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_7716767
_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(Cl O4), 2[CH3NO2]'
_chemical_formula_sum            'C53 H63 Cl2 Fe N11 O12'
_chemical_formula_weight         1172.89
_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             2024-07-09
_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                 99.778(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.8723(12)
_cell_length_b                   14.9781(5)
_cell_length_c                   25.2907(8)
_cell_measurement_reflns_used    10197
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      68.1540
_cell_measurement_theta_min      3.5210
_cell_volume                     11151.4(7)
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -106.00 -65.00   0.50   15.00    --  -43.75-139.00 136.00   82
  2  \w    -71.00 -16.00   0.50   15.00    --  -43.75 130.00  22.00  110
  3  \w    -96.00 -71.00   0.50   15.00    --  -43.75 139.00-163.00   50
  4  \w     33.00  96.00   0.50   15.00    --   45.32-130.00 -49.00  126
  5  \w     70.00  95.00   0.50   15.00    --   45.32 139.00-163.00   50
  6  \w     63.00  88.00   0.50   15.00    --   45.32-139.00 136.00   50
  7  \w    -99.00 -74.00   0.50   30.00    --  -93.31 139.00-163.00   50
  8  \w    -96.00 -71.00   0.50   30.00    --  -93.31 130.00  22.00   50
  9  \w   -139.00-112.00   0.50   30.00    --  -93.31-130.00 -49.00   54
 10  \w   -113.00 -71.00   0.50   30.00    --  -93.31-139.00 136.00   84
 11  \w     91.00 116.00   0.50   30.00    --   94.87 130.00  22.00   50
 12  \w     77.00 121.00   0.50   30.00    --   94.87-139.00 136.00   88
 13  \w     66.00 115.00   0.50   30.00    --   94.87-130.00 -49.00   98
 14  \w    -57.00  23.00   0.50   15.00    --  -43.75  54.00 150.00  160
 15  \w    -33.00  19.00   0.50   15.00    --  -43.75  32.00-120.00  104
 16  \w   -105.00 -71.00   0.50   15.00    --  -43.75 -54.00 -60.00   68
 17  \w    -66.00 -29.00   0.50   15.00    --  -43.75 -54.00 -60.00   74
 18  \w   -110.00 -65.00   0.50   15.00    --  -43.75-138.00-120.00   90
 19  \w     66.00  91.00   0.50   15.00    --   45.32 138.00 -30.00   50
 20  \w     66.00 110.00   0.50   15.00    --   45.32 138.00  90.00   88
 21  \w    -13.00  20.00   0.50   15.00    --   45.32 -21.00 120.00   66
 22  \w    -16.00  23.00   0.50   15.00    --   45.32 -11.00-180.00   78
 23  \w    -18.00   7.00   0.50   15.00    --   45.32 -11.00 120.00   50
 24  \w     86.00 111.00   0.50   15.00    --   45.32 138.00 -90.00   50
 25  \w    -58.00 -29.00   0.50   30.00    --  -93.31  96.00   0.00   58
 26  \w    -79.00 -23.00   0.50   30.00    --  -93.31  96.00  30.00  112
 27  \w   -161.00-132.00   0.50   30.00    --  -93.31 -25.00-150.00   58
 28  \w    -87.00 -29.00   0.50   30.00    --  -93.31 145.00  90.00  116
 29  \w    -57.00 -30.00   0.50   30.00    --  -93.31  68.00  60.00   54
 30  \w   -115.00 -90.00   0.50   30.00    --  -93.31 -25.00-150.00   50
 31  \w   -139.00 -81.00   0.50   30.00    --  -93.31 -86.00  60.00  116
 32  \w     30.00  83.00   0.50   30.00    --   94.87 -68.00  90.00  106
 33  \w     69.00 108.00   0.50   30.00    --   94.87-117.00-180.00   78
 34  \w     30.00  57.00   0.50   30.00    --   94.87 -50.00-150.00   54
 35  \w     29.00  57.00   0.50   30.00    --   94.87 -50.00-120.00   56
 36  \w     75.00 161.00   0.50   30.00    --   94.87  68.00 150.00  172
 37  \w     86.00 153.00   0.50   30.00    --   94.87  33.00 120.00  134
 38  \w     30.00 107.00   0.50   30.00    --   94.87-117.00-120.00  154
 39  \w     33.00 100.00   0.50   30.00    --   94.87-117.00  30.00  134
 40  \w     79.00 139.00   0.50   30.00    --   94.87 117.00-120.00  120
 41  \w     29.00  54.00   0.50   30.00    --   94.87 -50.00 -60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0507957000
_diffrn_orient_matrix_UB_12      -0.0238528000
_diffrn_orient_matrix_UB_13      0.0058588000
_diffrn_orient_matrix_UB_21      -0.0125807000
_diffrn_orient_matrix_UB_22      -0.0985175000
_diffrn_orient_matrix_UB_23      -0.0121846000
_diffrn_orient_matrix_UB_31      -0.0016747000
_diffrn_orient_matrix_UB_32      0.0176078000
_diffrn_orient_matrix_UB_33      -0.0602735000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0621
_diffrn_reflns_av_unetI/netI     0.0566
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            36301
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.559
_diffrn_reflns_theta_min         3.547
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.647
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61455
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (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    1.397
_exptl_crystal_description       prism
_exptl_crystal_F_000             4912
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.129
_refine_diff_density_min         -0.863
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     686
_refine_ls_number_reflns         10119
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.1339
_refine_ls_R_factor_gt           0.1035
_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^)+(0.1770P)^2^+40.2538P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2905
_refine_ls_wR_factor_ref         0.3150
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6873
_reflns_number_total             10119
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01338g2.cif
_cod_data_source_block           01
_cod_depositor_comments
'Adding full bibliography for 7716767--7716771.cif.'
_cod_database_code               7716767
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N O Fe S  Cl '
_shelx_estimated_absorpt_t_max   0.593
_shelx_estimated_absorpt_t_min   0.388
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-O6 \\sim Cl2A-O6A \\sim Cl2-O8 \\sim Cl2A-O8A \\sim Cl2-O5 \\sim Cl2A-O5A
\\sim Cl2-O7 \\sim Cl2A-O7A
 with sigma of 0.02
 Cl1-O1 \\sim Cl1A-O1A \\sim Cl1-O2 \\sim Cl1A-O2A \\sim Cl1-O3 \\sim Cl1A-O3A
 with sigma of 0.02
 C47-C48 \\sim C48-C49 \\sim C49-C50
 with sigma of 0.04
 O1-O2 \\sim O2-O3 \\sim O3-O1 \\sim O1A-O2A \\sim O2A-O3A \\sim O3A-O1A
 with sigma of 0.02
 O4-O1 \\sim O4-O2 \\sim O4-O3 \\sim O4-O1A \\sim O4-O2A \\sim O4-O3A
 with sigma of 0.02
 C47-C48 \\sim C47-C48A
 with sigma of 0.02
 O4-Cl1 \\sim O4-Cl1A
 with sigma of 0.02
 O6-O8 \\sim O6A-O8A
 with sigma of 0.04
 Cl1-O1 \\sim Cl1A-O1
 with sigma of 0.02
 O6-O5 \\sim O6A-O5A
 with sigma of 0.04
 Cl1-O2 \\sim Cl1A-O2
 with sigma of 0.02
 Cl1-O3 \\sim Cl1A-O3
 with sigma of 0.02
 O6-O7 \\sim O6A-O7A
 with sigma of 0.04
 Cl1-O4 \\sim Cl1A-O4
 with sigma of 0.02
 O8-O5 \\sim O8A-O5A
 with sigma of 0.04
 Cl1-O1A \\sim Cl1A-O1A
 with sigma of 0.02
 O8-O7 \\sim O8A-O7A
 with sigma of 0.04
 Cl1-O2A \\sim Cl1A-O2A
 with sigma of 0.02
 O5-O7 \\sim O5A-O7A
 with sigma of 0.04
 Cl1-O3A \\sim Cl1A-O3A
 with sigma of 0.02
 C48-C49 \\sim C48A-C49A
 with sigma of 0.02
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C48) = Uanis(C48A)
Uanis(O1) = Uanis(O1A)
Uanis(O2) = Uanis(O2A)
Uanis(O3) = Uanis(O3A)
Uanis(C49A) = Uanis(C49)
Uanis(C50) = Uanis(C50A)
Uanis(O1A) = Uanis(O2A) = Uanis(O3A)
Uanis(C51) = Uanis(C51A)
Uanis(O5) = Uanis(O5A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(O8) = Uanis(O8A)
Uanis(O7A) = Uanis(O7)
Uanis(O6) = Uanis(O6A)
Uanis(Cl2) = Uanis(Cl2A)
4. Others
 Sof(Cl2A)=Sof(O5A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=1-FVAR(1)
 Sof(Cl2)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(O8)=FVAR(1)
 Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=Sof(C49A)=Sof(H49C)=
 Sof(H49D)=Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C50A)=Sof(H50C)=
 Sof(H50D)=1-FVAR(2)
 Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(2)
 Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(Cl1A)=1-FVAR(3)
 Sof(Cl1)=Sof(O1)=Sof(O2)=Sof(O3)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C42(H42A,
 H42B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C47(H47A,H47B),
 C47(H47C,H47D), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B), C48A(H48C,
 H48D), C49A(H49C,H49D), C50A(H50C,H50D)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12),
 C19(H19), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28), C29(H29),
  C31(H31), C32(H32), C33(H33), C34(H34), C38(H38), C39(H39), C40(H40), C41(H41)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C46(H46A,H46B,H46C), C51(H51A,H51B,H51C), C51A(H51D,H51E,
 H51F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 566 electrons were 
found in a volume of 1888\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[CH3NO2] per formula unit 
which account for 512 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              47143
_shelx_fab_checksum              74333
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.937
_oxdiff_exptl_absorpt_empirical_full_min 0.496