Iron(II) spin crossover complexes of tetradentate Schiff-bases: tuning <i>T</i><sub>1/2</sub> by choice of formyl-heterocycle component.
Robb, Matthew G.; Chong, Shen V.; Brooker, Sally; Dalton transactions (Cambridge, England : 2003) 53 (2024) 10974–10981; doi:10.1039/d4dt00884g

data_7716344
_publ_section_title
;
 Iron(II) spin crossover complexes of tetradentate Schiff-bases: tuning
 <i>T</i><sub>1/2</sub> by choice of formyl-heterocycle component.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10974
_journal_page_last               10981
_journal_paper_doi               10.1039/d4dt00884g
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C17 H14 Br2 Fe N6 S2'
_chemical_formula_sum            'C17 H14 Br2 Fe N6 S2'
_chemical_formula_weight         582.13
_chemical_name_common            '[Fe(II) (LBrpyridine) (NCS)2]'
_chemical_name_systematic
'iron(II) thiocyanate complex of tetradentate Schiff base ligand'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-21 deposited with the CCDC.	2024-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.088(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0299(4)
_cell_length_b                   24.7177(9)
_cell_length_c                   10.4288(4)
_cell_measurement_reflns_used    4316
_cell_measurement_temperature    279.99(11)
_cell_measurement_theta_max      72.5540
_cell_measurement_theta_min      3.5390
_cell_volume                     2171.80(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      279.99(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1725
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.972
_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   -117.00 -18.00   1.00    1.33    --  -42.29 -38.00-150.00   99
  2  \w     27.00  94.00   1.00    1.33    --   42.29-125.00  60.00   67
  3  \w      6.00  33.00   1.00    1.33    --   42.29 -99.00-180.00   27
  4  \w     40.00  67.00   1.00    1.33    --   42.29-125.00 -90.00   27
  5  \w     29.00  60.00   1.00    5.32    --  104.32 -30.00-120.00   31
  6  \w     92.00 177.00   1.00    5.32    --  104.32  45.00-180.00   85
  7  \w    135.00 163.00   1.00    5.32    --  104.32  77.00-120.00   28
  8  \w     85.00 175.00   1.00    5.32    --  104.32  45.00 -90.00   90
  9  \w    121.00 162.00   1.00    5.32    --  104.32  77.00-150.00   41
 10  \w     35.00 132.00   1.00    5.32    --  104.32 -61.00  30.00   97
 11  \w    107.00 165.00   1.00    5.32    --  104.32  77.00 120.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0694706000
_diffrn_orient_matrix_UB_12      -0.0109563000
_diffrn_orient_matrix_UB_13      0.1557771000
_diffrn_orient_matrix_UB_21      -0.0736333000
_diffrn_orient_matrix_UB_22      0.0531184000
_diffrn_orient_matrix_UB_23      0.0263145000
_diffrn_orient_matrix_UB_31      -0.1523019000
_diffrn_orient_matrix_UB_32      -0.0307126000
_diffrn_orient_matrix_UB_33      -0.0100871000
_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  0.0466
_diffrn_reflns_av_unetI/netI     0.0662
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            8940
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.665
_diffrn_reflns_theta_min         3.576
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.809
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51823
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.780
_exptl_crystal_description       needle
_exptl_crystal_F_000             1144
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Crystallised from methanol reaction solution on standing'
_exptl_crystal_size_max          0.202
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.045
_refine_diff_density_max         3.039
_refine_diff_density_min         -0.800
_refine_diff_density_rms         0.219
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.496(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     506
_refine_ls_number_reflns         6330
_refine_ls_number_restraints     55
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0756
_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^)+(0.1479P)^2^+0.5122P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1915
_refine_ls_wR_factor_ref         0.2100
_reflns_Friedel_coverage         0.953
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                5575
_reflns_number_total             6330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00884g2.cif
_cod_data_source_block           mgr496_280k
_cod_depositor_comments
'Adding full bibliography for 7716343--7716348.cif.'
_cod_original_cell_volume        2171.80(16)
_cod_database_code               7716344
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHNFeBrS
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.504(13)
 0.496(13)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Rigid bond restraints
 C13, C12, C11, N4, C15, C14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C13 \\sim C12 \\sim C11 \\sim N4 \\sim C15 \\sim C14: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C13) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C27(H27A,H27B), C8(H8A,H8B), C9(H9A,H9B), C29(H29A,H29B),
 C28(H28A,H28B)
5.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C1(H1), C10(H10), C35(H35), C26(H26), C12(H12), C23(H23), C24(H24),
 C13(H13), C6(H6), C33(H33), C30(H30), C32(H32), C21(H21), C4(H4), C3(H3)
;
_shelx_res_checksum              72357
_shelx_hkl_checksum              65477
_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 1.595
_oxdiff_exptl_absorpt_empirical_full_min 0.704