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_7719400
_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 H22 Br4 Fe N4 O2, N O3'
_chemical_formula_sum            'C21 H22 Br4 Fe N5 O5'
_chemical_formula_weight         799.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-17
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.06 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-06-04 deposited with the CCDC.	2025-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.3991(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.36570(3)
_cell_length_b                   16.96833(6)
_cell_length_c                   14.72949(5)
_cell_measurement_reflns_used    41801
_cell_measurement_temperature    106.6(3)
_cell_measurement_theta_max      76.4200
_cell_measurement_theta_min      3.9530
_cell_volume                     2555.968(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_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      106.6(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3196
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -79.00  23.00   0.30    0.50    --  -41.70  91.00  92.00  340
  2  \w     -3.00  78.00   0.30    0.50    --   41.70 -91.00 -21.00  270
  3  \w     29.00 107.00   0.30    2.50    --  112.00 -91.00 -21.00  260
  4  \w    104.00 176.90   0.30    2.50    --  112.00  91.00  92.00  243
  5  \w    -66.00  33.00   0.30    0.50    --  -41.70  37.00 -60.00  330
  6  \w    -87.00  -6.00   0.30    0.50    --  -41.70 125.00-180.00  270
  7  \w   -115.00 -15.10   0.30    0.50    --  -41.70 -57.00 -90.00  333
  8  \w      9.00  42.00   0.30    0.50    --   41.70  77.00 -92.13  110
  9  \w     10.00  34.90   0.30    0.50    --   41.70  75.00-177.59   83
 10  \w      9.00  42.00   0.30    0.50    --   41.70  80.00-134.05  110
 11  \w      7.00  31.90   0.30    0.50    --   41.70  84.00-149.59   83
 12  \w    103.00 178.00   0.30    2.50    --  112.00  77.00  60.00  250
 13  \w     86.00 176.90   0.30    2.50    --  112.00  45.00-180.00  303
 14  \w     83.00 176.90   0.30    2.50    --  112.00  60.00 136.07  313
 15  \w     29.00 107.00   0.30    2.50    --  112.00 -94.00  90.00  260
 16  \w     86.00 176.90   0.30    2.50    --  112.00  45.00-150.00  303
 17  \w     40.00 139.90   0.30    2.50    --  112.00 -61.00-120.00  333
 18  \w     40.00 124.90   0.30    2.50    --  112.00-142.00  27.93  283
 19  \w     36.00 108.00   0.30    2.50    --  112.00-111.00  60.00  240
 20  \w    103.00 178.00   0.30    2.50    --  112.00  77.00-150.00  250
 21  \w     39.00 138.00   0.30    2.50    --  112.00 -45.00 -30.00  330
 22  \w    103.00 178.00   0.30    2.50    --  112.00  77.00   0.00  250
 23  \w    104.00 176.90   0.30    2.50    --  112.00 111.00 -90.00  243
 24  \w    103.00 178.00   0.30    2.50    --  112.00  77.00 150.00  250
 25  \w    104.00 176.90   0.30    2.50    --  112.00 111.00 -30.00  243
 26  \w     29.00 107.00   0.30    2.50    --  112.00 -94.00  60.00  260
 27  \w     81.00 177.00   0.30    2.50    --  112.00  70.00  74.80  320
 28  \w     36.00 108.00   0.30    2.50    --  112.00-111.00  30.00  240
 29  \w     82.00 178.00   0.30    2.50    --  112.00  65.00  38.48  320
 30  \w    104.00 176.90   0.30    2.50    --  112.00 111.00-150.00  243
 31  \w     36.00 138.90   0.30    2.50    --  112.00 -30.00 -60.00  343
 32  \w     81.00 177.00   0.30    2.50    --  112.00  70.00  46.50  320
 33  \w    104.00 176.90   0.30    2.50    --  112.00 111.00-120.00  243
 34  \w     84.00 177.00   0.30    2.50    --  112.00  54.00  31.52  310
 35  \w   -115.00 -15.10   0.30    0.50    --  -41.70 -57.00   0.00  333
 36  \w    -66.00  33.00   0.30    0.50    --  -41.70  37.00  60.00  330
 37  \w   -116.00 -17.00   0.30    0.50    --  -41.70 -37.00 120.00  330
 38  \w      9.00  42.00   0.30    0.50    --   41.70  79.00  82.90  110
 39  \w      8.00  41.00   0.30    0.50    --   41.70  81.00  50.14  110
 40  \w      8.00  41.00   0.30    0.50    --   41.70  82.00 -45.60  110
 41  \w      7.00  31.90   0.30    0.50    --   41.70  84.00 140.74   83
 42  \w      7.00  31.90   0.30    0.50    --   41.70  84.00 131.87   83
 43  \w     84.00 166.20   0.30    2.50    --  112.00  57.00 -12.45  274
 44  \w     86.00 176.90   0.30    2.50    --  112.00  45.00 -90.00  303
 45  \w     84.00 177.00   0.30    2.50    --  112.00  30.00 -30.00  310
;
_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      0.0863623000
_diffrn_orient_matrix_UB_12      -0.0677671000
_diffrn_orient_matrix_UB_13      -0.0254246000
_diffrn_orient_matrix_UB_21      -0.1234178000
_diffrn_orient_matrix_UB_22      -0.0479526000
_diffrn_orient_matrix_UB_23      -0.0376168000
_diffrn_orient_matrix_UB_31      -0.0017064000
_diffrn_orient_matrix_UB_32      0.0367621000
_diffrn_orient_matrix_UB_33      -0.0957994000
_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  0.0237
_diffrn_reflns_av_unetI/netI     0.0092
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            52223
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.735
_diffrn_reflns_theta_min         4.005
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.439
_exptl_absorpt_correction_T_max  0.372
_exptl_absorpt_correction_T_min  0.176
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    2.079
_exptl_crystal_description       block
_exptl_crystal_F_000             1556
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.614
_refine_diff_density_min         -0.609
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.199
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         5358
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.199
_refine_ls_R_factor_all          0.0224
_refine_ls_R_factor_gt           0.0223
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0211P)^2^+3.6111P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0548
_refine_ls_wR_factor_ref         0.0548
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5352
_reflns_number_total             5358
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01833a2.cif
_cod_data_source_block           1-8b_mor1742
_cod_depositor_comments
'Adding full bibliography for 7719387--7719420.cif.'
_cod_original_cell_volume        2555.969(15)
_cod_database_code               7719400
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C21 H22 N5 O5 Fe Br4'
_chemical_oxdiff_usercomment     'Eoin, EP33'
_shelx_estimated_absorpt_t_max   0.295
_shelx_estimated_absorpt_t_min   0.158
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
2. Restrained distances
 N4A-C14B
 1.47 with sigma of 0.02
 C15-N4B
 1.28 with sigma of 0.02
 N4B-C14A
 1.47 with sigma of 0.02
 N4A-C15
 1.28 with sigma of 0.02
3. Others
 Sof(H3B)=Sof(H15A)=Sof(C14B)=Sof(H14C)=Sof(H14D)=Sof(C13B)=Sof(H13C)=
 Sof(H13D)=Sof(N4B)=1-FVAR(1)
 Sof(H3A)=Sof(H15)=Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(C14A)=Sof(H14A)=Sof(H14B)=
 Sof(N4A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 N2(H2), N3(H3A), N3(H3B)
4.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C8(H8A,H8B), C10(H10A,H10B), C12(H12A,H12B), C11(H11A,H11B),
 C13A(H13A,H13B), C14A(H14A,H14B), C14B(H14C,H14D), C13B(H13C,H13D)
4.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C19(H19), C5(H5), C3(H3), C7(H7), C15(H15), C15(H15A)
;
_shelx_res_checksum              89678
_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 1.207
_oxdiff_exptl_absorpt_empirical_full_min 0.871