Interplay Between Ligand Field Strength and the Nephelauxetic Effect in Chromium(III) Complexes with Anionic Amido Ligands
Yaltseva, Polina; Wittwer, Benjamin; Leitner, Daniel; Neururer, Florian Rochus; Tambornino, Frank; Schmidt, Alina; Munz, Dominik; Wenger, Oliver S.; Hohloch, Stephan; Chemical Science  (2026) –; doi:10.1039/D5SC09069E

data_1576606
_publ_section_title
;
 Interplay between ligand field strength and the nephelauxetic effect in
 chromium(iii) complexes with anionic amido ligands.
;
_journal_issue                   17
_journal_name_full               'Chemical science'
_journal_page_first              8760
_journal_page_last               8771
_journal_paper_doi               10.1039/d5sc09069e
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C56 H64 Cr N10, B1 F4, 1.7[C3H6O1]'
_chemical_formula_sum            'C61.1 H74.2 B Cr F4 N10 O1.7'
_chemical_formula_weight         1114.71
_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             2024-03-27
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-27 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.368(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6942(9)
_cell_length_b                   23.5231(19)
_cell_length_c                   23.714(2)
_cell_measurement_reflns_used    8255
_cell_measurement_temperature    153.00
_cell_measurement_theta_max      21.084
_cell_measurement_theta_min      2.221
_cell_volume                     5955.2(9)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      153.00
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 Quest, Photon III'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1086
_diffrn_reflns_av_unetI/netI     0.0657
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            100688
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.113
_diffrn_reflns_theta_max         25.113
_diffrn_reflns_theta_min         1.908
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.255
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6577
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0830 before and 0.0457 after correction.
The Ratio of minimum to maximum transmission is 0.8826.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.243
_exptl_crystal_description       plate
_exptl_crystal_F_000             2358
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.299
_refine_diff_density_min         -0.504
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     742
_refine_ls_number_reflns         10567
_refine_ls_number_restraints     193
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0975
_refine_ls_R_factor_gt           0.0600
_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^)+(0.0900P)^2^+2.8287P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1562
_refine_ls_wR_factor_ref         0.1761
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6857
_reflns_number_total             10567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09069e2.cif
_cod_data_source_block           sh_446n_0m
_cod_depositor_comments
'Adding full bibliography for 1576605--1576606.cif.'
_cod_original_cell_volume        5955.3(9)
_cod_original_formula_sum        'C61.10 H74.20 B Cr F4 N10 O1.70'
_cod_database_code               1576606
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.951
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C29-C32 \\sim C29-C11
 with sigma of 0.02
 C29-C31 \\sim C29-C12
 with sigma of 0.02
 C29-C30 \\sim C29-C10
 with sigma of 0.02
 F2-B1 \\sim F2A-B1A
 with sigma of 0.02
 F4-B1 \\sim F4A-B1A
 with sigma of 0.02
 F3-B1 \\sim F3A-B1A
 with sigma of 0.02
 F1-B1 \\sim F1A-B1A
 with sigma of 0.02
 F2-F4 \\sim F2A-F4A
 with sigma of 0.04
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F2-F1 \\sim F2A-F1A
 with sigma of 0.04
 F4-F3 \\sim F4A-F3A
 with sigma of 0.04
 F4-F1 \\sim F4A-F1A
 with sigma of 0.04
 F3-F1 \\sim F3A-F1A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
F2 \\sim F4 \\sim F3 \\sim F1 \\sim B1 \\sim B1A \\sim F1A \\sim F3A \\sim F4A
\\sim F2A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.02
within 1.7A
C29 \\sim C32 \\sim C31 \\sim C30 \\sim C10 \\sim C11 \\sim C12: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.02 within 1.7A
4. Others
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=1-FVAR(1)
 Sof(C32)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C31)=Sof(H31D)=Sof(H31E)=Sof(H31F)=
 Sof(C30)=Sof(H30D)=Sof(H30E)=Sof(H30F)=FVAR(1)
 Sof(B1A)=Sof(F1A)=Sof(F3A)=Sof(F4A)=Sof(F2A)=1-FVAR(2)
 Sof(F2)=Sof(F4)=Sof(F3)=Sof(F1)=Sof(B1)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C15(H15), C20A(H20A), C17(H17), C20(H20), C17A(H17A), C22A(H22A), C15A(H15A),
 C4A(H4A), C6A(H6A), C22(H22), C5A(H5A), C3A(H3A), C4(H4), C6(H6), C5(H5),
 C3(H3)
5.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8A(H8AA,H8AB,H8AC), C8(H8A,H8B,H8C), C7A(H7AA,H7AB,H7AC),
 C28(H28A,H28B,H28C), C27(H27A,H27B,H27C), C26(H26A,H26B,H26C), C28A(H28D,H28E,
 H28F), C32A(H32A,H32B,H32C), C30A(H30A,H30B,H30C), C31A(H31A,H31B,H31C),
 C26A(H26D,H26E,H26F), C27A(H27D,H27E,H27F), C32(H32D,H32E,H32F), C31(H31D,H31E,
 H31F), C30(H30D,H30E,H30F), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 208 electrons were 
found in a volume of 1410\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.85[C3H6O1] per formula unit 
which account for 218 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              91296
_shelx_fab_checksum              75179
_olex2_submission_special_instructions 'No special instructions were received'