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_1573978
_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                 113.51(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.640(6)
_cell_length_b                   13.590(3)
_cell_length_c                   30.520(6)
_cell_measurement_reflns_used    2405
_cell_measurement_temperature    350.0(2)
_cell_measurement_theta_max      21.92
_cell_measurement_theta_min      1.6
_cell_volume                     10513(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      350.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.892
_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  0.0330
_diffrn_reflns_av_unetI/netI     0.0141
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.892
_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       39
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            140022
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.243
_diffrn_reflns_theta_max         29.345
_diffrn_reflns_theta_min         1.455
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.201
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6477
_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    1.198
_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         0.196
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.031
_refine_ls_extinction_coef       0.00085(9)
_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   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         12871
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0470
_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^)+(0.0712P)^2^+1.2298P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1208
_refine_ls_wR_factor_ref         0.1276
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10685
_reflns_number_total             12871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-037-mecn-ipr2o-350k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_original_cell_volume        10512(4)
_cod_database_code               1573978
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.921
_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(0.096) H5(0.109) H6(0.11) H8(0.111) H9(0.11) H10(0.094)
 H14(0.103) H15(0.143) H16(0.159) H17(0.144) H18(0.108) H20(0.091) H21(0.116)
 H22(0.124) H23(0.119) H24(0.097) H27(0.103) H28(0.128) H29(0.134) H33(0.088)
 H34(0.108) H35(0.116) H36(0.111) H37(0.089) H39(0.104) H40(0.119) H41(0.124)
 H42(0.125) H43(0.109) H45(0.122) H46(0.156) H47(0.162) H48(0.158) H49(0.129)
 H51(0.103) H52(0.113) H53(0.114) H54(0.112) H55(0.099) H57(0.115) H58(0.135)
 H59(0.128) H60(0.114) H61(0.096)
 Fixed X: Fe1(0.5) H4(0.698168) H5(0.748828) H6(0.711524) H8(0.623969)
 H9(0.534848) H10(0.486655) H14(0.441808) H15(0.369208) H16(0.329161)
 H17(0.357987) H18(0.431561) H20(0.601289) H21(0.673434) H22(0.735798)
 H23(0.727423) H24(0.654807) H27(0.518613) H28(0.516284) H29(0.505933) C30(0.5)
 C31(0.5) H33(0.600425) H34(0.619852) H35(0.557082) H36(0.474376) H37(0.45362)
 H39(0.950093) H40(1.040315) H41(1.088124) H42(1.044314) H43(0.953879)
 H45(0.795541) H46(0.76034) H47(0.792981) H48(0.857958) H49(0.89282)
 H51(0.901605) H52(0.857446) H53(0.774055) H54(0.735891) H55(0.780008)
 H57(0.881412) H58(0.873101) H59(0.850813) H60(0.83999) H61(0.849166)
 Fixed Y: H4(0.772167) H5(0.866733) H6(0.975002) H8(1.057452) H9(1.071376)
 H10(0.978296) H14(0.955686) H15(1.041161) H16(0.993937) H17(0.857342)
 H18(0.771171) H20(0.533638) H21(0.444185) H22(0.517138) H23(0.678034)
 H24(0.769407) H27(0.389115) H28(0.217869) H29(0.127088) H33(0.54528)
 H34(0.543366) H35(0.59011) H36(0.636596) H37(0.637508) H39(0.632321)
 H40(0.632164) H41(0.73555) H42(0.839273) H43(0.838367) H45(0.875216)
 H46(0.917998) H47(0.850117) H48(0.734068) H49(0.690288) H51(0.546751)
 H52(0.400231) H53(0.395723) H54(0.54038) H55(0.686042) H57(0.944524)
 H58(1.057943) H59(1.010561) H60(0.845632) H61(0.731273)
 Fixed Z: Fe1(0.25) H4(0.374066) H5(0.440546) H6(0.474463) H8(0.472564)
 H9(0.434628) H10(0.367034) H14(0.241144) H15(0.241515) H16(0.290169)
 H17(0.337302) H18(0.339606) H20(0.320999) H21(0.322826) H22(0.301896)
 H23(0.278545) H24(0.275213) H27(0.153008) H28(0.150773) H29(0.20892) C30(0.25)
 C31(0.25) H33(0.20579) H34(0.138377) H35(0.065466) H36(0.058276) H37(0.124721)
 H39(0.505702) H40(0.540559) H41(0.513147) H42(0.450337) H43(0.414522)
 H45(0.379438) H46(0.299924) H47(0.248067) H48(0.275673) H49(0.354371)
 H51(0.425524) H52(0.416375) H53(0.416556) H54(0.426322) H55(0.435706)
 H57(0.440909) H58(0.492342) H59(0.554229) H60(0.5649) H61(0.513806)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              67545
_shelx_fab_checksum              23869
_olex2_submission_special_instructions 'No special instructions were received'