Metal ligand cooperativity in the direct carboxylation and esterification of terminal alkynes by Cu-CNC complexes bearing 2,6-lutidine linkers.
Back, Nick; Guthrie, Emylie; Zhu, Chengxu; de Visser, Sam P.; Tahsini, Laleh; Chemical science 17 (2026) 2087–2101; doi:10.1039/d5sc08379f

data_1576742
_publ_section_title
;
 Metal ligand cooperativity in the direct carboxylation and esterification
 of terminal alkynes by Cu-CNC complexes bearing 2,6-lutidine linkers.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              2087
_journal_page_last               2101
_journal_paper_doi               10.1039/d5sc08379f
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C31 H32 Cu N5'
_chemical_formula_sum            'C31 H32 Cu N5'
_chemical_formula_weight         538.15
_chemical_properties_physical    Air-sensitive,Moisture-sensitive,Hygroscopic
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-28
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7311)
;
_audit_update_record
;
2025-09-15 deposited with the CCDC.	2026-01-08 downloaded from the CCDC.
;
_cell_angle_alpha                69.605(3)
_cell_angle_beta                 74.381(3)
_cell_angle_gamma                80.865(3)
_cell_formula_units_Z            2
_cell_length_a                   9.1454(8)
_cell_length_b                   11.5360(11)
_cell_length_c                   14.1953(15)
_cell_measurement_reflns_used    9921
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.235
_cell_measurement_theta_min      2.682
_cell_volume                     1348.4(2)
_computing_cell_refinement       'SAINT V8.41 (Bruker AXS Inc, 2024)'
_computing_data_reduction        'SAINT V8.41 (Bruker AXS Inc, 2024)'
_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)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker D8 Venture DUO with Photon 3'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0624
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            30906
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.877
_diffrn_reflns_theta_min         2.032
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.839
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6711
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1106 before and 0.0747 after correction.
The Ratio of minimum to maximum transmission is 0.9000.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       irregular
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.103
_refine_diff_density_max         0.551
_refine_diff_density_min         -0.737
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.313
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     554
_refine_ls_number_reflns         6386
_refine_ls_number_restraints     1089
_refine_ls_restrained_S_all      1.217
_refine_ls_R_factor_all          0.0931
_refine_ls_R_factor_gt           0.0774
_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^)+5.6145P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1825
_refine_ls_wR_factor_ref         0.1892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5291
_reflns_number_total             6386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08379f2.cif
_cod_data_source_block           tah25_06
_cod_database_code               1576742
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.828
_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. Uiso/Uaniso restraints and constraints
N1 \\sim C14A \\sim C14B \\sim C15A \\sim C15B \\sim C16A \\sim C16B \\sim C17A
\\sim C17B \\sim C18A \\sim C18B \\sim C19A \\sim C19B \\sim C20A \\sim C20B
\\sim C21A \\sim C21B \\sim C22A \\sim C22B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
N5 \\sim C23A \\sim C23B \\sim C24A \\sim C24B \\sim C25A \\sim C25B \\sim C26A
\\sim C26B \\sim C27A \\sim C27B \\sim C28A \\sim C28B \\sim C29A \\sim C29B
\\sim C30A \\sim C30B \\sim C31A \\sim C31B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
N3 \\sim C4A \\sim C4B \\sim C5 \\sim C6A \\sim C6B \\sim C7A \\sim C7B \\sim
C8A \\sim C8B \\sim C9 \\sim C10A \\sim C10B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
3. Rigid body (RIGU) restrains
 N1, C14A, C14B, C15A, C15B, C16A, C16B, C17A, C17B, C18A, C18B, C19A, C19B,
 C20A, C20B, C21A, C21B, C22A, C22B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N5, C23A, C23B, C24A, C24B, C25A, C25B, C26A, C26B, C27A, C27B, C28A, C28B,
 C29A, C29B, C30A, C30B, C31A, C31B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N3, C4A, C4B, C5, C6A, C6B, C7A, C7B, C8A, C8B, C9, C10A, C10B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C4B)=Sof(H4B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=
 Sof(C10B)=Sof(H10C)=Sof(H10D)=Sof(C14B)=Sof(C15B)=Sof(C16B)=Sof(H16B)=
 Sof(C17B)=Sof(C18B)=Sof(H18B)=Sof(C19B)=Sof(C20B)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=Sof(C23B)=Sof(C24B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=
 Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(C29B)=Sof(H29D)=Sof(H29E)=Sof(H29F)=
 Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31B)=Sof(H31D)=Sof(H31E)=
 Sof(H31F)=1-FVAR(1)
 Sof(C4A)=Sof(H4A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=
 Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(C14A)=Sof(C15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(H20B)=
 Sof(H20C)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=Sof(C23A)=Sof(C24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(C29A)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31A)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C10A(H10A,H10B), C10B(H10C,H10D)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4A(H4A), C4B(H4B), C6A(H6A), C6B(H6B), C7A(H7A), C7B(H7B),
 C8A(H8A), C8B(H8B), C12(H12), C13(H13), C16A(H16A), C16B(H16B), C18A(H18A),
 C18B(H18B), C25A(H25A), C25B(H25B), C27A(H27A), C27B(H27B)
5.c Idealised Me refined as rotating group:
 C20A(H20A,H20B,H20C), C20B(H20D,H20E,H20F), C21A(H21A,H21B,H21C), C21B(H21D,
 H21E,H21F), C22A(H22A,H22B,H22C), C22B(H22D,H22E,H22F), C29A(H29A,H29B,H29C),
 C29B(H29D,H29E,H29F), C30A(H30A,H30B,H30C), C30B(H30D,H30E,H30F), C31A(H31A,
 H31B,H31C), C31B(H31D,H31E,H31F)
;
_shelx_res_checksum              64385
_olex2_exptl_crystal_mounting_method 'MiTeGen 100 micron MicroLoop'
_olex2_submission_special_instructions 'No special instructions were received'