[2 + 2] Photocyclization converts thermally induced spin crossover effect into “hidden hysteresis” one
Kaźmierczak, Marcin; Weselski, Marek; Siczek, Miłosz; Wolny, Juliusz A.; Schünemann, Volker; Bronisz, Robert; Chemical Science 16 (2025) 7884–7893; doi:10.1039/D4SC05587J

data_1574231
_publ_section_title
;
 [2 + 2] Photocyclization converts thermally induced spin crossover effect
 into &#x201C;hidden hysteresis&#x201D; one
;
_journal_issue                   18
_journal_name_full               'Chemical Science'
_journal_page_first              7884
_journal_page_last               7893
_journal_paper_doi               10.1039/D4SC05587J
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C66 H48 Fe N24 O12, 2(B F4), 4(C2 H3 N)'
_chemical_formula_sum            'C74 H60 B2 F8 Fe N28 O12'
_chemical_formula_weight         1762.97
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-04-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-06-13 deposited with the CCDC.	2025-03-25 downloaded from the CCDC.
;
_cell_angle_alpha                81.53(3)
_cell_angle_beta                 82.54(3)
_cell_angle_gamma                68.41(2)
_cell_formula_units_Z            1
_cell_length_a                   10.710(2)
_cell_length_b                   12.918(3)
_cell_length_c                   14.735(4)
_cell_measurement_reflns_used    23625
_cell_measurement_temperature    80(2)
_cell_measurement_theta_max      49.4980
_cell_measurement_theta_min      2.0190
_cell_volume                     1868.6(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      80(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.975
_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     15.00  41.00   0.50    1.00    --    0.06  35.00-109.73   52
  2  \w     15.00  40.00   0.50    1.00    --    0.06  35.00 -86.08   50
  3  \w    -14.00  15.00   0.50    1.00    --   28.00 -32.00-132.79   58
  4  \w    -13.00  13.00   0.50    1.00    --   28.00 -32.00 -29.57   52
  5  \w    -16.00  13.00   0.50    1.00    --   24.00 -26.00  -1.90   58
  6  \w    -12.00  14.00   0.50    1.00    --   28.00 -32.00  25.96   52
  7  \w    -10.00  20.00   0.50    1.00    --   32.00 -32.00  65.88   60
  8  \w    -17.00  11.00   0.50    1.00    --  -32.00  32.00 -38.09   56
  9  \w    -29.00  -3.00   0.50    1.00    --  -16.00 111.00 -98.81   52
 10  \w    -40.00 -14.00   0.50    1.00    --  -20.00 124.00-149.52   52
 11  \w    -46.00 -20.00   0.50    1.00    --  -16.00 136.00 -41.96   52
 12  \w    -28.00  -3.00   0.50    1.00    --  -16.00 109.00  22.16   50
 13  \w    -47.00  19.00   0.50    1.00    --   -8.00 -10.00 114.34  132
;
_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      0.0090961000
_diffrn_orient_matrix_UB_12      0.0153627000
_diffrn_orient_matrix_UB_13      0.0422651000
_diffrn_orient_matrix_UB_21      0.0659354000
_diffrn_orient_matrix_UB_22      -0.0023941000
_diffrn_orient_matrix_UB_23      -0.0170900000
_diffrn_orient_matrix_UB_31      -0.0260253000
_diffrn_orient_matrix_UB_32      0.0573274000
_diffrn_orient_matrix_UB_33      -0.0175008000
_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  0.0277
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            29594
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.999
_diffrn_reflns_theta_min         2.052
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.306
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.643
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_density_diffrn    1.567
_exptl_crystal_description       plate
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.323
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.061
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     595
_refine_ls_number_reflns         10627
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0397P)^2^+0.7407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0885
_refine_ls_wR_factor_ref         0.0918
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9064
_reflns_number_total             10627
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05587j10.cif
_cod_data_source_block           206b29_mo_12_80_00
_cod_depositor_comments
'Adding full bibliography for 1574226--1574232.cif.'
_cod_original_cell_volume        1868.56(6)
_cod_database_code               1574231
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C74H60B2F8FeN28O12
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.907
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(F3A)=Sof(F2A)=Sof(F4A)=1-FVAR(1)
 Sof(F2)=Sof(F3)=Sof(F4)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C21(H21A,H21B), C32(H32A,H32B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17), C19(H19), C22(H22), C24(H24), C25(H25), C27(H27), C28(H28),
  C30(H30), C33(H33)
3.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              56345
_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 2.377
_oxdiff_exptl_absorpt_empirical_full_min 0.429