Hidden spin state accessed by light irradiation in an iron(III) high-spin complex.
Zenno, Hikaru; Hieda, Rui; Nakao, Ryosuke; Sekine, Yoshihiro; Hayami, Shinya; Dalton transactions (Cambridge, England : 2003) 54 (2025) 13426–13430; doi:10.1039/d5dt01604e

data_7719302
_publ_section_title
;
 Hidden spin state accessed by light irradiation in an iron(III) high-spin
 complex.
;
_journal_issue                   36
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13426
_journal_page_last               13430
_journal_paper_doi               10.1039/d5dt01604e
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C32 H22 Fe N4 O2, Cl, H2 O, C H3 O'
_chemical_formula_sum            'C33 H27 Cl Fe N4 O4'
_chemical_formula_weight         635.912
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-11-24 deposited with the CCDC.	2025-08-21 downloaded from the CCDC.
;
_cell_angle_alpha                92.724(2)
_cell_angle_beta                 103.828(2)
_cell_angle_gamma                110.816(2)
_cell_formula_units_Z            2
_cell_length_a                   8.7901(2)
_cell_length_b                   11.2361(2)
_cell_length_c                   15.8049(3)
_cell_measurement_reflns_used    7488
_cell_measurement_temperature    100
_cell_measurement_theta_max      74.8120
_cell_measurement_theta_min      2.9100
_cell_volume                     1401.64(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9922
_diffrn_measured_fraction_theta_max 0.9922
_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     35.00  97.00   0.50    0.07    --   44.46-139.00 151.00  124
  2  \w     73.00 107.00   0.50    0.29    --  107.00-139.00 151.00   68
  3  \w     45.00  70.00   0.50    0.29    --  107.00-131.00 -33.00   50
  4  \w     53.00  92.00   0.50    0.29    --  107.00 -94.00   0.00   78
  5  \w     35.00  91.00   0.50    0.29    --  107.00 -94.00 -30.00  112
  6  \w     34.00  91.00   0.50    0.29    --  107.00 -94.00 -60.00  114
  7  \w     33.00  91.00   0.50    0.29    --  107.00 -94.00-120.00  116
  8  \w     46.00  78.00   0.50    0.29    --  107.00 -94.00-180.00   64
  9  \w     65.00  92.00   0.50    0.29    --  107.00 -94.00-150.00   54
 10  \w     67.00  92.00   0.50    0.29    --  107.00 -92.00-175.53   50
 11  \w     67.00  92.00   0.50    0.29    --  107.00 -94.00 -90.00   50
 12  \w     56.00  86.00   0.50    0.07    --   44.46-131.00 -33.00   60
 13  \w     37.00  92.00   0.50    0.29    --  107.00 -94.00  30.00  110
 14  \w     33.00  92.00   0.50    0.29    --  107.00 -94.00 150.00  118
 15  \w     99.00 166.00   0.50    0.29    --  107.00  30.00  60.00  134
 16  \w    103.00 138.00   0.50    0.29    --  107.00  15.00  30.00   70
 17  \w    102.00 132.00   0.50    0.29    --  107.00  15.00 -30.00   60
 18  \w    100.00 166.00   0.50    0.29    --  107.00  30.00-150.00  132
 19  \w    100.00 127.00   0.50    0.29    --  107.00 139.00-147.00   54
 20  \w    101.00 132.00   0.50    0.29    --  107.00 131.00  37.00   62
 21  \w     38.00  63.00   0.50    0.29    --  107.00 -77.00 -30.00   50
 22  \w     43.00  68.00   0.50    0.29    --  107.00 -77.00  30.00   50
 23  \w    -16.00  22.00   0.50    0.07    --  -44.46  38.00   0.00   76
 24  \w    -10.00  28.00   0.50    0.07    --  -44.46  38.00 -30.00   76
 25  \w    -15.00  29.00   0.50    0.07    --  -44.46  38.00 -60.00   88
 26  \w    -17.00  23.00   0.50    0.07    --  -44.46  38.00-150.00   80
 27  \w    -76.00 -32.00   0.50    0.07    --  -44.46 139.00-147.00   88
 28  \w    -93.00 -68.00   0.50    0.29    -- -104.00 139.00-147.00   50
 29  \w    -48.00 -21.00   0.50    0.07    --  -44.46 131.00  37.00   54
 30  \w    -89.00 -63.00   0.50    0.07    --  -44.46 131.00  37.00   52
 31  \w    -97.00 -39.00   0.50    0.29    -- -104.00 131.00  37.00  116
 32  \w    -59.00 -31.00   0.50    0.29    -- -104.00  77.00  60.00   56
 33  \w    -67.00 -42.00   0.50    0.29    -- -104.00  77.00 120.00   50
 34  \w    -71.00 -40.00   0.50    0.29    -- -104.00  77.00 150.00   62
 35  \w    -65.00 -31.00   0.50    0.29    -- -104.00  77.00-180.00   68
 36  \w    -73.00 -32.00   0.50    0.29    -- -104.00  77.00-120.00   82
 37  \w   -131.00-101.00   0.50    0.29    -- -104.00 -15.00  90.00   60
 38  \w   -132.00 -99.00   0.50    0.29    -- -104.00 -15.00 120.00   66
 39  \w   -131.00 -95.00   0.50    0.29    -- -104.00 -15.00 150.00   72
 40  \w   -126.00 -95.00   0.50    0.29    -- -104.00 -15.00 -30.00   62
 41  \w   -129.00 -96.00   0.50    0.29    -- -104.00 -15.00 -60.00   66
 42  \w   -133.00-103.00   0.50    0.29    -- -104.00 -15.00-150.00   60
 43  \w   -111.00 -49.00   0.50    0.07    --  -44.46 -38.00-180.00  124
 44  \w   -119.00 -59.00   0.50    0.07    --  -44.46 -38.00  30.00  120
 45  \w   -109.00 -39.00   0.50    0.07    --  -44.46 -38.00  60.00  140
 46  \w   -127.00-102.00   0.50    0.29    -- -104.00-131.00 -33.00   50
 47  \w   -120.00 -85.00   0.50    0.29    -- -104.00-139.00 151.00   70
;
_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      0.0455301000
_diffrn_orient_matrix_UB_12      0.0164782000
_diffrn_orient_matrix_UB_13      0.1013572000
_diffrn_orient_matrix_UB_21      0.0806713000
_diffrn_orient_matrix_UB_22      0.1470254000
_diffrn_orient_matrix_UB_23      0.0037690000
_diffrn_orient_matrix_UB_31      -0.1715542000
_diffrn_orient_matrix_UB_32      0.0097996000
_diffrn_orient_matrix_UB_33      -0.0029340000
_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  0.0444
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.9922
_diffrn_reflns_Laue_measured_fraction_max 0.9922
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            15535
_diffrn_reflns_point_group_measured_fraction_full 0.9922
_diffrn_reflns_point_group_measured_fraction_max 0.9922
_diffrn_reflns_theta_full        67.0533
_diffrn_reflns_theta_max         67.05
_diffrn_reflns_theta_min         2.91
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.583
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62109
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.15 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull dark green'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_description       plate
_exptl_crystal_F_000             658.697
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.9453
_refine_diff_density_min         -0.6844
_refine_diff_density_rms         0.1105
_refine_ls_d_res_high            0.8372
_refine_ls_d_res_low             15.1825
_refine_ls_goodness_of_fit_ref   1.0777
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    55
_refine_ls_number_parameters     397
_refine_ls_number_reflns         4987
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0777
_refine_ls_R_factor_all          0.0630
_refine_ls_R_factor_gt           0.0591
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0909P)^2^+2.3132P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1589
_refine_ls_wR_factor_ref         0.1621
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              13
_reflns_limit_k_min              -13
_reflns_limit_l_max              18
_reflns_limit_l_min              0
_reflns_number_gt                4672
_reflns_number_total             4987
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5dt01604e2.cif
_cod_data_source_block           230714qsalFeCl
_cod_depositor_comments          'Adding full bibliography for 7719302.cif.'
_cod_database_code               7719302
_chemical_oxdiff_formula         'C H N O Fe Cl'
_chemical_oxdiff_usercomment     100
_reflns_odcompleteness_completeness 99.30
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, All O(H,H) groups
2. Others
 Fixed Sof: H2bd(0.6) H2be(0.6) H2bf(0.6) H2aa(0.4) H2ab(0.4) H2ac(0.4)
 O1(0.6) H1(0.6) O3(0.4) H3(0.4) H1(0.6) H1(0.6)
3.a Free rotating group:
 O013(H01a,H01b)
3.b Aromatic/amide H refined with riding coordinates:
 C00F(H00F), C00G(H00G), C00J(H00J), C00M(H00M), C00N(H00N), C00P(H00P),
 C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U), C00V(H00V),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011),
 C012(H012), C014(H014), C015(H015), C016(H016)
3.c Idealised Me refined as rotating group:
 C2(H2bd,H2be,H2bf), C2(H2aa,H2ab,H2ac)
;
_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 2.230
_oxdiff_exptl_absorpt_empirical_full_min 0.585