Crystal engineering of ionic cocrystals comprising Na/K salts of hesperetin with hesperetin molecules and solubility modulation.
Jin, Shasha; Haskins, Molly M.; Deng, Cheng Hua; Matos, Catiúcia R M O; Zaworotko, Michael J.; IUCrJ 10 (2023) –; doi:10.1107/S205225252300266X

data_1568922
_publ_section_title
;
 Crystal engineering of ionic cocrystals comprising Na/K salts of
 hesperetin with hesperetin molecules and solubility modulation.
;
_journal_issue                   3
_journal_name_full               IUCrJ
_journal_paper_doi               10.1107/S205225252300266X
_journal_volume                  10
_journal_year                    2023
_chemical_formula_moiety         'C32 H27 K O12, C2 H6 O'
_chemical_formula_sum            'C34 H33 K O13'
_chemical_formula_weight         688.70
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-21
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.006(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.4072(8)
_cell_length_b                   20.4384(8)
_cell_length_c                   17.3645(11)
_cell_measurement_reflns_used    11675
_cell_measurement_temperature    113.15
_cell_measurement_theta_max      33.5860
_cell_measurement_theta_min      2.0020
_cell_volume                     6682.9(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      113.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -120.00  60.00   1.00    4.00    --  -30.00  45.00   0.00  180
  2  \w   -120.00  30.00   1.00    4.00    --  -30.00  45.00  90.00  150
  3  \w   -120.00   0.00   1.00    4.00    --  -30.00  45.00 180.00  120
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0331376000
_diffrn_orient_matrix_UB_12      -0.0109915000
_diffrn_orient_matrix_UB_13      0.0234427000
_diffrn_orient_matrix_UB_21      -0.0046851000
_diffrn_orient_matrix_UB_22      0.0195593000
_diffrn_orient_matrix_UB_23      0.0320640000
_diffrn_orient_matrix_UB_31      -0.0173059000
_diffrn_orient_matrix_UB_32      -0.0264711000
_diffrn_orient_matrix_UB_33      0.0139660000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0619
_diffrn_reflns_av_unetI/netI     0.0484
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26486
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         1.729
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.226
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37334
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_description       prism
_exptl_crystal_F_000             2880
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.048
_refine_diff_density_min         -0.991
_refine_diff_density_rms         0.070
_refine_ls_extinction_coef       0.0018(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   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     485
_refine_ls_number_reflns         6841
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1026
_refine_ls_R_factor_gt           0.0798
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0733P)^2^+29.3626P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1886
_refine_ls_wR_factor_ref         0.2050
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5112
_reflns_number_total             6841
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            lq5051.cif
_cod_data_source_block           HESKHE_xEtOH
_cod_database_code               1568922
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.965
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All C(H,H,H,H,H,
  H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O2-H2
 0.85 with sigma of 0.01
 O5-H5
 0.85 with sigma of 0.01
 H5-O5
 0.84 with sigma of 0.02
 C8B-C9B
 1.42 with sigma of 0.005
 H2-O2
 0.84 with sigma of 0.02
 H6-O6
 0.84 with sigma of 0.02
 H8-O8
 0.84 with sigma of 0.02
 H11-O11
 0.84 with sigma of 0.02
 H11-O6
 2.2 with sigma of 0.02
 C8B-C9B \\sim C8A-C9A
 with sigma of 0.02
 C23B-C26 \\sim C23A-C26
 with sigma of 0.02
 C23B-C24 \\sim C23A-C24
 with sigma of 0.02
 C9A-C10 \\sim C9B-C10
 with sigma of 0.02
 O10-C23B \\sim O10-C23A
 with sigma of 0.02
 O3-C8B \\sim O3-C8A
 with sigma of 0.02
 C5-C8B \\sim C5-C8A
 with sigma of 0.02
3. Rigid bond restraints
 C23B, C23A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C9A, C9B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8A, C8B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C23A \\sim C23B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C8A \\sim C8B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C9B \\sim C9A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C23B) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(C9B) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
5. Others
 Sof(H24C)=Sof(H24D)=Sof(C23A)=Sof(H23A)=1-FVAR(1)
 Sof(H24A)=Sof(H24B)=Sof(C23B)=Sof(H23B)=FVAR(1)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=1-FVAR(2)
 Sof(C9B)=Sof(H9BA)=Sof(H9BB)=FVAR(2)
 Sof(C8A)=Sof(H8A)=1-FVAR(3)
 Sof(C8B)=Sof(H8B)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C23B(H23B), C8B(H8B), C23A(H23A), C8A(H8A)
6.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C24(H24C,H24D), C9B(H9BA,H9BB), C1E(H1EA,H1EB), C9A(H9AA,H9AB)
6.c Aromatic/amide H refined with riding coordinates:
 C18(H18), C22(H22), C31(H31), C30(H30), C27(H27), C15(H15), C13(H13), C4(H4),
 C7(H7), C6(H6A)
6.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C1(H1A,H1B,H1C), C2E(H2EA,H2EB,H2EC)
6.e Idealised tetrahedral OH refined as rotating group:
 O1E(H1E)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              25130
_shelx_hkl_checksum              84443
_shelx_fab_checksum              57597
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.658
_oxdiff_exptl_absorpt_empirical_full_min 0.511