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_1574370
_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 N7 Zn, C3 H8 O'
_chemical_formula_sum            'C17 H17 Au2 N7 O Zn'
_chemical_formula_weight         794.68
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-17
_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                   11.96862(20)
_cell_length_b                   16.9470(3)
_cell_length_c                   22.7781(3)
_cell_measurement_reflns_used    7553
_cell_measurement_temperature    299.99(10)
_cell_measurement_theta_max      74.9570
_cell_measurement_theta_min      5.2140
_cell_volume                     4620.13(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.95a 64-bit (release 03-11-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (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  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      299.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.957
_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     20.00 118.00   0.50    0.09    --   44.96  74.00  55.00  196
  2  \w     20.00 118.00   0.50    0.09    --   44.96  74.00  55.00  196
  3  \w     33.00  98.00   0.50    0.37    --  105.85 -74.00 -72.00  130
  4  \w     38.00  71.00   0.50    0.37    --  105.85 -61.00-180.00   66
  5  \w     41.00  73.00   0.50    0.37    --  105.85 -61.00-150.00   64
  6  \w     34.00  73.00   0.50    0.37    --  105.85 -61.00 -30.00   78
  7  \w     44.00  70.00   0.50    0.37    --  105.85 -61.00   0.00   52
  8  \w     39.00 106.00   0.50    0.37    --  105.85 -94.00 -60.00  134
  9  \w    -24.00  33.00   0.50    0.09    --  -44.96  19.00  60.00  114
 10  \w    -24.00  33.00   0.50    0.09    --  -44.96  19.00 -60.00  114
 11  \w    -24.00  33.00   0.50    0.09    --  -44.96  19.00-150.00  114
 12  \w    -74.00 -26.00   0.50    0.37    -- -100.00  64.00 -69.00   96
 13  \w   -156.00 -84.00   0.50    0.37    -- -100.00 -61.00 120.00  144
 14  \w   -173.00 -79.50   0.50    0.37    -- -100.00 -84.00  43.00  187
;
_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      0.0713813000
_diffrn_orient_matrix_UB_12      -0.0735235000
_diffrn_orient_matrix_UB_13      0.0131607000
_diffrn_orient_matrix_UB_21      0.0634614000
_diffrn_orient_matrix_UB_22      0.0118986000
_diffrn_orient_matrix_UB_23      -0.0582084000
_diffrn_orient_matrix_UB_31      0.0863083000
_diffrn_orient_matrix_UB_32      0.0520808000
_diffrn_orient_matrix_UB_33      0.0318432000
_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  0.0476
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11328
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.518
_diffrn_reflns_theta_min         3.881
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    24.786
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.23700
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.285
_exptl_crystal_description       block
_exptl_crystal_F_000             2912
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.153
_refine_diff_density_min         -1.848
_refine_diff_density_rms         0.264
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2305
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.178
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0635P)^2^+26.2954P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1174
_refine_ls_wR_factor_ref         0.1199
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2109
_reflns_number_total             2305
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08032g2.cif
_cod_data_source_block           Zn_iPrOH_300K
_cod_depositor_comments
'Adding full bibliography for 1574366--1574373.cif.'
_cod_database_code               1574370
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Zn Au'
_chemical_oxdiff_usercomment     'C H N O'
_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
Uanis(C2) \\sim Ueq, Uanis(C7B) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(C8A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C8B)=Sof(H8B)=Sof(C7B)=Sof(H7B)=1-FVAR(1)
 Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=FVAR(1)
 Fixed Sof: H4(0.5) N5(0.5) H5A(0.5) H5B(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 Riding coordinates:
 O1(H1), C11(H11A,H11B,H11C)
5.b Ternary CH refined with riding coordinates:
 C10(H10)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7A(H7A), C8A(H8A), C8B(H8B), C7B(H7B)
5.d X=CH2 refined with riding coordinates:
 N5(H5A,H5B)
5.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_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 2.405
_oxdiff_exptl_absorpt_empirical_full_min 0.634