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_1573977
_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                 113.83(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.440(6)
_cell_length_b                   13.470(3)
_cell_length_c                   30.390(6)
_cell_measurement_reflns_used    3484
_cell_measurement_temperature    250.0(2)
_cell_measurement_theta_max      23.38
_cell_measurement_theta_min      1.61
_cell_volume                     10275(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      250.0(2)
_diffrn_detector_area_resol_mean 13.3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.889
_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  0.0300
_diffrn_reflns_av_unetI/netI     0.0134
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.889
_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       -41
_diffrn_reflns_number            134435
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.889
_diffrn_reflns_theta_full        25.243
_diffrn_reflns_theta_max         29.340
_diffrn_reflns_theta_min         1.465
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.205
_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    1.225
_exptl_crystal_description       needle
_exptl_crystal_F_000             4008
_exptl_crystal_size_max          0.417
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.00105(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   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         12544
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0405
_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^)+(0.0646P)^2^+2.8475P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1163
_refine_ls_wR_factor_ref         0.1222
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11099
_reflns_number_total             12544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj3-037-mecn-ipr2o-250k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_database_code               1573977
_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(0.07) H5(0.077) H6(0.077) H8(0.077) H9(0.077) H10(0.067)
 H14(0.073) H15(0.1) H16(0.11) H17(0.101) H18(0.078) H20(0.064) H21(0.08)
 H22(0.086) H23(0.081) H24(0.068) H27(0.074) H28(0.09) H29(0.096) H33(0.063)
 H34(0.076) H35(0.083) H36(0.079) H37(0.064) H39(0.073) H40(0.083) H41(0.085)
 H42(0.086) H43(0.076) H45(0.086) H46(0.11) H47(0.115) H48(0.111) H49(0.09)
 H51(0.072) H52(0.078) H53(0.079) H54(0.078) H55(0.07) H57(0.083) H58(0.098)
 H59(0.094) H60(0.082) H61(0.069)
 Fixed X: Fe1(0.5) H4(0.70001) H5(0.751361) H6(0.713273) H8(0.624676)
 H9(0.53379) H10(0.485129) H14(0.441112) H15(0.368066) H16(0.327146)
 H17(0.356489) H18(0.430526) H20(0.600542) H21(0.67363) H22(0.738021)
 H23(0.72986) H24(0.656218) H27(0.518888) H28(0.516411) H29(0.506314) C30(0.5)
 C31(0.5) H33(0.601643) H34(0.621183) H35(0.557601) H36(0.473767) H37(0.452928)
 H39(0.950303) H40(1.042241) H41(1.090392) H42(1.045165) H43(0.953283)
 H45(0.794267) H46(0.758463) H47(0.790654) H48(0.857466) H49(0.892604)
 H51(0.901604) H52(0.85709) H53(0.772786) H54(0.73406) H55(0.778864)
 H57(0.881184) H58(0.873446) H59(0.85139) H60(0.83985) H61(0.849046)
 Fixed Y: H4(0.773354) H5(0.870032) H6(0.979467) H8(1.060446) H9(1.073252)
 H10(0.978276) H14(0.9566) H15(1.044214) H16(0.994896) H17(0.854931)
 H18(0.767757) H20(0.529665) H21(0.438542) H22(0.513319) H23(0.677812)
 H24(0.769999) H27(0.387326) H28(0.213325) H29(0.1215) H33(0.542696)
 H34(0.540286) H35(0.589069) H36(0.638129) H37(0.638901) H39(0.629527)
 H40(0.630134) H41(0.735979) H42(0.840763) H43(0.838746) H45(0.876728)
 H46(0.921017) H47(0.851802) H48(0.734135) H49(0.688547) H51(0.544039)
 H52(0.395554) H53(0.389721) H54(0.536301) H55(0.684582) H57(0.945458)
 H58(1.060658) H59(1.012554) H60(0.844901) H61(0.728621)
 Fixed Z: Fe1(0.25) H4(0.374431) H5(0.441391) H6(0.475666) H8(0.473818)
 H9(0.435134) H10(0.366734) H14(0.240502) H15(0.24131) H16(0.290227)
 H17(0.337548) H18(0.339014) H20(0.320443) H21(0.322843) H22(0.302891)
 H23(0.280041) H24(0.276134) H27(0.152318) H28(0.150009) H29(0.209094)
 C30(0.25) C31(0.25) H33(0.206576) H34(0.138701) H35(0.064728) H36(0.057201)
 H37(0.124309) H39(0.506197) H40(0.541885) H41(0.514197) H42(0.450048)
 H43(0.413727) H45(0.379239) H46(0.299021) H47(0.246236) H48(0.274354)
 H49(0.354118) H51(0.424762) H52(0.415269) H53(0.416141) H54(0.42653)
 H55(0.436659) H57(0.440397) H58(0.492615) H59(0.555382) H60(0.566135)
 H61(0.514493)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              46960
_shelx_fab_checksum              79775
_olex2_submission_special_instructions 'No special instructions were received'