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_7226197
_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 O P Ru, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C50.5 H64 Cl3 N2 O P Ru'
_chemical_formula_weight         953.42
_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             2016-02-16
_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                 112.309(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   31.4469(8)
_cell_length_b                   14.5027(4)
_cell_length_c                   24.1761(5)
_cell_measurement_reflns_used    2000
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28
_cell_measurement_theta_min      2
_cell_volume                     10200.6(5)
_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 0.998
_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  0.0352
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.998
_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            45508
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         1.943
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.531
_exptl_absorpt_correction_T_max  0.9447
_exptl_absorpt_correction_T_min  0.8936
_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    1.242
_exptl_crystal_description       cuboid
_exptl_crystal_F_000             3992
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.459
_refine_diff_density_min         -0.664
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     667
_refine_ls_number_reflns         9687
_refine_ls_number_restraints     218
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0638
_refine_ls_R_factor_gt           0.0475
_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^)+(0.0617P)^2^+48.7258P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1253
_refine_ls_wR_factor_ref         0.1384
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7870
_reflns_number_total             9687
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra18210k2.cif
_cod_data_source_block           5b
_cod_original_formula_sum        'C50.50 H64 Cl3 N2 O P Ru'
_cod_database_code               7226197
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.901
_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
 C2R-Cl3
 1.6 with sigma of 0.02
 Cl4-C2R
 1.6 with sigma of 0.02
 Cl5-C1R
 1.7 with sigma of 0.02
 C1R-Cl6
 1.6 with sigma of 0.002
 Cl4-Cl3
 2.6 with sigma of 0.04
 Cl6-Cl5
 2.6 with sigma of 0.04
 C21A-C26A \\sim C21B-C26B
 with sigma of 0.02
3. Restrained planarity
 C14, C16A, C15A, C17A, O1A
 with sigma of 0.1
 C14, C16B, C15B, C17B, O1B
 with sigma of 0.1
4. Rigid bond restraints
 C21A, C21B, C22A, C22B, C23A, C23B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C27A, C27B, C28A, C28B, C29A, C29B, C30A, C30B, C31A, C31B, C32A, C32B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C21A \\sim C21B \\sim C22A \\sim C22B \\sim C23A \\sim C23B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C27A \\sim C27B \\sim C28A \\sim C28B \\sim C29A \\sim C29B \\sim C30A \\sim
C30B \\sim C31A \\sim C31B \\sim C32A \\sim C32B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
C20A \\sim C20B \\sim C25A \\sim C25B \\sim C26A \\sim C26B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O1B) = Uanis(C15A)
Uanis(C16B) = Uanis(C17B)
Uanis(C16A) = Uanis(C17A)
6. Same fragment restrains
{Ru1, C18B, C19B, C20B, C26B, C25B} sigma for 1-2: 0.02, 1-3: 0.04
as
{Ru1, C18A, C19A, C20A, C26A, C25A}
7. Others
 Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=Sof(C17A)=Sof(H17A)=Sof(O1A)=1-FVAR(1)
 Sof(C16B)=Sof(H16B)=Sof(C15B)=Sof(H15B)=Sof(C17B)=Sof(H17B)=Sof(O1B)=FVAR(1)
 Sof(Cl6)=Sof(C1R)=Sof(H1RA)=Sof(H1RB)=Sof(Cl5)=0.5*(1-FVAR(3))
 Sof(Cl3)=Sof(Cl4)=Sof(C2R)=Sof(H2RA)=Sof(H2RB)=0.5*FVAR(3)
 Sof(C18B)=Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(C26B)=Sof(C25B)=Sof(C21B)=
 Sof(H21B)=Sof(C22B)=Sof(H22B)=Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24B)=
 Sof(C27B)=Sof(C28B)=Sof(H28B)=Sof(C29B)=Sof(H29B)=Sof(C30B)=Sof(H30B)=
 Sof(C31B)=Sof(H31B)=Sof(C32B)=Sof(H32B)=1-FVAR(3)
 Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(C26A)=Sof(C25A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=FVAR(3)
8.a Ternary CH refined with riding coordinates:
 C33(H33), C39(H39), C46(H46)
8.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C13(H13A,H13B), C34(H34A,H34B), C35(H35A,H35B),
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C40(H40A,H40B), C41(H41A,H41B),
  C42(H42A,H42B), C44(H44A,H44B), C45(H45A,H45B), C47(H47A,H47B), C48(H48A,
 H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C1R(H1RA,H1RB),
 C2R(H2RA,H2RB)
8.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C19A(H19A), C19B(H19B), C21A(H21A), C22A(H22A), C23A(H23A),
 C24A(H24A), C28A(H28A), C29A(H29A), C30A(H30A), C31A(H31A), C32A(H32A),
 C21B(H21B), C22B(H22B), C23B(H23B), C24B(H24B), C28B(H28B), C29B(H29B),
 C30B(H30B), C31B(H31B), C32B(H32B), C16B(H16B), C15B(H15B), C17B(H17B),
 C16A(H16A), C15A(H15A), C17A(H17A)
8.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              81135
_olex2_submission_special_instructions 'No special instructions were received'