Fluorinated Click-Derived Tripodal Ligands Drive Spin Crossover in both Iron(II) and Cobalt(II) Complexes
Nößler, Maite; Hunger, David; Neuman, Nicolás Ignacio; Reimann, Marc; Reichert, Felix; Winkler, Mario; Klein, Johannes; Bens, Tobias; Suntrup, Lisa; Demeshko, Serhiy; Stubbe, Jessica; Kaupp, Martin; van Slageren, Joris; Sarkar, Biprajit; Dalton Transactions  (2022) –; doi:10.1039/D2DT01005D

data_7710470
_publ_section_title
;
 Fluorinated Click-Derived Tripodal Ligands Drive Spin Crossover in both
 Iron(II) and Cobalt(II) Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01005D
_journal_year                    2022
_chemical_formula_moiety         'C60 H53 F6 Fe N20, B2 F8, C2 O'
_chemical_formula_sum            'C62 H53 B2 F14 Fe N20 O'
_chemical_formula_weight         1437.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-09-25
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2021-03-12 deposited with the CCDC.	2022-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.184(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.8403(4)
_cell_length_b                   20.3972(10)
_cell_length_c                   19.7649(9)
_cell_measurement_reflns_used    5036
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      25.410
_cell_measurement_theta_min      1.997
_cell_volume                     3136.0(3)
_computing_cell_refinement       'APEX3 (Bruker, 2015)'
_computing_data_collection       'APEX3 (Bruker, 2015)'
_computing_data_reduction        'SAINT+ (Bruker, 2009)'
_computing_molecular_graphics
'Olex2 1.3 (Dolomanov et al., 2009),Diamond 3D, Version 4.0 (Brandenburg, 2014)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL n/a (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega + phi scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0725
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            89633
_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         25.410
_diffrn_reflns_theta_min         1.997
_exptl_absorpt_coefficient_mu    0.344
_exptl_absorpt_correction_T_max  0.7445
_exptl_absorpt_correction_T_min  0.6979
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1472 before and 0.0972 after correction.
The Ratio of minimum to maximum transmission is 0.9374.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.523
_exptl_crystal_description       block
_exptl_crystal_F_000             1470
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.537
_refine_diff_density_min         -1.058
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     577
_refine_ls_number_reflns         5774
_refine_ls_number_restraints     178
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0655
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0657P)^2^+6.2783P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1615
_refine_ls_wR_factor_ref         0.1679
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5036
_reflns_number_total             5774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01005d2.cif
_cod_data_source_block           mn111_a
_cod_database_code               7710470
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.973
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C31_$1-O1
 1.4 with sigma of 0.02
 C30-O2_$1
 1.4 with sigma of 0.02
 C26-C27
 1.38 with sigma of 0.02
3. Rigid bond restraints
 C22A, C23A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C23B, N10B, C23A, N10A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C23B, N9B, C23A, N9A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N10B, N9B, N10A, N9A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N10B, N8B, N10A, N8A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C22B, N8B, C22A, N8A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C22A \\sim C23A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
N10B \\sim C23B \\sim N10A \\sim C23A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C23B \\sim N9B \\sim C23A \\sim N9A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
N10B \\sim N9B \\sim N10A \\sim N9A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
N10B \\sim N8B \\sim N10A \\sim N8A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C22B \\sim N8B \\sim C22A \\sim N8A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C24A \\sim C24B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C22B) \\sim Ueq, Uanis(C22A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C23B) \\sim Ueq, Uanis(C22B) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C9) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C25) \\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
Uanis(C15) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C28) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Others
 Fixed Sof: H26(0.5) C24A(0.4) H24A(0.4) H24B(0.4) C21A(0.4) H21A(0.4)
 H21B(0.4) C1A(0.5) H1AA(0.5) H1AB(0.5) C11B(0.5) H11A(0.5) H11B(0.5) C11A(0.5)
 H11C(0.5) H11D(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) N8A(0.4) N9A(0.4) C23A(0.4)
 H23A(0.4) N10A(0.4) C22A(0.4) N8B(0.6) N9B(0.6) C23B(0.6) H23B(0.6) C22B(0.6)
 N10B(0.6) F17(0.5) F5(0.5) F11(0.25) F19(0.25) F13(0.25) F15(0.25) F6(0.25)
 F16(0.125) F18(0.5) F7(0.25) F10(0.25) F14(0.25) B1A(0.4) B1B(0.6) F8(0.125)
 F12(0.25) C24B(0.6) H24C(0.6) H24D(0.6) C12A(0.5) C12B(0.5) C13A(0.5)
 H13A(0.5) C13B(0.5) H13B(0.5) C21B(0.6) H21C(0.6) H21D(0.6) O2(0.25) C29(0.5)
 O1(0.25) C31(0.25) C30(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C4(H4A,H4B), C24A(H24A,H24B), C21A(H21A,H21B), C1A(H1AA,H1AB),
  C11B(H11A,H11B), C11A(H11C,H11D), C1B(H1BA,H1BB), C24B(H24C,H24D), C21B(H21C,
 H21D)
6.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C20(H20), C19(H19), C9(H9), C8(H8), C16(H16), C7(H7), C3(H3),
 C17(H17), C6(H6), C26(H26), C11(H11), C23A(H23A), C23B(H23B), C1(H1),
 C13A(H13A), C13B(H13B)
;
_shelx_res_checksum              65767
_olex2_submission_special_instructions 'No special instructions were received'