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_1576306
_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(C5 H12 N1 O1)'
_chemical_formula_sum            'C5 H12 I3 N O Pb'
_chemical_formula_weight         690.05
_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             2025-09-26
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-10-06 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                   9.904(3)
_cell_length_b                   9.904(3)
_cell_length_c                   8.060(3)
_cell_measurement_reflns_used    403
_cell_measurement_temperature    393.00(10)
_cell_measurement_theta_max      30.4210
_cell_measurement_theta_min      2.3920
_cell_volume                     684.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (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 2025/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      393.00(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 1.000
_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     -4.00  78.00   0.50    1.00    --    4.83  38.00  30.00  164
  2  \w    -48.00 -23.00   0.50    1.00    --   -5.61 -17.00  48.00   50
  3  \w    -12.00  26.00   0.50    1.00    --    4.83 -99.00 -30.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0817213000
_diffrn_orient_matrix_UB_12      -0.0348913000
_diffrn_orient_matrix_UB_13      0.0121810000
_diffrn_orient_matrix_UB_21      -0.0091412000
_diffrn_orient_matrix_UB_22      -0.0746062000
_diffrn_orient_matrix_UB_23      -0.0150015000
_diffrn_orient_matrix_UB_31      0.0101550000
_diffrn_orient_matrix_UB_32      -0.0079408000
_diffrn_orient_matrix_UB_33      0.0857995000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1715
_diffrn_reflns_av_unetI/netI     0.0775
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            2750
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.964
_diffrn_reflns_theta_max         24.964
_diffrn_reflns_theta_min         2.375
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    19.048
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.18647
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    3.347
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             596
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.530
_refine_diff_density_min         -1.045
_refine_diff_density_rms         0.188
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.143
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     67
_refine_ls_number_reflns         259
_refine_ls_number_restraints     99
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.1575
_refine_ls_R_factor_gt           0.0848
_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^)+(0.0900P)^2^+4.5988P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1988
_refine_ls_wR_factor_ref         0.2551
_reflns_Friedel_coverage         0.000
_reflns_number_gt                103
_reflns_number_total             259
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06333g9.cif
_cod_data_source_block           1-393k
_cod_original_cell_volume        684.7(5)
_cod_database_code               1576306
_shelx_shelxl_version_number     2025/1
_shelx_estimated_absorpt_t_max   0.252
_shelx_estimated_absorpt_t_min   0.191
_exptl_crystal_mounting_method
;
 Crystals were removed from the crystallisation vial and immediately coated
 with PDMS (polydimethylsiloxane/Dimethicone, CAS: 9006-65-9 on a glass slide.
 A suitable single crystal was selected and mounted on a glass fiber using
 vacuum silicone grease as adhesive. The glass fiber with single crystal was
 mounted on copper pin with solid paraffin. Operator: DJ_Tokyo.
;
_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
 C1-N1 = N1-C4
 1.47 with sigma of 0.005
 C4-C3 = C3-C2 = C2-C1 = C5-C1
 1.54 with sigma of 0.005
 O1-C5
 1.43 with sigma of 0.005
 C1-C3 = C2-C4 = C2-C5
 2.515 with sigma of 0.01
 N1-C3 = N1-C2 = N1-C5
 2.458 with sigma of 0.01
 C1-C4
 2.401 with sigma of 0.01
 C1-O1
 2.426 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C3 \\sim C2 \\sim C1 \\sim C5 \\sim C4 \\sim O1 \\sim N1: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C3) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(O1) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: C2(0.08333) H2A(0.08333) H2B(0.08333) C1(0.08333) H1(0.08333)
 C5(0.08333) H5A(0.08333) H5B(0.08333) O1(0.08333) H1A(0.08333) C4(0.08333)
 H4A(0.08333) H4B(0.08333) C3(0.08333) H3A(0.08333) H3B(0.08333) N1(0.08333)
 H1B(0.08333) H1C(0.08333)
 Fixed Y: C2(0.38595) C4(0.39733) C3(0.3737)
5.a Riding coordinates:
 O1(H1A)
5.b Ternary CH refined with riding coordinates:
 C1(H1)
5.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B), C4(H4A,H4B), C3(H3A,H3B), N1(H1B,H1C)
;
_shelx_res_checksum              47009
_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 2.431
_oxdiff_exptl_absorpt_empirical_full_min 0.598