Organic cation conformational flexibility governs mechanical response in organic-inorganic hybrid materials.
Yang, Ya-Wen; Xu, Ke; Zhou, Zi-Ning; Jin, Ming-Liang; Tsunashima, Ryo; Nakamura, Takayoshi; Chai, Chao-Yang; Ye, Qiong; Chemical science  (2025) –; doi:10.1039/d5sc06333g

data_1576307
_publ_section_title
;
 Organic cation conformational flexibility governs mechanical response in
 organic-inorganic hybrid materials.
;
_journal_name_full               'Chemical science'
_journal_paper_doi               10.1039/d5sc06333g
_journal_year                    2025
_chemical_formula_moiety         'I3 Pb1, 1(C6 H14 N1 O1)'
_chemical_formula_sum            'C6 H14 I3 N O Pb'
_chemical_formula_weight         704.07
_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_Hall           '-P 6c 2c'
_space_group_name_H-M_alt        'P 63/m m c'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-01-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-07-28 deposited with the CCDC.	2025-11-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   10.281(4)
_cell_length_b                   10.281(4)
_cell_length_c                   8.133(2)
_cell_measurement_reflns_used    419
_cell_measurement_temperature    440.00(10)
_cell_measurement_theta_max      71.4400
_cell_measurement_theta_min      7.3830
_cell_volume                     744.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.129a 64-bit (release 29-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      440.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.966
_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     32.00  91.00   0.50    0.60    --   86.44-111.00-180.00  118
  2  \w     18.00  68.00   0.50    0.60    --   58.44 -79.00-158.00  100
  3  \w     40.00  76.00   0.50    0.60    --   86.44 -77.00-120.00   72
  4  \w     49.00  74.00   0.50    0.60    --   93.56 -85.00  94.00   50
  5  \w     44.00  69.00   0.50    0.60    --   93.56 -77.00  30.00   50
  6  \w     39.00  89.00   0.50    0.60    --   86.44 -93.00 -47.00  100
  7  \w      4.00  32.00   0.50    0.60    --   58.44 -45.00-120.00   56
  8  \w     89.00 137.00   0.50    0.60    --   86.44  63.00-152.00   96
  9  \w    104.00 129.00   0.50    0.60    --   93.56 111.00 -30.00   50
 10  \w    102.00 127.00   0.50    0.60    --   93.56 111.00  60.00   50
 11  \w    -47.00 -22.00   0.50    0.60    --  -77.03  61.00 120.00   50
 12  \w    -74.00 -36.00   0.50    0.60    --  -77.03  93.00  63.00   76
 13  \w    -23.00   2.00   0.50    0.60    --  -59.02  45.00 150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1365865000
_diffrn_orient_matrix_UB_12      0.0223097000
_diffrn_orient_matrix_UB_13      -0.0193055000
_diffrn_orient_matrix_UB_21      0.0679987000
_diffrn_orient_matrix_UB_22      0.0892614000
_diffrn_orient_matrix_UB_23      -0.1597808000
_diffrn_orient_matrix_UB_31      -0.0815607000
_diffrn_orient_matrix_UB_32      -0.1463272000
_diffrn_orient_matrix_UB_33      -0.1001739000
_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  0.1200
_diffrn_reflns_av_unetI/netI     0.0911
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            2104
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.675
_diffrn_reflns_theta_min         4.967
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    70.634
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.13045
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.129a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    3.141
_exptl_crystal_description       block
_exptl_crystal_F_000             612
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.972
_refine_diff_density_min         -0.597
_refine_diff_density_rms         0.211
_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     79
_refine_ls_number_reflns         310
_refine_ls_number_restraints     113
_refine_ls_restrained_S_all      0.925
_refine_ls_R_factor_all          0.1499
_refine_ls_R_factor_gt           0.0978
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2776
_refine_ls_wR_factor_ref         0.3689
_reflns_Friedel_coverage         0.000
_reflns_number_gt                110
_reflns_number_total             310
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06333g9.cif
_cod_data_source_block           2-rac_CCDC1
_cod_original_cell_volume        744.5(6)
_cod_database_code               1576307
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O Pb I '
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 C6-N1 = N1-C2
 1.47 with sigma of 0.01
 O1-C1
 1.43 with sigma of 0.01
 C1-C2 = C3-C2 = C4-C3 = C5-C4 = C6-C5
 1.54 with sigma of 0.01
 C6-C2
 2.401 with sigma of 0.02
 N1-C1 = N1-C3 = N1-C5
 2.458 with sigma of 0.02
 C2-O1
 2.426 with sigma of 0.02
 C1-C3 = C2-C4 = C3-C5 = C4-C6
 2.515 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C5 \\sim C2 \\sim C6 \\sim C3 \\sim C1 \\sim C4 \\sim N1 \\sim O1: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C5) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C1) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(O1)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: C5(0.08333) H5A(0.08333) H5B(0.08333) N1(0.08333) H1A(0.08333)
 H1B(0.08333) C2(0.08333) H2(0.08333) C6(0.08333) H6A(0.08333) H6B(0.08333)
 C3(0.08333) H3A(0.08333) H3B(0.08333) C1(0.08333) H1C(0.08333) H1D(0.08333)
 O1(0.08333) H1(0.08333) C4(0.08333) H4A(0.08333) H4B(0.08333)
5.a Riding coordinates:
 O1(H1)
5.b Ternary CH refined with riding coordinates:
 C2(H2)
5.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), N1(H1A,H1B), C6(H6A,H6B), C3(H3A,H3B), C1(H1C,H1D), C4(H4A,H4B)
;
_shelx_res_checksum              74386
_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 7.292
_oxdiff_exptl_absorpt_empirical_full_min 0.160