Linker Permethylation as a Means to Foster Valence Tautomerism and Thwart Dimerization in Ferrocenyl-Triarylmethylium Cations
Nau, Moritz; Casper, Larissa Alina; Haug, Gernot; Linseis, Michael; Demeshko, Serhiy; Winter, Rainer R.F.; Dalton Transactions  (2023) –; doi:10.1039/D3DT00857F

data_7712689
_publ_section_title
;
 Linker Permethylation as a Means to Foster Valence Tautomerism and Thwart
 Dimerization in Ferrocenyl-Triarylmethylium Cations
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00857F
_journal_year                    2023
_chemical_formula_moiety         '2(C35 H27 F6 Fe S), 2(C32 H12 B F24)'
_chemical_formula_sum            'C67 H39 B F30 Fe S'
_chemical_formula_weight         1512.70
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive,Light-sensitive
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-08 deposited with the CCDC.	2023-03-28 downloaded from the CCDC.
;
_cell_angle_alpha                80.916(2)
_cell_angle_beta                 75.471(2)
_cell_angle_gamma                85.239(2)
_cell_formula_units_Z            2
_cell_length_a                   11.9778(3)
_cell_length_b                   12.5044(3)
_cell_length_c                   21.1080(6)
_cell_measurement_reflns_used    22097
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.10
_cell_measurement_theta_min      2.64
_cell_volume                     3018.86(14)
_computing_cell_refinement       'X-Area Recipe 1.33.0.0 (STOE, 2015)'
_computing_data_collection       'X-Area WinXpose 2.0.22.0 (STOE, 2016)'
_computing_data_reduction
;
X-Area Integrate 1.74.2.0 (STOE, 2018)
X-Area LANA 1.75.3.0 (STOE, 2018)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE Imaging Plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details      '261 frames, detector distance = 100 mm'
_diffrn_measurement_device       '2-circle diffractometer'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            31264
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.557
_diffrn_reflns_theta_min         2.591
_diffrn_source
'Sealed Mo X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_current           40
_diffrn_source_power             2.000
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.422
_exptl_absorpt_correction_T_max  0.9684
_exptl_absorpt_correction_T_min  0.7485
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Afterwards a spherical absorption correction was performed within STOE LANA.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.664
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       fragment
_exptl_crystal_F_000             1516
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2'
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.005
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.729
_refine_diff_density_min         -0.750
_refine_diff_density_rms         0.089
_refine_ls_extinction_coef       0.0032(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     906
_refine_ls_number_reflns         13839
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0814
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0592P)^2^+2.9470P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1094
_refine_ls_wR_factor_ref         0.1394
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9350
_reflns_number_total             13839
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00857f2.cif
_cod_data_source_block           lc73
_cod_database_code               7712689
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.996
_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.a Aromatic/amide H refined with riding coordinates:
 C33(H33), C34(H34), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40),
 C41(H41), C42(H42), C43(H43), C44(H44), C58(H58), C59(H59), C62(H62), C65(H65),
  C2(H2), C4(H4), C6(H6), C10(H10), C12(H12), C14(H14), C18(H18), C20(H20),
 C22(H22), C26(H26), C28(H28), C30(H30)
2.b Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C53(H53A,H53B,H53C), C55(H55A,H55B,
 H55C)
;
_shelx_res_checksum              39331
_shelx_hkl_checksum              79698
_olex2_submission_special_instructions 'No special instructions were received'