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_1573976
_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                 113.99(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.380(6)
_cell_length_b                   13.440(3)
_cell_length_c                   30.330(6)
_cell_measurement_reflns_used    3469
_cell_measurement_temperature    200.0(2)
_cell_measurement_theta_max      23.88
_cell_measurement_theta_min      1.61
_cell_volume                     10197(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      200.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.897
_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  0.0339
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.897
_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       38
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            132654
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_theta_full        25.243
_diffrn_reflns_theta_max         29.284
_diffrn_reflns_theta_min         1.470
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.207
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6796
_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    1.235
_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         0.334
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.00100(8)
_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   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         12486
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0471
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0591P)^2^+3.3507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1099
_refine_ls_wR_factor_ref         0.1202
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11114
_reflns_number_total             12486
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-037-mecn-ipr2o-200k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_database_code               1573976
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.919
_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(0.064) H5(0.07) H6(0.069) H8(0.068) H9(0.068) H10(0.06)
 H14(0.067) H15(0.088) H16(0.095) H17(0.088) H18(0.071) H20(0.058) H21(0.07)
 H22(0.076) H23(0.073) H24(0.062) H27(0.065) H28(0.079) H29(0.085) H33(0.058)
 H34(0.067) H35(0.073) H36(0.071) H37(0.059) H39(0.065) H40(0.072) H41(0.074)
 H42(0.075) H43(0.068) H45(0.076) H46(0.095) H47(0.1) H48(0.097) H49(0.079)
 H51(0.064) H52(0.069) H53(0.069) H54(0.07) H55(0.063) H57(0.075) H58(0.088)
 H59(0.084) H60(0.074) H61(0.063)
 Fixed X: Fe1(0.5) H4(0.700911) H5(0.752769) H6(0.714274) H8(0.625281)
 H9(0.533596) H10(0.484558) H14(0.440871) H15(0.367629) H16(0.326648)
 H17(0.356032) H18(0.430522) H20(0.600398) H21(0.673901) H22(0.739208)
 H23(0.730811) H24(0.65685) H27(0.518727) H28(0.515883) H29(0.506099) C30(0.5)
 C31(0.5) H33(0.602072) H34(0.621665) H35(0.557767) H36(0.473166) H37(0.452338)
 H39(0.950117) H40(1.042952) H41(1.091413) H42(1.045388) H43(0.952805)
 H45(0.793676) H46(0.757468) H47(0.789741) H48(0.857605) H49(0.892931)
 H51(0.901824) H52(0.85695) H53(0.772125) H54(0.733114) H55(0.77826)
 H57(0.88094) H58(0.87288) H59(0.851261) H60(0.839832) H61(0.849109)
 Fixed Y: H4(0.773976) H5(0.871862) H6(0.982163) H8(1.062181) H9(1.073779)
 H10(0.977962) H14(0.956331) H15(1.045252) H16(0.994497) H17(0.852547)
 H18(0.764635) H20(0.527857) H21(0.435905) H22(0.511826) H23(0.67783)
 H24(0.770605) H27(0.385725) H28(0.210505) H29(0.118082) H33(0.54041)
 H34(0.537869) H35(0.587885) H36(0.638013) H37(0.638755) H39(0.628148)
 H40(0.629174) H41(0.735907) H42(0.841623) H43(0.83913) H45(0.877374)
 H46(0.92167) H47(0.850934) H48(0.732848) H49(0.687145) H51(0.543254)
 H52(0.393419) H53(0.387175) H54(0.534864) H55(0.684558) H57(0.945586)
 H58(1.062312) H59(1.013692) H60(0.844874) H61(0.727317)
 Fixed Z: Fe1(0.25) H4(0.374353) H5(0.441836) H6(0.476087) H8(0.474382)
 H9(0.435711) H10(0.366709) H14(0.240316) H15(0.2416) H16(0.29114)
 H17(0.338138) H18(0.339156) H20(0.320341) H21(0.322663) H22(0.303216)
 H23(0.280184) H24(0.276549) H27(0.151687) H28(0.149222) H29(0.20877) C30(0.25)
 C31(0.25) H33(0.206929) H34(0.138588) H35(0.063991) H36(0.056299)
 H37(0.124003) H39(0.506426) H40(0.542844) H41(0.514907) H42(0.449986)
 H43(0.413395) H45(0.378931) H46(0.298021) H47(0.244868) H48(0.273719)
 H49(0.354176) H51(0.424578) H52(0.414738) H53(0.415981) H54(0.426544)
 H55(0.436705) H57(0.439745) H58(0.492107) H59(0.555855) H60(0.566866)
 H61(0.515021)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              76619
_shelx_fab_checksum              65583
_olex2_submission_special_instructions 'No special instructions were received'