A neutral homoaromatic heavy allene as a platform for selective conversion to a germylene-coordinated digermavinylidene.
Uchida, Daichi; Yamada, Hiroko; Mizuhata, Yoshiyuki; Chemical science 16 (2025) 22597–22602; doi:10.1039/d5sc07177a

data_1576067
_publ_section_title
;
 A neutral homoaromatic heavy allene as a platform for selective
 conversion to a germylene-coordinated digermavinylidene.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22597
_journal_page_last               22602
_journal_paper_doi               10.1039/d5sc07177a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C49 H100 Ge2 K2 Si8, 3(C6 H6)'
_chemical_formula_sum            'C67 H118 Ge2 K2 Si8'
_chemical_formula_weight         1371.71
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-09-04
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-04 deposited with the CCDC.	2025-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.740(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.649(4)
_cell_length_b                   13.124(2)
_cell_length_c                   26.722(4)
_cell_measurement_reflns_used    9485
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.58
_cell_measurement_theta_min      2.18
_cell_volume                     7939(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service vV6.2.12'
_computing_data_reduction        'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_computing_molecular_graphics    'Yadokari-XG 2009 (Wakita Nemoto et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      90(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 goniometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1237
_diffrn_reflns_av_unetI/netI     0.0559
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            195929
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.533
_diffrn_reflns_theta_min         1.938
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.017
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5997
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1713 before and 0.0867 after correction.
The Ratio of minimum to maximum transmission is 0.8043.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.148
_exptl_crystal_description       plate
_exptl_crystal_F_000             2936
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene'
_exptl_crystal_size_max          0.195
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.583
_refine_diff_density_min         -0.530
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     750
_refine_ls_number_reflns         18229
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0406
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0355P)^2^+4.6681P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0849
_refine_ls_wR_factor_ref         0.0959
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13834
_reflns_number_total             18229
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07177a3.cif
_cod_data_source_block           Tbb2Ge2CH2_dianion
_cod_depositor_comments
'Adding full bibliography for 1576066--1576068.cif.'
_cod_database_code               1576067
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.822
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, {H42B,H42C} of C42, H42A of C1
 At 1.2 times of:
  H28 of C28, H32 of C32, H33 of C33, H30 of C30, {H1A,H1B} of C1, H50 of C50,
   H55 of C55, H51 of C51, H58 of C58, H52 of C52, H59 of C59, H61 of C61, H62
  of C62, H57 of C57, H56 of C56, H63 of C63, H60 of C60, H64 of C64, H53 of
  C53, H54 of C54, H9 of C9, H4 of C4, H65 of C65, H8 of C8, H66 of C66, H67 of
  C67, H6 of C6
2.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C32(H32), C33(H33)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.c Aromatic/amide H refined with riding coordinates:
 C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56),
 C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64),
  C65(H65), C66(H66), C67(H67), C4(H4), C6(H6), C28(H28), C30(H30)
2.d Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C10(H10A,H10B,H10C), C11(H11A,
 H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              4838
_olex2_submission_special_instructions 'No special instructions were received'