Stepwise alkyne insertion in Au(i) acetylides: influence of the nuclearity.
Cayuela-Castillo, Juan; Fernández-de-Córdova, Francisco J; See, Matthew S.; Fernández, Israel; Ríos, Pablo; Chemical science 16 (2025) 4684–4694; doi:10.1039/d4sc08227c

data_1573910
_publ_section_title
;
 Stepwise alkyne insertion in Au(i) acetylides: influence of the
 nuclearity.
;
_journal_issue                   11
_journal_name_full               'Chemical science'
_journal_page_first              4684
_journal_page_last               4694
_journal_paper_doi               10.1039/d4sc08227c
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C83 H108 Au3 N6, C F3 O3 S, 3[C4H8O], 1[C4H8O]'
_chemical_formula_sum            'C84 H108 Au3 F3 N6 O3 S'
_chemical_formula_weight         1929.72
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-22 deposited with the CCDC.	2025-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.380(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3416(6)
_cell_length_b                   20.8456(8)
_cell_length_c                   30.6473(12)
_cell_measurement_reflns_used    9386
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      27.820
_cell_measurement_theta_min      2.250
_cell_volume                     10269.2(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      193.00
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0637
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            397960
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.298
_diffrn_reflns_theta_min         1.941
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    4.341
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.4577
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1100 before and 0.0632 after correction.
The Ratio of minimum to maximum transmission is 0.6138.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       prism
_exptl_crystal_F_000             3832
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: THF'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.411
_refine_diff_density_min         -0.926
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     998
_refine_ls_number_reflns         25501
_refine_ls_number_restraints     303
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0503
_refine_ls_R_factor_gt           0.0312
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0223P)^2^+23.6376P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0657
_refine_ls_wR_factor_ref         0.0768
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19662
_reflns_number_total             25501
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08227c6.cif
_cod_data_source_block           pr2323a_0m
_cod_depositor_comments
'Adding full bibliography for 1573902--1573910.cif.'
_cod_database_code               1573910
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.509
_shelx_estimated_absorpt_t_min   0.276
_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. Restrained distances
 C1A-F1 = C1A-F2 = C1A-F5
 1.33 with sigma of 0.02
 C1A-S6
 1.82 with sigma of 0.02
 S6-O1 = S6-O8 = S6-O9
 1.44 with sigma of 0.02
 C1A-O1
 2.58 with sigma of 0.04
 C1A-O8
 2.56 with sigma of 0.04
 C1A-O9
 2.57 with sigma of 0.04
 C1A-F1 \\sim C1A-F2 \\sim C1A-F5
 with sigma of 0.02
 F1-F2 \\sim F2-F5 \\sim F5-F1
 with sigma of 0.04
 S6-F1 \\sim S6-F2 \\sim S6-F5
 with sigma of 0.04
 S6-O1 \\sim S6-O8 \\sim S6-O9
 with sigma of 0.02
 O1-O8 \\sim O8-O9 \\sim O1-O9
 with sigma of 0.04
 C1A-O1 \\sim C1A-O8 \\sim C1A-O9
 with sigma of 0.04
 C1A-F1 \\sim C1B-F1A
 with sigma of 0.02
 C1A-F2 \\sim C1B-F2A
 with sigma of 0.02
 C1A-F5 \\sim C1B-F5A
 with sigma of 0.02
 C1A-S6 \\sim C1B-S6A
 with sigma of 0.02
 S6-O1 \\sim S6A-O1A
 with sigma of 0.02
 S6-O8 \\sim S6A-O8A
 with sigma of 0.02
 S6-O9 \\sim S6A-O9A
 with sigma of 0.02
 C1A-O1 \\sim C1B-O1A
 with sigma of 0.04
 C1A-O8 \\sim C1B-O8A
 with sigma of 0.04
 C1A-O9 \\sim C1B-O9A
 with sigma of 0.04
 F1-F2 \\sim F1A-F2A
 with sigma of 0.04
 F1-F5 \\sim F1A-F5A
 with sigma of 0.04
 F1-S6 \\sim F1A-S6A
 with sigma of 0.04
 F2-F5 \\sim F2A-F5A
 with sigma of 0.04
 F2-S6 \\sim F2A-S6A
 with sigma of 0.04
 F5-S6 \\sim F5A-S6A
 with sigma of 0.04
 O1-O8 \\sim O1A-O8A
 with sigma of 0.04
 O1-O9 \\sim O1A-O9A
 with sigma of 0.04
 O8-O9 \\sim O8A-O9A
 with sigma of 0.04
3. Rigid bond restraints
 C42, C43, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C43, C42, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1A \\sim F1 \\sim F2 \\sim F5 \\sim S6 \\sim O1 \\sim O8 \\sim O9: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C42 \\sim C43 \\sim C44: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C40 \\sim C39 \\sim C41: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C43 \\sim C42 \\sim C44: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C70, C69, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, F1, F2, F5, S6, O1, O8, O9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1B, F1A, F2A, F5A, S6A, O1A, O8A, O9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C52, C51, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C42, C1B, C43, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C1B)=Sof(F1A)=Sof(F2A)=Sof(F5A)=Sof(S6A)=Sof(O1A)=Sof(O8A)=Sof(O9A)=1-
 FVAR(1)
 Sof(C1A)=Sof(F1)=Sof(F2)=Sof(F5)=Sof(S6)=Sof(O1)=Sof(O8)=Sof(O9)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C15(H15), C81(H81), C39(H39), C12(H12), C78(H78), C24(H24), C54(H54),
 C27(H27), C66(H66), C51(H51), C69(H69), C42(H42)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C59(H59), C5(H5), C58(H58), C37(H37), C8(H8), C10(H10), C62(H62),
 C31(H31), C9(H9), C47(H47), C64(H64), C32(H32), C20(H20), C36(H36), C63(H63),
 C48(H48), C74(H74), C76(H76), C75(H75), C21(H21), C35(H35), C22(H22), C49(H49)
7.c Idealised Me refined as rotating group:
 C80(H80A,H80B,H80C), C17(H17A,H17B,H17C), C16(H16A,H16B,H16C), C67(H67A,H67B,
 H67C), C56(H56A,H56B,H56C), C41(H41A,H41B,H41C), C82(H82A,H82B,H82C), C13(H13A,
 H13B,H13C), C68(H68A,H68B,H68C), C79(H79A,H79B,H79C), C29(H29A,H29B,H29C),
 C83(H83A,H83B,H83C), C55(H55A,H55B,H55C), C52(H52A,H52B,H52C), C28(H28A,H28B,
 H28C), C53(H53A,H53B,H53C), C14(H14A,H14B,H14C), C26(H26A,H26B,H26C), C40(H40A,
 H40B,H40C), C70(H70A,H70B,H70C), C43(H43A,H43B,H43C), C25(H25A,H25B,H25C),
 C71(H71A,H71B,H71C), C44(H44A,H44B,H44C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              95098
_shelx_fab_checksum              92769
_olex2_submission_special_instructions 'No special instructions were received'