Synthesis and catalytic activity of ruthenium indenylidene complexes bearing unsymmetrical NHC containing a heteroaromatic moiety
Smoleń, Michał; Kosnik, Wioletta; Loska, Rafał; Gajda, Roman; Malinska, Maura; Wozniak, Krzysztof; Grela, Karol; RSC Adv.  (2016) –; doi:10.1039/C6RA18210K

data_7226199
_publ_section_title
;
 Synthesis and catalytic activity of ruthenium indenylidene complexes
 bearing unsymmetrical NHC containing a heteroaromatic moiety
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C6RA18210K
_journal_year                    2016
_chemical_formula_moiety         'C54 H65 Cl2 N2 O P Ru'
_chemical_formula_sum            'C54 H65 Cl2 N2 O P Ru'
_chemical_formula_weight         961.02
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-02-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-02-16 deposited with the CCDC.
2016-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.926(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   32.4848(12)
_cell_length_b                   13.6107(3)
_cell_length_c                   24.3944(7)
_cell_measurement_reflns_used    13710
_cell_measurement_temperature    89.9(5)
_cell_measurement_theta_max      75.8250
_cell_measurement_theta_min      2.9580
_cell_volume                     10140.1(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      89.9(5)
_diffrn_detector_area_resol_mean 5.2195
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
  1 omega  -50.00   33.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   38.0000 -120.0000 83

  2 omega  -50.00   33.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   38.0000   90.0000 83

  3 omega  -72.00   39.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   19.0000    0.0000 111

  4 omega   27.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       42.9484 -129.0000   -6.0000 71

  5 omega   38.00   91.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000  -60.0000 53

  6 omega   38.00  116.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -111.0000  -60.0000 78

  7 omega   84.00  109.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -111.0000   90.0000 25

  8 omega   72.00  115.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  178.0000  120.0000 43

  9 omega   71.00   98.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000   60.0000 27

 10 omega   34.00   60.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000 -150.0000 26

 11 omega   69.00  106.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000 -150.0000 37

 12 omega   76.00  104.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -111.0000    0.0000 28

 13 omega   70.00  101.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  -30.0000 31

 14 omega   58.00  107.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  178.0000  -90.0000 49

 15 omega   48.00  109.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -129.0000   -6.0000 61

 16 omega   39.00   64.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -120.0000 25

 17 omega   43.00   93.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -40.0000   78.9906 50

 18 omega   42.00   98.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000 -180.0000 56

 19 omega   41.00  129.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -77.0000    0.0000 88

 20 omega   52.00   97.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000   30.0000 45

 21 omega   49.00  102.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -61.0000  150.0000 53

 22 omega   71.00   98.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -77.0000 -120.0000 27

 23 omega   71.00  116.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000 -150.0000 45

 24 omega   46.00   78.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000    0.0000 32

 25 omega  119.00  151.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  178.0000  -90.0000 32

 26 omega  131.00  160.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  111.0000   60.0000 29

 27 omega  110.00  137.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  111.0000  -30.0000 27

 28 omega   83.00  109.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000    0.0000 26

 29 omega  137.00  177.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   30.0000 -180.0000 40

 30 omega   93.00  120.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   30.0000 -120.0000 27

 31 omega   50.00   84.00   1.0000   55.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000   90.0000 34
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0434951000
_diffrn_orient_matrix_UB_12      -0.0541157000
_diffrn_orient_matrix_UB_13      -0.0302126000
_diffrn_orient_matrix_UB_21      -0.0254970000
_diffrn_orient_matrix_UB_22      0.0948549000
_diffrn_orient_matrix_UB_23      0.0015788000
_diffrn_orient_matrix_UB_31      0.0020326500
_diffrn_orient_matrix_UB_32      0.0298014500
_diffrn_orient_matrix_UB_33      -0.0599111000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0492
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            45437
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.230
_diffrn_reflns_theta_min         1.926
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.056
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.432
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.259
_exptl_crystal_description       plate
_exptl_crystal_F_000             4032
_exptl_crystal_size_max          0.1494
_exptl_crystal_size_mid          0.0784
_exptl_crystal_size_min          0.0338
_refine_diff_density_max         1.883
_refine_diff_density_min         -1.214
_refine_diff_density_rms         0.135
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.491(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1232
_refine_ls_number_reflns         19297
_refine_ls_number_restraints     473
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0573
_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^)+(0.1072P)^2^+8.5421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1661
_refine_ls_wR_factor_ref         0.1794
_reflns_Friedel_coverage         0.917
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                15821
_reflns_number_total             19297
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra18210k2.cif
_cod_data_source_block           5d
_cod_database_code               7226199
_shelxl_version_number           2013-3
_chemical_oxdiff_formula         'C54 H65 Cl2 N2 O1 P1 Ru1'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.509(16) 0.491(16)
2. 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
3. Rigid bond restraints
 C58, C59, C60, C61, C62, C63, C64, C65, C66, C4, C5, C6, C7, C8, C9, C10, C11,
  C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C22A, C23A, C28A, C29A, C30A, C76, C77, C82, C83, C84, C22B, C23B, C28B, C29B,
  C30B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C43, C44, C45, C46, C47, C48, C91, C92, C93, C94, C95, C96
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim
C66 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11
\\sim C12: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C22A \\sim C23A \\sim C28A \\sim C29A \\sim C30A \\sim C76 \\sim C77 \\sim C82
\\sim C83 \\sim C84 \\sim C22B \\sim C23B \\sim C28B \\sim C29B \\sim C30B:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C91 \\sim C92 \\sim
C93 \\sim C94 \\sim C95 \\sim C96: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
5. Same fragment restrains
{C22B, C23B, C28B, C29B, C30B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C22A, C23A, C28A, C29A, C30A}
{C31B, C32B, C33B, C34B, C35B, C36B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C31A, C32A, C33A, C34A, C35A, C36A}
6. Others
 Sof(C22B)=Sof(C23B)=Sof(C28B)=Sof(C29B)=Sof(C30B)=Sof(H30B)=Sof(C24B)=
 Sof(H24B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26B)=Sof(C27B)=Sof(H27B)=
 Sof(C31B)=Sof(C32B)=Sof(H32B)=Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34B)=
 Sof(C35B)=Sof(H35B)=Sof(C36B)=Sof(H36B)=1-FVAR(1)
 Sof(C22A)=Sof(C23A)=Sof(C28A)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C24A)=
 Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=
 Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=
 Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36A)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C37(H37), C43(H43), C49(H49), C91(H91), C97(H97), C103(H103)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C2(H2A,H2B), C13(H13A,H13B), C38(H38A,H38B), C39(H39A,H39B),
 C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B),
  C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C56(H56A,H56B),
 C57(H57A,H57B), C67(H67A,H67B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B),
  C95(H95A,H95B), C96(H96A,H96B), C98(H98A,H98B), C99(H99A,H99B), C100(H10D,
 H10E), C101(H10F,H10G), C102(H10H,H10I), C104(H10J,H10K), C105(H10L,H10M),
 C106(H10N,H10O), C107(H10P,H10Q), C108(H10R,H10S)
7.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C30A(H30A),
 C30B(H30B), C24A(H24A), C25A(H25A), C26A(H26A), C27A(H27A), C24B(H24B),
 C25B(H25B), C26B(H26B), C27B(H27B), C32A(H32A), C33A(H33A), C34A(H34A),
 C35A(H35A), C36A(H36A), C32B(H32B), C33B(H33B), C34B(H34B), C35B(H35B),
 C36B(H36B), C78(H78), C79(H79), C80(H80), C81(H81), C84(H84), C60(H60),
 C62(H62), C69(H69), C71(H71), C72(H72), C73(H73), C74(H74), C86(H86), C87(H87),
  C88(H88), C89(H89), C90(H90)
7.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C)
;
_shelx_res_checksum              30775
_olex2_submission_special_instructions 'No special instructions were received'