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_7719414
_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         '2(C23 H28 Br2 Fe N4 O4), 2(Cl O4), C H4 O'
_chemical_formula_sum            'C47 H60 Br4 Cl2 Fe2 N8 O17'
_chemical_formula_weight         1511.27
_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             2025-05-19
_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                90
_cell_angle_beta                 97.7602(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.5886(2)
_cell_length_b                   25.6773(4)
_cell_length_c                   15.4561(2)
_cell_measurement_reflns_used    13140
_cell_measurement_temperature    115(2)
_cell_measurement_theta_max      73.5970
_cell_measurement_theta_min      3.0270
_cell_volume                     5736.77(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.75a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      115(2)
_diffrn_detector_area_resol_mean 10.3196
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.968
_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    -60.00 -33.00   1.00   21.00    --  -42.33  95.00-166.00   27
  2  \w      6.00  74.00   1.00   21.00    --   42.33 -95.00  83.00   68
  3  \w    107.00 178.00   1.00   24.00    --  108.06  95.00-166.00   71
  4  \w    -70.00 -43.00   1.00   21.00    --  -42.33  57.00 -30.00   27
  5  \w   -117.00 -19.00   1.00   21.00    --  -42.33 -37.00 150.00   98
  6  \w     20.00 117.00   1.00   21.00    --   42.33  37.00  30.00   97
  7  \w     39.00  66.00   1.00   24.00    --  108.06-111.00-120.00   27
  8  \w     37.00  95.00   1.00   24.00    --  108.06-111.00-180.00   58
  9  \w    124.00 177.00   1.00   24.00    --  108.06  77.00 -30.00   53
 10  \w    133.00 168.00   1.00   24.00    --  108.06 111.00-120.00   35
 11  \w    109.00 177.00   1.00   24.00    --  108.06 111.00  90.00   68
 12  \w     79.00 177.00   1.00   24.00    --  108.06  61.00-120.00   98
 13  \w    134.00 176.00   1.00   24.00    --  108.06 111.00 -60.00   42
 14  \w    104.00 175.00   1.00   24.00    --  108.06 111.00  60.00   71
 15  \w    -32.00  -6.00   1.00   21.00    --  -42.33 125.00   0.00   26
 16  \w    -74.00 -14.00   1.00   21.00    --  -42.33 -57.00 150.00   60
 17  \w    -91.00 -14.00   1.00   21.00    --  -42.33 -57.00 -30.00   77
 18  \w    -67.00  18.00   1.00   21.00    --  -42.33  77.00 -30.00   85
 19  \w    -87.00 -14.00   1.00   21.00    --  -42.33 -57.00  60.00   73
 20  \w   -108.00 -14.00   1.00   21.00    --  -42.33 -57.00-120.00   94
 21  \w      8.00  33.00   1.00   21.00    --   42.33  83.00 -43.50   25
 22  \w    -21.00  73.00   1.00   21.00    --   42.33 -77.00 120.00   94
 23  \w    -27.00  18.00   1.00   21.00    --   42.33 -37.00-150.00   45
 24  \w     10.00  35.00   1.00   21.00    --   42.33  76.00 -80.39   25
 25  \w     10.00  40.00   1.00   21.00    --   42.33  82.00   7.88   30
 26  \w      9.00  42.00   1.00   21.00    --   42.33  79.00 114.58   33
 27  \w     27.00  65.00   1.00   21.00    --   42.33 -37.00-150.00   38
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0696
_diffrn_reflns_av_unetI/netI     0.0747
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            48266
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.446
_diffrn_reflns_theta_min         3.057
_exptl_absorpt_coefficient_mu    8.820
_exptl_absorpt_correction_T_max  0.813
_exptl_absorpt_correction_T_min  0.542
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.75a (Rigaku Oxford Diffraction, 2022)
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    1.750
_exptl_crystal_description       plate
_exptl_crystal_F_000             3040
_exptl_crystal_size_max          0.119
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.732
_refine_diff_density_min         -0.914
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     765
_refine_ls_number_reflns         11359
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0953
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0623P)^2^+2.3822P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1117
_refine_ls_wR_factor_ref         0.1346
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7520
_reflns_number_total             11359
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01833a2.cif
_cod_data_source_block           2-7_mor1863
_cod_depositor_comments
'Adding full bibliography for 7719387--7719420.cif.'
_cod_original_cell_volume        5736.78(16)
_cod_database_code               7719414
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C47H60Br4Cl2Fe2N8O17
_chemical_oxdiff_usercomment     EP-164-1_EoinPasquetti_MorganGroup
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O16A-Cl2 \\sim Cl2-O16B
 with sigma of 0.02
 O12B-Cl1 \\sim Cl1-O12A
 with sigma of 0.02
 O15B-Cl2 \\sim Cl2-O15A
 with sigma of 0.02
 O11A-Cl1 \\sim Cl1-O11B
 with sigma of 0.02
3. Rigid bond restraints
 Cl2, O16B, O16A, O15B, O15A, O13, O14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl1, O12A, O12B, O11A, O11B, O9, O10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Rigid body (RIGU) restrains
 O16A, O16B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15A, O15B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O12B, O12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O11A, O11B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O16A)=Sof(O15A)=1-FVAR(1)
 Sof(O16B)=Sof(O15B)=FVAR(1)
 Sof(O11A)=Sof(O12A)=1-FVAR(2)
 Sof(O12B)=Sof(O11B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 N7(H7), N6(H6), N3(H3), N2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C34(H34A,
 H34B), C35(H35A,H35B), C32(H32A,H32B), C33(H33A,H33B), C12(H12A,H12B),
 C11(H11A,H11B), C9(H9A,H9B), C15(H15A,H15B), C14(H14A,H14B), C13(H13A,H13B)
6.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C27(H27), C31(H31), C43(H43), C42(H42), C39(H39), C4(H4), C3(H3A),
 C8(H8), C19(H19), C20(H20), C16(H16)
6.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C46(H46A,H46B,H46C), C7(H7A,H7B,H7C), C23(H23A,H23B,
 H23C), C47(H47A,H47B,H47C)
6.e Idealised tetrahedral OH refined as rotating group:
 O17(H17)
;
_shelx_res_checksum              50649
_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 1.945
_oxdiff_exptl_absorpt_empirical_full_min 0.619