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_7719419
_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 Br2 Cl2 Fe N4 O2, Cl O4, 0.25[H2O], 0.25[CH4O]'
_chemical_formula_sum            'C21.25 H23.5 Br2 Cl3 Fe N4 O6.5'
_chemical_formula_weight         760.96
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-19
_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                94.646(2)
_cell_angle_beta                 100.438(2)
_cell_angle_gamma                91.507(2)
_cell_formula_units_Z            4
_cell_length_a                   10.9180(2)
_cell_length_b                   14.9925(4)
_cell_length_c                   16.8669(3)
_cell_measurement_reflns_used    24327
_cell_measurement_temperature    105(2)
_cell_measurement_theta_max      72.5700
_cell_measurement_theta_min      2.9210
_cell_volume                     2703.94(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 42.75a 64-bit (release 29-11-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_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      105(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3196
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.976
_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    -89.00  39.00   1.00    1.25    --  -42.08  17.00 -93.00  128
  2  \w   -123.00   5.00   1.00    1.25    --  -42.08 -17.00  97.00  128
  3  \w    -39.00  89.00   1.00    1.25    --   42.08 -17.00  97.00  128
  4  \w     -5.00 123.00   1.00    1.25    --   42.08  17.00 -93.00  128
  5  \w     58.00 178.00   1.00    5.01    --  104.49  17.00 -93.00  120
  6  \w     24.00 151.00   1.00    5.01    --  104.49 -17.00  97.00  127
  7  \w    -87.00  -6.00   1.00    1.25    --  -42.08 125.00 -90.00   81
  8  \w     10.00  42.00   1.00    1.25    --   42.08  76.00  88.06   32
  9  \w      8.00  34.00   1.00    1.25    --   42.08  83.00 151.96   26
 10  \w      9.00  42.00   1.00    1.25    --   42.08  81.00-167.57   33
 11  \w      8.00  34.00   1.00    1.25    --   42.08  83.00 109.77   26
 12  \w    103.00 178.00   1.00    5.01    --  104.49  77.00  90.00   75
 13  \w     31.00 109.00   1.00    5.01    --  104.49-111.00 120.00   78
 14  \w     31.00 130.00   1.00    5.01    --  104.49 -45.00 -60.00   99
 15  \w    104.00 178.00   1.00    5.01    --  104.49 111.00-150.00   74
 16  \w    104.00 178.00   1.00    5.01    --  104.49 111.00-180.00   74
 17  \w     31.00 109.00   1.00    5.01    --  104.49-111.00 -60.00   78
 18  \w     31.00 109.00   1.00    5.01    --  104.49-111.00-150.00   78
 19  \w     32.00 134.00   1.00    5.01    --  104.49 -61.00-180.00  102
 20  \w     77.00 177.00   1.00    5.01    --  104.49  53.00 122.36  100
 21  \w     22.00 106.00   1.00    5.01    --  104.49 -94.00 150.00   84
 22  \w   -114.00 -14.00   1.00    1.25    --  -42.08 -57.00 -60.00  100
 23  \w      7.00  33.00   1.00    1.25    --   42.08  84.00  19.37   26
 24  \w      9.00  42.00   1.00    1.25    --   42.08  79.00 -96.70   33
 25  \w     27.00  96.00   1.00    1.25    --   42.08-125.00-180.00   69
 26  \w      9.00  42.00   1.00    1.25    --   42.08  79.00 -34.99   33
 27  \w      9.00  42.00   1.00    1.25    --   42.08  80.00  53.91   33
 28  \w     74.00 178.00   1.00    5.01    --  104.49  67.00 -24.23  104
 29  \w     75.00 177.00   1.00    5.01    --  104.49  62.00  84.37  102
 30  \w     75.00 177.00   1.00    5.01    --  104.49  61.00-120.00  102
 31  \w     75.00 177.00   1.00    5.01    --  104.49  63.00  17.08  102
 32  \w     73.00 178.00   1.00    5.01    --  104.49  71.00 -81.86  105
 33  \w     75.00 177.00   1.00    5.01    --  104.49  61.00  60.00  102
 34  \w     77.00 177.00   1.00    5.01    --  104.49  54.00 -88.07  100
 35  \w     75.00 177.00   1.00    5.01    --  104.49  61.00-150.00  102
 36  \w     77.00 114.00   1.00    5.01    --  104.49  52.00 -34.32   37
 37  \w     52.00 178.00   1.00    5.01    --  104.49  15.00  30.00  126
;
_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      0.0235287000
_diffrn_orient_matrix_UB_12      0.0960235000
_diffrn_orient_matrix_UB_13      -0.0217470000
_diffrn_orient_matrix_UB_21      0.1375407000
_diffrn_orient_matrix_UB_22      -0.0198486000
_diffrn_orient_matrix_UB_23      -0.0007314000
_diffrn_orient_matrix_UB_31      -0.0339220000
_diffrn_orient_matrix_UB_32      -0.0321323000
_diffrn_orient_matrix_UB_33      -0.0906536000
_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  0.0786
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            51318
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.534
_diffrn_reflns_theta_min         2.674
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.082
_exptl_absorpt_correction_T_max  0.714
_exptl_absorpt_correction_T_min  0.153
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
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            'metallic dark black'
_exptl_crystal_density_diffrn    1.869
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.969
_refine_diff_density_min         -1.157
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     766
_refine_ls_number_reflns         10477
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0561
_refine_ls_R_factor_gt           0.0510
_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^)+(0.0496P)^2^+8.7942P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1259
_refine_ls_wR_factor_ref         0.1292
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9424
_reflns_number_total             10477
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01833a2.cif
_cod_data_source_block           2-6a_mor1847
_cod_depositor_comments
'Adding full bibliography for 7719387--7719420.cif.'
_cod_original_cell_volume        2703.93(10)
_cod_original_formula_sum        'C21.25 H23.50 Br2 Cl3 Fe N4 O6.50'
_cod_database_code               7719419
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C42 H44 N8 O12 Cl6 Fe2 Br4 '
_chemical_oxdiff_usercomment     EoinPasquetti_Morgan_EP127-1
_cell_oxdiff_angle_alpha         94.6461(18)
_cell_oxdiff_angle_beta          100.4376(16)
_cell_oxdiff_angle_gamma         91.5067(17)
_cell_oxdiff_length_a            10.91799(19)
_cell_oxdiff_length_b            14.9925(4)
_cell_oxdiff_length_c            16.8669(3)
_cell_oxdiff_measurement_reflns_used 24327
_cell_oxdiff_volume              2703.95(9)
_shelx_estimated_absorpt_t_max   0.404
_shelx_estimated_absorpt_t_min   0.131
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl6A-O11A = Cl6A-O12A = Cl6A-O10A = Cl6A-O9A
 1.5 with sigma of 0.02
 Cl6A-O11A \\sim Cl6A-O12A \\sim Cl6A-O10A \\sim Cl6A-O9A
 with sigma of 0.02
 O11A-O10A \\sim O12A-O9A \\sim O11A-O9A \\sim O12A-O10A \\sim O11A-O12A \\sim
O10A-O9A
 with sigma of 0.04
 Cl6A-O11A \\sim Cl6B-O12B
 with sigma of 0.02
 Cl6A-O12A \\sim Cl6B-O11B
 with sigma of 0.02
 Cl6A-O10A \\sim Cl6B-O9B
 with sigma of 0.02
 Cl6A-O9A \\sim Cl6B-O10B
 with sigma of 0.02
 O11A-O12A \\sim O12B-O11B
 with sigma of 0.04
 O11A-O10A \\sim O12B-O9B
 with sigma of 0.04
 O11A-O9A \\sim O12B-O10B
 with sigma of 0.04
 O12A-O10A \\sim O11B-O9B
 with sigma of 0.04
 O12A-O9A \\sim O11B-O10B
 with sigma of 0.04
 O10A-O9A \\sim O9B-O10B
 with sigma of 0.04
 Cl5A-O7A \\sim Cl5B-O7B
 with sigma of 0.02
 Cl5A-O6A \\sim Cl5B-O6B
 with sigma of 0.02
 Cl5A-O8A \\sim Cl5B-O8B
 with sigma of 0.02
 O7A-O6A \\sim O7B-O6B
 with sigma of 0.04
 O7A-O8A \\sim O7B-O8B
 with sigma of 0.04
 O6A-O8A \\sim O6B-O8B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Cl6A \\sim O11A \\sim O12A \\sim O10A \\sim O9A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 Cl6A, O11A, O12A, O10A, O9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl6B)=Sof(O9B)=Sof(O12B)=Sof(O11B)=Sof(O10B)=1-FVAR(1)
 Sof(Cl6A)=Sof(O11A)=Sof(O12A)=Sof(O10A)=Sof(O9A)=FVAR(1)
 Sof(Cl5B)=Sof(O6B)=Sof(O7B)=Sof(O8B)=1-FVAR(2)
 Sof(Cl5A)=Sof(O7A)=Sof(O6A)=Sof(O8A)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C11(H11A,H11B), C30(H30A,H30B), C32(H32A,H32B), C9(H9A,H9B),
 C35(H35A,H35B), C29(H29A,H29B), C10(H10A,H10B), C14(H14A,H14B), C12(H12A,H12B),
  C8(H8A,H8B), C34(H34A,H34B), C13(H13A,H13B), C33(H33A,H33B)
6.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C28(H28), C19(H19), C36(H36), C24(H24), C15(H15), C40(H40), C3(H3A),
  C7(H7A), C5(H5), C17(H17), C38(H38)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              88716
_shelx_fab_checksum              4818
_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 4.096
_oxdiff_exptl_absorpt_empirical_full_min 0.476