Ring-Expansion and Desulfurisation of Thiophenes with an Aluminium(I) Reagent
McMullen, Jacob; White, Andrew J. P.; Crimmin, Mark Richard; Chemical Communications  (2023) –; doi:10.1039/D3CC04594C

data_7132354
_publ_section_title
;
 Ring-Expansion and Desulfurisation of Thiophenes with an Aluminium(I)
 Reagent
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04594C
_journal_year                    2023
_chemical_formula_moiety         'C34 H47 Al1 N2 O1 S1, 0.3[C5H12]'
_chemical_formula_sum            'C35.5 H50.6 Al N2 O S'
_chemical_formula_weight         580.42
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-03
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-03 deposited with the CCDC.	2023-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.717(5)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   27.9297(10)
_cell_length_b                   12.4390(4)
_cell_length_c                   41.634(2)
_cell_measurement_reflns_used    6315
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      73.0460
_cell_measurement_theta_min      3.8990
_cell_volume                     13989.8(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4115
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.954
_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    -27.00  58.00   1.00   34.70    --   42.36 -38.00 -60.00   85
  2  \w     25.00 109.00   1.00   34.70    --   42.36  38.00 120.00   84
  3  \w     78.00 166.00   1.00   76.69    --  105.75  61.00-180.00   88
  4  \w     55.00 133.00   1.00   76.69    --  105.75 -61.00 150.00   78
  5  \w     40.00 134.00   1.00   76.69    --  105.75 -30.00   0.00   94
  6  \w     69.00 152.00   1.00   76.69    --  105.75 -15.00 120.00   83
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0334659000
_diffrn_orient_matrix_UB_12      0.0026504000
_diffrn_orient_matrix_UB_13      0.0242565000
_diffrn_orient_matrix_UB_21      -0.0335901000
_diffrn_orient_matrix_UB_22      0.0836642000
_diffrn_orient_matrix_UB_23      -0.0221154000
_diffrn_orient_matrix_UB_31      -0.0317053000
_diffrn_orient_matrix_UB_32      -0.0913025000
_diffrn_orient_matrix_UB_33      -0.0195958000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            22402
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.818
_diffrn_reflns_theta_min         3.446
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.265
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76158
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_density_diffrn    1.102
_exptl_crystal_description       block
_exptl_crystal_F_000             5034
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     725
_refine_ls_number_reflns         13527
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0513
_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^)+(0.0536P)^2^+11.4341P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1207
_refine_ls_wR_factor_ref         0.1407
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9881
_reflns_number_total             13527
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04594c3.cif
_cod_data_source_block           2c
_cod_original_cell_volume        13989.8(11)
_cod_original_formula_sum        'C35.50 H50.60 Al1 N2 O1 S1'
_cod_database_code               7132354
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H47 Al1 N2 O1 S1'
_chemical_oxdiff_usercomment     JSM053
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.895
_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.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C44(H44), C58(H58), C7(H7), C41(H41), C10(H10), C61(H61)
2.b Aromatic/amide H refined with riding coordinates:
 C48(H48), C14(H14), C22(H22), C20(H20), C37(H37), C66(H66), C3(H3), C21(H21),
 C4(H4), C39(H39), C64(H64), C30(H30), C38(H38), C32(H32), C65(H65), C5(H5),
 C55(H55), C54(H54), C31(H31), C56(H56)
2.c Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C), C17(H17A,H17B,H17C), C29(H29A,H29B,H29C), C50(H50A,H50B,
 H50C), C16(H16A,H16B,H16C), C68(H68A,H68B,H68C), C25(H25A,H25B,H25C), C45(H45A,
 H45B,H45C), C46(H46A,H46B,H46C), C28(H28A,H28B,H28C), C9(H9A,H9B,H9C),
 C26(H26A,H26B,H26C), C59(H59A,H59B,H59C), C8(H8A,H8B,H8C), C34(H34A,H34B,H34C),
  C63(H63A,H63B,H63C), C60(H60A,H60B,H60C), C43(H43A,H43B,H43C), C42(H42A,H42B,
 H42C), C62(H62A,H62B,H62C), C12(H12A,H12B,H12C), C11(H11A,H11B,H11C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 220 electrons were 
found in a volume of 1736\%A^3 in 1 void per unit cell. 
This is consistent with the presence of 
0.6[C5H12] per Asymmetric Unit 
which account for 202 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              18695
_shelx_hkl_checksum              24150
_shelx_fab_checksum              49913
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.364
_oxdiff_exptl_absorpt_empirical_full_min 0.812