[Cu(NHC)(OR)] (R = C(CF<sub>3</sub>)<sub>3</sub>) complexes for N-H and S-H bond activation and as pre-catalysts in the Chan-Evans-Lam reaction.
Ruggiero, Tommaso; Van Hecke, Kristof; Cazin, Catherine S. J.; Nolan, Steven P.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 1329–1333; doi:10.1039/d4dt03322a

data_7717684
_publ_section_title
;
 [Cu(NHC)(OR)] (R = C(CF<sub>3</sub>)<sub>3</sub>) complexes for N-H and
 S-H bond activation and as pre-catalysts in the Chan-Evans-Lam reaction.
;
_journal_issue                   4
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1329
_journal_page_last               1333
_journal_paper_doi               10.1039/d4dt03322a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C33 H40 Cu F9 N2 O3, 0.5[C6H14]'
_chemical_formula_sum            'C36 H47 Cu F9 N2 O3'
_chemical_formula_weight         790.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-18
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-22 deposited with the CCDC.	2024-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.525(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.4331(4)
_cell_length_b                   19.1734(3)
_cell_length_c                   21.8553(4)
_cell_measurement_reflns_used    24661
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.6210
_cell_measurement_theta_min      3.1660
_cell_volume                     7789.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -114.00 -13.00   1.00    4.13    --  -41.55 -57.00-150.00  101
  2  \w    -70.00  32.00   1.00    4.13    --  -41.55  57.00   0.00  102
  3  \w    -87.00  -6.00   1.00    4.13    --  -41.55 125.00-180.00   81
  4  \w     30.00 134.00   1.00   11.53    --  106.01 -30.00-150.00  104
  5  \w     23.00 107.00   1.00   11.53    --  106.01 -94.00 120.00   84
  6  \w     80.00 178.00   1.00   11.53    --  106.01  45.00-120.00   98
  7  \w     23.00 107.00   1.00   11.53    --  106.01 -94.00   0.00   84
  8  \w    103.00 178.00   1.00   11.53    --  106.01  77.00 -30.00   75
  9  \w     97.00 177.00   1.00   11.53    --  106.01 125.00 -30.00   80
 10  \w     23.00 107.00   1.00   11.53    --  106.01 -94.00  60.00   84
 11  \w    -70.00  32.00   1.00    4.13    --  -41.55  57.00 120.00  102
 12  \w   -114.00 -13.00   1.00    4.13    --  -41.55 -57.00 -30.00  101
 13  \w   -114.00 -13.00   1.00    4.13    --  -41.55 -57.00  90.00  101
 14  \w     78.00 178.00   1.00   11.53    --  106.01  30.00-180.00  100
 15  \w     77.00 178.00   1.00   11.53    --  106.01  61.00 -60.00  101
 16  \w     23.00 105.00   1.00   11.53    --  106.01 -94.00 -90.00   82
 17  \w     78.00 178.00   1.00   11.53    --  106.01  30.00  60.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            75383
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.822
_diffrn_reflns_theta_min         3.202
_exptl_absorpt_coefficient_mu    1.487
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.624
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.348
_exptl_crystal_description       plate
_exptl_crystal_F_000             3288
_exptl_crystal_preparation       synthesis
_exptl_crystal_recrystallization_method synthesis
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.004
_refine_diff_density_min         -0.710
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1001
_refine_ls_number_reflns         15547
_refine_ls_number_restraints     284
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0497
_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^)+(0.0699P)^2^+7.7510P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1279
_refine_ls_wR_factor_ref         0.1388
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12368
_reflns_number_total             15547
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03322a2.cif
_cod_data_source_block           tr_ome_dcm_hex
_cod_depositor_comments
'Adding full bibliography for 7717681--7717684.cif.'
_cod_database_code               7717684
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.681
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F8-C33 = F9-C33 = F7-C33 = F8A-C33A = F9A-C33A = F7A-C33A
 1.33 with sigma of 0.01
 F4-C32 = F5-C32 = F6-C32 = F4A-C32A = F5A-C32A = F6A-C32A
 1.33 with sigma of 0.01
 F1-C31 = F2-C31 = F3-C31 = F1A-C31A = F2A-C31A = F3A-C31A
 1.33 with sigma of 0.01
 C30-C31 = C30-C32 = C30-C33
 1.55 with sigma of 0.01
 C30A-C31A = C30A-C32A = C30A-C33A
 1.55 with sigma of 0.01
 F1-F2 = F1-F3 = F2-F3 = F4-F5 = F4-F6 = F5-F6 = F7-F8 = F7-F9 = F8-F9
 2.15 with sigma of 0.02
 F1A-F2A = F1A-F3A = F2A-F3A = F4A-F5A = F4A-F6A = F5A-F6A = F7A-F8A = F7A-F9A
 = F8A-F9A
 2.15 with sigma of 0.02
 C30-F1 = C30-F2 = C30-F3 = C30-F4 = C30-F5 = C30-F6 = C30-F7 = C30-F8 = C30-F9
 2.39 with sigma of 0.02
 C30A-F1A = C30A-F2A = C30A-F3A = C30A-F4A = C30A-F5A = C30A-F6A = C30A-F7A =
 C30A-F8A = C30A-F9A
 2.39 with sigma of 0.02
 C31-C32 = C32-C33 = C33-C31 = C31A-C32A = C32A-C33A = C33A-C31A
 2.53 with sigma of 0.02
 O1-C31 = O1-C32 = O1-C33 = O1A-C31A = O1A-C32A = O1A-C33A
 2.38 with sigma of 0.04
 O1A-C30A \\sim O1-C30
 with sigma of 0.02
 Cu1-O1 \\sim Cu1-O1A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C23 \\sim C24 \\sim C25: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(F1) = Uanis(F1A)
Uanis(F2) = Uanis(F2A)
Uanis(F3) = Uanis(F3A)
Uanis(F4) = Uanis(F4A)
Uanis(F5) = Uanis(F5A)
Uanis(F6) = Uanis(F6A)
Uanis(F7) = Uanis(F7A)
Uanis(F8) = Uanis(F8A)
Uanis(F9) = Uanis(F9A)
Uanis(C31) = Uanis(C31A)
Uanis(C32) = Uanis(C32A)
Uanis(C33) = Uanis(C33A)
Uanis(C30) = Uanis(C30A)
Uanis(O1) = Uanis(O1A)
4. Rigid body (RIGU) restrains
 F1, F2, F3, F4, F5, F6, F7, F8, F9, C30, C31, C32, C33
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F1A, F2A, F3A, F4A, F5A, F6A, F7A, F8A, F9A, C30A, C31A, C32A, C33A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=
 Sof(F9A)=Sof(O1A)=Sof(C30A)=Sof(C31A)=Sof(C32A)=Sof(C33A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=
 Sof(O1)=Sof(C30)=Sof(C31)=Sof(C32)=Sof(C33)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C23(H23), C26(H26), C43(H43), C46(H46), C56(H56), C59(H59)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C19(H19), C21(H21), C35(H35), C36(H36),
 C39(H39), C41(H41), C52(H52), C54(H54)
6.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C16(H16A,H16B,H16C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C60(H60A,H60B,H60C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 194 electrons were 
found in a volume of 1336\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.5[C6H14] per formula unit 
which account for 200 electrons 
per unit cell.
;
_shelx_res_checksum              68561
_shelx_fab_checksum              50397
_olex2_exptl_crystal_mounting_method 'mounted on a LithoLoop'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- B-factor correction
;