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_7135618
_publ_section_title
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 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         'C86 H130 K2 Mg2 N4 O6 S2'
_chemical_formula_sum            'C86 H130 K2 Mg2 N4 O6 S2'
_chemical_formula_weight         1506.87
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-06-23
_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                 107.346(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.214(2)
_cell_length_b                   19.393(2)
_cell_length_c                   27.132(3)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    180.00
_cell_measurement_theta_max      21.63
_cell_measurement_theta_min      2.24
_cell_volume                     8645.6(17)
_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 0.985
_diffrn_measured_fraction_theta_max 0.985
_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  0.1145
_diffrn_reflns_av_unetI/netI     0.1405
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            48970
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.121
_diffrn_reflns_theta_max         25.121
_diffrn_reflns_theta_min         2.243
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.224
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6039
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1001 before and 0.0611 after correction.
The Ratio of minimum to maximum transmission is 0.8104.
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    1.158
_exptl_crystal_description       block
_exptl_crystal_F_000             3264
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.664
_refine_diff_density_min         -0.579
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1022
_refine_ls_number_reflns         15196
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.2013
_refine_ls_R_factor_gt           0.0816
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1199P)^2^+1.2754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1961
_refine_ls_wR_factor_ref         0.2563
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6717
_reflns_number_total             15196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00381h2.cif
_cod_data_source_block           a_a
_cod_depositor_comments
'Adding full bibliography for 7135613--7135622.cif.'
_cod_original_cell_volume        8645.4(17)
_cod_database_code               7135618
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.971
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O3-C71 \\sim O3-C71A
 with sigma of 0.02
 C71-C72 \\sim C71A-C72A
 with sigma of 0.02
 C72-C73 \\sim C72A-C73A
 with sigma of 0.02
 C73-C74 \\sim C73A-C74
 with sigma of 0.02
 O3-C72 \\sim O3-C72A
 with sigma of 0.04
 C71-C73 \\sim C71A-C73A
 with sigma of 0.04
 C72-C74 \\sim C72A-C74
 with sigma of 0.04
 S1-C29 \\sim S1A-C29
 with sigma of 0.02
 S1-C32 \\sim S1A-C32A
 with sigma of 0.02
 S2-C31 \\sim S2A-C31A
 with sigma of 0.02
 S2-C34 \\sim S2A-C34
 with sigma of 0.02
 C29-C30 \\sim C29-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
 C33-C34 \\sim C33A-C34
 with sigma of 0.02
 K1-S1 \\sim K1-S1A
 with sigma of 0.04
 K1-S2 \\sim K1-S2A
 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
 K1-C32 \\sim K1-C32A
 with sigma of 0.04
 K1-C33 \\sim K1-C33A
 with sigma of 0.04
 K2-S1 \\sim K2-S1A
 with sigma of 0.04
 K2-S2 \\sim K2-S2A
 with sigma of 0.04
 K2-C30 \\sim K2-C30A
 with sigma of 0.04
 K2-C31 \\sim K2-C31A
 with sigma of 0.04
 K2-C32 \\sim K2-C32A
 with sigma of 0.04
 K2-C33 \\sim K2-C33A
 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
 S2-C30 \\sim S2A-C30A
 with sigma of 0.04
 S2-C32 \\sim S2A-C32A
 with sigma of 0.04
 C29-C31 \\sim C29-C31A
 with sigma of 0.04
 C29-C32 \\sim C29-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
 C31-C34 \\sim C31A-C34
 with sigma of 0.04
 C32-C34 \\sim C32A-C34
 with sigma of 0.04
3. Rigid bond restraints
 C81, C82
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Uanis(C30) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C33) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C81) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C33A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C81) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C34) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C81) \\sim Ueq, Uanis(C82) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O5) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 S1, S2, C29, C30, C31, C32, C33, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C71, C72, C73
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C71A, C72A, C73A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C68, C69
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, S2, C30, C31, C32, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1A, S2A, C30A, C31A, C32A, C33A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H74C)=Sof(H74D)=Sof(C71A)=Sof(H71C)=Sof(H71D)=Sof(C72A)=Sof(H72C)=
 Sof(H72D)=Sof(C73A)=Sof(H73C)=Sof(H73D)=1-FVAR(1)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=Sof(H74A)=Sof(H74B)=FVAR(1)
 Sof(C33A)=Sof(H33A)=Sof(C32A)=Sof(C31A)=Sof(S2A)=Sof(C30A)=Sof(H30A)=Sof(S1A)=
 1-FVAR(2)
 Sof(S1)=Sof(S2)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(C32)=Sof(C33)=Sof(H33)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C45(H45), C48(H48), C57(H57), C60(H60)
7.b Secondary CH2 refined with riding coordinates:
 C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,
 H67B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B),
 C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C74(H74C,H74D), C75(H75A,H75B),
  C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,
 H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B),
 C85(H85A,H85B), C86(H86A,H86B), C71A(H71C,H71D), C72A(H72C,H72D), C73A(H73C,
 H73D)
7.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C30(H30), C33(H33),
 C41(H41), C42(H42), C43(H43), C53(H53), C54(H54), C55(H55), C33A(H33A),
 C30A(H30A)
7.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C12(H12C,H12B,H12A), 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), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C)
;
_olex2_submission_special_instructions 'No special instructions were received'