Symmetric and asymmetric ligands for Fe<sup>III</sup> spin crossover - the influence of the <i>C</i><sub>2</sub> axis.
Kelly, Conor T.; Cuza, Emmelyne; Pasquetti, Eoin; Quinn, Niall; Griffin, Michael; Nockemann, Peter; Müller-Bunz, Helge; Bruno-Colmenarez, Julia; Felton, Solveig; Lada, Zoi G.; Morgan, Grace G.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 14522–14532; doi:10.1039/d5dt01833a

data_7719413
_publ_section_title
;
 Symmetric and asymmetric ligands for Fe<sup>III</sup> spin crossover -
 the influence of the <i>C</i><sub>2</sub> axis.
;
_journal_issue                   38
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14522
_journal_page_last               14532
_journal_paper_doi               10.1039/d5dt01833a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C21 H24 Br2 Fe N4 O2, Cl O4'
_chemical_formula_sum            'C21 H24 Br2 Cl Fe N4 O6'
_chemical_formula_weight         679.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-23
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.06 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-06-26 deposited with the CCDC.	2025-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.2897(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.12715(4)
_cell_length_b                   21.06361(10)
_cell_length_c                   14.63035(7)
_cell_measurement_reflns_used    22637
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.5490
_cell_measurement_theta_min      4.1760
_cell_volume                     2503.89(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.144a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.144a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3218
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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    -82.00  11.00   0.50    0.50    --  -42.23 105.00-159.00  186
  2  \w     11.00  85.00   0.50    0.50    --   42.23-105.00 100.00  148
  3  \w     34.00 108.00   0.50    3.00    --  112.00-105.00 100.00  148
  4  \w    104.00 178.00   0.50    3.00    --  112.00 105.00-159.00  148
  5  \w    -70.00  31.00   0.50    0.50    --  -42.23  57.00 -60.00  202
  6  \w    -67.00  32.00   0.50    0.50    --  -42.23  37.00  60.00  198
  7  \w      9.00  42.00   0.50    0.50    --   42.23  79.00 -29.48   66
  8  \w     10.00  42.00   0.50    0.50    --   42.23  76.00  -6.60   64
  9  \w      6.00  82.00   0.50    0.50    --   42.23 -99.00-120.00  152
 10  \w     10.00  42.00   0.50    0.50    --   42.23  76.00-157.87   64
 11  \w     14.00 114.00   0.50    0.50    --   42.23  57.00  30.00  200
 12  \w     36.00 140.00   0.50    3.00    --  112.00 -30.00 -90.00  208
 13  \w    104.00 178.00   0.50    3.00    --  112.00 111.00 150.00  148
 14  \w     39.00 109.00   0.50    3.00    --  112.00-111.00-120.00  140
 15  \w     29.00 107.00   0.50    3.00    --  112.00 -94.00 -90.00  156
 16  \w    104.00 178.00   0.50    3.00    --  112.00 111.00-120.00  148
 17  \w     39.00 109.00   0.50    3.00    --  112.00-111.00-150.00  140
 18  \w     36.00 140.00   0.50    3.00    --  112.00 -30.00 -90.00  208
 19  \w     39.00 109.00   0.50    3.00    --  112.00-111.00 -60.00  140
 20  \w     39.00 138.00   0.50    3.00    --  112.00 -45.00 -30.00  198
 21  \w     39.00 109.00   0.50    3.00    --  112.00-111.00   0.00  140
 22  \w     39.00 138.00   0.50    3.00    --  112.00 -45.00 120.00  198
 23  \w     39.00 109.00   0.50    3.00    --  112.00-111.00-180.00  140
 24  \w     39.00 138.00   0.50    3.00    --  112.00 -45.00 -30.00  198
 25  \w     39.00 109.00   0.50    3.00    --  112.00-111.00  60.00  140
 26  \w    103.00 178.00   0.50    3.00    --  112.00  77.00  30.00  150
 27  \w     86.00 178.00   0.50    3.00    --  112.00  45.00 -60.00  184
 28  \w     86.00 178.00   0.50    3.00    --  112.00  45.00 -60.00  184
 29  \w     86.00 178.00   0.50    3.00    --  112.00  45.00 150.00  184
 30  \w     39.00 109.00   0.50    3.00    --  112.00-111.00  90.00  140
 31  \w     84.00 178.00   0.50    3.00    --  112.00  30.00 -30.00  188
 32  \w     39.00 109.00   0.50    3.00    --  112.00-111.00 -30.00  140
 33  \w     39.00 109.00   0.50    3.00    --  112.00-111.00 150.00  140
 34  \w     29.00 107.00   0.50    3.00    --  112.00 -94.00-120.00  156
 35  \w     86.00 178.00   0.50    3.00    --  112.00  45.00  30.00  184
 36  \w     36.00 140.00   0.50    3.00    --  112.00 -30.00  60.00  208
 37  \w     36.00 140.00   0.50    3.00    --  112.00 -30.00  60.00  208
 38  \w      8.00  42.00   0.50    0.50    --   42.23  82.00 -93.88   68
 39  \w     18.00 117.00   0.50    0.50    --   42.23  37.00 -90.00  198
 40  \w     14.00 114.00   0.50    0.50    --   42.23  57.00 120.00  200
 41  \w    -32.00  58.00   0.50    0.50    --   42.23 -37.00  90.00  180
 42  \w      9.00  42.00   0.50    0.50    --   42.23  79.00 128.62   66
;
_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      -0.1002739000
_diffrn_orient_matrix_UB_12      0.0612500000
_diffrn_orient_matrix_UB_13      -0.0154114000
_diffrn_orient_matrix_UB_21      -0.1576112000
_diffrn_orient_matrix_UB_22      -0.0350533000
_diffrn_orient_matrix_UB_23      0.0278341000
_diffrn_orient_matrix_UB_31      0.0327851000
_diffrn_orient_matrix_UB_32      0.0191409000
_diffrn_orient_matrix_UB_33      0.1004003000
_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  0.0226
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            26089
_diffrn_reflns_point_group_measured_fraction_full 0.848
_diffrn_reflns_point_group_measured_fraction_max 0.830
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.740
_diffrn_reflns_theta_min         3.679
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.946
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75525
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.144a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.803
_exptl_crystal_description       block
_exptl_crystal_F_000             1356
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.003(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     324
_refine_ls_number_reflns         4381
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0217
_refine_ls_R_factor_gt           0.0215
_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^)+(0.0365P)^2^+3.0409P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0562
_refine_ls_wR_factor_ref         0.0564
_reflns_Friedel_coverage         0.663
_reflns_Friedel_fraction_full    0.695
_reflns_Friedel_fraction_max     0.664
_reflns_number_gt                4367
_reflns_number_total             4381
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01833a2.cif
_cod_data_source_block           2-3_mor1918
_cod_depositor_comments
'Adding full bibliography for 7719387--7719420.cif.'
_cod_database_code               7719413
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C21 H24 N4 O6 Fe Br2 Cl'
_chemical_oxdiff_usercomment     'Conor, CK-556-1'
_cell_oxdiff_angle_alpha         90.0149(9)
_cell_oxdiff_angle_beta          91.2910(10)
_cell_oxdiff_angle_gamma         90.0433(12)
_cell_oxdiff_length_a            8.12481(12)
_cell_oxdiff_length_b            21.0687(3)
_cell_oxdiff_length_c            14.63104(13)
_cell_oxdiff_measurement_reflns_used 22638
_cell_oxdiff_volume              2503.89(6)
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C12(H12A,H12B), C10(H10A,H10B), C8(H8A,H8B), C13(H13A,H13B),
 C11(H11A,H11B), C14(H14A,H14B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3A), C7(H7), C19(H19), C2(H2A), C15(H15), C17(H17), C20(H20)
;
_shelx_res_checksum              29799
_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 1.873
_oxdiff_exptl_absorpt_empirical_full_min 0.800