Thermal- and light-induced valence tautomerism with a concerted spin transition in an iron tris(diimine) complex.
Janetzki, Jett T.; Brown, Dominic S.; Daumann, Florian; Ismail, I. Haseena; Gable, Robert W.; Hay, Moya A.; Mulder, Roger J.; Starikova, Alyona A.; Weber, Birgit; Giansiracusa, Marcus J.; Boskovic, Colette; Chemical science 16 (2025) 5857–5871; doi:10.1039/d4sc07798a

data_1573969
_publ_section_title
;
 Thermal- and light-induced valence tautomerism with a concerted spin
 transition in an iron tris(diimine) complex.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5857
_journal_page_last               5871
_journal_paper_doi               10.1039/d4sc07798a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C72 H48 N6 Zn, 2(C24 H20 B), 3[CH2Cl2]'
_chemical_formula_sum            'C123 H94 B2 Cl6 N6 Zn'
_chemical_formula_weight         1955.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-10-24 deposited with the CCDC.	2025-02-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.5370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.5951(2)
_cell_length_b                   13.48310(10)
_cell_length_c                   29.7605(2)
_cell_measurement_reflns_used    45139
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.7790
_cell_measurement_theta_min      3.6630
_cell_volume                     10072.96(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14a (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  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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   -119.00 -77.00   0.50    0.73    --  -48.17-125.00 -60.00   84
  2  \w   -118.00 -78.00   0.50    0.73    --  -48.17-125.00   0.00   80
  3  \w   -108.00 -82.00   0.50    2.92    --  -86.25 -15.00  60.00   52
  4  \w    -44.00  22.00   0.50    0.73    --  -48.17  38.00 120.00  132
  5  \w    -47.00 -17.00   0.50    2.92    --  -86.25  45.00  60.00   60
  6  \w    -54.00 -27.00   0.50    2.92    --  -86.25  61.00 -90.00   54
  7  \w    -30.00  22.00   0.50    0.73    --  -48.17  19.00-180.00  104
  8  \w    -42.00 -15.00   0.50    2.92    --  -86.25  45.00-180.00   54
  9  \w    -84.00 -15.00   0.50    0.73    --  -48.17 125.00-150.00  138
 10  \w    -18.00  27.00   0.50    0.73    --   48.17 -19.00 -30.00   90
 11  \w    -14.00  44.00   0.50    0.73    --   48.17 -38.00 -90.00  116
 12  \w     64.00  90.00   0.50    0.73    --   48.17-125.00  30.00   52
 13  \w     43.00  70.00   0.50    2.92    --  107.75 -61.00  60.00   54
 14  \w     80.00 106.00   0.50    2.92    --  107.75 -94.00 120.00   52
 15  \w     77.00 106.00   0.50    2.92    --  107.75 -94.00  60.00   58
 16  \w     62.00 104.00   0.50    2.92    --  107.75 -94.00  90.00   84
 17  \w     49.00 102.00   0.50    2.92    --  107.75 -94.00 150.00  106
 18  \w     46.00  98.00   0.50    2.92    --  107.75 -77.00 150.00  104
 19  \w     42.00  68.00   0.50    2.92    --  107.75 -77.00 120.00   52
 20  \w     43.00  69.00   0.50    2.92    --  107.75 -94.00  60.00   52
 21  \w     41.00  70.00   0.50    2.92    --  107.75 -61.00  30.00   58
 22  \w     45.00  99.00   0.50    2.92    --  107.75 -94.00  30.00  108
 23  \w     44.00 103.00   0.50    2.92    --  107.75 -94.00 -60.00  118
 24  \w     80.00 106.00   0.50    2.92    --  107.75 -94.00-120.00   52
 25  \w     81.00 106.00   0.50    2.92    --  107.75 -94.00-150.00   50
 26  \w     81.00 106.00   0.50    2.92    --  107.75 -94.00-180.00   50
 27  \w     55.00  94.00   0.50    2.92    --  107.75 -94.00 -90.00   78
 28  \w     73.00  99.00   0.50    2.92    --  107.75 -77.00 -60.00   52
 29  \w     46.00  72.00   0.50    2.92    --  107.75 -94.00-150.00   52
 30  \w     42.00  68.00   0.50    2.92    --  107.75 -94.00-180.00   52
 31  \w     38.00  73.00   0.50    2.92    --  107.75 -94.00-120.00   70
 32  \w     36.00  61.00   0.50    2.92    --  107.75 -61.00 -60.00   50
 33  \w     37.00  69.00   0.50    2.92    --  107.75 -61.00-120.00   64
 34  \w     39.00  65.00   0.50    2.92    --  107.75 -61.00-180.00   52
 35  \w     97.00 177.00   0.50    2.92    --  107.75  15.00-180.00  160
 36  \w    111.00 171.00   0.50    2.92    --  107.75  15.00 -60.00  120
 37  \w    104.00 175.00   0.50    2.92    --  107.75  30.00  60.00  142
 38  \w    119.00 160.00   0.50    2.92    --  107.75 125.00   0.00   82
 39  \w    101.00 172.00   0.50    2.92    --  107.75  30.00 -30.00  142
 40  \w    102.00 175.00   0.50    2.92    --  107.75  30.00-150.00  146
 41  \w    109.00 159.00   0.50    2.92    --  107.75  30.00  30.00  100
 42  \w     98.00 153.00   0.50    2.92    --  107.75  15.00 120.00  110
 43  \w     36.00  62.00   0.50    2.92    --  107.75 -61.00  90.00   52
 44  \w     36.00 106.00   0.50    2.92    --  107.75 -98.00  10.57  140
 45  \w     40.00  66.00   0.50    2.92    --  107.75 -77.00 -30.00   52
 46  \w   -116.00 -81.00   0.50    0.73    --  -48.17-125.00-180.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0436611000
_diffrn_orient_matrix_UB_12      -0.0036017000
_diffrn_orient_matrix_UB_13      0.0531705000
_diffrn_orient_matrix_UB_21      -0.0269347000
_diffrn_orient_matrix_UB_22      -0.0913716000
_diffrn_orient_matrix_UB_23      0.0108014000
_diffrn_orient_matrix_UB_31      0.0336908000
_diffrn_orient_matrix_UB_32      -0.0685142000
_diffrn_orient_matrix_UB_33      -0.0171730000
_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  0.0310
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            68269
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.067
_diffrn_reflns_theta_min         3.676
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.223
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.599
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14a (Rigaku Oxford Diffraction, 2018)
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            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             4064
_exptl_crystal_size_max          0.255
_exptl_crystal_size_mid          0.193
_exptl_crystal_size_min          0.125
_refine_diff_density_max         0.291
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.000068(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         10656
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0348
_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^)+(0.0487P)^2^+5.8860P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.0978
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9886
_reflns_number_total             10656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj2-057-bph4-dcm-ether-blocks-redabs
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_original_cell_volume        10072.95(14)
_cod_database_code               1573969
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C120 H88 B2 N6 Zn O'
_chemical_oxdiff_usercomment
'DCM ether crystals with high conc 0.05g in 3 mL DCM block crystals different space group'
_olex2_refinement_description
;
1.a Aromatic/amide H refined with riding coordinates:
 C20(H20), C4(H4), C33(H33), C37(H37), C10(H10), C34(H34), C43(H43), C35(H35),
 C49(H49), C58(H58), C42(H42), C36(H36), C21(H21), C9(H9), C51(H51), C41(H41),
 C45(H45), C27(H27), C24(H24), C39(H39), C40(H40), C5(H5), C6(H6), C59(H59),
 C52(H52), C22(H22), C60(H60), C62(H62), C53(H53), C61(H61), C46(H46), C8(H8),
 C14(H14), C47(H47), C23(H23), C56(H56), C48(H48), C54(H54), C28(H28), C55(H55),
  C17(H17), C15(H15), C16(H16), C29(H29)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              99204
_shelx_fab_checksum              25088
_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 1.402
_oxdiff_exptl_absorpt_empirical_full_min 0.765