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_7708903
_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 H60 Cu F N2), 3(C H2 Cl2)'
_chemical_formula_sum            'C157 H126 Cl6 Cu2 F2 N4'
_chemical_formula_weight         2446.39
_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     direct
_audit_creation_date             2021-03-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6257)
;
_audit_update_record
;
2021-09-23 deposited with the CCDC.	2021-11-22 downloaded from the CCDC.
;
_cell_angle_alpha                115.904(2)
_cell_angle_beta                 96.6271(17)
_cell_angle_gamma                97.9268(16)
_cell_formula_units_Z            2
_cell_length_a                   13.3492(3)
_cell_length_b                   22.3222(4)
_cell_length_c                   23.8523(5)
_cell_measurement_reflns_used    27119
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.7540
_cell_measurement_theta_min      3.6120
_cell_volume                     6208.1(3)
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_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 0.980
_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    -70.00  31.00   1.00   10.00    --  -41.68  57.00 120.00  101
  2  \w   -116.00 -17.00   1.00   10.00    --  -41.68 -40.00 -35.00   99
  3  \w    -74.00  34.00   1.00   10.00    --  -41.68  77.00-120.00  108
  4  \w      7.00  33.00   1.00   10.00    --   41.68  84.00 -34.88   26
  5  \w     34.00 135.00   1.00   25.00    --  106.01 -61.00  90.00  101
  6  \w     30.00 139.00   1.00   25.00    --  106.01 -77.00 -30.00  109
  7  \w     26.00 107.00   1.00   25.00    --  106.01-100.00 -74.59   81
  8  \w     23.00 107.00   1.00   25.00    --  106.01 -94.00 120.00   84
  9  \w    103.00 178.00   1.00   25.00    --  106.01  77.00 150.00   75
 10  \w     33.00 132.00   1.00   25.00    --  106.01 -45.00-120.00   99
 11  \w     33.00 112.00   1.00   25.00    --  106.01-125.00 -90.00   79
 12  \w     18.00 178.00   1.00   25.00    --  106.01   0.00 150.00  160
 13  \w     31.00 103.00   1.00   25.00    --  106.01-116.00  79.61   72
 14  \w     33.00 125.00   1.00   25.00    --  106.01 -45.00  30.00   92
 15  \w     30.00 134.00   1.00   25.00    --  106.01 -30.00 120.00  104
 16  \w      9.00  42.00   1.00   10.00    --   41.68  80.00-131.37   33
 17  \w      8.00  42.00   1.00   10.00    --   41.68  82.00 159.03   34
 18  \w      8.00  42.00   1.00   10.00    --   41.68  82.00 119.51   34
 19  \w     74.00 178.00   1.00   25.00    --  106.01  73.00 -10.86  104
 20  \w    130.00 178.00   1.00   25.00    --  106.01  68.00 179.35   48
 21  \w     86.00 178.00   1.00   25.00    --  106.01  59.00 -98.89   92
 22  \w     78.00 178.00   1.00   25.00    --  106.01  30.00 -30.00  100
 23  \w     89.00 178.00   1.00   25.00    --  106.01  74.00  73.52   89
 24  \w     78.00 178.00   1.00   25.00    --  106.01  56.00  39.10  100
 25  \w     76.00 178.00   1.00   25.00    --  106.01  66.00 123.08  102
 26  \w    134.00 178.00   1.00   25.00    --  106.01  71.00 156.48   44
 27  \w    104.00 178.00   1.00   25.00    --  106.01  30.00-120.00   74
 28  \w    -66.00  33.00   1.00   10.00    --  -41.68  38.00  30.00   99
 29  \w      7.00  34.00   1.00   10.00    --   41.68  83.00  84.50   27
 30  \w     77.00 172.00   1.00   25.00    --  106.01  61.00  60.00   95
 31  \w    127.00 178.00   1.00   25.00    --  106.01  74.00-142.91   51
 32  \w     77.00 178.00   1.00   25.00    --  106.01  59.00 -34.27  101
;
_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      -0.0910299000
_diffrn_orient_matrix_UB_12      0.0293979000
_diffrn_orient_matrix_UB_13      0.0278253000
_diffrn_orient_matrix_UB_21      0.0632460000
_diffrn_orient_matrix_UB_22      0.0727668000
_diffrn_orient_matrix_UB_23      0.0243040000
_diffrn_orient_matrix_UB_31      -0.0428850000
_diffrn_orient_matrix_UB_32      -0.0009316000
_diffrn_orient_matrix_UB_33      -0.0632376000
_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  0.0553
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            107588
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.120
_diffrn_reflns_theta_min         3.410
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.070
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.572
_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    1.309
_exptl_crystal_description       block
_exptl_crystal_F_000             2548
_exptl_crystal_size_max          0.281
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.056
_refine_diff_density_max         1.905
_refine_diff_density_min         -2.045
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1574
_refine_ls_number_reflns         24758
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0873
_refine_ls_R_factor_gt           0.0694
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1191P)^2^+9.2020P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1909
_refine_ls_wR_factor_ref         0.2097
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19560
_reflns_number_total             24758
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03710b2.cif
_cod_data_source_block           27_03-f
_cod_depositor_comments
'Adding full bibliography for 7708897--7708904.cif.'
_cod_original_cell_volume        6208.1(2)
_cod_database_code               7708903
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C154H120F2Cu2N4
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.594
_reflns_odcompleteness_completeness 99.88
_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
 C159-Cl6A
 1.746 with sigma of 0.01
 C159-Cl5A
 1.746 with sigma of 0.01
 C160-Cl6B
 1.746 with sigma of 0.01
 C160-Cl5B
 1.746 with sigma of 0.01
 C158-Cl3B
 1.746 with sigma of 0.01
 C158-Cl4B
 1.746 with sigma of 0.01
 C157-Cl4A
 1.746 with sigma of 0.01
 C157-Cl3A
 1.746 with sigma of 0.01
 C156-Cl1B
 1.746 with sigma of 0.01
 C156-Cl2B
 1.746 with sigma of 0.01
 C155-Cl1A
 1.746 with sigma of 0.01
 C155-Cl2A
 1.746 with sigma of 0.01
 Cl6A-Cl5A
 2.9 with sigma of 0.02
 Cl6B-Cl5B
 2.9 with sigma of 0.02
 Cl3B-Cl4B
 2.9 with sigma of 0.02
 Cl3A-Cl4A
 2.9 with sigma of 0.02
 Cl1B-Cl2B
 2.9 with sigma of 0.02
 Cl1A-Cl2A
 2.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl6B) = Uanis(Cl6A)
Uanis(Cl5A) = Uanis(Cl5B)
Uanis(C159) = Uanis(C160)
Uanis(Cl3A) = Uanis(Cl3B)
Uanis(Cl4A) = Uanis(Cl4B)
Uanis(C157) = Uanis(C158)
Uanis(Cl1A) = Uanis(Cl1B)
Uanis(Cl2A) = Uanis(Cl2B)
Uanis(C156) = Uanis(C155)
4. Others
 Sof(Cl5B)=Sof(Cl6B)=Sof(C160)=Sof(H16A)=Sof(H16B)=1-FVAR(1)
 Sof(Cl5A)=Sof(Cl6A)=Sof(C159)=Sof(H15I)=Sof(H15J)=FVAR(1)
 Sof(Cl3B)=Sof(Cl4B)=Sof(C158)=Sof(H15G)=Sof(H15H)=1-FVAR(2)
 Sof(Cl3A)=Sof(Cl4A)=Sof(C157)=Sof(H15E)=Sof(H15F)=FVAR(2)
 Sof(Cl1B)=Sof(Cl2B)=Sof(C156)=Sof(H15C)=Sof(H15D)=1-FVAR(3)
 Sof(Cl1A)=Sof(Cl2A)=Sof(C155)=Sof(H15A)=Sof(H15B)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C24(H24), C43(H43), C57(H57), C87(H87), C101(H101), C120(H120),
 C134(H134)
5.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)
5.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),
  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), C95(H95), C96(H96),
  C97(H97), C98(H98), C99(H99), 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)
5.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              27703
_shelx_hkl_checksum              15226
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.258
_oxdiff_exptl_absorpt_empirical_full_min 0.803