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_1573972
_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                 114.31(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.310(6)
_cell_length_b                   13.370(3)
_cell_length_c                   30.170(6)
_cell_measurement_reflns_used    3195
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      25.09
_cell_measurement_theta_min      1.62
_cell_volume                     10039(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      100.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.895
_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  0.0377
_diffrn_reflns_av_unetI/netI     0.0163
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.895
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            132131
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        25.243
_diffrn_reflns_theta_max         29.226
_diffrn_reflns_theta_min         1.481
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.210
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6495
_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    1.254
_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         0.251
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.00045(6)
_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         12209
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0558P)^2^+5.3594P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1084
_refine_ls_wR_factor_ref         0.1122
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11118
_reflns_number_total             12209
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-037-mecn-ipr2o-100k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_database_code               1573972
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.917
_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(0.05) H5(0.053) H6(0.051) H8(0.048) H9(0.047) H10(0.044)
 H14(0.049) H15(0.062) H16(0.069) H17(0.068) H18(0.057) H20(0.043) H21(0.05)
 H22(0.057) H23(0.057) H24(0.05) H27(0.042) H28(0.05) H29(0.056) H33(0.042)
 H34(0.046) H35(0.051) H36(0.053) H37(0.047) H39(0.044) H40(0.047) H41(0.047)
 H42(0.046) H43(0.043) H45(0.052) H46(0.069) H47(0.074) H48(0.064) H49(0.049)
 H51(0.041) H52(0.043) H53(0.046) H54(0.05) H55(0.046) H57(0.056) H58(0.068)
 H59(0.067) H60(0.057) H61(0.048)
 Fixed X: Fe1(0.5) H4(0.702094) H5(0.75441) H6(0.715754) H8(0.626001)
 H9(0.533668) H10(0.484232) H14(0.440356) H15(0.367399) H16(0.326353)
 H17(0.355695) H18(0.430063) H20(0.600549) H21(0.674397) H22(0.740095)
 H23(0.731994) H24(0.657704) H27(0.518484) H28(0.515285) H29(0.506039) C30(0.5)
 C31(0.5) H33(0.602114) H34(0.621627) H35(0.557501) H36(0.472582) H37(0.45193)
 H39(0.950391) H40(1.043594) H41(1.092209) H42(1.045644) H43(0.952293)
 H45(0.792565) H46(0.755597) H47(0.788481) H48(0.857557) H49(0.893374)
 H51(0.901284) H52(0.856585) H53(0.771393) H54(0.73239) H55(0.777849)
 H57(0.879962) H58(0.87175) H59(0.850301) H60(0.839835) H61(0.849317)
 Fixed Y: H4(0.775102) H5(0.874519) H6(0.986178) H8(1.064854) H9(1.073783)
 H10(0.976122) H14(0.955036) H15(1.044995) H16(0.992685) H17(0.848576)
 H18(0.760035) H20(0.524044) H21(0.431783) H22(0.508812) H23(0.676336)
 H24(0.769535) H27(0.381923) H28(0.205405) H29(0.112603) H33(0.535764)
 H34(0.533441) H35(0.585677) H36(0.637212) H37(0.637498) H39(0.625987)
 H40(0.628184) H41(0.735801) H42(0.842305) H43(0.839416) H45(0.876926)
 H46(0.919809) H47(0.848612) H48(0.730551) H49(0.686124) H51(0.541765)
 H52(0.39075) H53(0.383929) H54(0.532492) H55(0.683118) H57(0.945667)
 H58(1.064142) H59(1.015751) H60(0.845776) H61(0.726613)
 Fixed Z: Fe1(0.25) H4(0.374448) H5(0.44195) H6(0.476272) H8(0.474831)
 H9(0.436403) H10(0.367082) H14(0.240536) H15(0.242428) H16(0.292213)
 H17(0.338652) H18(0.339353) H20(0.319874) H21(0.322261) H22(0.303051)
 H23(0.280711) H24(0.277248) H27(0.151081) H28(0.148343) H29(0.208597)
 C30(0.25) C31(0.25) H33(0.206989) H34(0.138191) H35(0.062923) H36(0.05509)
 H37(0.123238) H39(0.506777) H40(0.543989) H41(0.515692) H42(0.4503)
 H43(0.413154) H45(0.377726) H46(0.296078) H47(0.242815) H48(0.272721)
 H49(0.354087) H51(0.423712) H52(0.414285) H53(0.415593) H54(0.426971)
 H55(0.437316) H57(0.438707) H58(0.490962) H59(0.555428) H60(0.567484)
 H61(0.515666)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              59758
_shelx_fab_checksum              84537
_olex2_submission_special_instructions 'No special instructions were received'