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_1573517
_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                 113.63(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.469(14)
_cell_length_b                   4.4857(2)
_cell_length_c                   19.042(4)
_cell_measurement_reflns_used    1908
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      26.5520
_cell_measurement_theta_min      4.6470
_cell_volume                     1288.8(12)
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_pressure         2760000
_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 0.287
_diffrn_measured_fraction_theta_max 0.262
_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     -7.00  57.00   1.00   15.00    --   -0.35 -42.00 179.00   64
  2  \w    -35.00  33.00   1.00   15.00    --   -0.35  42.00 -28.00   68
  3  \w    -25.00  33.00   1.00   20.00    --   28.60  42.00 -28.00   58
  4  \w      3.00  60.00   1.00   20.00    --   28.60 -42.00 179.00   57
  5  \w    -35.00  33.00   1.00   20.00    --  -29.30  42.00 -28.00   68
  6  \w     -7.00  28.00   1.00   20.00    --  -29.30 -42.00 179.00   35
  7  \w     -2.00  57.00   1.00   20.00    --   28.60 -67.00-157.00   59
  8  \w    -17.00  17.00   1.00   20.00    --   28.60  53.00 -17.00   34
  9  \w     -4.00  52.00   1.00   20.00    --   28.60 -53.00  17.00   56
 10  \w    -46.00  11.00   1.00   20.00    --   28.60  37.00-180.00   57
 11  \w    -17.00  17.00   1.00   20.00    --   28.60  53.00 162.00   34
 12  \w     32.00  91.00   1.00   20.00    --   28.60-134.00-123.00   59
 13  \w    -70.00  -1.00   1.00   20.00    --  -29.30  97.00 -35.00   69
 14  \w    -26.00  43.00   1.00   20.00    --  -29.30 -26.00   7.00   69
 15  \w     22.00  48.00   1.00   20.00    --  -29.30-134.00  56.00   26
 16  \w    -22.00  36.00   1.00   20.00    --  -29.30 -39.00-167.00   58
 17  \w    -17.00  16.00   1.00   20.00    --  -29.30 -53.00-162.00   33
 18  \w     22.00  48.00   1.00   20.00    --  -29.30-134.00-123.00   26
 19  \w    -43.00  26.00   1.00   20.00    --  -29.30  26.00 172.00   69
 20  \w     -9.00  17.00   1.00   20.00    --  -29.30 -77.00  30.00   26
 21  \w     61.00  99.00   1.00   15.00    --   -0.35-178.00 -90.00   38
 22  \w     76.00 102.00   1.00   20.00    --   28.60 178.00  90.00   26
 23  \w    -47.00  -8.00   1.00   20.00    --   28.60  19.00-150.00   39
 24  \w    -35.00  26.00   1.00   20.00    --   28.60  26.00  -7.00   61
 25  \w     10.00  34.00   1.00   20.00    --  -29.30-114.00-136.00   24
 26  \w    -17.00  16.00   1.00   20.00    --  -29.30 -53.00  17.00   33
 27  \w    -52.00  17.00   1.00   20.00    --  -29.30  53.00 162.00   69
 28  \w    -52.00 -27.00   1.00   20.00    --  -29.30  53.00 -17.00   25
 29  \w    -47.00  22.00   1.00   20.00    --  -29.30  39.00 -12.00   69
;
_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      -0.0446581000
_diffrn_orient_matrix_UB_12      -0.0256503000
_diffrn_orient_matrix_UB_13      -0.0055752000
_diffrn_orient_matrix_UB_21      -0.0126838000
_diffrn_orient_matrix_UB_22      0.1352048000
_diffrn_orient_matrix_UB_23      -0.0209021000
_diffrn_orient_matrix_UB_31      -0.0072936000
_diffrn_orient_matrix_UB_32      -0.0779375000
_diffrn_orient_matrix_UB_33      -0.0344227000
_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  0.0809
_diffrn_reflns_av_unetI/netI     0.0421
_diffrn_reflns_Laue_measured_fraction_full 0.287
_diffrn_reflns_Laue_measured_fraction_max 0.262
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_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            4834
_diffrn_reflns_point_group_measured_fraction_full 0.287
_diffrn_reflns_point_group_measured_fraction_max 0.262
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.765
_diffrn_reflns_theta_min         4.674
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.113
_exptl_absorpt_correction_T_max  0.996
_exptl_absorpt_correction_T_min  0.995
_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    1.558
_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          0.311
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.305
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     46
_refine_ls_number_reflns         361
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.1295
_refine_ls_R_factor_gt           0.0878
_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^)+(0.1571P)^2^+5.0593P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2301
_refine_ls_wR_factor_ref         0.2812
_reflns_Friedel_coverage         0.000
_reflns_number_gt                229
_reflns_number_total             361
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            yc5049.cif
_cod_data_source_block           ETYSUC_276
_cod_original_cell_volume        1288.7(12)
_cod_database_code               1573517
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C12H12N2, C4O4H6'
_shelx_estimated_absorpt_t_max   0.996
_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-C2
 1.337 with sigma of 0.02
 N1-C6
 1.337 with sigma of 0.02
 O2A-C1A
 1.214 with sigma of 0.02
 O1A-C1A
 1.308 with sigma of 0.02
 C1A-O2A
 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              50743
_shelx_hkl_checksum              2396
_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_280 in I2/a 
REM I2/a (#15 in standard setting)
CELL 0.71073  16.468743   4.485657  19.041734  90.0000 113.6293  90.0000
ZERR    3.00   0.013527   0.000240   0.003714   0.0000   0.0529   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 0.03 0.15 0.31
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 3.73(2) GPa, and then decompressed
down to 2.76(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 10.341
_oxdiff_exptl_absorpt_empirical_full_min 0.519