The “pogo stick” complex [FeCp*{N(SiMe3)2}]: spin state properties, adduct formation with Lewis bases, and reactivity towards weakly Brønsted acidic protonated NHCs
Zinke, Julian; Bruhn, Clemens; Demeshko, Serhiy; Siemeling, Ulrich; Dalton Transactions 54 (2025) 5812–5828; doi:10.1039/D5DT00300H

data_7718191
_publ_section_title
;
 The &#x201C;pogo stick&#x201D; complex [FeCp*{N(SiMe3)2}]: spin state
 properties, adduct formation with Lewis bases, and reactivity towards
 weakly Br\/onsted acidic protonated NHCs
;
_journal_issue                   14
_journal_name_full               'Dalton Transactions'
_journal_page_first              5812
_journal_page_last               5828
_journal_paper_doi               10.1039/D5DT00300H
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C23 H43 Fe N3 Si2'
_chemical_formula_sum            'C23 H43 Fe N3 Si2'
_chemical_formula_weight         473.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-05 deposited with the CCDC.	2025-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.754(2)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   18.9537(4)
_cell_length_b                   19.2088(4)
_cell_length_c                   29.7352(6)
_cell_measurement_reflns_used    67877
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.40
_cell_measurement_theta_min      1.39
_cell_volume                     10699.8(4)
_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 1.71.0.0 (STOE, 2016)
X-Area LANA 1.71.4.0 (STOE, 2017)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 1.77, Darmstadt 2016
;
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
 308 frames, detector distance = 120 mm
;
_diffrn_measurement_device       '2-circle diffractometer'
_diffrn_measurement_device_type  'STOE IPDS II'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2, 0.6 mm diameter, multiple pinhole'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0597
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            30799
_diffrn_reflns_point_group_measured_fraction_full 0.898
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.386
_diffrn_source                   'Genix Mo HF'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.667
_exptl_absorpt_correction_T_max  0.8786
_exptl_absorpt_correction_T_min  0.5141
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270.
Afterwards scaling of reflection intensities was performed within STOE LANA.
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.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.176
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4096
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.237
_exptl_crystal_size_min          0.11
_refine_diff_density_max         1.132
_refine_diff_density_min         -0.873
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_coef       0.00115(16)
_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   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1098
_refine_ls_number_reflns         18847
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0744
_refine_ls_R_factor_gt           0.0619
_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^)+(0.1148P)^2^+31.1269P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1589
_refine_ls_wR_factor_ref         0.1910
_reflns_Friedel_coverage         0.791
_reflns_Friedel_fraction_full    0.797
_reflns_Friedel_fraction_max     0.791
_reflns_number_gt                16368
_reflns_number_total             18847
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00300h2.cif
_cod_data_source_block           i3010
_cod_depositor_comments
'Adding full bibliography for 7718189--7718202.cif.'
_cod_database_code               7718191
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.815
_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:
 C11(H11), C12(H12), C14(H14), C15(H15), C34(H34), C35(H35), C37(H37),
 C38(H38), C57(H57), C58(H58), C60(H60), C61(H61), C80(H80), C81(H81), C83(H83),
  C84(H84)
2.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C52(H52A,
 H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C),
 C56(H56A,H56B,H56C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,
 H68B,H68C), C69(H69A,H69B,H69C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C85(H85A,H85B,
 H85C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,
 H89B,H89C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C)
;
_shelx_res_checksum              82236
_shelx_hkl_checksum              71596
_olex2_submission_special_instructions 'No special instructions were received'