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_1573975
_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 Fe N6, 2(C24 H20 B), 2[C6H14O]'
_chemical_formula_sum            'C132 H116 B2 Fe N6 O2'
_chemical_formula_weight         1895.77
_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             2023-11-14
_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                 114.19(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.350(6)
_cell_length_b                   13.400(3)
_cell_length_c                   30.240(6)
_cell_measurement_reflns_used    3564
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      22.58
_cell_measurement_theta_min      1.62
_cell_volume                     10110(4)
_computing_cell_refinement       'XDS (Kabsch, 2010)'
_computing_data_collection       'AS QEGUI'
_computing_data_reduction        'XDS (Kabsch, 2010)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.893
_diffrn_measurement_device_type  'MX1 Beamline Australian Synchrotron'
_diffrn_measurement_method       'Omega Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.893
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            131953
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        25.243
_diffrn_reflns_theta_max         29.207
_diffrn_reflns_theta_min         1.477
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.209
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6183
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'XDS (Kabsch, 2010)'
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_description       needle
_exptl_crystal_F_000             4008
_exptl_crystal_size_max          0.417
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.283
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.00069(7)
_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   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         12229
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0398
_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^)+(0.0588P)^2^+4.4425P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1090
_refine_ls_wR_factor_ref         0.1142
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11025
_reflns_number_total             12229
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-037-mecn-ipr2o-150k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_original_cell_volume        10109(4)
_cod_database_code               1573975
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.918
_exptl_absorpt_special_details
;
XDS does not report the values of _exptl_absorpt_correction_T_min and
_exptl_absorpt_correction_T_max.  Even though the data was processed by XDS
the values of the absorption corrections reported by SADABS are reported.
;
_diffrn_measurement_detector_type 'Dectris Eiger2 9M'
_olex2_refinement_description
;
1. Others
 Fixed Sof: Fe1(0.5) C30(0.5) C31(0.5)
 Fixed U12: Fe1(0) C30(0) C31(0)
 Fixed U23: Fe1(0) C30(0) C31(0)
 Fixed Uiso: H4(0.054) H5(0.058) H6(0.057) H8(0.055) H9(0.054) H10(0.049)
 H14(0.055) H15(0.072) H16(0.079) H17(0.075) H18(0.062) H20(0.047) H21(0.056)
 H22(0.064) H23(0.063) H24(0.054) H27(0.049) H28(0.061) H29(0.067) H33(0.046)
 H34(0.053) H35(0.059) H36(0.06) H37(0.05) H39(0.051) H40(0.057) H41(0.057)
 H42(0.056) H43(0.051) H45(0.06) H46(0.078) H47(0.084) H48(0.076) H49(0.059)
 H51(0.049) H52(0.051) H53(0.054) H54(0.056) H55(0.051) H57(0.062) H58(0.074)
 H59(0.074) H60(0.063) H61(0.052)
 Fixed X: Fe1(0.5) H4(0.701644) H5(0.753811) H6(0.715285) H8(0.625913)
 H9(0.533787) H10(0.484544) H14(0.440547) H15(0.36771) H16(0.326644)
 H17(0.356031) H18(0.430375) H20(0.600591) H21(0.674184) H22(0.73954)
 H23(0.731664) H24(0.657177) H27(0.518329) H28(0.515164) H29(0.505954) C30(0.5)
 C31(0.5) H33(0.601946) H34(0.621448) H35(0.557321) H36(0.472657) H37(0.452077)
 H39(0.950341) H40(1.043282) H41(1.091861) H42(1.045631) H43(0.952584)
 H45(0.792863) H46(0.756323) H47(0.788995) H48(0.857629) H49(0.893263)
 H51(0.901487) H52(0.856669) H53(0.771781) H54(0.732811) H55(0.778067)
 H57(0.880116) H58(0.872289) H59(0.850601) H60(0.839924) H61(0.849296)
 Fixed Y: H4(0.774463) H5(0.873052) H6(0.984064) H8(1.063179) H9(1.073585)
 H10(0.976552) H14(0.955619) H15(1.04495) H16(0.99307) H17(0.849776)
 H18(0.761558) H20(0.525513) H21(0.433349) H22(0.509612) H23(0.676842)
 H24(0.769765) H27(0.383425) H28(0.207468) H29(0.114929) H33(0.537453)
 H34(0.535102) H35(0.586353) H36(0.637451) H37(0.638109) H39(0.626794)
 H40(0.628495) H41(0.735638) H42(0.841994) H43(0.83933) H45(0.876813)
 H46(0.920496) H47(0.849491) H48(0.731602) H49(0.686607) H51(0.542338)
 H52(0.392058) H53(0.38522) H54(0.533371) H55(0.683693) H57(0.94575)
 H58(1.063259) H59(1.014711) H60(0.845425) H61(0.726821)
 Fixed Z: Fe1(0.25) H4(0.374306) H5(0.441792) H6(0.476206) H8(0.474735)
 H9(0.436118) H10(0.366991) H14(0.240572) H15(0.242401) H16(0.29196)
 H17(0.338512) H18(0.339211) H20(0.320154) H21(0.322407) H22(0.302883)
 H23(0.280652) H24(0.276767) H27(0.151211) H28(0.148585) H29(0.208596)
 C30(0.25) C31(0.25) H33(0.206886) H34(0.1383) H35(0.06326) H36(0.055553)
 H37(0.123579) H39(0.506623) H40(0.543419) H41(0.515374) H42(0.450275)
 H43(0.413227) H45(0.378092) H46(0.296809) H47(0.243629) H48(0.273028)
 H49(0.354144) H51(0.423987) H52(0.414273) H53(0.415685) H54(0.426829)
 H55(0.437067) H57(0.438969) H58(0.491438) H59(0.555416) H60(0.567135)
 H61(0.515308)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              98212
_shelx_fab_checksum              60687
_olex2_submission_special_instructions 'No special instructions were received'