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_7226196
_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         'C50 H63 Cl2 N2 P Ru S, 0.5(C1 H2 Cl2)'
_chemical_formula_sum            'C50.5 H64 Cl3 N2 P Ru S'
_chemical_formula_weight         969.48
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-02-08
_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                 112.519(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   31.4399(9)
_cell_length_b                   14.5840(5)
_cell_length_c                   24.2430(7)
_cell_measurement_reflns_used    16958
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.6294
_cell_measurement_theta_min      1.8150
_cell_volume                     10268.3(6)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'KUMA4 CCD'
_diffrn_measurement_method       'omega scan'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0520
_diffrn_reflns_av_unetI/netI     0.0418
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            51125
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.680
_diffrn_reflns_theta_min         1.938
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.567
_exptl_absorpt_correction_T_max  0.9455
_exptl_absorpt_correction_T_min  0.8050
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET)
(compiled Aug  3 2011,13:03:54)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       plate
_exptl_crystal_F_000             4056
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.179
_refine_diff_density_min         -0.589
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     631
_refine_ls_number_reflns         9735
_refine_ls_number_restraints     82
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0811
_refine_ls_R_factor_gt           0.0543
_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^)+(0.0701P)^2^+48.8624P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1395
_refine_ls_wR_factor_ref         0.1563
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7283
_reflns_number_total             9735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra18210k2.cif
_cod_data_source_block           5a
_cod_original_formula_sum        'C50.50 H64 Cl3 N2 P Ru S'
_cod_database_code               7226196
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.805
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C100-Cl3
 1.79 with sigma of 0.01
 Cl3A-C101
 1.79 with sigma of 0.01
 C101-Cl4A
 1.79 with sigma of 0.01
 C26A-C31A \\sim C26B-C31B
 with sigma of 0.02
3. Restrained planarity
 S1B, C15B, C16B, C14B, C13B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C17B \\sim C18B \\sim C19B \\sim C20B \\sim C21B \\sim C22B \\sim C23B \\sim
C24B \\sim C25B \\sim C26B \\sim C27B \\sim C28B \\sim C29B \\sim C30B \\sim
C31B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(Cl4) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl3A) \\sim Ueq, Uanis(Cl4A)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C100) \\sim Ueq, Uanis(C101) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(Cl4) = Uanis(Cl3)
Uanis(C13A) = Uanis(C13B)
Uanis(S1) = Uanis(C14B)
Uanis(C16A) = Uanis(C15B)
Uanis(C16B) = Uanis(C15A)
Uanis(C14A) = Uanis(S1B)
Uanis(Cl3A) = Uanis(Cl4A)
Uanis(C100) = Uanis(C101)
5. Same fragment restrains
{Ru1, C17B, C18B, C19B, C25B, C24B} sigma for 1-2: 0.02, 1-3: 0.04
as
{Ru1, C17A, C18A, C19A, C25A, C24A}
{S1B, C16B, C15B, C14B, C13B} sigma for 1-2: 0.02, 1-3: 0.04
as
{S1, C16A, C15A, C14A, C13A}
6. Others
 Sof(Cl3A)=Sof(Cl4A)=Sof(C101)=Sof(H10F)=Sof(H10G)=0.5*(1-FVAR(2))
 Sof(C100)=Sof(H10D)=Sof(H10E)=Sof(Cl4)=Sof(Cl3)=0.5*FVAR(2)
 Sof(H12C)=Sof(H12D)=Sof(S1B)=Sof(C16B)=Sof(H16B)=Sof(C15B)=Sof(H15B)=
 Sof(C14B)=Sof(H14B)=Sof(C13B)=1-FVAR(2)
 Sof(H12A)=Sof(H12B)=Sof(S1)=Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=Sof(C14A)=
 Sof(H14A)=Sof(C13A)=FVAR(2)
 Sof(C17B)=Sof(C18B)=Sof(H18B)=Sof(C19B)=Sof(C25B)=Sof(C24B)=Sof(C23B)=
 Sof(H23B)=Sof(C22B)=Sof(H22B)=Sof(C21B)=Sof(H21B)=Sof(C20B)=Sof(H20B)=
 Sof(C26B)=Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29B)=
 Sof(C30B)=Sof(H30B)=Sof(C31B)=Sof(H31B)=1-FVAR(3)
 Sof(C17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(C25A)=Sof(C24A)=Sof(C20A)=
 Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=
 Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C32(H32), C38(H38), C44(H44)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C12(H12A,H12B), C12(H12C,H12D), C33(H33A,H33B),
 C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C39(H39A,H39B),
  C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C45(H45A,
 H45B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B),
 C100(H10D,H10E), C101(H10F,H10G)
7.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C18A(H18A), C18B(H18B), C20A(H20A), C21A(H21A), C22A(H22A),
 C23A(H23A), C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A), C31A(H31A),
 C23B(H23B), C22B(H22B), C21B(H21B), C20B(H20B), C27B(H27B), C28B(H28B),
 C29B(H29B), C30B(H30B), C31B(H31B), C16A(H16A), C15A(H15A), C14A(H14A),
 C16B(H16B), C15B(H15B), C14B(H14B)
7.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C50(H50A,H50B,H50C)
;
_shelx_res_checksum              42310
_olex2_submission_special_instructions 'No special instructions were received'