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_1573524
_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
_audit_creation_date             2023-08-24
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_cell_angle_alpha                90
_cell_angle_beta                 114.0(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.44(9)
_cell_length_b                   4.4104(11)
_cell_length_c                   18.97(3)
_cell_measurement_reflns_used    540
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      23.9380
_cell_measurement_theta_min      2.3120
_cell_volume                     1257(8)
_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)'
_diffrn_ambient_pressure         3470000
_diffrn_ambient_temperature      295(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0169
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.244
_diffrn_measured_fraction_theta_max 0.224
_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    -52.00  27.00   1.00   35.00    --  -26.40  39.00 -12.00   79
  2  \w    -16.00  17.00   1.00   35.00    --  -26.40 -67.00  23.00   33
  3  \w    -38.00  -9.00   1.00   35.00    --  -26.40  77.00 150.00   29
  4  \w    -32.00  47.00   1.00   35.00    --  -26.40 -26.00-171.00   79
  5  \w    -97.00 -18.00   1.00   35.00    --  -26.40 135.00 -57.00   79
  6  \w     -4.00  17.00   1.00   35.00    --  -26.40 -57.00-150.00   21
  7  \w    -27.00  39.00   1.00   35.00    --  -26.40 -39.00  12.00   66
  8  \w      5.00  37.00   1.00   35.00    --  -26.40-114.00-135.00   32
  9  \w      5.00  37.00   1.00   35.00    --  -26.40-114.00  45.00   32
 10  \w    -38.00  27.00   1.00   35.00    --   27.26  39.00 -12.00   65
 11  \w    -22.00  52.00   1.00   35.00    --   27.26 -39.00  12.00   74
 12  \w    -14.00  52.00   1.00   35.00    --   27.26 -39.00-167.00   66
 13  \w   -112.00 -68.00   1.00   35.00    --  -26.40 178.00  90.00   44
 14  \w    -63.00  -2.00   1.00   35.00    --  -26.40  67.00 157.00   61
 15  \w    -18.00  22.00   1.00   35.00    --   27.26  53.00 -17.00   40
 16  \w    -29.00   4.00   1.00   35.00    --   27.26  97.00 143.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0467288000
_diffrn_orient_matrix_UB_12      -0.0176020000
_diffrn_orient_matrix_UB_13      0.0114898000
_diffrn_orient_matrix_UB_21      0.0075969000
_diffrn_orient_matrix_UB_22      0.1387372000
_diffrn_orient_matrix_UB_23      0.0204307000
_diffrn_orient_matrix_UB_31      0.0030787000
_diffrn_orient_matrix_UB_32      -0.0785584000
_diffrn_orient_matrix_UB_33      0.0335243000
_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  0.0945
_diffrn_reflns_av_unetI/netI     0.0950
_diffrn_reflns_Laue_measured_fraction_full 0.244
_diffrn_reflns_Laue_measured_fraction_max 0.224
_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            1431
_diffrn_reflns_point_group_measured_fraction_full 0.244
_diffrn_reflns_point_group_measured_fraction_max 0.224
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.304
_diffrn_reflns_theta_min         2.351
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.116
_exptl_absorpt_correction_T_max  0.998
_exptl_absorpt_correction_T_min  0.998
_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    1.598
_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          0.19
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     46
_refine_ls_number_reflns         289
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.1214
_refine_ls_R_factor_gt           0.0663
_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^)+(0.0916P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1559
_refine_ls_wR_factor_ref         0.1866
_reflns_Friedel_coverage         0.000
_reflns_number_gt                181
_reflns_number_total             289
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            yc5049.cif
_cod_data_source_block           ETYSUC_347
_cod_original_cell_volume        1256(8)
_cod_database_code               1573524
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C4O4H6, N2C12H12'
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.978
_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-C2
 1.337 with sigma of 0.02
 O1A-C1A
 1.308 with sigma of 0.02
 N1-C6
 1.337 with sigma of 0.02
 O2A-C1A
 1.214 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              22418
_shelx_hkl_checksum              54326
_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_347_2 in I2/a 
REM I2/a (#15 in standard setting)
CELL 0.71073  16.439978   4.410407  18.973588  90.0000 114.0318  90.0000
ZERR    3.00   0.093434   0.001109   0.030845   0.0000   0.4070   0.0000
LATT  2
SYMM -x+1/2, y,-z 
SFAC C H N O
UNIT 48.00 54.00 6.00 12.00
SIZE 0.02 0.09 0.19
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 3.47(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 2.211
_oxdiff_exptl_absorpt_empirical_full_min 0.494