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_7719420
_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         'C27 H34 Fe N4 O2, Cl O4'
_chemical_formula_sum            'C27 H34 Cl Fe N4 O6'
_chemical_formula_weight         601.88
_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             2025-06-03
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-06-26 deposited with the CCDC.	2025-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                74.685(3)
_cell_angle_beta                 73.576(3)
_cell_angle_gamma                71.684(3)
_cell_formula_units_Z            4
_cell_length_a                   12.8580(4)
_cell_length_b                   14.0569(5)
_cell_length_c                   17.2548(5)
_cell_measurement_reflns_used    29907
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.6320
_cell_measurement_theta_min      2.6950
_cell_volume                     2786.78(17)
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3196
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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    -77.00  33.00   1.00    8.63    --  -42.33  84.00  38.00  110
  2  \w    101.00 178.00   1.00   14.51    --  104.49  84.00  38.00   77
  3  \w     24.00 139.00   1.00   14.51    --  104.49 -84.00 -81.00  115
  4  \w    -67.00  32.00   1.00    8.63    --  -42.33  37.00 150.00   99
  5  \w     27.00  96.00   1.00    8.63    --   42.33-125.00 120.00   69
  6  \w      9.00  42.00   1.00    8.63    --   42.33  81.00  28.87   33
  7  \w      8.00  34.00   1.00    8.63    --   42.33  83.00-112.71   26
  8  \w      9.00  42.00   1.00    8.63    --   42.33  79.00 159.03   33
  9  \w     18.00 117.00   1.00    8.63    --   42.33  37.00-150.00   99
 10  \w    -11.00  77.00   1.00    8.63    --   42.33 -84.00 -81.00   88
 11  \w     10.00  36.00   1.00    8.63    --   42.33  74.00 -58.29   26
 12  \w     31.00 109.00   1.00   14.51    --  104.49-111.00   0.00   78
 13  \w    103.00 178.00   1.00   14.51    --  104.49  77.00 120.00   75
 14  \w     76.00 178.00   1.00   14.51    --  104.49  30.00  90.00  102
 15  \w     31.00 109.00   1.00   14.51    --  104.49-111.00-180.00   78
 16  \w     76.00 178.00   1.00   14.51    --  104.49  30.00   0.00  102
 17  \w    104.00 178.00   1.00   14.51    --  104.49 111.00 -60.00   74
 18  \w     75.00 177.00   1.00   14.51    --  104.49  63.00  16.48  102
 19  \w     31.00 109.00   1.00   14.51    --  104.49-111.00-120.00   78
 20  \w     31.00 109.00   1.00   14.51    --  104.49-111.00  60.00   78
 21  \w    103.00 178.00   1.00   14.51    --  104.49  77.00 -90.00   75
 22  \w    104.00 178.00   1.00   14.51    --  104.49 111.00   0.00   74
 23  \w     22.00 106.00   1.00   14.51    --  104.49 -94.00  90.00   84
 24  \w     31.00 130.00   1.00   14.51    --  104.49 -45.00  60.00   99
 25  \w   -115.00 -14.00   1.00    8.63    --  -42.33 -57.00-180.00  101
 26  \w   -117.00 -18.00   1.00    8.63    --  -42.33 -37.00  30.00   99
 27  \w      8.00  42.00   1.00    8.63    --   42.33  82.00  -7.16   34
 28  \w    -32.00  67.00   1.00    8.63    --   42.33 -37.00 150.00   99
 29  \w     18.00 117.00   1.00    8.63    --   42.33  37.00 -30.00   99
 30  \w      9.00  42.00   1.00    8.63    --   42.33  81.00 131.66   33
 31  \w      9.00  42.00   1.00    8.63    --   42.33  80.00  80.89   33
 32  \w     75.00 177.00   1.00   14.51    --  104.49  61.00  90.00  102
 33  \w     75.00 177.00   1.00   14.51    --  104.49  61.00-150.00  102
 34  \w     75.00 177.00   1.00   14.51    --  104.49  61.00 150.00  102
 35  \w     76.00 178.00   1.00   14.51    --  104.49  58.00 -69.65  102
 36  \w     75.00 177.00   1.00   14.51    --  104.49  61.00 120.00  102
 37  \w     75.00 177.00   1.00   14.51    --  104.49  62.00-104.41  102
 38  \w     77.00 177.00   1.00   14.51    --  104.49  53.00  -1.22  100
 39  \w     75.00 177.00   1.00   14.51    --  104.49  64.00  50.20  102
 40  \w     75.00 177.00   1.00   14.51    --  104.49  61.00-120.00  102
 41  \w     73.00 178.00   1.00   14.51    --  104.49  71.00 -51.38  105
 42  \w     75.00 129.00   1.00   14.51    --  104.49  61.00-180.00   54
 43  \w     76.00 178.00   1.00   14.51    --  104.49  30.00-150.00  102
;
_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      -0.0475398000
_diffrn_orient_matrix_UB_12      0.0485815000
_diffrn_orient_matrix_UB_13      0.0772253000
_diffrn_orient_matrix_UB_21      0.0863089000
_diffrn_orient_matrix_UB_22      0.0642881000
_diffrn_orient_matrix_UB_23      -0.0319833000
_diffrn_orient_matrix_UB_31      -0.0837550000
_diffrn_orient_matrix_UB_32      0.0857134000
_diffrn_orient_matrix_UB_33      -0.0448419000
_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  0.0729
_diffrn_reflns_av_unetI/netI     0.0455
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            61806
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.638
_diffrn_reflns_theta_min         2.721
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.627
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.268
_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 red'
_exptl_crystal_density_diffrn    1.435
_exptl_crystal_description       block
_exptl_crystal_F_000             1260
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.384
_refine_diff_density_min         -0.549
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     719
_refine_ls_number_reflns         10937
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0639
_refine_ls_R_factor_gt           0.0525
_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^)+(0.0859P)^2^+3.4869P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1463
_refine_ls_wR_factor_ref         0.1535
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9431
_reflns_number_total             10937
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01833a2.cif
_cod_data_source_block           2-10_mor1854
_cod_depositor_comments
'Adding full bibliography for 7719387--7719420.cif.'
_cod_database_code               7719420
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C24H34N4O2FeClO4
_chemical_oxdiff_usercomment     EP136-1_EoinPasquetti_MorganGroup
_cell_oxdiff_angle_alpha         74.684(3)
_cell_oxdiff_angle_beta          73.576(3)
_cell_oxdiff_angle_gamma         71.684(3)
_cell_oxdiff_length_a            12.8580(4)
_cell_oxdiff_length_b            14.0569(5)
_cell_oxdiff_length_c            17.2548(5)
_cell_oxdiff_measurement_reflns_used 29907
_cell_oxdiff_volume              2786.79(16)
_shelx_estimated_absorpt_t_max   0.694
_shelx_estimated_absorpt_t_min   0.243
_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:
 C44(H44A,H44B), C42(H42A,H42B), C41(H41A,H41B), C38(H38A,H38B), C7(H7A,H7B),
 C11(H11A,H11B), C40(H40A,H40B), C12(H12A,H12B), C34(H34A,H34B), C14(H14A,H14B),
  C17(H17A,H17B), C39(H39A,H39B), C16(H16A,H16B), C13(H13A,H13B), C43(H43A,
 H43B), C52(H52A,H52B), C15(H15A,H15B), C25(H25A,H25B)
2.b Aromatic/amide H refined with riding coordinates:
 C45(H45), C18(H18), C22(H22), C5(H5), C10(H10), C47(H47), C21(H21), C37(H37),
 C20(H20), C48(H48), C49(H49), C32(H32), C3(H3A), C8(H8), C31(H31), C30(H30),
 C35(H35), C4(H4), C53(H53), C26(H26)
2.c X=CH2 refined with riding coordinates:
 C9(H9A,H9B), C36(H36A,H36B), C27(H27A,H27B), C54(H54A,H54B)
;
_shelx_res_checksum              5032
_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 3.604
_oxdiff_exptl_absorpt_empirical_full_min 0.382