Straightforward synthesis of [Cu(NHC)(alkynyl)] and [Cu(NHC)(thiolato)] complexes (NHC = N-heterocyclic carbene).
Ibni Hashim, Ishfaq; Scattolin, Thomas; Tzouras, Nikolaos V.; Bourda, Laurens; Van Hecke, Kristof; Ritacco, Ida; Caporaso, Lucia; Cavallo, Luigi; Nolan, Steven P.; Cazin, Catherine S. J.; Dalton transactions (Cambridge, England : 2003) 51 (2021) 231–240; doi:10.1039/d1dt03710b

data_7708897
_publ_section_title
;
 Straightforward synthesis of [Cu(NHC)(alkynyl)] and [Cu(NHC)(thiolato)]
 complexes (NHC = N-heterocyclic carbene).
;
_journal_issue                   1
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              231
_journal_page_last               240
_journal_paper_doi               10.1039/d1dt03710b
_journal_volume                  51
_journal_year                    2021
_chemical_formula_moiety         '2(C77 H61 Cu N2), 3(C H2 Cl2)'
_chemical_formula_sum            'C157 H128 Cl6 Cu2 N4'
_chemical_formula_weight         2410.41
_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             2020-10-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-09-23 deposited with the CCDC.	2021-11-22 downloaded from the CCDC.
;
_cell_angle_alpha                115.5500(10)
_cell_angle_beta                 96.8220(10)
_cell_angle_gamma                98.4180(10)
_cell_formula_units_Z            2
_cell_length_a                   13.3632(2)
_cell_length_b                   22.3687(3)
_cell_length_c                   23.7840(3)
_cell_measurement_reflns_used    33263
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      73.6730
_cell_measurement_theta_min      3.3860
_cell_volume                     6211.89(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4839
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -74.00  34.00   1.00    1.00    --  -41.68  77.00-180.00  108
  2  \w   -116.00 -17.00   1.00    1.00    --  -41.68 -38.00 -90.00   99
  3  \w    -66.00  33.00   1.00    1.00    --  -41.68  38.00  90.00   99
  4  \w      7.00  34.00   1.00    1.00    --   41.68  83.00 -96.68   27
  5  \w      8.00  42.00   1.00    1.00    --   41.68  82.00 -66.44   34
  6  \w      8.00  42.00   1.00    1.00    --   41.68  81.00  54.06   34
  7  \w    103.00 178.00   1.00    6.00    --  106.01  77.00-150.00   75
  8  \w     79.00 178.00   1.00    6.00    --  106.01  53.00-117.95   99
  9  \w     24.00 107.00   1.00    6.00    --  106.01 -97.00  41.24   83
 10  \w     33.00 132.00   1.00    6.00    --  106.01 -45.00-120.00   99
 11  \w     34.00 135.00   1.00    6.00    --  106.01 -61.00  90.00  101
 12  \w     33.00 132.00   1.00    6.00    --  106.01 -45.00  90.00   99
 13  \w     23.00 107.00   1.00    6.00    --  106.01 -94.00  90.00   84
 14  \w     18.00 178.00   1.00    6.00    --  106.01   0.00  30.00  160
 15  \w     37.00 127.00   1.00    6.00    --  106.01-145.00 -39.88   90
 16  \w     23.00 107.00   1.00    6.00    --  106.01 -94.00 -60.00   84
 17  \w     26.00 108.00   1.00    6.00    --  106.01-102.00-164.34   82
 18  \w   -116.00 -17.00   1.00    1.00    --  -41.68 -38.00  90.00   99
 19  \w    -87.00  -6.00   1.00    1.00    --  -41.68 125.00-120.00   81
 20  \w      7.00  34.00   1.00    1.00    --   41.68  83.00-144.49   27
 21  \w      9.00  42.00   1.00    1.00    --   41.68  76.00 105.62   33
 22  \w      7.00  34.00   1.00    1.00    --   41.68  83.00  17.78   27
 23  \w     79.00 178.00   1.00    6.00    --  106.01  51.00-176.09   99
 24  \w     77.00 178.00   1.00    6.00    --  106.01  61.00-150.00  101
 25  \w     53.00 178.00   1.00    6.00    --  106.01  15.00 150.00  125
 26  \w     75.00 178.00   1.00    6.00    --  106.01  71.00 126.98  103
 27  \w     74.00 178.00   1.00    6.00    --  106.01  73.00 -86.01  104
 28  \w     76.00 178.00   1.00    6.00    --  106.01  64.00 -29.17  102
 29  \w     77.00 178.00   1.00    6.00    --  106.01  61.00   0.00  101
 30  \w     74.00 178.00   1.00    6.00    --  106.01  74.00  84.18  104
 31  \w     75.00 178.00   1.00    6.00    --  106.01  69.00-102.50  103
 32  \w     75.00 178.00   1.00    6.00    --  106.01  69.00  35.23  103
 33  \w   -116.00 -17.00   1.00    1.00    --  -41.68 -38.00   0.00   99
 34  \w      9.00  42.00   1.00    1.00    --   41.68  80.00-129.32   33
 35  \w      7.00  33.00   1.00    1.00    --   41.68  84.00-168.66   26
 36  \w      7.00  34.00   1.00    1.00    --   41.68  83.00 149.64   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0377628000
_diffrn_orient_matrix_UB_12      0.0762607000
_diffrn_orient_matrix_UB_13      0.0463380000
_diffrn_orient_matrix_UB_21      0.0002732000
_diffrn_orient_matrix_UB_22      0.0159925000
_diffrn_orient_matrix_UB_23      -0.0568372000
_diffrn_orient_matrix_UB_31      -0.1128893000
_diffrn_orient_matrix_UB_32      0.0073431000
_diffrn_orient_matrix_UB_33      -0.0003995000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0623
_diffrn_reflns_av_unetI/netI     0.0454
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            108742
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         3.415
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.037
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.517
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.289
_exptl_crystal_description       block
_exptl_crystal_F_000             2516
_exptl_crystal_size_max          0.447
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.106
_refine_diff_density_max         1.659
_refine_diff_density_min         -1.030
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1575
_refine_ls_number_reflns         21899
_refine_ls_number_restraints     124
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0912
_refine_ls_R_factor_gt           0.0751
_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^)+20.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1474
_refine_ls_wR_factor_ref         0.1564
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17564
_reflns_number_total             21899
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03710b2.cif
_cod_data_source_block           exp_1571
_cod_depositor_comments
'Adding full bibliography for 7708897--7708904.cif.'
_cod_original_cell_volume        6211.88(16)
_cod_database_code               7708897
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C77H61CuN2
_shelx_estimated_absorpt_t_max   0.813
_shelx_estimated_absorpt_t_min   0.463
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C94A-C95A
 1.397 with sigma of 0.01
 C98A-C99A
 1.397 with sigma of 0.01
 C97A-C98A
 1.397 with sigma of 0.01
 C95A-C96A
 1.397 with sigma of 0.01
 C99A-C94A
 1.397 with sigma of 0.01
 C96A-C97A
 1.397 with sigma of 0.01
 C94B-C95B
 1.397 with sigma of 0.01
 C98B-C99B
 1.397 with sigma of 0.01
 C97B-C98B
 1.397 with sigma of 0.01
 C95B-C96B
 1.397 with sigma of 0.01
 C99B-C94B
 1.397 with sigma of 0.01
 C96B-C97B
 1.397 with sigma of 0.01
 C87-C94B
 1.52 with sigma of 0.01
 C87-C94A
 1.52 with sigma of 0.01
 C157-Cl3A
 1.746 with sigma of 0.01
 C157-Cl4A
 1.746 with sigma of 0.01
 C158-Cl4B
 1.746 with sigma of 0.01
 C158-Cl3B
 1.746 with sigma of 0.01
 C155-Cl2A
 1.746 with sigma of 0.01
 C155-Cl1A
 1.746 with sigma of 0.01
 C156-Cl2B
 1.746 with sigma of 0.01
 C156-Cl1B
 1.746 with sigma of 0.01
 C159-Cl6A
 1.746 with sigma of 0.01
 C159-Cl5A
 1.746 with sigma of 0.01
 C160-Cl5B
 1.746 with sigma of 0.01
 C160-Cl6B
 1.746 with sigma of 0.01
 C94A-C96A
 2.41 with sigma of 0.02
 C99A-C95A
 2.41 with sigma of 0.02
 C98A-C94A
 2.41 with sigma of 0.02
 C95A-C97A
 2.41 with sigma of 0.02
 C96A-C98A
 2.41 with sigma of 0.02
 C97A-C99A
 2.41 with sigma of 0.02
 C96B-C98B
 2.41 with sigma of 0.02
 C99B-C95B
 2.41 with sigma of 0.02
 C94B-C96B
 2.41 with sigma of 0.02
 C95B-C97B
 2.41 with sigma of 0.02
 C97B-C99B
 2.41 with sigma of 0.02
 C98B-C94B
 2.41 with sigma of 0.02
 C94A-C82
 2.52 with sigma of 0.02
 C94B-C82
 2.52 with sigma of 0.02
 Cl3A-Cl4A
 2.9 with sigma of 2
 Cl3B-Cl4B
 2.9 with sigma of 2
 Cl1A-Cl2A
 2.9 with sigma of 2
 Cl2B-Cl1B
 2.9 with sigma of 2
 Cl6A-Cl5A
 2.9 with sigma of 0.02
 Cl5B-Cl6B
 2.9 with sigma of 0.02
3. Restrained planarity
 C94A, C95A, C96A, C97A, C98A, C99A
 with sigma of 0.1
 C94B, C95B, C96B, C97B, C98B, C99B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C94A \\sim C95A \\sim C96A \\sim C97A \\sim C98A \\sim C99A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C94B \\sim C95B \\sim C96B \\sim C97B \\sim C98B \\sim C99B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C97B) = Uanis(C97A)
Uanis(C96B) = Uanis(C96A)
Uanis(C98A) = Uanis(C98B)
Uanis(C99B) = Uanis(C99A)
Uanis(C94B) = Uanis(C94A)
Uanis(C95B) = Uanis(C95A)
Uanis(Cl3A) = Uanis(Cl3B)
Uanis(Cl4A) = Uanis(Cl4B)
Uanis(C158) = Uanis(C157)
Uanis(Cl2A) = Uanis(Cl2B)
Uanis(C155) = Uanis(C156)
Uanis(Cl1A) = Uanis(Cl1B)
Uanis(Cl6A) = Uanis(Cl5B)
Uanis(Cl5A) = Uanis(Cl6B)
Uanis(C160) = Uanis(C159)
5. Others
 Sof(H87A)=Sof(C94B)=Sof(C95B)=Sof(H95B)=Sof(C96B)=Sof(H96B)=Sof(C97B)=
 Sof(H97B)=Sof(C98B)=Sof(H98B)=Sof(C99B)=Sof(H99B)=1-FVAR(1)
 Sof(H87)=Sof(C94A)=Sof(C95A)=Sof(H95A)=Sof(C96A)=Sof(H96A)=Sof(C97A)=
 Sof(H97A)=Sof(C98A)=Sof(H98A)=Sof(C99A)=Sof(H99A)=FVAR(1)
 Sof(Cl5B)=Sof(Cl6B)=Sof(C160)=Sof(H16A)=Sof(H16B)=1-FVAR(2)
 Sof(Cl5A)=Sof(Cl6A)=Sof(C159)=Sof(H15I)=Sof(H15J)=FVAR(2)
 Sof(Cl3B)=Sof(Cl4B)=Sof(C158)=Sof(H15G)=Sof(H15H)=1-FVAR(3)
 Sof(Cl3A)=Sof(Cl4A)=Sof(C157)=Sof(H15E)=Sof(H15F)=FVAR(3)
 Sof(Cl1B)=Sof(Cl2B)=Sof(C156)=Sof(H15C)=Sof(H15D)=1-FVAR(4)
 Sof(Cl1A)=Sof(Cl2A)=Sof(C155)=Sof(H15A)=Sof(H15B)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C24(H24), C43(H43), C57(H57), C87(H87), C87(H87A), C101(H101),
 C120(H120), C134(H134)
6.b Secondary CH2 refined with riding coordinates:
 C155(H15A,H15B), C156(H15C,H15D), C157(H15E,H15F), C158(H15G,H15H), C159(H15I,
 H15J), C160(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35),
 C36(H36), C39(H39), C41(H41), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49),
  C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C59(H59), C60(H60),
 C61(H61), C62(H62), C63(H63), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69),
  C73(H73), C74(H74), C75(H75), C76(H76), C77(H77), C79(H79), C80(H80),
 C83(H83), C85(H85), C89(H89), C90(H90), C91(H91), C92(H92), C93(H93),
 C95A(H95A), C95B(H95B), C96A(H96A), C96B(H96B), C97A(H97A), C97B(H97B),
 C98A(H98A), C98B(H98B), C99A(H99A), C99B(H99B), C103(H103), C104(H104),
 C105(H105), C106(H106), C107(H107), C109(H109), C110(H110), C111(H111),
 C112(H112), C113(H113), C116(H116), C118(H118), C122(H122), C123(H123),
 C124(H124), C125(H125), C126(H126), C128(H128), C129(H129), C130(H130),
 C131(H131), C132(H132), C136(H136), C137(H137), C138(H138), C139(H139),
 C140(H140), C142(H142), C143(H143), C144(H144), C145(H145), C146(H146),
 C150(H150), C151(H151), C152(H152), C153(H153), C154(H154)
6.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C56(H56A,H56B,H56C), C100(H10A,H10B,H10C), C133(H13A,
 H13B,H13C)
;
_shelx_res_checksum              51691
_shelx_hkl_checksum              87103
_olex2_exptl_crystal_mounting_method 'Mounted on a LythoLoop'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.062
_oxdiff_exptl_absorpt_empirical_full_min 0.612