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_1573974
_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_absolute_configuration unk
_chemical_formula_moiety
'C72 H48 Co N6, 2(C24 H20 B), 1[CH2Cl2], 2[C6H14O]'
_chemical_formula_sum            'C133 H118 B2 Cl2 Co N6 O2'
_chemical_formula_weight         1983.78
_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             2023-11-10
_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                 114.30(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.429(6)
_cell_length_b                   13.479(3)
_cell_length_c                   29.817(6)
_cell_measurement_reflns_used    1453
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.51
_cell_measurement_theta_min      2.04
_cell_volume                     10047(4)
_computing_cell_refinement       'XDS (Kabsch, 1993)'
_computing_data_collection       'AS QEQUI'
_computing_data_reduction        'XDS (Kabsch, 1993)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.828
_diffrn_measurement_device       synchrotron
_diffrn_measurement_device_type  'Dectris Eiger 16M'
_diffrn_measurement_method       'Omega Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.71076
_diffrn_reflns_av_R_equivalents  0.0711
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.828
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            104807
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.828
_diffrn_reflns_theta_full        25.243
_diffrn_reflns_theta_max         32.436
_diffrn_reflns_theta_min         1.629
_diffrn_source                   'MX2 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.285
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.5398
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2012/1 (Bruker,2012)'
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             4180
_exptl_crystal_recrystallization_method
'50 mg sample in 3 mL dichloromethane layered with 6 mL diisopropylether'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.722
_refine_diff_density_min         -0.727
_refine_diff_density_rms         0.059
_refine_ls_extinction_coef       0.0031(4)
_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   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     584
_refine_ls_number_reflns         14973
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0558
_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^)+(0.1143P)^2^+1.0326P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1750
_refine_ls_wR_factor_ref         0.1813
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12597
_reflns_number_total             14973
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj2-069-dcmiprether
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_database_code               1573974
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.927
_olex2_refinement_description
;
1. Others
 Fixed Sof: Co1(0.5) C27(0.5) C31(0.5)
 Fixed U12: Co1(0) C27(0) C31(0)
 Fixed U23: Co1(0) C27(0) C31(0)
 Fixed Uiso: H4(0.061) H5(0.067) H6(0.068) H10(0.056) H11(0.063) H12(0.065)
 H14(0.053) H15(0.062) H16(0.069) H17(0.068) H18(0.06) H20(0.072) H21(0.093)
 H22(0.101) H23(0.091) H24(0.066) H28(0.06) H29(0.073) H30(0.08) H33(0.055)
 H34(0.064) H35(0.065) H36(0.061) H37(0.054) H39(0.061) H40(0.066) H41(0.066)
 H42(0.066) H43(0.062) H45(0.072) H46(0.081) H47(0.083) H48(0.079) H49(0.068)
 H51(0.06) H52(0.065) H53(0.072) H54(0.075) H55(0.069) H57(0.061) H58(0.068)
 H59(0.068) H60(0.067) H61(0.062)
 Fixed X: Co1(0.5) H4(0.296927) H5(0.245408) H6(0.284757) H10(0.514792)
 H11(0.466252) H12(0.374425) H14(0.395247) H15(0.32321) H16(0.26037)
 H17(0.26811) H18(0.339456) H20(0.567693) H21(0.644305) H22(0.675255)
 H23(0.634786) H24(0.559943) C27(0.5) H28(0.479185) H29(0.482316) H30(0.49395)
 C31(0.5) H33(0.546626) H34(0.524336) H35(0.438738) H36(0.375662) H37(0.397235)
 H39(0.049906) H40(-0.04245) H41(-0.090578) H42(-0.04411) H43(0.04865)
 H45(0.107321) H46(0.142212) H47(0.210053) H48(0.242937) H49(0.207485)
 H51(0.150696) H52(0.16148) H53(0.151865) H54(0.131355) H55(0.121594)
 H57(0.222353) H58(0.267314) H59(0.228433) H60(0.14355) H61(0.098677)
 Fixed Y: H4(0.218581) H5(0.114633) H6(0.002375) H10(0.025882) H11(-0.076867)
 H12(-0.073564) H14(0.474291) H15(0.565381) H16(0.488285) H17(0.321114)
 H18(0.228296) H20(0.24426) H21(0.163259) H22(0.021497) H23(-0.035154)
 H24(0.048286) H28(0.630406) H29(0.805367) H30(0.897275) H33(0.379049)
 H34(0.373113) H35(0.418483) H36(0.470795) H37(0.476745) H39(0.372325)
 H40(0.371192) H41(0.263381) H42(0.15686) H43(0.160163) H45(0.31671)
 H46(0.274596) H47(0.156321) H48(0.083114) H49(0.126093) H51(0.2727)
 H52(0.154345) H53(-0.013915) H54(-0.061435) H55(0.05675) H57(0.315239)
 H58(0.464566) H59(0.611768) H60(0.605551) H61(0.456116)
 Fixed Z: Co1(0.75) H4(0.623313) H5(0.556807) H6(0.524224) H10(0.630543)
 H11(0.562987) H12(0.525859) H14(0.6771) H15(0.678233) H16(0.700376)
 H17(0.720211) H18(0.718523) H20(0.656626) H21(0.659115) H22(0.705937)
 H23(0.755304) H24(0.756424) C27(0.75) H28(0.848473) H29(0.851386)
 H30(0.791717) C31(0.75) H33(0.879169) H34(0.946983) H35(0.937759)
 H36(0.861713) H37(0.793532) H39(0.490565) H40(0.454005) H41(0.482333)
 H42(0.547729) H43(0.585112) H45(0.645118) H46(0.727352) H47(0.758303)
 H48(0.704986) H49(0.622528) H51(0.482022) H52(0.430716) H53(0.443522)
 H54(0.509022) H55(0.560724) H57(0.562712) H58(0.573) H59(0.58402)
 H60(0.584382) H61(0.574652)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              84574
_shelx_fab_checksum              28221
_olex2_submission_special_instructions 'No special instructions were received'