Synthon hierarchy in theobromine cocrystals with hydroxybenzoic acids as coformers
Gołdyn, Mateusz; Larowska, Daria; Nowak, Weronika; Bartoszak-Adamska, Elżbieta; CrystEngComm  (2019) –; doi:10.1039/C9CE01195A

data_7235246
_publ_section_title
;
 Synthon hierarchy in theobromine cocrystals with hydroxybenzoic acids as
 coformers
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/C9CE01195A
_journal_year                    2019
_chemical_formula_moiety         'C7 H8 N4 O2, C7 H6 O4'
_chemical_formula_sum            'C14 H14 N4 O6'
_chemical_formula_weight         334.29
_chemical_name_systematic        'theobromine-2,4-dihydroxybenzoic acid'
_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             2019-07-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-03 deposited with the CCDC.	2019-11-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.093(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.9392(3)
_cell_length_b                   6.3569(2)
_cell_length_c                   28.7601(7)
_cell_measurement_reflns_used    2746
_cell_measurement_temperature    132(1)
_cell_measurement_theta_max      74.9190
_cell_measurement_theta_min      5.6550
_cell_volume                     1443.29(8)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      132(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5357
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_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     59.00 109.00   1.00   12.50    --   41.24  57.00  90.00   50
  2  \w     13.00 112.00   1.00   12.50    --   41.24  57.00-150.00   99
  3  \w      3.00  87.00   1.00   12.50    --   41.24-125.00  90.00   84
  4  \w     46.00  77.00   1.00   29.00    --  112.00 -45.00  60.00   31
  5  \w     36.00  88.00   1.00   29.00    --  112.00-111.00  30.00   52
  6  \w     36.00  65.00   1.00   29.00    --  112.00 -30.00  30.00   29
  7  \w     46.00  74.00   1.00   29.00    --  112.00 -45.00  90.00   28
  8  \w     39.00  65.00   1.00   29.00    --  112.00 -30.00   0.00   26
  9  \w     42.00 101.00   1.00   29.00    --  112.00 -94.00  90.00   59
 10  \w     40.00  67.00   1.00   29.00    --  112.00 -45.00 120.00   27
 11  \w    120.00 152.00   1.00   29.00    --  112.00  30.00-120.00   32
 12  \w     50.00  77.00   1.00   29.00    --  112.00 -45.00 -90.00   27
 13  \w     54.00  82.00   1.00   29.00    --  112.00 -77.00 120.00   28
 14  \w    113.00 139.00   1.00   29.00    --  112.00 -77.00 120.00   26
 15  \w     88.00 114.00   1.00   29.00    --  112.00  30.00-120.00   26
 16  \w    109.00 142.00   1.00   29.00    --  112.00 -15.00-150.00   33
 17  \w     45.00 107.00   1.00   29.00    --  112.00-111.00  60.00   62
 18  \w     30.00 105.00   1.00   29.00    --  112.00 -15.00-150.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1893770000
_diffrn_orient_matrix_UB_12      0.0096879000
_diffrn_orient_matrix_UB_13      -0.0073181000
_diffrn_orient_matrix_UB_21      -0.0096113000
_diffrn_orient_matrix_UB_22      -0.2262095000
_diffrn_orient_matrix_UB_23      -0.0193290000
_diffrn_orient_matrix_UB_31      -0.0465081000
_diffrn_orient_matrix_UB_32      0.0862326000
_diffrn_orient_matrix_UB_33      -0.0497330000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0181
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            5993
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.088
_diffrn_reflns_theta_min         3.091
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.049
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73397
_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    1.538
_exptl_crystal_description       plate
_exptl_crystal_F_000             696
_exptl_crystal_preparation
'theobromine and 2,4-dihydroxybenzoic acid in stoichometric ratio (1:1) was dissolved in methanol-water mixture'
_exptl_crystal_recrystallization_method
'cocrystallization by slow evaporation from methanol-water solution'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         2932
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0751P)^2^+0.7315P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1363
_refine_ls_wR_factor_ref         0.1414
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2574
_reflns_number_total             2932
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ce01195a2.cif
_cod_data_source_block           tb-k24dhb-1-1bspr
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               7235246
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C14 H14 N4 O6'
_chemical_oxdiff_usercomment     '131.2 K 0.03x0.07x0.30, sprawdzenie'
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.744
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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. Restrained distances
 O3-H3
 1 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3A), C6(H6), C12(H12)
3.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              79061
_olex2_date_sample_data_collection 2019-03-10
_olex2_exptl_crystal_mounting_method 'crystal was mounted on loop by glue'
_olex2_submission_original_sample_id TBR-24DHBA
_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 1.337
_oxdiff_exptl_absorpt_empirical_full_min 0.702