Fundamentally intertwined: anharmonic intermolecular interactions dictate both thermal expansion and terahertz lattice dynamics in molecular crystals.
Juneja, Navkiran; Hastings, Josephine L.; Stoll, William B.; Brennessel, William W.; Zarrella, Salvatore; Sornberger, Parker; Catalano, Luca; Korter, Timothy M.; Ruggiero, Michael T.; Chemical communications (Cambridge, England) 60 (2024) 12169–12172; doi:10.1039/d4cc03307h

data_7133650
_publ_section_title
;
 Fundamentally intertwined: anharmonic intermolecular interactions dictate
 both thermal expansion and terahertz lattice dynamics in molecular
 crystals.
;
_journal_issue                   84
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              12169
_journal_page_last               12172
_journal_paper_doi               10.1039/d4cc03307h
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C9 H6 O6, 2(C10 H8 N4)'
_chemical_formula_sum            'C29 H22 N8 O6'
_chemical_formula_weight         578.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-14 deposited with the CCDC.	2024-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.4010(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.9468(2)
_cell_length_b                   12.38920(10)
_cell_length_c                   16.6087(2)
_cell_measurement_reflns_used    20645
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.7590
_cell_measurement_theta_min      3.5820
_cell_volume                     2689.81(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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   -121.00 -34.00   0.50    0.28    --  -47.28 -24.00 178.00  174
  2  \w    -15.00  27.00   0.50    0.28    --  -47.28  24.00 -16.00   84
  3  \w     35.00 122.00   0.50    0.28    --   47.28  24.00 -16.00  174
  4  \w    -27.00  35.00   0.50    0.28    --   47.28 -24.00 178.00  124
  5  \w   -166.00 -78.00   0.50    1.10    --  -91.75 -24.00 178.00  176
  6  \w    101.00 178.00   0.50    1.10    --  113.25  24.00 -16.00  154
  7  \w    -31.00  26.00   0.50    0.28    --  -47.28  38.00 120.00  114
  8  \w    -10.00  28.00   0.50    0.28    --  -47.28  19.00  30.00   76
  9  \w    -31.00  26.00   0.50    0.28    --  -47.28  38.00 -60.00  114
 10  \w    -86.00 -13.00   0.50    0.28    --  -47.28 125.00-180.00  146
 11  \w    -63.00 -19.00   0.50    1.10    --  -91.75  61.00 150.00   88
 12  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00-180.00   82
 13  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00 -30.00   82
 14  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00-150.00   82
 15  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00 -60.00   82
 16  \w     44.00 111.00   0.50    1.10    --  113.25-125.00 120.00  134
 17  \w     41.00 178.00   0.50    1.10    --  113.25   0.00 120.00  274
 18  \w    101.00 178.00   0.50    1.10    --  113.25  30.00 -90.00  154
 19  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00  30.00   82
 20  \w     42.00 106.00   0.50    1.10    --  113.25 -94.00 120.00  128
 21  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00-120.00   82
 22  \w     44.00 111.00   0.50    1.10    --  113.25-125.00 120.00  134
 23  \w     42.00 106.00   0.50    1.10    --  113.25 -94.00  90.00  128
 24  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00 150.00   82
 25  \w     42.00  83.00   0.50    1.10    --  113.25 -61.00 -90.00   82
 26  \w    101.00 178.00   0.50    1.10    --  113.25  30.00 -60.00  154
 27  \w     42.00 106.00   0.50    1.10    --  113.25 -94.00 -30.00  128
 28  \w     41.00 178.00   0.50    1.10    --  113.25   0.00 -60.00  274
 29  \w     42.00 102.00   0.50    1.10    --  113.25 -94.00-180.00  120
 30  \w     69.00  95.00   0.50    1.10    --  113.25 -94.00 -90.00   52
 31  \w     50.00  77.00   0.50    1.10    --  113.25 -61.00  60.00   54
 32  \w     50.00  83.00   0.50    1.10    --  113.25 -61.00   0.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1013959000
_diffrn_orient_matrix_UB_12      0.0066030000
_diffrn_orient_matrix_UB_13      0.0766955000
_diffrn_orient_matrix_UB_21      0.0550872000
_diffrn_orient_matrix_UB_22      0.0388496000
_diffrn_orient_matrix_UB_23      -0.0605667000
_diffrn_orient_matrix_UB_31      -0.0238327000
_diffrn_orient_matrix_UB_32      0.1179628000
_diffrn_orient_matrix_UB_33      0.0156483000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0526
_diffrn_reflns_av_unetI/netI     0.0311
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            34952
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.121
_diffrn_reflns_theta_min         3.381
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.867
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.458
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_description       Irregular
_exptl_crystal_F_000             1200
_exptl_crystal_recrystallization_method 'Crystals were grown from DMSO'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.354
_exptl_crystal_size_min          0.126
_refine_diff_density_max         0.374
_refine_diff_density_min         -0.309
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     391
_refine_ls_number_reflns         5799
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0494
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0829P)^2^+1.2251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1420
_refine_ls_wR_factor_ref         0.1447
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5352
_reflns_number_total             5799
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc03307h3.cif
_cod_data_source_block           TMA_azo_1_100_00_auto
_cod_depositor_comments
'Adding full bibliography for 7133650--7133654.cif.'
_cod_original_cell_volume        2689.80(6)
_cod_database_code               7133650
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C116  H100  N32  O24  '
_shelx_estimated_absorpt_t_max   0.899
_shelx_estimated_absorpt_t_min   0.723
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6A), C4(H4), C26(H26), C28(H28), C27(H27), C24(H24), C21(H21),
 C13(H13), C23(H23), C20(H20), C19(H19), C16(H16), C29(H29), C14(H14), C10(H10),
  C11(H11), C17(H17), C18(H18)
2.b Idealised tetrahedral OH refined as rotating group:
 O6(H6), O1(H1), O3(H3)
;
_shelx_res_checksum              17996
_shelx_hkl_checksum              58880
_olex2_exptl_crystal_mounting_method
'Crystal was mounted on a 100 um MiTeGen cryoloop'
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.817
_oxdiff_exptl_absorpt_empirical_full_min 0.692