Hoveyda-Grubbs catalyst analogues bearing derivatives of N-phenylpyrrol in carbene ligand - structure, stability, activity and unique ruthenium-phenyl interactions
Grudzień, Krzysztof; Trzaskowski, Bartosz; Smoleń, Michał; Gajda, Roman; Wozniak, Krzysztof; Grela, Karol; Dalton Trans.  (2017) –; doi:10.1039/C7DT02180A

data_7043952
_publ_section_title
;
 Hoveyda-Grubbs catalyst analogues bearing derivatives of N-phenylpyrrol
 in carbene ligand - structure, stability, activity and unique
 ruthenium-phenyl interactions
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT02180A
_journal_year                    2017
_chemical_formula_moiety         'C30 H33 Cl Cu N3'
_chemical_formula_sum            'C30 H33 Cl Cu N3'
_chemical_formula_weight         534.58
_chemical_name_systematic
'(1-(2,6-diisopropylphenyl)-3-((1-phenyl-1H-indol-2-yl)methyl)imidazolidin-2-ylidene)copper(I) chloride'
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-12-21
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2017-04-13 deposited with the CCDC.
2017-08-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.2603(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.47569(17)
_cell_length_b                   23.6537(4)
_cell_length_c                   12.2912(2)
_cell_measurement_reflns_used    40080
_cell_measurement_temperature    100.10(10)
_cell_measurement_theta_max      34.2750
_cell_measurement_theta_min      2.2810
_cell_volume                     2747.28(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.34a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.34a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.34a (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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100.10(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2195
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9998
_diffrn_measured_fraction_theta_max 0.9998
_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    -10.00 130.00   1.00   17.00    --   31.97  77.00-150.00  140
  2  \w    -10.00 130.00   1.00   17.00    --   31.97  77.00  90.00  140
  3  \w    -10.00 130.00   1.00   17.00    --   31.97  77.00 -30.00  140
  4  \w    -20.00  82.00   1.00   17.00    --   31.97 -99.00  30.00  102
  5  \w    -57.00  71.00   1.00   17.00    --   31.97 -37.00  90.00  128
  6  \w    -58.00  72.00   1.00   17.00    --   31.97 -57.00-120.00  130
  7  \w   -123.00   7.00   1.00   17.00    --  -33.06 -57.00-180.00  130
  8  \w   -131.00 -55.00   1.00   17.00    --  -33.06 178.00 -30.00   76
  9  \w   -133.00 -57.00   1.00   17.00    --  -33.06-178.00  90.00   76
 10  \w    -57.00  71.00   1.00   17.00    --   31.97 -37.00-120.00  128
 11  \w    -13.00 121.00   1.00   17.00    --   31.97  37.00-150.00  134
 12  \w     -8.00 122.00   1.00   17.00    --   31.97  57.00 -90.00  130
 13  \w   -131.00 -55.00   1.00   17.00    --  -33.06 178.00-150.00   76
 14  \w      6.00  36.00   1.00   17.00    --  -33.06-131.00  -0.08   30
 15  \w   -122.00  12.00   1.00   17.00    --  -33.06 -37.00 -60.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0670151000
_diffrn_orient_matrix_UB_12      0.0066838000
_diffrn_orient_matrix_UB_13      -0.0186420000
_diffrn_orient_matrix_UB_21      0.0273472000
_diffrn_orient_matrix_UB_22      0.0044407000
_diffrn_orient_matrix_UB_23      0.0546565000
_diffrn_orient_matrix_UB_31      0.0197445000
_diffrn_orient_matrix_UB_32      -0.0288965000
_diffrn_orient_matrix_UB_33      0.0041093000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0397
_diffrn_reflns_av_unetI/netI     0.0177
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            122730
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.141
_diffrn_reflns_theta_min         1.871
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.915
_exptl_absorpt_correction_T_max  0.800
_exptl_absorpt_correction_T_min  0.682
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.34a (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    1.292
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.273
_exptl_crystal_size_mid          0.201
_exptl_crystal_size_min          0.146
_refine_diff_density_max         1.375
_refine_diff_density_min         -1.388
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.284
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         10467
_refine_ls_number_restraints     279
_refine_ls_restrained_S_all      1.268
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0567
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0233P)^2^+5.1408P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1315
_refine_ls_wR_factor_ref         0.1338
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9447
_reflns_number_total             10467
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt02180a2.cif
_cod_data_source_block           CuCl_4
_cod_database_code               7043952
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         C30H33N3CuCl
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.07
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 C25A, C25B, C26A, C26B, C27A, C27B, C28A, C28B, C29A, C29B, C30A, C30B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C25A \\sim C25B \\sim C26A \\sim C26B \\sim C27A \\sim C27B \\sim C28A \\sim
C28B \\sim C29A \\sim C29B \\sim C30A \\sim C30B: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(C25A) \\sim Ueq, Uanis(C25B) \\sim Ueq, Uanis(C26A) \\sim Ueq,
Uanis(C26B) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C27B) \\sim Ueq,
Uanis(C28A) \\sim Ueq, Uanis(C28B) \\sim Ueq, Uanis(C29A) \\sim Ueq,
Uanis(C29B) \\sim Ueq, Uanis(C30A) \\sim Ueq, Uanis(C30B) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
4. Same fragment restrains
{N3, C25B, C26B, C27B, C28B, C29B, C30B} sigma for 1-2: 0.02, 1-3: 0.04
as
{N3, C25A, C26A, C27A, C28A, C29A, C30A}
5. Others
 Sof(C25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=
 Sof(C29B)=Sof(H29B)=Sof(C30B)=Sof(H30B)=1-FVAR(1)
 Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B)
6.b Aromatic/amide H refined with riding coordinates:
 C26A(H26A), C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A), C26B(H26B),
 C27B(H27B), C28B(H28B), C29B(H29B), C30B(H30B)
;
_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 1.186
_oxdiff_exptl_absorpt_empirical_full_min 0.714