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_7718201
_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         'C60 H59 Fe3 N4, F6 P, C4 H8 O'
_chemical_formula_sum            'C64 H67 F6 Fe3 N4 O P'
_chemical_formula_weight         1220.73
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2024-08-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-26 deposited with the CCDC.	2025-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                87.754(6)
_cell_angle_beta                 70.742(6)
_cell_angle_gamma                61.971(6)
_cell_formula_units_Z            1
_cell_length_a                   11.2935(9)
_cell_length_b                   11.4184(9)
_cell_length_c                   12.7670(10)
_cell_measurement_reflns_used    41043
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.37
_cell_measurement_theta_min      1.71
_cell_volume                     1358.6(2)
_computing_cell_refinement
;
X-Area Recipe 1.36.0.0 (STOE, 2020)
;
_computing_data_collection
;
X-Area WinXpose 2.0.22.0 (STOE, 2016)
;
_computing_data_reduction
;
X-Area Integrate 1.78.3.0 (STOE, 2020)
X-Area LANA 1.83.8.0 (STOE, 2020)
;
_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 1.90, Darmstadt 2020
;
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_details
;
 713 frames, detector distance = 130 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  0.0590
_diffrn_reflns_av_unetI/netI     0.0740
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            28329
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.001
_diffrn_reflns_theta_min         1.706
_diffrn_source                   'Genix Mo HF'
_diffrn_source_current           1.000
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.889
_exptl_absorpt_correction_T_max  0.9649
_exptl_absorpt_correction_T_min  0.5685
_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, Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136-140.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.492
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             634
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.785
_refine_diff_density_min         -0.855
_refine_diff_density_rms         0.118
_refine_ls_abs_structure_details
;
 Flack x determined using 2489 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     663
_refine_ls_number_reflns         9900
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.1348
_refine_ls_R_factor_gt           0.0871
_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^)+(0.0684P)^2^+10.9894P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1904
_refine_ls_wR_factor_ref         0.2216
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    0.922
_reflns_Friedel_fraction_max     0.883
_reflns_number_gt                7009
_reflns_number_total             9900
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00300h2.cif
_cod_data_source_block           i3251
_cod_depositor_comments
'Adding full bibliography for 7718189--7718202.cif.'
_cod_database_code               7718201
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.878
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C38) = Uanis(C43) = Uanis(C42) = Uanis(C41) = Uanis(C40) = Uanis(C39)
Uanis(O1) = Uanis(C64) = Uanis(C63) = Uanis(C62) = Uanis(C61)
3. Rigid body (RIGU) restrains
 P1, F1, F3, F6, F4, F2, F5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.0001
 C13, C18, C17, C16, C15, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C25, C24, C23, C22, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C19(H19A,H19B), C37(H37A,H37B), C44(H44A,H44B), C61(H61A,
 H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C24(H24),
  C25(H25), C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34),
 C35(H35), C36(H36), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C46(H46),
  C47(H47), C48(H48), C49(H49), C50(H50)
4.c Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C)
;
_shelx_res_checksum              48855
_shelx_hkl_checksum              89599
_olex2_submission_special_instructions 'No special instructions were received'