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_7135614
_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         'C76 H110 K2 Mg2 N4 O2 S2, C7 H8'
_chemical_formula_sum            'C83 H118 K2 Mg2 N4 O2 S2'
_chemical_formula_weight         1394.75
_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
_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                91.745(2)
_cell_angle_beta                 92.462(2)
_cell_angle_gamma                90.652(2)
_cell_formula_units_Z            2
_cell_length_a                   14.3040(8)
_cell_length_b                   14.3229(8)
_cell_length_c                   20.2313(11)
_cell_measurement_reflns_used    9234
_cell_measurement_temperature    180.00
_cell_measurement_theta_max      25.19
_cell_measurement_theta_min      2.22
_cell_volume                     4138.8(4)
_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 0.998
_diffrn_measured_fraction_theta_max 0.996
_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  0.0570
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            43390
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.415
_diffrn_reflns_theta_min         2.216
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.225
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6615
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0994 before and 0.0455 after correction.
The Ratio of minimum to maximum transmission is 0.8877.
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    1.119
_exptl_crystal_description       block
_exptl_crystal_F_000             1508
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.890
_refine_diff_density_min         -1.118
_refine_diff_density_rms         0.075
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     981
_refine_ls_number_reflns         15231
_refine_ls_number_restraints     2410
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.1337
_refine_ls_R_factor_gt           0.0821
_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^)+(0.1471P)^2^+3.8874P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2274
_refine_ls_wR_factor_ref         0.2674
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9381
_reflns_number_total             15231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00381h2.cif
_cod_data_source_block           2_a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7135613--7135622.cif.'
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               7135614
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1A-C1B
 1.51 with sigma of 0.02
 C1B-C1C = C1B-C1G = C1D-C1E
 1.39 with sigma of 0.02
 C1C-C1D = C1E-C1F = C1F-C1G
 1.38 with sigma of 0.02
 C1A-C1C = C1A-C1G
 2.52 with sigma of 0.04
 C1B-C1D
 2.42 with sigma of 0.04
 C1B-C1F
 2.41 with sigma of 0.04
 C1C-C1E
 2.39 with sigma of 0.04
 C1D-C1F = C1E-C1G
 2.4 with sigma of 0.04
 C67-C68 \\sim C67A-C68A
 with sigma of 0.02
 C66-C68 \\sim C66A-C68A
 with sigma of 0.04
 O1-C69 \\sim O1-C69A
 with sigma of 0.02
 O1-C72 \\sim O1-C72A
 with sigma of 0.02
 C69-C70 \\sim C69A-C70A
 with sigma of 0.02
 C70-C71 \\sim C70A-C71A
 with sigma of 0.02
 C71-C72 \\sim C71A-C72A
 with sigma of 0.02
 O1-C70 \\sim O1-C70A
 with sigma of 0.04
 O1-C71 \\sim O1-C71A
 with sigma of 0.04
 C69-C71 \\sim C69A-C71A
 with sigma of 0.04
 C70-C72 \\sim C70A-C72A
 with sigma of 0.04
 Mg2-C63 \\sim Mg2-C63A
 with sigma of 0.02
 C63-S2 \\sim C63A-S2A
 with sigma of 0.02
 C63-C64 \\sim C63A-C64A
 with sigma of 0.02
 S2-C66 \\sim S2A-C66A
 with sigma of 0.02
 C64-C65 \\sim C64A-C65A
 with sigma of 0.02
 C66-C65 \\sim C66A-C65A
 with sigma of 0.02
 C66-C67 \\sim C66A-C67A
 with sigma of 0.02
 Mg2-S2 \\sim Mg2-S2A
 with sigma of 0.04
 Mg2-C64 \\sim Mg2-C64A
 with sigma of 0.04
 C63-C66 \\sim C63A-C66A
 with sigma of 0.04
 C63-C65 \\sim C63A-C65A
 with sigma of 0.04
 S2-C64 \\sim S2A-C64A
 with sigma of 0.04
 S2-C65 \\sim S2A-C65A
 with sigma of 0.04
 S2-C67 \\sim S2A-C67A
 with sigma of 0.04
 C64-C66 \\sim C64A-C66A
 with sigma of 0.04
 C65-C67 \\sim C65A-C67A
 with sigma of 0.04
 C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F \\sim C1F-C1G \\sim C1G-C1B
 with sigma of 0.02
 C1B-C1F \\sim C1B-C1D \\sim C1G-C1E \\sim C1C-C1G \\sim C1D-C1F \\sim C1C-C1E
 with sigma of 0.04
 C1A-C1G \\sim C1A-C1C
 with sigma of 0.04
3. Restrained planarity
 C1A, C1B, C1C, C1D, C1E, C1F, C1G
 with sigma of 0.1
4. Rigid bond restraints
 C67A, C68A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Uiso/Uaniso restraints and constraints
C67A \\sim C68A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F \\sim C1G: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63A \\sim C64A \\sim
C65A \\sim C66A \\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim C71A \\sim
C72A \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C1A \\sim C1B \\sim C1C
\\sim C1D \\sim C1E \\sim C1F \\sim C1G \\sim C63 \\sim C64 \\sim C65 \\sim C66
\\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72: within 3.8A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
Uanis(C64A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C67A) \\sim Ueq, Uanis(C68A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C70A) \\sim Ueq, Uanis(C71A) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C72A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C72) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 S2A, C63A, C64A, C65A, C66A, C67A, C68A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C69, C70, C71, C72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C69A, C70A, C71A, C72A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, C63, C64, C65, C66, C67, C68
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1B, C1C, C1D, C1E, C1F, C1G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C69A)=Sof(H69A)=Sof(H69B)=Sof(C70A)=Sof(H70A)=Sof(H70B)=Sof(C71A)=
 Sof(H71A)=Sof(H71B)=Sof(C72A)=Sof(H72A)=Sof(H72B)=1-FVAR(1)
 Sof(C69)=Sof(H69C)=Sof(H69D)=Sof(C70)=Sof(H70C)=Sof(H70D)=Sof(C71)=Sof(H71C)=
 Sof(H71D)=Sof(C72)=Sof(H72C)=Sof(H72D)=FVAR(1)
 Sof(S2A)=Sof(C63A)=Sof(C64A)=Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=
 Sof(C67A)=Sof(H67A)=Sof(H67B)=Sof(C68A)=Sof(H68A)=Sof(H68B)=Sof(H68C)=1-FVAR(2)
 Sof(S2)=Sof(C63)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=Sof(C66)=Sof(C67)=
 Sof(H67C)=Sof(H67D)=Sof(C68)=Sof(H68D)=Sof(H68E)=Sof(H68F)=FVAR(2)
8.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C45(H45), C48(H48), C57(H57), C60(H60)
8.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C67A(H67A,H67B), C69A(H69A,H69B), C70A(H70A,H70B), C71A(H71A,
 H71B), C72A(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B),
 C76(H76A,H76B), C67(H67C,H67D), C69(H69C,H69D), C70(H70C,H70D), C71(H71C,H71D),
  C72(H72C,H72D)
8.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C30(H30), C31(H31),
 C41(H41), C42(H42), C43(H43), C53(H53), C54(H54), C55(H55), C64A(H64A),
 C65A(H65A), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1G(H1G), C64(H64),
 C65(H65)
8.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), C34(H34A,H34B,H34C), 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), C68A(H68A,H68B,H68C),
 C1A(H1AA,H1AB,H1AC), C68(H68D,H68E,H68F)
;
_olex2_submission_special_instructions 'No special instructions were received'