Above room temperature spin crossover in mononuclear iron(II) complexes featuring pyridyl-benzimidazole bidentate ligands adorned with aliphatic chains.
Šagátová, Alexandra; Kotrle, Kamil; Brachňaková, Barbora; Havlíček, Lubomír; Nemec, Ivan; Herchel, Radovan; Hofbauerova, Monika; Halahovets, Yuriy; Šiffalovič, Peter; Čižmár, Erik; Fellner, Ondřej F; Šalitroš, Ivan; Dalton transactions (Cambridge, England : 2003) 53 (2024) 14037–14045; doi:10.1039/d4dt01338g

data_7716768
_publ_section_title
;
 Above room temperature spin crossover in mononuclear iron(II) complexes
 featuring pyridyl-benzimidazole bidentate ligands adorned with aliphatic
 chains.
;
_journal_issue                   33
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14037
_journal_page_last               14045
_journal_paper_doi               10.1039/d4dt01338g
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C51 H57 Fe N9, 2(C F3 O3 S)'
_chemical_formula_sum            'C53 H57 F6 Fe N9 O6 S2'
_chemical_formula_weight         1150.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-06-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-11 deposited with the CCDC.	2024-07-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.119(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6483(3)
_cell_length_b                   22.5038(3)
_cell_length_c                   17.2162(4)
_cell_measurement_reflns_used    9168
_cell_measurement_temperature    200.0(2)
_cell_measurement_theta_max      68.8670
_cell_measurement_theta_min      3.7030
_cell_volume                     5443.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      200.0(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15717
_diffrn_reflns_point_group_measured_fraction_full 0.712
_diffrn_reflns_point_group_measured_fraction_max 0.701
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.689
_diffrn_reflns_theta_min         3.709
_exptl_absorpt_coefficient_mu    3.609
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92888
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.57a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_colour_primary    purple
_exptl_crystal_density_diffrn    1.403
_exptl_crystal_description       block
_exptl_crystal_F_000             2392
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.464
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 1708 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.002(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     738
_refine_ls_number_reflns         7196
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0510
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0826P)^2^+5.3154P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1368
_refine_ls_wR_factor_ref         0.1401
_reflns_Friedel_coverage         0.418
_reflns_Friedel_fraction_full    0.425
_reflns_Friedel_fraction_max     0.414
_reflns_number_gt                6628
_reflns_number_total             7196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01338g2.cif
_cod_data_source_block           03
_cod_depositor_comments
'Adding full bibliography for 7716767--7716771.cif.'
_cod_database_code               7716768
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C43-C44 \\sim C44-C45 \\sim C45-C46
 with sigma of 0.04
 C38-C39 \\sim C38A-C39A
 with sigma of 0.04
 C39-C40 \\sim C39A-C40A
 with sigma of 0.04
 C40-C41 \\sim C40A-C41
 with sigma of 0.04
 C39-C38 \\sim C39A-C38A
 with sigma of 0.02
 N8-C37 \\sim N8-C37A
 with sigma of 0.02
 C37-C38 \\sim C37A-C38A
 with sigma of 0.02
 N8-C38 \\sim N8-C38A
 with sigma of 0.04
 S2-O4 \\sim S2A-O4A
 with sigma of 0.02
 S2-O6 \\sim S2A-O6A
 with sigma of 0.02
 S2-O5 \\sim S2A-O5A
 with sigma of 0.02
 S2-C53 \\sim S2A-C53A
 with sigma of 0.02
 F4-C53 \\sim F4A-C53A
 with sigma of 0.02
 F5-C53 \\sim F5A-C53A
 with sigma of 0.02
 C53-F6 \\sim C53A-F6A
 with sigma of 0.02
 C53-F4 \\sim C53A-F4A \\sim C53-F5 \\sim C53A-F5A \\sim C53-F6 \\sim C53A-F6A
 with sigma of 0.02
 O4-O6 \\sim O4A-O6A \\sim O4-O5 \\sim O4A-O5A \\sim O6-O5 \\sim O6A-O5A
 with sigma of 0.04
 O4-S2 \\sim O4A-S2A \\sim O6-S2 \\sim O6A-S2A \\sim O5-S2 \\sim O5A-S2A
 with sigma of 0.04
 F4-F5 \\sim F4A-F5A \\sim F5-F6 \\sim F5A-F6A \\sim F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 S1-O1 \\sim S1-O1A \\sim S1-O3 \\sim S1-O3A \\sim S1-O2 \\sim S1-O2A
 with sigma of 0.02
 O1-O2 \\sim O2-O3 \\sim O3-O1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C37A \\sim C38A \\sim C37 \\sim C38 \\sim C39 \\sim C39A \\sim C40A \\sim C40
\\sim C41: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
O4 \\sim O6 \\sim O5: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
C53 \\sim S2: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
O2 \\sim O2A \\sim O1 \\sim O1A \\sim O3 \\sim O3A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C39) = Uanis(C39A)
Uanis(C37) = Uanis(C37A)
Uanis(C38) = Uanis(C38A)
Uanis(F4A) = Uanis(F4) = Uanis(F5) = Uanis(F5A)
Uanis(F6) = Uanis(F6A)
Uanis(O4A) = Uanis(O5) = Uanis(O5A) = Uanis(O6A) = Uanis(O6) = Uanis(O4)
Uanis(S2) = Uanis(S2A)
Uanis(C53A) = Uanis(C53)
Uanis(O1) = Uanis(O1A)
Uanis(O3A) = Uanis(O3)
4. Rigid body (RIGU) restrains
 C43, C44, C45, C46
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C38A)=
 Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=
 Sof(H40D)=1-FVAR(1)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C40)=Sof(H40A)=Sof(H40B)=FVAR(1)
 Sof(O4A)=Sof(O6A)=Sof(S2A)=Sof(O5A)=Sof(F6A)=Sof(C53A)=Sof(F5A)=Sof(F4A)=1-
 FVAR(2)
 Sof(S2)=Sof(O4)=Sof(O6)=Sof(O5)=Sof(F4)=Sof(F5)=Sof(C53)=Sof(F6)=FVAR(2)
 Sof(O2A)=Sof(O3A)=Sof(O1A)=1-FVAR(3)
 Sof(O1)=Sof(O3)=Sof(O2)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C48(H48A,H48B), C37(H37A,H37B), C39(H39A,H39B), C38(H38A,
 H38B), C50(H50A,H50B), C49(H49A,H49B), C42(H42A,H42B), C43(H43A,H43B),
 C44(H44A,H44B), C45(H45A,H45B), C37A(H37C,H37D), C38A(H38C,H38D), C39A(H39C,
 H39D), C40(H40A,H40B), C40A(H40C,H40D)
6.b Me refined with riding coordinates:
 C46(H46A,H46B,H46C)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C33(H33), C3(H3), C11(H11), C32(H32), C13(H13), C8(H8), C35(H35),
 C10(H10), C25(H25), C34(H34), C26(H26), C1(H1), C2(H2), C14(H14), C23(H23),
 C15(H15), C21(H21), C28(H28), C9(H9), C27(H27), C20(H20), C22(H22), C16(H16)
6.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C41(H41D,H41E,H41F), C51(H51A,H51B,H51C)
;
_shelx_res_checksum              20495
_olex2_submission_special_instructions 'No special instructions were received'