In Situ Formation of N-Heterocyclic Carbene-Bound Single-Molecule Junctions.
Doud, Evan A.; Inkpen, Michael S.; Lovat, Giacomo; Montes, Enrique; Paley, Daniel W.; Steigerwald, Michael L.; Vázquez, Héctor; Venkataraman, Latha; Roy, Xavier; Journal of the American Chemical Society 140 (2018) 8944–8949; doi:10.1021/jacs.8b05184

data_4132627
_publ_section_title
;
 In Situ Formation of N-Heterocyclic Carbene-Bound Single-Molecule
 Junctions.
;
_journal_issue                   28
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8944
_journal_page_last               8949
_journal_paper_doi               10.1021/jacs.8b05184
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C20 H24 Cl Cu N2 S, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C20.5 H25 Cl2 Cu N2 S'
_chemical_formula_weight         465.92
_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             2018-03-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.263(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3475(8)
_cell_length_b                   7.5762(7)
_cell_length_c                   23.0412(16)
_cell_measurement_reflns_used    1807
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      24.5590
_cell_measurement_theta_min      3.8680
_cell_volume                     2089.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.832
_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    -81.00 -38.00   1.00    7.50    --  -14.01 153.00 -18.00   43
  2  \w    -16.00  47.00   1.00    7.50    --  -14.01  77.00 -30.00   63
  3  \w    -43.00  77.00   1.00    7.50    --   16.51   0.00   0.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0003738000
_diffrn_orient_matrix_UB_12      0.0575657000
_diffrn_orient_matrix_UB_13      0.0243569000
_diffrn_orient_matrix_UB_21      -0.0316117000
_diffrn_orient_matrix_UB_22      0.0626739000
_diffrn_orient_matrix_UB_23      -0.0200715000
_diffrn_orient_matrix_UB_31      -0.0501056000
_diffrn_orient_matrix_UB_32      -0.0391497000
_diffrn_orient_matrix_UB_33      0.0035769000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0665
_diffrn_reflns_av_unetI/netI     0.1169
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.832
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            9914
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.832
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.654
_diffrn_reflns_theta_min         3.405
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.409
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.805
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.481
_exptl_crystal_description       prism
_exptl_crystal_F_000             964
_exptl_crystal_size_max          0.251
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.027
_refine_diff_density_max         0.934
_refine_diff_density_min         -1.132
_refine_diff_density_rms         0.124
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         4913
_refine_ls_number_restraints     156
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.1138
_refine_ls_R_factor_gt           0.0680
_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^)+(0.0397P)^2^+2.8003P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1294
_refine_ls_wR_factor_ref         0.1621
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3134
_reflns_number_total             4913
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05184_si_006.cif
_cod_data_source_block           ed04201
_cod_original_formula_sum        'C20.50 H25 Cl2 Cu N2 S'
_cod_database_code               4132627
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C20 N2 S1 Cl2 Cu1'
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 planarity
 C12, C16, C17, C18, C19, C20, C21, S22
 with sigma of 0.1
 C12, C16B, C17B, C18B, C19B, C20B, C21B, S22B
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.01
C16B \\sim C17B \\sim C18B \\sim C19B \\sim C20B \\sim C21B \\sim S22B \\sim
C23B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Cl32) = Uanis(Cl33)
4. Rigid body (RIGU) restrains
 C12, C16, C17, C18, C19, C20, C21, S22, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, Cl32, Cl33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C12, C13, C14, C15, C16B, C17B, C18B, C19B, C20B, C21B, S22B, C23B} sigma for
1-2: 0.02, 1-3: 0.04
as
{C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, S22, C23}
6. Others
 Sof(C16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(C19B)=Sof(C20B)=
 Sof(H20B)=Sof(C21B)=Sof(H21B)=Sof(S22B)=Sof(C23B)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=1-FVAR(1)
 Sof(C16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(C20)=Sof(H20)=
 Sof(C21)=Sof(H21)=Sof(S22)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Fixed Sof: C31(0.5) H31A(0.5) H31B(0.5) Cl32(0.5) Cl33(0.5)
7.a Free rotating group:
 C31(Cl32,Cl33)
7.b Ternary CH refined with riding coordinates:
 C3(H3), C7(H7)
7.c Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B)
7.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C14(H14), C17(H17), C18(H18), C20(H20), C21(H21),
 C17B(H17B), C18B(H18B), C20B(H20B), C21B(H21B)
7.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C23(H23A,
 H23B,H23C), C23B(H23D,H23E,H23F)
;
_shelx_res_checksum              60389
_shelx_hkl_checksum              80265
_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 1.214
_oxdiff_exptl_absorpt_empirical_full_min 0.869