Synthesis, structure, photochemical and electrochemical properties of α-germyl ferrocenyl ketones.
Heurix, Madeleine; Harmach, Petr; Torvisco, Ana; Fischer, Roland C.; Wiech, Mathias; Císařová, Ivana; Gescheidt, Georg; Štěpnička, Petr; Haas, Michael; Dalton transactions (Cambridge, England : 2003) 54 (2025) 17611–17620; doi:10.1039/d5dt02029h

data_7719846
_publ_section_title
;
 Synthesis, structure, photochemical and electrochemical properties of
 &#x3b1;-germyl ferrocenyl ketones.
;
_journal_issue                   47
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              17611
_journal_page_last               17620
_journal_paper_doi               10.1039/d5dt02029h
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C41 H42 Fe Ge O4'
_chemical_formula_sum            'C41 H42 Fe Ge O4'
_chemical_formula_weight         727.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-12-11
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-08-04 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.39641(10)
_cell_length_b                   14.34083(10)
_cell_length_c                   26.21799(18)
_cell_measurement_reflns_used    53732
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.1520
_cell_measurement_theta_min      3.3680
_cell_volume                     6916.82(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution
'olex2.solve 1.5-ac6-020 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -48.00 -13.00   0.50    0.88    --    4.00 125.00 -25.50   70
  2  \w    -46.00 -13.00   0.50    0.88    --    8.00 126.00 103.44   66
  3  \w    -31.00  -1.00   0.50    0.88    --   12.00 110.00-147.25   60
  4  \w    -14.00  12.00   0.50    0.88    --   20.00  93.00 -89.60   52
  5  \w      3.00  31.00   0.50    0.88    --   24.00  72.00  54.67   56
  6  \w      2.00  30.00   0.50    0.88    --   24.00  73.00 171.40   56
  7  \w      8.00  37.00   0.50    0.88    --   28.00  67.00 117.64   58
  8  \w   -139.00 -47.00   0.50    0.88    --  -64.00 -54.00 113.59  184
  9  \w   -139.00 -47.00   0.50    0.88    --  -64.00 -55.00-172.05  184
 10  \w    -71.00  -7.00   0.50    0.88    --  -80.25  61.00  30.00  128
 11  \w    -35.00  -2.00   0.50    0.88    --  -80.25  30.00   0.00   66
 12  \w   -105.00 -13.00   0.50    0.88    --  -80.25  77.00  90.00  184
 13  \w   -105.00 -13.00   0.50    0.88    --  -80.25  77.00 -90.00  184
 14  \w    -51.00  -4.00   0.50    0.88    --  -80.25  45.00 -30.00   94
 15  \w   -105.00 -13.00   0.50    0.88    --  -80.25  77.00 -90.00  184
 16  \w   -165.00 -73.00   0.50    0.88    --  -88.50 -46.00-101.15  184
 17  \w     36.00 112.00   0.50    0.88    --  106.74-125.00-150.00  152
 18  \w     36.00 112.00   0.50    0.88    --  106.74-125.00-150.00  152
 19  \w     92.00 178.00   0.50    0.88    --  106.74  45.00-120.00  172
 20  \w     36.00 112.00   0.50    0.88    --  106.74-125.00 -30.00  152
 21  \w     40.00 105.00   0.50    0.88    --  106.74 -95.00  60.00  130
 22  \w    101.00 174.00   0.50    0.88    --  106.74  77.00-180.00  146
 23  \w     95.00 177.00   0.50    0.88    --  106.74 125.00  90.00  164
 24  \w     90.00 178.00   0.50    0.88    --  106.74  30.00 -30.00  176
 25  \w    101.00 174.00   0.50    0.88    --  106.74  77.00 -90.00  146
 26  \w     90.00 178.00   0.50    0.88    --  106.74  30.00  30.00  176
 27  \w     34.00  71.00   0.50    0.88    --  106.74 -61.00-120.00   74
 28  \w     92.00 178.00   0.50    0.88    --  106.74  45.00 -90.00  172
 29  \w     40.00 105.00   0.50    0.88    --  106.74 -77.00-150.00  130
 30  \w     36.00 112.00   0.50    0.88    --  106.74-125.00  60.00  152
 31  \w     40.00 105.00   0.50    0.88    --  106.74 -95.00   0.00  130
 32  \w     40.00 105.00   0.50    0.88    --  106.74 -77.00-180.00  130
 33  \w     90.00 178.00   0.50    0.88    --  106.74  30.00-150.00  176
 34  \w     36.00 112.00   0.50    0.88    --  106.74-125.00 120.00  152
 35  \w     40.00 105.00   0.50    0.88    --  106.74 -95.00-180.00  130
 36  \w     40.00 105.00   0.50    0.88    --  106.74 -95.00 150.00  130
 37  \w     40.00 105.00   0.50    0.88    --  106.74 -95.00  30.00  130
 38  \w     40.00 110.00   0.50    0.88    --  110.00-121.00  -9.29  140
 39  \w     40.00 110.00   0.50    0.88    --  110.00-123.00 -90.42  140
 40  \w     41.00 108.00   0.50    0.88    --  110.00-107.00 129.06  134
 41  \w     17.00  44.00   0.50    0.88    --   36.00  63.00 -19.02   54
 42  \w   -139.00 -47.00   0.50    0.88    --  -64.00 -53.00   6.71  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0096197000
_diffrn_orient_matrix_UB_12      -0.0513326000
_diffrn_orient_matrix_UB_13      -0.0511844000
_diffrn_orient_matrix_UB_21      -0.0425782000
_diffrn_orient_matrix_UB_22      0.0778788000
_diffrn_orient_matrix_UB_23      -0.0273118000
_diffrn_orient_matrix_UB_31      0.0714502000
_diffrn_orient_matrix_UB_32      0.0532938000
_diffrn_orient_matrix_UB_33      -0.0093708000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0124
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            127927
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.493
_diffrn_reflns_theta_max         67.493
_diffrn_reflns_theta_min         3.371
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.756
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.727
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.397
_exptl_crystal_description       block
_exptl_crystal_F_000             3024
_exptl_crystal_size_max          0.197
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.092
_refine_diff_density_max         0.279
_refine_diff_density_min         -0.246
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     489
_refine_ls_number_reflns         6219
_refine_ls_number_restraints     450
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0240
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0296P)^2^+3.4376P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0598
_refine_ls_wR_factor_ref         0.0611
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5791
_reflns_number_total             6219
_reflns_threshold_expression     'I > 2\s(I)'
_publcif_datablock.id            {62dd459e-ed6a-4b66-bde5-e9e92db90ab4}
_cod_data_source_file            d5dt02029h2.cif
_cod_data_source_block           at1607-mhx373
_cod_depositor_comments
'Adding full bibliography for 7719844--7719848.cif.'
_cod_database_code               7719846
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C43H42GeO5Fe
_chemical_oxdiff_usercomment     MHX373
_shelx_estimated_absorpt_t_max   0.669
_shelx_estimated_absorpt_t_min   0.454
_olex2_refinement_description
;
1. Restrained distances
 O3-C3 \\sim O3A-C3
 with sigma of 0.02
 C40-C41 \\sim C41-C37
 with sigma of 0.02
 C37-C38 \\sim C37A-C38A
 with sigma of 0.02
 C37-C41 \\sim C37A-C41A
 with sigma of 0.02
 C38-C39 \\sim C38A-C39A
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 Fe1-C37 \\sim Fe1-C37A
 with sigma of 0.04
 Fe1-C38 \\sim Fe1-C38A
 with sigma of 0.04
 Fe1-C39 \\sim Fe1-C39A
 with sigma of 0.04
 Fe1-C40 \\sim Fe1-C40A
 with sigma of 0.04
 Fe1-C41 \\sim Fe1-C41A
 with sigma of 0.04
 C37-C39 \\sim C37A-C39A
 with sigma of 0.04
 C37-C40 \\sim C37A-C40A
 with sigma of 0.04
 C38-C40 \\sim C38A-C40A
 with sigma of 0.04
 C38-C41 \\sim C38A-C41A
 with sigma of 0.04
 C39-C41 \\sim C39A-C41A
 with sigma of 0.04
2. Rigid bond restraints
 C37, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C41, C40
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C37, C41, C40, C39, C38
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
Uanis(C41) \\sim Ueq, Uanis(C40) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C39A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 C37, C41, C40, C39, C38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(O3A)=1-FVAR(1)
 Sof(O3)=FVAR(1)
 Sof(C40A)=Sof(H40A)=Sof(C39A)=Sof(H39A)=Sof(C38A)=Sof(H38A)=Sof(C37A)=
 Sof(H37A)=Sof(C41A)=Sof(H41A)=1-FVAR(2)
 Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=
 Sof(C41)=Sof(H41)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C16(H16), C18(H18), C25(H25), C27(H27), C33(H33), C34(H34),
 C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41),
 C40A(H40A), C39A(H39A), C38A(H38A), C37A(H37A), C41A(H41A)
6.b Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              31031
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.388
_oxdiff_exptl_absorpt_empirical_full_min 0.818
_publcif_funding_html
;
;