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_7135619
_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         'C88 H132 K2 Mg2 N4 O6 S2'
_chemical_formula_sum            'C88 H132 K2 Mg2 N4 O6 S2'
_chemical_formula_weight         1532.91
_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             2025-06-26
_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                 113.102(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.0904(10)
_cell_length_b                   13.4627(8)
_cell_length_c                   20.4918(12)
_cell_measurement_reflns_used    9981
_cell_measurement_temperature    180.00
_cell_measurement_theta_max      25.29
_cell_measurement_theta_min      2.45
_cell_volume                     4590.5(5)
_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 0.995
_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  0.0799
_diffrn_reflns_av_unetI/netI     0.0448
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            56228
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.445
_diffrn_reflns_theta_min         2.448
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.212
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6438
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1161 before and 0.0737 after correction.
The Ratio of minimum to maximum transmission is 0.8639.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.109
_exptl_crystal_description       block
_exptl_crystal_F_000             1660
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.812
_refine_diff_density_min         -0.466
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     544
_refine_ls_number_reflns         8456
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0926
_refine_ls_R_factor_gt           0.0547
_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^)+(0.0684P)^2^+3.2866P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1316
_refine_ls_wR_factor_ref         0.1543
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5723
_reflns_number_total             8456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00381h2.cif
_cod_data_source_block           1_a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7135613--7135622.cif.'
_cod_database_code               7135619
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.973
_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
 K1-O2 \\sim K1-O2A
 with sigma of 0.02
 O2-C37 \\sim O2A-C37A
 with sigma of 0.02
 O2-C40 \\sim O2A-C40A
 with sigma of 0.02
 C37-C38 \\sim C37A-C38A
 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
 K1-C37 \\sim K1-C37A
 with sigma of 0.04
 K1-C40 \\sim K1-C40A
 with sigma of 0.04
 O2-C38 \\sim O2A-C38A
 with sigma of 0.04
 O2-C39 \\sim O2A-C39A
 with sigma of 0.04
 C37-C39 \\sim C37A-C39A
 with sigma of 0.04
 C37-C40 \\sim C37A-C40A
 with sigma of 0.04
 C38-C40 \\sim C38A-C40A
 with sigma of 0.04
 C36-C35 \\sim C36-C35A
 with sigma of 0.02
 C33-C34 \\sim C33-C34A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C36-C34 \\sim C36-C34A
 with sigma of 0.04
 C33-C35 \\sim C33-C35A
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 O2, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2A, C37A, C38A, C39A, C40A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34A, C35A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(O2A)=Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=1-FVAR(1)
 Sof(O2)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=
 Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=FVAR(1)
 Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(H35C)=
 Sof(H35D)=Sof(H36C)=Sof(H36D)=1-FVAR(2)
 Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=
 Sof(H36A)=Sof(H36B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C30(H30)
5.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C33(H33C,H33D), C34(H34A,H34B), C34A(H34C,H34D), C35(H35A,
 H35B), C35A(H35C,H35D), C36(H36A,H36B), C36(H36C,H36D), C37(H37A,H37B),
 C37A(H37C,H37D), C38(H38A,H38B), C38A(H38C,H38D), C39(H39A,H39B), C39A(H39C,
 H39D), C40(H40A,H40B), C40A(H40C,H40D), C41(H41A,H41B), C42(H42A,H42B),
 C43(H43A,H43B), C44(H44A,H44B)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C31(H31)
5.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4B,H4C,H4A), 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)
;
_olex2_submission_special_instructions 'No special instructions were received'