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_1573973
_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                 113.46(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.710(6)
_cell_length_b                   13.640(3)
_cell_length_c                   30.550(6)
_cell_measurement_reflns_used    2197
_cell_measurement_temperature    375.0(2)
_cell_measurement_theta_max      21.02
_cell_measurement_theta_min      1.59
_cell_volume                     10592(5)
_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      375.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.896
_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  0.0294
_diffrn_reflns_av_unetI/netI     0.0121
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.896
_diffrn_reflns_limit_h_max       36
_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       -41
_diffrn_reflns_number            141171
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.896
_diffrn_reflns_theta_full        25.243
_diffrn_reflns_theta_max         29.327
_diffrn_reflns_theta_min         1.453
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.199
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6767
_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    1.189
_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         0.195
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.031
_refine_ls_extinction_coef       0.00085(11)
_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   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         13005
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0551
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0821P)^2^+0.7305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1301
_refine_ls_wR_factor_ref         0.1435
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9936
_reflns_number_total             13005
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-037-mecn-ipr2o-375k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_original_cell_volume        10592(4)
_cod_database_code               1573973
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.922
_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(0.111) H5(0.127) H6(0.128) H8(0.129) H9(0.129) H10(0.11)
 H14(0.121) H15(0.164) H16(0.185) H17(0.166) H18(0.125) H20(0.107) H21(0.134)
 H22(0.144) H23(0.139) H24(0.114) H27(0.12) H28(0.148) H29(0.154) H33(0.103)
 H34(0.125) H35(0.134) H36(0.128) H37(0.105) H39(0.121) H40(0.137) H41(0.143)
 H42(0.146) H43(0.126) H45(0.14) H46(0.174) H47(0.181) H48(0.179) H49(0.147)
 H51(0.121) H52(0.132) H53(0.132) H54(0.13) H55(0.115) H57(0.132) H58(0.153)
 H59(0.145) H60(0.131) H61(0.111)
 Fixed X: Fe1(0.5) H4(0.697938) H5(0.748474) H6(0.71155) H8(0.624158)
 H9(0.535375) H10(0.487207) H14(0.442199) H15(0.369236) H16(0.329561)
 H17(0.358542) H18(0.432018) H20(0.601691) H21(0.673838) H22(0.735323)
 H23(0.72674) H24(0.654757) H27(0.518307) H28(0.516361) H29(0.505128) C30(0.5)
 C31(0.5) H33(0.600183) H34(0.619431) H35(0.556976) H36(0.474303) H37(0.453732)
 H39(0.94984) H40(1.039698) H41(1.087589) H42(1.044069) H43(0.953865)
 H45(0.796173) H46(0.760936) H47(0.793647) H48(0.857995) H49(0.893658)
 H51(0.901694) H52(0.857671) H53(0.774258) H54(0.736243) H55(0.780317)
 H57(0.881514) H58(0.872352) H59(0.850713) H60(0.839971) H61(0.849125)
 Fixed Y: H4(0.772556) H5(0.866576) H6(0.975075) H8(1.057525) H9(1.070965)
 H10(0.978416) H14(0.955675) H15(1.039785) H16(0.992236) H17(0.856358)
 H18(0.771626) H20(0.535292) H21(0.445917) H22(0.518248) H23(0.678643)
 H24(0.76965) H27(0.388416) H28(0.217533) H29(0.127383) H33(0.544111)
 H34(0.5437) H35(0.58938) H36(0.634697) H37(0.635426) H39(0.633352)
 H40(0.632841) H41(0.734738) H42(0.838839) H43(0.838957) H45(0.875595)
 H46(0.918011) H47(0.850138) H48(0.734276) H49(0.69204) H51(0.547379)
 H52(0.401904) H53(0.397206) H54(0.541752) H55(0.686586) H57(0.944052)
 H58(1.057309) H59(1.009537) H60(0.845497) H61(0.73195)
 Fixed Z: Fe1(0.25) H4(0.374051) H5(0.440426) H6(0.474125) H8(0.472343)
 H9(0.434898) H10(0.367214) H14(0.241864) H15(0.242211) H16(0.290588)
 H17(0.337903) H18(0.34001) H20(0.321359) H21(0.322864) H22(0.301609)
 H23(0.27793) H24(0.275196) H27(0.152936) H28(0.150965) H29(0.208509) C30(0.25)
 C31(0.25) H33(0.20537) H34(0.138027) H35(0.065469) H36(0.058286) H37(0.124689)
 H39(0.505794) H40(0.540747) H41(0.513106) H42(0.45046) H43(0.415135)
 H45(0.379565) H46(0.300083) H47(0.248453) H48(0.276061) H49(0.354738)
 H51(0.425699) H52(0.416816) H53(0.416611) H54(0.425966) H55(0.435618)
 H57(0.44093) H58(0.492224) H59(0.554287) H60(0.564657) H61(0.513797)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              33351
_shelx_fab_checksum              82651
_olex2_submission_special_instructions 'No special instructions were received'