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_7235241
_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, H2 O'
_chemical_formula_sum            'C14 H16 N4 O7'
_chemical_formula_weight         352.31
_chemical_name_systematic
'theobromine-2,3-dihydroxybenzoic acid monohydrate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 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                 106.180(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.2358(3)
_cell_length_b                   15.2794(2)
_cell_length_c                   7.8074(2)
_cell_measurement_reflns_used    6522
_cell_measurement_temperature    132(2)
_cell_measurement_theta_max      75.5370
_cell_measurement_theta_min      4.4910
_cell_volume                     1516.39(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 (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(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5357
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_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   -113.00 -13.00   1.00    1.50    --  -41.24 -57.00  30.00  100
  2  \w    -69.00  32.00   1.00    1.50    --  -41.24  57.00-180.00  101
  3  \w    -66.00  33.00   1.00    1.50    --  -41.24  37.00 -30.00   99
  4  \w      2.00  97.00   1.00    1.50    --   41.24-125.00   0.00   95
  5  \w      2.00  97.00   1.00    1.50    --   41.24-125.00-120.00   95
  6  \w     39.00  77.00   1.00    4.75    --  112.00 -45.00-150.00   38
  7  \w     36.00 113.00   1.00    4.75    --  112.00-111.00 -90.00   77
  8  \w     36.00 145.00   1.00    4.75    --  112.00 -77.00  90.00  109
  9  \w     36.00 113.00   1.00    4.75    --  112.00-111.00  60.00   77
 10  \w     36.00  69.00   1.00    4.75    --  112.00 -30.00  60.00   33
 11  \w     29.00 110.00   1.00    4.75    --  112.00 -94.00  90.00   81
 12  \w     39.00  77.00   1.00    4.75    --  112.00 -45.00 120.00   38
 13  \w     36.00  69.00   1.00    4.75    --  112.00 -30.00  30.00   33
 14  \w     39.00  77.00   1.00    4.75    --  112.00 -45.00 -90.00   38
 15  \w     83.00 158.00   1.00    4.75    --  112.00  61.00 -60.00   75
 16  \w     36.00 113.00   1.00    4.75    --  112.00-111.00 -30.00   77
 17  \w     79.00 158.00   1.00    4.75    --  112.00 111.00-180.00   79
 18  \w     36.00  69.00   1.00    4.75    --  112.00 -30.00-120.00   33
 19  \w     36.00  69.00   1.00    4.75    --  112.00 -30.00 150.00   33
 20  \w     24.00 158.00   1.00    4.75    --  112.00   0.00   0.00  134
 21  \w     36.00 113.00   1.00    4.75    --  112.00-111.00  90.00   77
 22  \w     39.00  77.00   1.00    4.75    --  112.00 -45.00  90.00   38
 23  \w     83.00 158.00   1.00    4.75    --  112.00  61.00   0.00   75
 24  \w     72.00 112.00   1.00    4.75    --  112.00-111.00-120.00   40
 25  \w     70.00 113.00   1.00    4.75    --  112.00-111.00  30.00   43
 26  \w     37.00 107.00   1.00    4.75    --  112.00-111.00 -60.00   70
 27  \w     58.00  83.00   1.00    4.75    --  112.00-111.00   0.00   25
 28  \w     36.00  56.00   1.00    4.75    --  112.00 -30.00   0.00   20
;
_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      -0.0455255000
_diffrn_orient_matrix_UB_12      0.0193768000
_diffrn_orient_matrix_UB_13      0.1574727000
_diffrn_orient_matrix_UB_21      -0.1067395000
_diffrn_orient_matrix_UB_22      -0.0382169000
_diffrn_orient_matrix_UB_23      -0.1066693000
_diffrn_orient_matrix_UB_31      0.0349734000
_diffrn_orient_matrix_UB_32      -0.0912248000
_diffrn_orient_matrix_UB_33      0.0778867000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0167
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            7869
_diffrn_reflns_point_group_measured_fraction_full 0.907
_diffrn_reflns_point_group_measured_fraction_max 0.898
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.883
_diffrn_reflns_theta_min         4.525
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90850
_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    1.543
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_preparation
'Stoichometric ratio of thebromine and 2,3-dihydroxybenzoic acid (1:1) was dissolved in methanol-water solution'
_exptl_crystal_recrystallization_method
'cocrystallization from methanol-water mixture (v/v 1:1) by slow evaporation'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1245 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     252
_refine_ls_number_reflns         2847
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0261
_refine_ls_R_factor_gt           0.0260
_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^)+(0.0499P)^2^+0.3660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0728
_refine_ls_wR_factor_ref         0.0730
_reflns_Friedel_coverage         0.801
_reflns_Friedel_fraction_full    0.816
_reflns_Friedel_fraction_max     0.801
_reflns_number_gt                2834
_reflns_number_total             2847
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ce01195a2.cif
_cod_data_source_block           tb-23dhb-wat-1-1a
_cod_original_sg_symbol_H-M      Cc
_cod_database_code               7235241
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C14 H16 N4 O7'
_chemical_oxdiff_usercomment     '130 K, all of sphere'
_shelx_estimated_absorpt_t_max   0.855
_shelx_estimated_absorpt_t_min   0.767
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C12(H12), C6(H6), C4(H4a)
2.b Idealised Me refined as rotating group:
 C14(H14a,H14b,H14c), C13(H13a,H13b,H13c)
;
_shelx_res_checksum              67445
_olex2_date_sample_data_collection 2019-03-27
_olex2_exptl_crystal_mounting_method 'crystal was mounted on loop by glue'
_olex2_submission_original_sample_id TBR-23DHBA-WAT
_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 1.229
_oxdiff_exptl_absorpt_empirical_full_min 0.876