Managing negative linear compressibility and thermal expansion through steric hindrance: a case study of 1,2-bis(4'-pyridyl)ethane cocrystals.
Patyk-Kaźmierczak, Ewa; Szymańska, Kornelia; Kaźmierczak, Michał; IUCrJ 12 (2025) –; doi:10.1107/S2052252524011734

data_1573496
_publ_section_title
;
 Managing negative linear compressibility and thermal expansion through
 steric hindrance: a case study of 1,2-bis(4'-pyridyl)ethane cocrystals.
;
_journal_issue                   1
_journal_name_full               IUCrJ
_journal_paper_doi               10.1107/S2052252524011734
_journal_volume                  12
_journal_year                    2025
_chemical_formula_moiety         'C12 H12 N2, C4 H6 O4'
_chemical_formula_sum            'C16 H18 N2 O4'
_chemical_formula_weight         302.32
_chemical_name_systematic        '4,4'-Ethane-1,2-diyldipyridine succinic acid'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-08-21
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.32(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.60(4)
_cell_length_b                   4.7781(4)
_cell_length_c                   19.218(9)
_cell_measurement_reflns_used    682
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      19.6910
_cell_measurement_theta_min      4.3320
_cell_volume                     1429(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (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 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_pressure         640000
_diffrn_ambient_temperature      295(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1544
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.215
_diffrn_measured_fraction_theta_max 0.206
_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    -27.00  46.00   1.00   30.00    --   -0.27  45.00 -43.00   73
  2  \w    -19.00  46.00   1.00   30.00    --   26.72  45.00 -43.00   65
  3  \w    -27.00  46.00   1.00   30.00    --  -27.26  45.00 -43.00   73
  4  \w    -99.00 -69.00   1.00   30.00    --   -0.27 178.00 120.00   30
  5  \w     -4.00  56.00   1.00   30.00    --   -0.27 -97.00  35.00   60
  6  \w     65.00 111.00   1.00   30.00    --   26.72 178.00 -90.00   46
  7  \w     -9.00  62.00   1.00   30.00    --   26.72 -67.00-157.00   71
  8  \w    -39.00   9.00   1.00   30.00    --   26.72   0.00-150.00   48
  9  \w     13.00  84.00   1.00   30.00    --   26.72-114.00  44.00   71
 10  \w      9.00  38.00   1.00   30.00    --   26.72 -77.00  30.00   29
 11  \w    -31.00  48.00   1.00   30.00    --  -27.26 -26.00   7.00   79
 12  \w    -38.00  -9.00   1.00   30.00    --  -27.26  77.00 -30.00   29
 13  \w    -39.00   9.00   1.00   30.00    --  -27.26   0.00-150.00   48
 14  \w     -4.00  16.00   1.00   30.00    --  -27.26 -57.00   0.00   20
 15  \w     29.00  57.00   1.00   30.00    --   -0.27 -99.00-150.00   28
 16  \w     59.00  99.00   1.00   30.00    --   -0.27 178.00-120.00   40
 17  \w     -4.00  18.00   1.00   30.00    --   26.72 -57.00  60.00   22
 18  \w    -35.00 -15.00   1.00   30.00    --   26.72  37.00   0.00   20
 19  \w    -52.00  -6.00   1.00   30.00    --  -27.26  19.00-180.00   46
 20  \w     17.00  50.00   1.00   30.00    --  -27.26-134.00  56.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0453120000
_diffrn_orient_matrix_UB_12      -0.0082602000
_diffrn_orient_matrix_UB_13      0.0108914000
_diffrn_orient_matrix_UB_21      0.0039149000
_diffrn_orient_matrix_UB_22      0.1298275000
_diffrn_orient_matrix_UB_23      0.0188555000
_diffrn_orient_matrix_UB_31      0.0016571000
_diffrn_orient_matrix_UB_32      -0.0717000000
_diffrn_orient_matrix_UB_33      0.0328038000
_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  0.0886
_diffrn_reflns_av_unetI/netI     0.0843
_diffrn_reflns_Laue_measured_fraction_full 0.215
_diffrn_reflns_Laue_measured_fraction_max 0.206
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            1787
_diffrn_reflns_point_group_measured_fraction_full 0.215
_diffrn_reflns_point_group_measured_fraction_max 0.206
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.813
_diffrn_reflns_theta_min         4.369
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.102
_exptl_absorpt_correction_T_max  0.997
_exptl_absorpt_correction_T_min  0.996
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model (Absorb Angel (2004) J. Appl. Cryst. 37:486-492)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       plate
_exptl_crystal_F_000             640
_exptl_crystal_recrystallization_method
; Single crystals were grown by slow evaporation of a solution obtained 
dissolving 4,4'-ethane-1,2-diyldipyridine and succinic acid in 1:1 mol
ratio in hot methanol 99.8%.
;
_exptl_crystal_size_max          0.345
_exptl_crystal_size_mid          0.161
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.170
_refine_diff_density_min         -0.212
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     46
_refine_ls_number_reflns         283
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.1430
_refine_ls_R_factor_gt           0.0799
_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^)+(0.1079P)^2^+4.6707P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1933
_refine_ls_wR_factor_ref         0.2267
_reflns_Friedel_coverage         0.000
_reflns_number_gt                167
_reflns_number_total             283
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            yc5049.cif
_cod_data_source_block           ETYSUC_064
_cod_database_code               1573496
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C4H6O4, C10H12N2'
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.966
_exptl_oxdiff_absorpt_process_details
;
Gaussian integration over a grid
of 16 x 16 x 16 points =  4096 total grid points
  Based upon method of Burnham (1966)
;
_diffrn_ambient_pressure_su      20000
_diffrn_orient_matrix_axis[1]    matrixX
_diffrn_orient_matrix_axis[2]    matrixY
_diffrn_orient_matrix_axis[3]    matrixZ
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 N1-C6
 1.337 with sigma of 0.02
 C1A-O1A
 1.308 with sigma of 0.02
 N1-C2
 1.337 with sigma of 0.02
 C4-C3
 1.379 with sigma of 0.02
 C2-C3
 1.379 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C7(H7A,H7B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6)
3.c Idealised tetrahedral OH refined as rotating group:
 O1A(H1A)
;
_shelx_res_checksum              79730
_shelx_hkl_checksum              75721
_hp_anvil_anvil_thickness        1.95
_hp_anvil_material               diamond
_hp_cell_type                    'Diamond anvil cell'
_hp_open_angle                   30.00
_ins_header
;
TITL ETYSUC_064_1 in I2/a 
REM I2/a (#15 in standard setting)
CELL 0.71073  16.599761   4.778052  19.218345  90.0000 110.3147  90.0000
ZERR    4.00   0.037450   0.000408   0.009077   0.0000   0.1351   0.0000
LATT  2
SYMM -x+1/2, y,-z 
SFAC C H N O
UNIT 56.00 72.00 8.00 16.00
SIZE 0.03 0.16 0.34
TREF
HKLF 4
END
;
_olex2_exptl_crystal_mounting_method
;Single crystal grown at ambient conditions was mounted in Merrill-Bassett
diamond anvil cell and compressed to 0.64(2) GPa. Daphne oil 7575 was 
used as hydrostatic medium.
;
_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 1.926
_oxdiff_exptl_absorpt_empirical_full_min 0.626