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_7133654
_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             2024-07-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-08-14 deposited with the CCDC.	2024-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.9430(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.02950(10)
_cell_length_b                   12.38390(10)
_cell_length_c                   16.6344(2)
_cell_measurement_reflns_used    21521
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      79.5070
_cell_measurement_theta_min      3.3270
_cell_volume                     2716.75(5)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(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 0.985
_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      0.1008934000
_diffrn_orient_matrix_UB_12      0.0070204000
_diffrn_orient_matrix_UB_13      0.0754054000
_diffrn_orient_matrix_UB_21      0.0538314000
_diffrn_orient_matrix_UB_22      0.0388931000
_diffrn_orient_matrix_UB_23      -0.0614253000
_diffrn_orient_matrix_UB_31      -0.0237644000
_diffrn_orient_matrix_UB_32      0.1179509000
_diffrn_orient_matrix_UB_33      0.0158224000
_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  0.0460
_diffrn_reflns_av_unetI/netI     0.0309
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_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            35755
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.473
_diffrn_reflns_theta_min         3.351
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.858
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77855
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
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    1.414
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1200
_exptl_crystal_recrystallization_method 'Crystals were grown using DMSO.'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.354
_exptl_crystal_size_min          0.126
_refine_diff_density_max         0.276
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         5862
_refine_ls_number_restraints     360
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0423
_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^)+(0.0685P)^2^+0.7375P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1210
_refine_ls_wR_factor_ref         0.1234
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5411
_reflns_number_total             5862
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc03307h3.cif
_cod_data_source_block           TMA_azo_5_170_00_auto
_cod_depositor_comments
'Adding full bibliography for 7133650--7133654.cif.'
_cod_database_code               7133654
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.725
_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. Uiso/Uaniso restraints and constraints
C24B \\sim C24A \\sim C23B \\sim C23A \\sim C22B \\sim C22A \\sim C21A \\sim
C21B \\sim C20A \\sim C20B \\sim N5B \\sim N5A \\sim N6B \\sim N6A \\sim N7A
\\sim N7B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
3. Rigid body (RIGU) restrains
 N5B, N5A, C20A, C20B, C24B, C24A, C23B, C23A, C22B, C22A, C21B, C21A, N6A,
 N6B, N7B, N7A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C23B)=Sof(H23B)=Sof(C22B)=Sof(C21B)=Sof(H21B)=Sof(C20B)=Sof(H20B)=
 Sof(N5B)=Sof(C24B)=Sof(H24B)=Sof(N7B)=Sof(N6B)=1-FVAR(1)
 Sof(N5A)=Sof(N6A)=Sof(N7A)=Sof(C22A)=Sof(C24A)=Sof(H24A)=Sof(C21A)=Sof(H21A)=
 Sof(C23A)=Sof(H23A)=Sof(C20A)=Sof(H20A)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6A), C4(H4), C26(H26), C28(H28), C27(H27), C24A(H24A), C21A(H21A),
  C13(H13), C23A(H23A), C20A(H20A), C19(H19), C16(H16), C29(H29), C14(H14),
 C10(H10), C11(H11), C17(H17), C18(H18), C23B(H23B), C21B(H21B), C20B(H20B),
 C24B(H24B)
5.b Fitted hexagon refined as free rotating group:
 C23B(C22B,C21B,C20B,N5B,C24B)
5.c Idealised tetrahedral OH refined as rotating group:
 O6(H6), O1(H1), O3(H3)
;
_shelx_res_checksum              79602
_shelx_hkl_checksum              66510
_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 1.336
_oxdiff_exptl_absorpt_empirical_full_min 0.715