Trapping Carbon Suboxide with a Carbene and Isolation of the Carbene-stabilized Carbon Suboxide Dimer
George, Tanner; Johnson, Erin R.; Masuda, Jason Douglas; Chemical Science  (2025) –; doi:10.1039/D5SC06444A

data_1576004
_publ_section_title
;
 Trapping Carbon Suboxide with a Carbene and Isolation of the
 Carbene-stabilized Carbon Suboxide Dimer
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC06444A
_journal_year                    2025
_chemical_formula_moiety         'C80 H88 Au8 S16, 2(C7 H8)'
_chemical_formula_sum            'C94 H104 Au8 S16'
_chemical_formula_weight         3322.46
_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
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/ccdc.csd.cc1z0w84
_audit_creation_date             2018-02-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-15 deposited with the CCDC.	2025-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                99.791(5)
_cell_angle_beta                 102.539(5)
_cell_angle_gamma                106.269(5)
_cell_formula_units_Z            1
_cell_length_a                   11.5867(6)
_cell_length_b                   14.9898(9)
_cell_length_c                   15.6467(10)
_cell_measurement_reflns_used    11819
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      72.5350
_cell_measurement_theta_min      4.0270
_cell_volume                     2468.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.964
_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   -116.00 -10.00   1.00   22.50    --  -41.83 -77.00 -30.00  106
  2  \w   -115.00 -19.00   1.00   22.50    --  -41.83 -37.00 -60.00   96
  3  \w   -116.00 -10.00   1.00   22.50    --  -41.83 -77.00  60.00  106
  4  \w   -112.00 -15.00   1.00   22.50    --  -41.83 -57.00  90.00   97
  5  \w   -115.00 -19.00   1.00   22.50    --  -41.83 -37.00 150.00   96
  6  \w   -116.00 -10.00   1.00   22.50    --  -41.83 -77.00 150.00  106
  7  \w   -116.00 -10.00   1.00   22.50    --  -41.83 -77.00-120.00  106
  8  \w    -68.00  28.00   1.00   22.50    --  -41.83  57.00  90.00   96
  9  \w   -115.00 -19.00   1.00   22.50    --  -41.83 -37.00-150.00   96
 10  \w      1.00  82.00   1.00   22.50    --   41.83 -99.00   0.00   81
 11  \w    -31.00  64.00   1.00   22.50    --   41.83 -37.00-150.00   95
 12  \w      5.00 120.00   1.00   22.50    --   41.83  19.00  30.00  115
 13  \w      1.00  82.00   1.00   22.50    --   41.83 -99.00-180.00   81
 14  \w     80.00 178.00   1.00   56.50    --  111.00  77.00-120.00   98
 15  \w     30.00 109.00   1.00   56.50    --  111.00 -94.00-150.00   79
 16  \w     84.00 178.00   1.00   56.50    --  111.00  57.00  17.35   94
 17  \w     30.00 109.00   1.00   56.50    --  111.00 -94.00  60.00   79
 18  \w     83.00 178.00   1.00   56.50    --  111.00  61.00   0.00   95
 19  \w     80.00 178.00   1.00   56.50    --  111.00  77.00 -90.00   98
 20  \w     83.00 178.00   1.00   56.50    --  111.00  61.00  30.00   95
 21  \w     83.00 178.00   1.00   56.50    --  111.00  61.00 120.00   95
 22  \w     83.00 178.00   1.00   56.50    --  111.00  61.00 150.00   95
 23  \w     83.00 178.00   1.00   56.50    --  111.00  61.00-150.00   95
 24  \w     84.00 178.00   1.00   56.50    --  111.00  58.00-131.09   94
 25  \w     83.00 125.00   1.00   56.50    --  111.00  61.00-180.00   42
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0057630000
_diffrn_orient_matrix_UB_12      0.0537730000
_diffrn_orient_matrix_UB_13      -0.0753962000
_diffrn_orient_matrix_UB_21      -0.0718909000
_diffrn_orient_matrix_UB_22      0.0610797000
_diffrn_orient_matrix_UB_23      0.0395421000
_diffrn_orient_matrix_UB_31      0.1249509000
_diffrn_orient_matrix_UB_32      0.0747035000
_diffrn_orient_matrix_UB_33      0.0598588000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            10066
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.710
_diffrn_reflns_theta_min         2.985
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    25.253
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.052
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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            'clear brownish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.235
_exptl_crystal_description       needle
_exptl_crystal_F_000             1556
_exptl_crystal_size_max          0.494
_exptl_crystal_size_mid          0.023
_exptl_crystal_size_min          0.016
_refine_diff_density_max         2.576
_refine_diff_density_min         -2.604
_refine_diff_density_rms         0.287
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         10066
_refine_ls_number_restraints     297
_refine_ls_restrained_S_all      0.987
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0431
_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^)+(0.0983P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1162
_refine_ls_wR_factor_ref         0.1230
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8478
_reflns_number_total             10066
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9131\% 
 around [0.00 -0.71 0.71] (reciprocal) or [-0.08 -0.76 0.65] (direct)
;
_cod_data_source_file            d5sc06444a2.cif
_cod_data_source_block           jojo_twin1_hklf4
_cod_database_code               1576004
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C40 H48 Au4 S8'
_shelx_estimated_absorpt_t_max   0.688
_shelx_estimated_absorpt_t_min   0.028
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7637(15)
 0.2363(15)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C10A) \\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(C7B) \\sim Ueq, Uanis(C7A)
\\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C17B) \\sim Ueq,
Uanis(C17A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C16B) \\sim Ueq,
Uanis(C20B) \\sim Ueq, Uanis(C20A) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
Uanis(C46) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C50) \\sim Ueq, :
with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C44) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C50) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C52)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C51) \\sim Ueq:
with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C6A) = Uanis(C6B) = Uanis(C7B) = Uanis(C10B) = Uanis(C7A) = Uanis(C10A)
Uanis(C16B) = Uanis(C17B) = Uanis(C20B) = Uanis(C17A) = Uanis(C16A) =
Uanis(C20A)
4. Rigid body (RIGU) restrains
 C10A, C10B, C7B, C7A, C6A, C6B, C17B, C17A, C16A, C16B, C20B, C20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, C48, C49, C50, C51, C52, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, C42, C43, C44, C45, C40, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C40, C45, C44, C43, C42, C41, C46} sigma for 1-2: 0.02, 1-3: 0.04
as
{C47, C48, C49, C50, C51, C52, C53}
6. Others
 Fixed Sof: C6A(0.5) H6A(0.5) C7A(0.5) C10A(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
 C16A(0.5) H16A(0.5) C17A(0.5) C20A(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C6B(0.5)
 H6B(0.5) C7B(0.5) C10B(0.5) H10D(0.5) H10E(0.5) H10F(0.5) C16B(0.5) H16B(0.5)
 C17B(0.5) C20B(0.5) H20D(0.5) H20E(0.5) H20F(0.5) C40(0.5) C45(0.5) H45(0.5)
 C44(0.5) H44(0.5) C43(0.5) H43(0.5) C42(0.5) H42(0.5) C41(0.5) H41(0.5)
 C46(0.5) H46A(0.5) H46B(0.5) H46C(0.5) C47(0.5) C48(0.5) H48(0.5) C49(0.5)
 H49(0.5) C50(0.5) H50(0.5) C51(0.5) H51(0.5) C52(0.5) H52(0.5) C53(0.5)
 H53A(0.5) H53B(0.5) H53C(0.5)
7.a Me refined with riding coordinates:
 C46(H46A,H46B,H46C)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C14(H14), C24(H24), C26(H26), C34(H34), C36(H36), C6A(H6A),
 C16A(H16A), C6B(H6B), C16B(H16B), C45(H45), C44(H44), C43(H43), C42(H42),
 C41(H41), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52)
7.c Fitted hexagon refined as free rotating group:
 C40(C45,C44,C43,C42,C41), C47(C48,C49,C50,C51,C52)
7.d Idealised Me refined as rotating group:
 C3AA(H3AA,H3AB,H3AC), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C10A(H10A,H10B,H10C),
 C20A(H20A,H20B,H20C), C10B(H10D,H10E,H10F), C20B(H20D,H20E,H20F), C53(H53A,
 H53B,H53C)
;
_olex2_exptl_crystal_mounting_method mounted
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.894
_oxdiff_exptl_absorpt_empirical_full_min 0.597
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2