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_1576605
_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
'C64 H76 Cr N14, B0.406 F1.521, B0.303 F1.316, 0.291(B F4)'
_chemical_formula_sum            'C82 H118 B Cr F4 N14'
_chemical_formula_weight         1438.71
_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
_audit_block_doi                 10.5517/ccdc.csd.cc2hchds
_audit_creation_date             2023-10-31
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-31 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.868(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.9525(9)
_cell_length_b                   32.012(3)
_cell_length_c                   17.1940(14)
_cell_measurement_reflns_used    10488
_cell_measurement_temperature    172(2)
_cell_measurement_theta_max      24.999
_cell_measurement_theta_min      2.156
_cell_volume                     7566.0(11)
_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      172(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Quest, Photon III'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0845
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            173087
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.156
_exptl_absorpt_coefficient_mu    0.216
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6927
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 SADABS 2016/2: Krause, L., Herbst-Irmer, R., Sheldrick G.M. & Stalke D.,
 J. Appl. Cryst. 48 (2015) 3-10
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       block
_exptl_crystal_F_000             3092
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.183
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     926
_refine_ls_number_reflns         13290
_refine_ls_number_restraints     119
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0890
_refine_ls_R_factor_gt           0.0732
_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^)+(0.1117P)^2^+9.6177P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1989
_refine_ls_wR_factor_ref         0.2138
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10488
_reflns_number_total             13290
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09069e2.cif
_cod_data_source_block           ft_sh_001n_bw_0m
_cod_depositor_comments
'Adding full bibliography for 1576605--1576606.cif.'
_cod_original_cell_volume        7566.1(10)
_cod_database_code               1576605
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.930
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C25C-C27C
 1.54 with sigma of 0.01
 C27A-C25A
 1.54 with sigma of 0.01
3. Rigid bond restraints
 C2AA, C1AA, C0AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C32A, C30A, C31A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C35 \\sim C16A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
F9 \\sim F6 \\sim F11 \\sim F2: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
F4 \\sim F1 \\sim F3 \\sim F5: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
F10 \\sim F12 \\sim F7 \\sim F38: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(C15A) \\sim Ueq, Uanis(C33) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C14A) \\sim Ueq, Uanis(C34) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C35) \\sim Ueq, Uanis(C16A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C16A) \\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
: with sigma of 0.1 and sigma for terminal atoms of 0.2
: with sigma of 0.1 and sigma for terminal atoms of 0.2
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C28C) \\sim Ueq, Uanis(C27C) \\sim Ueq, Uanis(C26C) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C27A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C26A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C30A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C0AA) \\sim Ueq, Uanis(C2AA) \\sim Ueq, Uanis(C1AA) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Others
 1*[Sof(B9)+Sof(F12)+Sof(F10)+Sof(F38)+Sof(F7)]+1*[Sof(F1)+Sof(F2)+Sof(B12)+
 Sof(F6)+Sof(F11)]+1*[Sof(F3)+Sof(F4)+Sof(F5)+Sof(F9)+Sof(B5)]=1 with esd of
 0.001
 Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=1-FVAR(1)
 Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31A)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
 Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(C14A)=Sof(H14A)=Sof(C25C)=Sof(C26C)=
 Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27C)=Sof(H27G)=Sof(H27H)=Sof(H27I)=
 Sof(C28C)=Sof(H28G)=Sof(H28H)=Sof(H28I)=1-FVAR(2)
 Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27A)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C33)=Sof(C34)=
 Sof(H34)=Sof(C35)=Sof(H35)=FVAR(2)
 Sof(H11E)=Sof(H11F)=Sof(H7BE)=Sof(H7BF)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=1-FVAR(3)
 Sof(H11C)=Sof(H11D)=Sof(H7AC)=Sof(H7AD)=Sof(C9)=Sof(H9A)=Sof(H9B)=FVAR(3)
 Sof(C30C)=Sof(H30G)=Sof(H30H)=Sof(H30I)=Sof(C31C)=Sof(H31G)=Sof(H31H)=
 Sof(H31I)=Sof(C32C)=Sof(H32G)=Sof(H32H)=Sof(H32I)=1-FVAR(4)
 Sof(C30)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C32)=Sof(H32D)=Sof(H32E)=Sof(H32F)=
 Sof(C31)=Sof(H31D)=Sof(H31E)=Sof(H31F)=FVAR(4)
 Sof(B9)=Sof(F12)=Sof(F10)=Sof(F38)=Sof(F7)=FVAR(5)
 Sof(F1)=Sof(F2)=Sof(B12)=Sof(F6)=Sof(F11)=FVAR(6)
 Sof(F3)=Sof(F4)=Sof(F5)=Sof(F9)=Sof(B5)=FVAR(7)
6.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C12(H12A,H12B), C10(H10A,H10B), C8(H8A,H8B), C11A(H11A,H11B),
 C5A(H5AA,H5AB), C6A(H6AA,H6AB), C7A(H7AA,H7AB), C9A(H9AA,H9AB), C12A(H12C,
 H12D), C11(H11C,H11D), C11(H11E,H11F), C10A(H10C,H10D), C8A(H8AA,H8AB),
 C7(H7AC,H7AD), C7(H7BE,H7BF), C5(H5A,H5B), C9(H9A,H9B), C9B(H9BA,H9BB)
6.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C20(H20), C22A(H22A), C20A(H20A), C16(H16), C16A(H16A), C14(H14),
 C14A(H14A), C34(H34), C35(H35)
6.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30A(H30A,H30B,H30C), C31A(H31A,
 H31B,H31C), C32A(H32A,H32B,H32C), C0AA(H0AA,H0AB,H0AC), C1AA(H1AA,H1AB,H1AC),
 C2AA(H2AA,H2AB,H2AC), C26A(H26A,H26B,H26C), C27A(H27D,H27E,H27F), C28A(H28D,
 H28E,H28F), C26C(H26D,H26E,H26F), C27C(H27G,H27H,H27I), C28C(H28G,H28H,H28I),
 C30(H30D,H30E,H30F), C32(H32D,H32E,H32F), C31(H31D,H31E,H31F), C30C(H30G,H30H,
 H30I), C31C(H31G,H31H,H31I), C32C(H32G,H32H,H32I), C39(H39A,H39B,H39C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              64203
_shelx_fab_checksum              94376
_olex2_submission_special_instructions 'No special instructions were received'