Direct C-H magnesiation of thiophenes with a Mg-Mg-bonded compound
Yang, Li; Sun, Zhenzhou; Wang, Lin; Geng, Jianqi; Wu, Biao; Yang, Xiao-Juan; Chemical Communications  (2026) –; doi:10.1039/D6CC00381H

data_7135621
_publ_section_title
;
 Direct C-H magnesiation of thiophenes with an Mg-Mg-bonded compound.
;
_journal_issue                   27
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7172
_journal_page_last               7175
_journal_paper_doi               10.1039/d6cc00381h
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C42 H63 K Mg N2 O2 S'
_chemical_formula_sum            'C42 H63 K Mg N2 O2 S'
_chemical_formula_weight         723.41
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-06-22
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2026-01-16 deposited with the CCDC.	2026-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.0887(19)
_cell_length_b                   21.608(3)
_cell_length_c                   23.849(3)
_cell_measurement_reflns_used    7425
_cell_measurement_temperature    180.00
_cell_measurement_theta_max      21.35
_cell_measurement_theta_min      2.33
_cell_volume                     8291.0(18)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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)'
_diffrn_ambient_temperature      180.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1669
_diffrn_reflns_av_unetI/netI     0.0854
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            65236
_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         25.391
_diffrn_reflns_theta_min         2.126
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.229
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6637
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1503 before and 0.0775 after correction.
The Ratio of minimum to maximum transmission is 0.8906.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.159
_exptl_crystal_description       block
_exptl_crystal_F_000             3136
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.612
_refine_diff_density_min         -0.698
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         7616
_refine_ls_number_restraints     58
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.1759
_refine_ls_R_factor_gt           0.0849
_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^)+(0.1381P)^2^+10.4047P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2257
_refine_ls_wR_factor_ref         0.2818
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3891
_reflns_number_total             7616
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00381h2.cif
_cod_data_source_block           3_a
_cod_depositor_comments
'Adding full bibliography for 7135613--7135622.cif.'
_cod_database_code               7135621
_shelx_shelxl_version_number     2019/1
_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
 O2-C39 \\sim O2-C39A
 with sigma of 0.02
 O2-C42 \\sim O2-C42A
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.02
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 C41-C42 \\sim C41A-C42A
 with sigma of 0.02
 O2-C40 \\sim O2-C40A
 with sigma of 0.04
 O2-C41 \\sim O2-C41A
 with sigma of 0.04
 C39-C41 \\sim C39A-C41A
 with sigma of 0.04
 C40-C42 \\sim C40A-C42A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C42A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C39A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 C39, C40, C41, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39A, C40A, C41A, C42A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, C32, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=
 Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=1-FVAR(1)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=
 Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26)
6.b Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C36(H36A,H36B), C37(H37B,H37A), C38(H38A,H38B), C39(H39A,
 H39B), C39A(H39C,H39D), C40(H40A,H40B), C40A(H40C,H40D), C41(H41A,H41B),
 C41A(H41C,H41D), C42(H42A,H42B), C42A(H42C,H42D)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C30(H30)
6.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C)
;
_olex2_submission_special_instructions 'No special instructions were received'