  \w     63.00 107.00   0.50    0.05    --  105.82-125.00 150.00   88
 18  \w     34.00  74.00   0.50    0.05    --  105.82 -95.00  90.00   80
 19  \w    -27.00  27.00   0.50    0.05    --   47.37 -19.00-150.00  108
 20  \w    -70.00  25.00   0.50    0.05    --  -47.37  78.00 -98.00  190
 21  \w   -110.00 -19.00   0.50    0.05    --  -91.75  78.00 -98.00  182
 22  \w    -51.00 -20.00   0.50    0.05    --  -91.75  45.00-150.00   62
 23  \w    -51.00 -20.00   0.50    0.05    --  -91.75  45.00-120.00   62
 24  \w    -27.00  28.00   0.50    0.05    --  -47.37  19.00-120.00  110
 25  \w    -51.00 -20.00   0.50    0.05    --  -91.75  45.00 -90.00   62
 26  \w    -51.00 -20.00   0.50    0.05    --  -91.75  45.00 -30.00   62
 27  \w    -43.00  26.00   0.50    0.05    --  -47.37  38.00 150.00  138
 28  \w    -51.00 -20.00   0.50    0.05    --  -91.75  45.00 120.00   62
 29  \w    -51.00 -20.00   0.50    0.05    --  -91.75  45.00  90.00   62
 30  \w   -166.00 -78.00   0.50    0.05    --  -91.75 -15.00 -30.00  176
 31  \w   -163.00 -79.00   0.50    0.05    --  -91.75 -78.00 136.00  168
 32  \w   -120.00 -32.00   0.50    0.05    --  -47.37 -57.00 150.00  176
 33  \w   -163.00 -75.00   0.50    0.05    --  -91.75 -61.00  90.00  176
 34  \w   -163.00 -79.00   0.50    0.05    --  -91.75 -45.00  60.00  168
 35  \w   -163.00 -79.00   0.50    0.05    --  -91.75 -45.00  60.00  168
 36  \w   -166.00 -79.00   0.50    0.05    --  -91.75 -30.00  30.00  174
 37  \w   -163.00 -69.00   0.50    0.05    --  -91.75 -77.00-150.00  188
 38  \w   -163.00 -79.00   0.50    0.05    --  -91.75 -45.00-150.00  168
 39  \w   -163.00 -79.00   0.50    0.05    --  -91.75 -45.00-150.00  168
 40  \w   -163.00 -83.00   0.50    0.05    --  -91.75 -95.00   0.00  160
 41  \w   -163.00 -83.00   0.50    0.05    --  -91.75 -95.00  30.00  160
;
_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      0.0089322000
_diffrn_orient_matrix_UB_12      -0.1218742000
_diffrn_orient_matrix_UB_13      0.0564696000
_diffrn_orient_matrix_UB_21      -0.0950778000
_diffrn_orient_matrix_UB_22      -0.0421516000
_diffrn_orient_matrix_UB_23      -0.0406355000
_diffrn_orient_matrix_UB_31      0.0356659000
_diffrn_orient_matrix_UB_32      -0.0818595000
_diffrn_orient_matrix_UB_33      -0.0631265000
_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  0.0500
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            46970
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.710
_diffrn_reflns_theta_min         3.512
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.015
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83122
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_density_diffrn    1.530
_exptl_crystal_description       block
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.347
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.065
_refine_ls_extinction_coef       0.00020(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         5242
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0247
_refine_ls_R_factor_gt           0.0225
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0263P)^2^+1.5778P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0567
_refine_ls_wR_factor_ref         0.0579
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4838
_reflns_number_total             5242
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp01211b2.cif
_cod_data_source_block           rb148_lt_auto
_cod_database_code               7250523
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C9 H20 N Se O4'
_shelx_estimated_absorpt_t_max   0.824
_shelx_estimated_absorpt_t_min   0.501
_olex2_refinement_description
;
1.a Free rotating group:
 O9(H9D,H9E)
1.b Secondary CH2 refined with riding coordinates:
 N2(H2A,H2B), N1(H1A,H1B), C12(H12A,H12B), C11(H11A,H11B), C13(H13A,H13B),
 C4(H4A,H4B), C2(H2C,H2D), C3(H3A,H3B)
1.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C15(H15A,H15B,H15C), C18(H18A,H18B,H18C), C17(H17A,H17B,
 H17C), C16(H16A,H16B,H16C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              40261
_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 1.317
_oxdiff_exptl_absorpt_empirical_full_min 0.843