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_7135613
_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         'C41 H61 K Mg N2 O2 S'
_chemical_formula_sum            'C41 H61 K Mg N2 O2 S'
_chemical_formula_weight         709.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_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                 101.14(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.84(4)
_cell_length_b                   13.453(14)
_cell_length_c                   36.71(4)
_cell_measurement_reflns_used    7058
_cell_measurement_temperature    180.00
_cell_measurement_theta_max      23.02
_cell_measurement_theta_min      2.36
_cell_volume                     8644(2)
_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 0.990
_diffrn_measured_fraction_theta_max 0.990
_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  0.0592
_diffrn_reflns_av_unetI/netI     0.0616
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            30279
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.212
_diffrn_reflns_theta_max         25.212
_diffrn_reflns_theta_min         2.262
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.218
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6095
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0770 before and 0.0518 after correction.
The Ratio of minimum to maximum transmission is 0.8179.
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    1.090
_exptl_crystal_description       block
_exptl_crystal_F_000             3072
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.289
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     634
_refine_ls_number_reflns         7735
_refine_ls_number_restraints     220
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.1080
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0647P)^2^+5.1896P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1430
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4538
_reflns_number_total             7735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00381h2.cif
_cod_data_source_block           2_a
_cod_depositor_comments
'Adding full bibliography for 7135613--7135622.cif.'
_cod_original_cell_volume        8645(23)
_cod_original_sg_symbol_H-M      C2/c
_cod_database_code               7135613
_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
 C10-C14 \\sim C10-C14A
 with sigma of 0.02
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 C14-C16 \\sim C14A-C16A
 with sigma of 0.02
 C10-C15 \\sim C10-C15A
 with sigma of 0.04
 C10-C16 \\sim C10-C16A
 with sigma of 0.04
 C15-C16 \\sim C15A-C16A
 with sigma of 0.04
 C14-C10 \\sim C14A-C10
 with sigma of 0.02
 O2-C34 \\sim O2-C34A
 with sigma of 0.02
 O2-C37 \\sim O2-C37A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C35-C36 \\sim C35A-C36A
 with sigma of 0.02
 C36-C37 \\sim C36A-C37A
 with sigma of 0.02
 O2-C35 \\sim O2-C35A
 with sigma of 0.04
 O2-C36 \\sim O2-C36A
 with sigma of 0.04
 C34-C36 \\sim C34A-C36A
 with sigma of 0.04
 C35-C37 \\sim C35A-C37A
 with sigma of 0.04
 O1-C38 \\sim O1-C38A
 with sigma of 0.02
 O1-C41 \\sim O1-C41A
 with sigma of 0.02
 C38-C39 \\sim C38A-C39A
 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
 O1-C39 \\sim O1-C39A
 with sigma of 0.04
 O1-C40 \\sim O1-C40A
 with sigma of 0.04
 C38-C40 \\sim C38A-C40A
 with sigma of 0.04
 C39-C41 \\sim C39A-C41A
 with sigma of 0.04
 S1-C29 \\sim S1A-C29A
 with sigma of 0.02
 S1-C32 \\sim S1A-C32A
 with sigma of 0.02
 Mg1-C29 \\sim Mg1-C29A
 with sigma of 0.02
 C29-C30 \\sim C29A-C30A
 with sigma of 0.02
 C30-C31 \\sim C30A-C31A
 with sigma of 0.02
 C31-C32 \\sim C31A-C32A
 with sigma of 0.02
 C32-C33 \\sim C32A-C33A
 with sigma of 0.02
 K1-S1 \\sim K1-S1A
 with sigma of 0.04
 K1-C29 \\sim K1-C29A
 with sigma of 0.04
 K1-C30 \\sim K1-C30A
 with sigma of 0.04
 K1-C31 \\sim K1-C31A
 with sigma of 0.04
 S1-Mg1 \\sim S1A-Mg1
 with sigma of 0.04
 S1-C30 \\sim S1A-C30A
 with sigma of 0.04
 S1-C31 \\sim S1A-C31A
 with sigma of 0.04
 S1-C33 \\sim S1A-C33A
 with sigma of 0.04
 Mg1-C30 \\sim Mg1-C30A
 with sigma of 0.04
 C29-C31 \\sim C29A-C31A
 with sigma of 0.04
 C29-C32 \\sim C29A-C32A
 with sigma of 0.04
 C30-C32 \\sim C30A-C32A
 with sigma of 0.04
 C31-C33 \\sim C31A-C33A
 with sigma of 0.04
 C18-C23 \\sim C18-C23A
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C23-C25 \\sim C23A-C25A
 with sigma of 0.02
 C18-C24 \\sim C18-C24A
 with sigma of 0.04
 C18-C25 \\sim C18-C25A
 with sigma of 0.04
 C24-C25 \\sim C24A-C25A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C32A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 C14, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14A, C15A, C16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, C35, C36, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34A, C35A, C36A, C37A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38, C39, C40, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38A, C39A, C40A, C41A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, C29, C30, C31, C32, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1A, C29A, C30A, C31A, C32A, C33A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, C24, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23A, C24A, C25A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C14A)=Sof(H14A)=Sof(C15A)=
 Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=
 Sof(H16B)=Sof(H16C)=FVAR(1)
 Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(C36A)=
 Sof(H36C)=Sof(H36D)=Sof(C37A)=Sof(H37C)=Sof(H37D)=1-FVAR(2)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=FVAR(2)
 Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C39A)=
 Sof(H39C)=Sof(H39D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=1-FVAR(3)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=
 Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=FVAR(3)
 Sof(S1A)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=
 Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(4)
 Sof(S1)=Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(C33)=
 Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(4)
 Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C23A)=Sof(H23A)=Sof(C25A)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(5)
 Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(H25C)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C14A(H14A), C23A(H23A)
6.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C34A(H34C,H34D),
 C35A(H35C,H35D), C36A(H36C,H36D), C37A(H37C,H37D), C41A(H41C,H41D), C40A(H40C,
 H40D), C39A(H39C,H39D), C38A(H38C,H38D)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C30(H30), C31(H31),
 C30A(H30A), C31A(H31A)
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),
 C16A(H16D,H16E,H16F), C15A(H15D,H15E,H15F), C33A(H33D,H33E,H33F), C24A(H24D,
 H24E,H24F), C25A(H25D,H25E,H25F)
;
_olex2_submission_special_instructions 'No special instructions were received'