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_1573971
_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                 113.40(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.790(6)
_cell_length_b                   13.680(3)
_cell_length_c                   30.560(6)
_cell_measurement_reflns_used    2179
_cell_measurement_temperature    400.0(2)
_cell_measurement_theta_max      18.91
_cell_measurement_theta_min      1.58
_cell_volume                     10662(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      400.0(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  0.0297
_diffrn_reflns_av_unetI/netI     0.0127
_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       -33
_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            141625
_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         29.346
_diffrn_reflns_theta_min         1.452
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.198
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6358
_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    1.181
_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         0.206
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.00135(14)
_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   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         13115
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0459
_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^)+(0.0942P)^2^+0.5695P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1389
_refine_ls_wR_factor_ref         0.1556
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9471
_reflns_number_total             13115
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-037-mecn-ipr2o-400k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_original_cell_volume        10662(4)
_cod_database_code               1573971
_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(0.126) H5(0.143) H6(0.146) H8(0.146) H9(0.144) H10(0.123)
 H14(0.135) H15(0.184) H16(0.204) H17(0.187) H18(0.14) H20(0.12) H21(0.151)
 H22(0.162) H23(0.157) H24(0.129) H27(0.135) H28(0.168) H29(0.173) H33(0.117)
 H34(0.139) H35(0.15) H36(0.142) H37(0.118) H39(0.136) H40(0.153) H41(0.162)
 H42(0.162) H43(0.141) H45(0.156) H46(0.193) H47(0.202) H48(0.199) H49(0.165)
 H51(0.135) H52(0.149) H53(0.149) H54(0.146) H55(0.129) H57(0.146) H58(0.17)
 H59(0.16) H60(0.145) H61(0.124)
 Fixed X: Fe1(0.5) H4(0.697557) H5(0.748252) H6(0.71143) H8(0.624238)
 H9(0.535942) H10(0.487755) H14(0.442546) H15(0.369755) H16(0.330018)
 H17(0.359353) H18(0.432547) H20(0.602715) H21(0.6743) H22(0.735017)
 H23(0.72653) H24(0.654517) H27(0.517982) H28(0.515275) H29(0.505638) C30(0.5)
 C31(0.5) H33(0.599905) H34(0.619442) H35(0.556819) H36(0.474682) H37(0.453956)
 H39(0.949583) H40(1.039279) H41(1.086872) H42(1.043638) H43(0.953944)
 H45(0.796611) H46(0.76127) H47(0.794767) H48(0.858773) H49(0.893618)
 H51(0.901731) H52(0.857854) H53(0.77463) H54(0.736612) H55(0.780767)
 H57(0.881472) H58(0.871802) H59(0.850262) H60(0.839886) H61(0.849263)
 Fixed Y: H4(0.772645) H5(0.866863) H6(0.975064) H8(1.057205) H9(1.070336)
 H10(0.977975) H14(0.955005) H15(1.038608) H16(0.990262) H17(0.855691)
 H18(0.770724) H20(0.536651) H21(0.448251) H22(0.519974) H23(0.679917)
 H24(0.770171) H27(0.387094) H28(0.216661) H29(0.126879) H33(0.542578)
 H34(0.543812) H35(0.588507) H36(0.6331) H37(0.632677) H39(0.634566)
 H40(0.632457) H41(0.734568) H42(0.839902) H43(0.838206) H45(0.874487)
 H46(0.91733) H47(0.849545) H48(0.733415) H49(0.691659) H51(0.548817)
 H52(0.403759) H53(0.399771) H54(0.543386) H55(0.687453) H57(0.944458)
 H58(1.056453) H59(1.008462) H60(0.845205) H61(0.732205)
 Fixed Z: Fe1(0.25) H4(0.374347) H5(0.440291) H6(0.474136) H8(0.47237)
 H9(0.435268) H10(0.367744) H14(0.24306) H15(0.242825) H16(0.291267)
 H17(0.338733) H18(0.340665) H20(0.321894) H21(0.322983) H22(0.300759)
 H23(0.277762) H24(0.275193) H27(0.15294) H28(0.150702) H29(0.208863) C30(0.25)
 C31(0.25) H33(0.20519) H34(0.137955) H35(0.065411) H36(0.058452) H37(0.124737)
 H39(0.506077) H40(0.540498) H41(0.513018) H42(0.451043) H43(0.415154)
 H45(0.379714) H46(0.300528) H47(0.249094) H48(0.276387) H49(0.355158)
 H51(0.426152) H52(0.417307) H53(0.416314) H54(0.425992) H55(0.435555)
 H57(0.441341) H58(0.491956) H59(0.554286) H60(0.564492) H61(0.51372)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              69117
_shelx_fab_checksum              37633
_olex2_submission_special_instructions 'No special instructions were received'