Switchable colossal anisotropic thermal expansion in a spin crossover framework
Wu, Si-Guo; Cui, Wen; Ruan, Ze-Yu; Ni, Zhao-Ping; Tong, Ming-Liang; Chemical Science 16 (2025) 8845–8852; doi:10.1039/D4SC08032G

data_1574369
_publ_section_title
;
 Switchable colossal anisotropic thermal expansion in a spin crossover
 framework
;
_journal_issue                   20
_journal_name_full               'Chemical Science'
_journal_page_first              8845
_journal_page_last               8852
_journal_paper_doi               10.1039/D4SC08032G
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C14 H9 Au2 Fe N7, C3 H8 O'
_chemical_formula_sum            'C17 H17 Au2 Fe N7 O'
_chemical_formula_weight         785.16
_space_group_crystal_system      orthorhombic
_space_group_IT_number           73
_space_group_name_Hall           '-I 2b 2c'
_space_group_name_H-M_alt        'I b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-12
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-03-17 deposited with the CCDC.	2025-04-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.5562(4)
_cell_length_b                   17.2475(7)
_cell_length_c                   22.9494(6)
_cell_measurement_reflns_used    4148
_cell_measurement_temperature    224.98(10)
_cell_measurement_theta_max      72.3180
_cell_measurement_theta_min      3.8500
_cell_volume                     4574.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (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      224.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.945
_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    -75.00  29.00   0.50    1.50    --  -44.50  88.00 -38.00  208
  2  \w   -173.00-110.00   0.50    3.00    --  -99.00 -44.00 -35.00  126
  3  \w   -144.00 -81.00   0.50    3.00    --  -99.00 -88.00-155.00  126
  4  \w     28.00 106.00   0.50    3.00    --   99.00 -97.00 108.00  156
  5  \w    -29.00   3.00   0.50    1.50    --   44.50 -19.00-150.00   64
  6  \w   -104.00 -26.00   0.50    3.00    --  -99.00  77.00 -60.00  156
  7  \w     28.00  53.00   0.50    3.00    --   99.00 -45.00-120.00   50
;
_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      -0.1197801000
_diffrn_orient_matrix_UB_12      -0.0085267000
_diffrn_orient_matrix_UB_13      -0.0288329000
_diffrn_orient_matrix_UB_21      0.0354839000
_diffrn_orient_matrix_UB_22      -0.0799906000
_diffrn_orient_matrix_UB_23      -0.0240244000
_diffrn_orient_matrix_UB_31      -0.0465191000
_diffrn_orient_matrix_UB_32      -0.0390727000
_diffrn_orient_matrix_UB_33      0.0555733000
_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  0.0196
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            6147
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.563
_diffrn_reflns_theta_min         3.852
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    28.832
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57682
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    2.280
_exptl_crystal_description       block
_exptl_crystal_F_000             2880
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.082
_refine_diff_density_max         1.167
_refine_diff_density_min         -1.172
_refine_diff_density_rms         0.185
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.127
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     174
_refine_ls_number_reflns         2154
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0344
_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^)+(0.0530P)^2^+39.3389P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0965
_refine_ls_wR_factor_ref         0.0979
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2005
_reflns_number_total             2154
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08032g2.cif
_cod_data_source_block           Fe_iPrOH_225K_HS
_cod_depositor_comments
'Adding full bibliography for 1574366--1574373.cif.'
_cod_database_code               1574369
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_hkl
;
01d218ee3dc49bab66eada7ea351470d0d51e1
;
_reflns_odcompleteness_completeness 94.42
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.58
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C10-C9
 1.51 with sigma of 0.02
 C10-O1
 1.42 with sigma of 0.02
 C10-C11
 1.48 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C10 \\sim C11 \\sim C9 \\sim O1: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C14 \\sim C13 \\sim C16 \\sim C15: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C14)=Sof(H14)=Sof(C13)=Sof(H13)=1-FVAR(1)
 Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=FVAR(1)
 Fixed Sof: H4(0.5) N6(0.5) H6A(0.5) H6B(0.5) O1(0.5) H1(0.5) C9(0.5) H9A(0.5)
 H9B(0.5) H9C(0.5) C10(0.5) H10(0.5) C11(0.5) H11A(0.5) H11B(0.5) H11C(0.5)
5.a Ternary CH refined with riding coordinates:
 C10(H10)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C14(H14), C15(H15), C13(H13), C16(H16)
5.c X=CH2 refined with riding coordinates:
 N6(H6A,H6B)
5.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C11(H11A,H11B,H11C)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_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 1.615
_oxdiff_exptl_absorpt_empirical_full_min 0.721