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_1573903
_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         'C28.5 H36 Au N2 S, 2(C2 H3 N)'
_chemical_formula_sum            'C32.5 H42 Au N4 S'
_chemical_formula_weight         717.72
_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     iterative
_audit_creation_date             2024-10-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-19 deposited with the CCDC.	2025-02-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.657(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7024(6)
_cell_length_b                   27.5930(15)
_cell_length_c                   12.0247(6)
_cell_measurement_reflns_used    9724
_cell_measurement_temperature    194.00
_cell_measurement_theta_max      28.279
_cell_measurement_theta_min      2.410
_cell_volume                     3547.2(3)
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      194.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-III'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0541
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            96073
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.312
_diffrn_reflns_theta_min         2.043
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    4.230
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5904
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0797 before and 0.0614 after correction.
The Ratio of minimum to maximum transmission is 0.7917.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       prism
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.077
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.193
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     403
_refine_ls_number_reflns         8797
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.198
_refine_ls_R_factor_all          0.0386
_refine_ls_R_factor_gt           0.0320
_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^)+(0.0234P)^2^+4.9421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0719
_refine_ls_wR_factor_ref         0.0748
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7861
_reflns_number_total             8797
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08227c6.cif
_cod_data_source_block           pr03123a_0m
_cod_depositor_comments
'Adding full bibliography for 1573902--1573910.cif.'
_cod_original_formula_sum        'C32.50 H42 Au N4 S'
_cod_database_code               1573903
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.728
_shelx_estimated_absorpt_t_min   0.569
_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
 N3-C30
 1.14 with sigma of 0.02
 C30-N3
 1.137 with sigma of 0.01
 C30-C31
 1.456 with sigma of 0.01
 C31-N3
 2.593 with sigma of 0.02
 N4-C32
 1.14 with sigma of 0.02
 C32-N4
 1.137 with sigma of 0.01
 C32-C33
 1.456 with sigma of 0.01
 C33-N4
 2.593 with sigma of 0.02
 N5-C34
 1.14 with sigma of 0.02
 C34-N5
 1.137 with sigma of 0.01
 C34-C35
 1.456 with sigma of 0.01
 C35-N5
 2.593 with sigma of 0.02
 N3-C31
 2.59 with sigma of 0.04
 N4-C33
 2.59 with sigma of 0.04
 N5-C35
 2.59 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N3 \\sim C30 \\sim C31: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N4 \\sim C32 \\sim C33: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C33 \\sim N4 \\sim C32: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C30 \\sim N3 \\sim C31: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N5 \\sim C34 \\sim C35: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C35 \\sim N5 \\sim C34: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C28) = Uanis(S2)
4. Rigid body (RIGU) restrains
 N3, C30, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C32, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, C34, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N3)=Sof(C30)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=1-FVAR(1)
 Sof(N4)=Sof(C32)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(1)
 Fixed Sof: C27(0.5) C28(0.5) C29(0.5) S1(0.5) S2(0.5)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C14(H14), C19(H19), C20(H20)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C10(H10), C11(H11), C13(H13), C15(H15), C16(H16), C17(H17)
6.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C1A(H1AA,H1AB,H1AC), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C)
;
_shelx_res_checksum              66842
_olex2_submission_special_instructions 'No special instructions were received'