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_1573970
_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                 113.67(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.510(6)
_cell_length_b                   13.520(3)
_cell_length_c                   30.450(6)
_cell_measurement_reflns_used    3407
_cell_measurement_temperature    300.0(2)
_cell_measurement_theta_max      22.68
_cell_measurement_theta_min      1.61
_cell_volume                     10373(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      300.0(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  0.0301
_diffrn_reflns_av_unetI/netI     0.0138
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.896
_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       39
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            136550
_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         29.294
_diffrn_reflns_theta_min         1.460
_diffrn_source                   'MX1 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.203
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6493
_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    1.214
_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         0.201
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.032
_refine_ls_extinction_coef       0.00080(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   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         12698
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0429
_refine_ls_R_factor_gt           0.0378
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0670P)^2^+1.6738P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1153
_refine_ls_wR_factor_ref         0.1203
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11052
_reflns_number_total             12698
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-037-mecn-ipr2o-300k
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_original_cell_volume        10373(4)
_cod_database_code               1573970
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.920
_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(0.081) H5(0.092) H6(0.091) H8(0.092) H9(0.092) H10(0.079)
 H14(0.086) H15(0.12) H16(0.131) H17(0.119) H18(0.091) H20(0.076) H21(0.096)
 H22(0.103) H23(0.098) H24(0.081) H27(0.086) H28(0.107) H29(0.112) H33(0.074)
 H34(0.091) H35(0.097) H36(0.094) H37(0.075) H39(0.087) H40(0.099) H41(0.103)
 H42(0.104) H43(0.091) H45(0.103) H46(0.13) H47(0.136) H48(0.134) H49(0.108)
 H51(0.086) H52(0.094) H53(0.094) H54(0.093) H55(0.083) H57(0.098) H58(0.114)
 H59(0.109) H60(0.097) H61(0.081)
 Fixed X: Fe1(0.5) H4(0.698987) H5(0.749906) H6(0.712272) H8(0.624131)
 H9(0.534277) H10(0.485834) H14(0.441157) H15(0.368525) H16(0.328158)
 H17(0.356987) H18(0.430754) H20(0.600743) H21(0.67343) H22(0.736844)
 H23(0.728578) H24(0.655511) H27(0.518745) H28(0.516743) H29(0.506162) C30(0.5)
 C31(0.5) H33(0.601067) H34(0.620417) H35(0.557418) H36(0.474252) H37(0.453379)
 H39(0.950291) H40(1.041386) H41(1.089216) H42(1.044666) H43(0.953595)
 H45(0.794974) H46(0.759368) H47(0.791468) H48(0.857385) H49(0.892475)
 H51(0.901424) H52(0.857269) H53(0.773416) H54(0.735015) H55(0.77934)
 H57(0.881476) H58(0.873624) H59(0.851229) H60(0.839955) H61(0.849049)
 Fixed Y: H4(0.772678) H5(0.868494) H6(0.977041) H8(1.058889) H9(1.072191)
 H10(0.978566) H14(0.956271) H15(1.042881) H16(0.994708) H17(0.856783)
 H18(0.77016) H20(0.531496) H21(0.441319) H22(0.514956) H23(0.67751)
 H24(0.769274) H27(0.388518) H28(0.215888) H29(0.124912) H33(0.544843)
 H34(0.542153) H35(0.589723) H36(0.638079) H37(0.638651) H39(0.631072)
 H40(0.630842) H41(0.735966) H42(0.83948) H43(0.838205) H45(0.876074)
 H46(0.919605) H47(0.851483) H48(0.734927) H49(0.689615) H51(0.54503)
 H52(0.39767) H53(0.392518) H54(0.537554) H55(0.68484) H57(0.944854)
 H58(1.058985) H59(1.011293) H60(0.845387) H61(0.730325)
 Fixed Z: Fe1(0.25) H4(0.374374) H5(0.440947) H6(0.474869) H8(0.472926)
 H9(0.43472) H10(0.366679) H14(0.240527) H15(0.241202) H16(0.290098)
 H17(0.337006) H18(0.338938) H20(0.320485) H21(0.322964) H22(0.302694)
 H23(0.279408) H24(0.275723) H27(0.152767) H28(0.150731) H29(0.209012)
 C30(0.25) C31(0.25) H33(0.206167) H34(0.138541) H35(0.065338) H36(0.057939)
 H37(0.124608) H39(0.505775) H40(0.540857) H41(0.513632) H42(0.450075)
 H43(0.41407) H45(0.379266) H46(0.299715) H47(0.247388) H48(0.275048)
 H49(0.354086) H51(0.425033) H52(0.415941) H53(0.41636) H54(0.426497)
 H55(0.43619) H57(0.440794) H58(0.492728) H59(0.554846) H60(0.565395)
 H61(0.514051)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              36083
_shelx_fab_checksum              96902
_olex2_submission_special_instructions 'No special instructions were received'