Unveiling the Relationship between Counterion Size and Spin Crossover Dynamics in Hexadentate Schiff-Base Manganese(III) Complexes
Shang, Meng-Jia; Chen, Duyong; Zhou, Ren-He; Lu, Han-Han; Ma, Lin; Xiao, Jingyi; Zhao, Liang; Meng, Yin-Shan; Liu, Tao; Dalton Transactions  (2025) –; doi:10.1039/D5DT01347J

data_7719151
_publ_section_title
;
 Unveiling the Relationship between Counterion Size and Spin Crossover
 Dynamics in Hexadentate Schiff-Base Manganese(III) Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT01347J
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C22 H26 F2 Mn N4 O2, N O3'
_chemical_formula_sum            'C22 H26 F2 Mn N5 O5'
_chemical_formula_weight         533.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-07-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-07-05 deposited with the CCDC.	2025-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.202(2)
_cell_length_b                   16.360(5)
_cell_length_c                   18.422(5)
_cell_measurement_reflns_used    9592
_cell_measurement_temperature    400(2)
_cell_measurement_theta_max      23.483
_cell_measurement_theta_min      2.211
_cell_volume                     2472.0(12)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      400(2)
_diffrn_detector                 'Bruker PHOTON-II area detector'
_diffrn_detector_area_resol_mean 7.4
_diffrn_detector_type            'CMOS-PHOTONII area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker PHOTON-II area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0389
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            45048
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.739
_diffrn_reflns_theta_min         2.211
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.6
_diffrn_source_power             0.08
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.591
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6915
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1101 before and 0.0500 after correction.
The Ratio of minimum to maximum transmission is 0.9278.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic blackish black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.433
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.45(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     500
_refine_ls_number_reflns         4686
_refine_ls_number_restraints     748
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0583
_refine_ls_R_factor_gt           0.0417
_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^)+(0.0713P)^2^+0.3168P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1106
_refine_ls_wR_factor_ref         0.1245
_reflns_Friedel_coverage         0.754
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                3622
_reflns_number_total             4686
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01347j2.cif
_cod_data_source_block           2441910
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 
;
_cod_original_cell_volume        2471.9(12)
_cod_database_code               7719151
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.891
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.55(4)
 0.45(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
3. Restrained planarity
 C22, C20, C19, C17, C21, C18, F2, O2, C16
 with sigma of 0.02
 C22A, C20A, C19A, C17A, C21A, C18A, F2A, O2, C16A
 with sigma of 0.02
 C6, C4, C3, C1, C5, C2, F1, C7, O1
 with sigma of 0.02
 C6A, C4A, C3A, C1A, C5A, C2A, O1, C7A, F1A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O2 \\sim N3 \\sim F2 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim
C21 \\sim C22 \\sim F2A \\sim C16A \\sim C17A \\sim C18A \\sim C19A \\sim C20A
\\sim C21A \\sim C22A: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
O3 \\sim O4 \\sim O5 \\sim N5 \\sim O3A \\sim O4A \\sim O5A \\sim N5A: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
O1 \\sim N4 \\sim F1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6
\\sim C7 \\sim F1A \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A
\\sim C7A: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
5. Same fragment restrains
{O1, N4, F1A, C1A, C2A, C3A, C4A, C5A, C6A, C7A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O1, N4, F1, C1, C2, C3, C4, C5, C6, C7}
{O2, N3, F2A, C16A, C17A, C18A, C19A, C20A, C21A, C22A} sigma for 1-2: 0.01,
1-3: 0.04
as in
{O2, N3, F2, C16, C17, C18, C19, C20, C21, C22}
{O3A, O4A, O5A, N5A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O3, O4, O5, N5}
6. Others
 Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(N5A)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(O5)=Sof(N5)=FVAR(1)
 Sof(F2A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=
 Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=1-FVAR(2)
 Sof(F2)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=
 Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=FVAR(2)
 Sof(F1A)=Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=1-FVAR(3)
 Sof(F1)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(C6)=
 Sof(H6)=Sof(C7)=Sof(H7)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 N1(H1), N2(H2)
7.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C16(H16), C19(H19), C21(H21), C22(H22),
 C3A(H3A), C4A(H4A), C6A(H6A), C7A(H7A), C16A(H16A), C19A(H19A), C21A(H21A),
 C22A(H22A)
;
_shelx_res_checksum              72087
_shelx_hkl_checksum              32031
_olex2_submission_special_instructions 'No special instructions were received'