1,2-Insertion reactions of alkynes into Ge-C bonds of arylbromogermylene.
Sugahara, Tomohiro; Espinosa Ferao, Arturo; Rey Planells, Alicia; Guo, Jing-Dong; Aoyama, Shin; Igawa, Kazunobu; Tomooka, Katsuhiko; Sasamori, Takahiro; Hashizume, Daisuke; Nagase, Shigeru; Tokitoh, Norihiro; Dalton transactions (Cambridge, England : 2003) 49 (2020) 7189–7196; doi:10.1039/d0dt01223h

data_7704307
_publ_section_title
;
 1,2-Insertion reactions of alkynes into Ge-C bonds of arylbromogermylene.
;
_journal_issue                   21
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7189
_journal_page_last               7196
_journal_paper_doi               10.1039/d0dt01223h
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C47 H77 Br Ge N2 O4 S2 Si4, 2.408(C3 H3)'
_chemical_formula_sum            'C54.22 H84.22 Br Ge N2 O4 S2 Si4'
_chemical_formula_weight         1157.07
_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
_audit_block_doi                 10.5517/ccdc.csd.cc220v54
_audit_creation_date             2020-05-01
_audit_creation_method
;
Olex2 1.3-dev
(compiled 2020.04.27 svn.r7e0b91c7 for OlexSys, GUI svn.r5830)
;
_audit_update_record
;
2020-05-02 deposited with the CCDC.	2020-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                74.247(2)
_cell_angle_beta                 88.954(2)
_cell_angle_gamma                65.242(2)
_cell_formula_units_Z            2
_cell_length_a                   11.8162(2)
_cell_length_b                   12.9307(3)
_cell_length_c                   23.7235(6)
_cell_measurement_reflns_used    22677
_cell_measurement_temperature    103(2)
_cell_measurement_theta_max      30.7110
_cell_measurement_theta_min      2.1820
_cell_volume                     3149.01(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       CrystalClear
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      103.15
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Rigaku VariMax Saturn 724+'
_diffrn_measurement_method       \w
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0698
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            55460
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.500
_diffrn_reflns_theta_min         2.148
_exptl_absorpt_coefficient_mu    1.304
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.903
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.220
_exptl_crystal_description       block
_exptl_crystal_F_000             1221
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.233
_refine_diff_density_min         -0.712
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     753
_refine_ls_number_reflns         11710
_refine_ls_number_restraints     96
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0674
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0735P)^2^+7.2411P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1639
_refine_ls_wR_factor_ref         0.1788
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8689
_reflns_number_total             11710
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01223h3.cif
_cod_data_source_block           compound6b
_cod_depositor_comments
'Adding full bibliography for 7704306--7704311.cif.'
_cod_original_cell_volume        3149.01(13)
_cod_database_code               7704307
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.903
_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. Restrained distances
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 C1-C7 \\sim C1A-C7A
 with sigma of 0.02
 S1-C13 \\sim S1A-C13A
 with sigma of 0.04
 S2-C22 \\sim S2A-C22A
 with sigma of 0.04
 C2-C3 \\sim C2A-C3A
 with sigma of 0.02
 C3-N1 \\sim C3A-N1A
 with sigma of 0.02
 O1-C8 \\sim O1A-C8A
 with sigma of 0.04
 N1-C4 \\sim N1A-C4A
 with sigma of 0.02
 C8-C12 \\sim C8A-C12A
 with sigma of 0.04
 N1-S1 \\sim N1A-S1A
 with sigma of 0.02
 C15-C16 \\sim C15A-C16A
 with sigma of 0.04
 C4-C5 \\sim C4A-C5A
 with sigma of 0.02
 C6-C15 \\sim C6A-C15A
 with sigma of 0.04
 C5-C6 \\sim C5A-C6A
 with sigma of 0.02
 C5-C15 \\sim C5A-C15A
 with sigma of 0.02
 C5-C16 \\sim C5A-C16A
 with sigma of 0.02
 C6-N2 \\sim C6A-N2A
 with sigma of 0.02
 N2-C7 \\sim N2A-C7A
 with sigma of 0.02
 N2-S2 \\sim N2A-S2A
 with sigma of 0.02
 C17-C19 \\sim C17A-C19A
 with sigma of 0.04
 C19-C21 \\sim C19A-C21A
 with sigma of 0.04
 S1-O1 \\sim S1A-O1A
 with sigma of 0.02
 S1-O2 \\sim S1A-O2A
 with sigma of 0.02
 S1-C8 \\sim S1A-C8A
 with sigma of 0.02
 C6-S2 \\sim C6A-S2A
 with sigma of 0.04
 N2-O4 \\sim N2A-O4A
 with sigma of 0.04
 C8-C9 \\sim C8A-C9A
 with sigma of 0.02
 C8-C13 \\sim C8A-C13A
 with sigma of 0.02
 C9-C10 \\sim C9A-C10A
 with sigma of 0.02
 C10-C11 \\sim C10A-C11A
 with sigma of 0.02
 C11-C12 \\sim C11A-C12A
 with sigma of 0.02
 C9-C13 \\sim C9A-C13A
 with sigma of 0.04
 C11-C14 \\sim C11A-C14A
 with sigma of 0.02
 C10-C12 \\sim C10A-C12A
 with sigma of 0.04
 C11-C13 \\sim C11A-C13A
 with sigma of 0.04
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 O3-O4 \\sim O3A-O4A
 with sigma of 0.04
 S2-O3 \\sim S2A-O3A
 with sigma of 0.02
 C18-C20 \\sim C18A-C20A
 with sigma of 0.04
 S2-O4 \\sim S2A-O4A
 with sigma of 0.02
 S2-C17 \\sim S2A-C17A
 with sigma of 0.02
 C21-C23 \\sim C21A-C23A
 with sigma of 0.04
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 C6-C7 \\sim C6A-C7A
 with sigma of 0.04
 C17-C22 \\sim C17A-C22A
 with sigma of 0.02
 C6-C16 \\sim C6A-C16A
 with sigma of 0.04
 C18-C19 \\sim C18A-C19A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 N2-O3 \\sim N2A-O3A
 with sigma of 0.04
 N2-C17 \\sim N2A-C17A
 with sigma of 0.04
 C20-C21 \\sim C20A-C21A
 with sigma of 0.02
 C20-C23 \\sim C20A-C23A
 with sigma of 0.02
 C7-S2 \\sim C7A-S2A
 with sigma of 0.04
 C21-C22 \\sim C21A-C22A
 with sigma of 0.02
 S1-C9 \\sim S1A-C9A
 with sigma of 0.04
 O1-O2 \\sim O1A-O2A
 with sigma of 0.04
 C1-C3 \\sim C1A-C3A
 with sigma of 0.04
 C1-N2 \\sim C1A-N2A
 with sigma of 0.04
 O2-C8 \\sim O2A-C8A
 with sigma of 0.04
 C8-C10 \\sim C8A-C10A
 with sigma of 0.04
 C9-C11 \\sim C9A-C11A
 with sigma of 0.04
 C2-N1 \\sim C2A-N1A
 with sigma of 0.04
 C2-C7 \\sim C2A-C7A
 with sigma of 0.04
 C10-C14 \\sim C10A-C14A
 with sigma of 0.04
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
 C3-C4 \\sim C3A-C4A
 with sigma of 0.04
 C3-S1 \\sim C3A-S1A
 with sigma of 0.04
 S2-C18 \\sim S2A-C18A
 with sigma of 0.04
 O3-C17 \\sim O3A-C17A
 with sigma of 0.04
 O4-C17 \\sim O4A-C17A
 with sigma of 0.04
 N1-C5 \\sim N1A-C5A
 with sigma of 0.04
 N1-O1 \\sim N1A-O1A
 with sigma of 0.04
 C17-C21 \\sim C17A-C21A
 with sigma of 0.04
 N1-O2 \\sim N1A-O2A
 with sigma of 0.04
 N1-C8 \\sim N1A-C8A
 with sigma of 0.04
 C18-C22 \\sim C18A-C22A
 with sigma of 0.04
 C19-C23 \\sim C19A-C23A
 with sigma of 0.04
 C4-C6 \\sim C4A-C6A
 with sigma of 0.04
 C4-S1 \\sim C4A-S1A
 with sigma of 0.04
 C4-C15 \\sim C4A-C15A
 with sigma of 0.04
 C20-C22 \\sim C20A-C22A
 with sigma of 0.04
 C4-C16 \\sim C4A-C16A
 with sigma of 0.04
 C5-N2 \\sim C5A-N2A
 with sigma of 0.04
3. Restrained planarity
 C17A, C22A, C21A, C20A, C19A, C23A, C18A
 with sigma of 0.001
 C9A, C8A, C13A, C10A, C11A, C12A, C14A
 with sigma of 0.001
 S2A, C17A, C22A, C21A, C20A, C18A, C19A, C23A
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
C40: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.01 within 3A
Uanis(S2) = Uanis(S2A)
Uanis(S1) = Uanis(S1A)
Uanis(Ge1) = Uanis(Ge2)
5. Others
 Sof(C51)=Sof(H51)=FVAR(1)
 Sof(C56)=Sof(H56)=FVAR(2)
 Sof(C55)=Sof(H55)=FVAR(3)
 Sof(C54)=Sof(H54)=FVAR(4)
 Sof(C53)=Sof(H53)=FVAR(5)
 Sof(C52)=Sof(H52)=FVAR(6)
 Fixed Sof: Ge1(0.9) Br1(0.9) C1(0.9) C2(0.9) C3(0.9) H3A(0.9) H3B(0.9)
 N1(0.9) C4(0.9) H4A(0.9) H4B(0.9) C5(0.9) C6(0.9) H6A(0.9) H6B(0.9) N2(0.9)
 C7(0.9) H7A(0.9) H7B(0.9) S1(0.9) O1(0.9) O2(0.9) C8(0.9) C9(0.9) H9(0.9)
 C10(0.9) H10(0.9) C11(0.9) C12(0.9) H12(0.9) C13(0.9) H13(0.9) C14(0.9)
 H14A(0.9) H14B(0.9) H14C(0.9) C15(0.9) H15A(0.9) H15B(0.9) H15C(0.9) C16(0.9)
 H16A(0.9) H16B(0.9) H16C(0.9) S2(0.9) O3(0.9) O4(0.9) C17(0.9) C18(0.9)
 H18(0.9) C19(0.9) H19(0.9) C20(0.9) C21(0.9) H21(0.9) C22(0.9) H22(0.9)
 C23(0.9) H23A(0.9) H23B(0.9) H23C(0.9) Ge2(0.1) Br2(0.1) C16A(0.1) H16D(0.1)
 H16E(0.1) H16F(0.1) C1A(0.1) C2A(0.1) C7A(0.1) H7AA(0.1) H7AB(0.1) C3A(0.1)
 H3AA(0.1) H3AB(0.1) N2A(0.1) N1A(0.1) C6A(0.1) H6AA(0.1) H6AB(0.1) S2A(0.1)
 C4A(0.1) H4AA(0.1) H4AB(0.1) S1A(0.1) C5A(0.1) O3A(0.1) O4A(0.1) C17A(0.1)
 C18A(0.1) H18A(0.1) C19A(0.1) H19A(0.1) C20A(0.1) C21A(0.1) H21A(0.1)
 C22A(0.1) H22A(0.1) O1A(0.1) O2A(0.1) C8A(0.1) C15A(0.1) H15D(0.1) H15E(0.1)
 H15F(0.1) C9A(0.1) H9A(0.1) C13A(0.1) H13A(0.1) C10A(0.1) H10A(0.1) C12A(0.1)
 H12A(0.1) C11A(0.1) C23A(0.1) H23D(0.1) H23E(0.1) H23F(0.1) C14A(0.1)
 H14D(0.1) H14E(0.1) H14F(0.1)
 Fixed Uiso: C16A(0.04) H16D(0.04) H16E(0.04) H16F(0.04) C1A(0.04) C2A(0.04)
 C7A(0.04) H7AA(0.04) H7AB(0.04) C3A(0.04) H3AA(0.04) H3AB(0.04) N2A(0.04)
 N1A(0.04) C6A(0.04) H6AA(0.04) H6AB(0.04) C4A(0.04) H4AA(0.04) H4AB(0.04)
 C5A(0.04) O3A(0.04) O4A(0.04) C17A(0.04) C18A(0.04) H18A(0.04) C19A(0.04)
 H19A(0.04) C20A(0.04) C21A(0.04) H21A(0.04) C22A(0.04) H22A(0.04) O1A(0.04)
 O2A(0.04) C8A(0.04) C15A(0.04) H15D(0.04) H15E(0.04) H15F(0.04) C9A(0.04)
 H9A(0.04) C13A(0.04) H13A(0.04) C10A(0.04) H10A(0.04) C12A(0.04) H12A(0.04)
 C11A(0.04) C23A(0.04) H23D(0.04) H23E(0.04) H23F(0.04) C14A(0.04) H14D(0.04)
 H14E(0.04) H14F(0.04)
6.a Ternary CH refined with riding coordinates:
 C30(H30), C41(H41)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C7A(H7AA,H7AB), C3A(H3AA,
 H3AB), C6A(H6AA,H6AB), C4A(H4AA,H4AB)
6.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13), C18(H18), C19(H19), C21(H21), C22(H22),
 C26(H26), C28(H28), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53),
  C54(H54), C55(H55), C56(H56), C18A(H18A), C19A(H19A), C21A(H21A), C22A(H22A),
 C9A(H9A), C13A(H13A), C10A(H10A), C12A(H12A)
6.d Fitted hexagon refined as free rotating group:
 C17A(C18A,C19A,C20A,C21A,C22A)
6.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C23(H23A,H23B,
 H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C16A(H16D,H16E,H16F), C15A(H15D,H15E,H15F), C23A(H23D,H23E,H23F),
 C14A(H14D,H14E,H14F)
;
_shelx_res_checksum              19730
_olex2_submission_special_instructions 'No special instructions were received'