Aerobic dehydrogenation of amines to nitriles catalyzed by triazolylidene ruthenium complexes with O<sub>2</sub> as terminal oxidant.
Olivares, Marta; Knörr, Pascal; Albrecht, Martin; Dalton transactions (Cambridge, England : 2003) 49 (2020) 1981–1991; doi:10.1039/c9dt04873a

data_7703330
_publ_section_title
;
 Aerobic dehydrogenation of amines to nitriles catalyzed by triazolylidene
 ruthenium complexes with O<sub>2</sub> as terminal oxidant.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1981
_journal_page_last               1991
_journal_paper_doi               10.1039/c9dt04873a
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C22 H28 Cl N4 O3 Ru, C F3 O3 S'
_chemical_formula_sum            'C23 H28 Cl F3 N4 O6 Ru S'
_chemical_formula_weight         682.07
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-10 deposited with the CCDC.	2020-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.1456(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.45753(10)
_cell_length_b                   28.13655(18)
_cell_length_c                   7.85029(6)
_cell_measurement_reflns_used    31230
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      27.7620
_cell_measurement_theta_min      1.7870
_cell_volume                     2730.25(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0965
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.951
_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     35.00 122.00   1.00   20.00    --   27.42 178.00 150.00   87
  2  \w     35.00 122.00   1.00   20.00    --   27.42 178.00-150.00   87
  3  \w    -28.00 109.00   1.00   20.00    --   27.42  38.00 -90.00  137
  4  \w    -57.00  71.00   1.00   20.00    --   27.42 -77.00-120.00  128
  5  \w    -64.00 118.00   1.00   20.00    --   27.42   0.00   0.00  182
  6  \w     35.00 122.00   1.00   20.00    --   27.42 178.00 -90.00   87
  7  \w    -20.00  32.00   1.00   20.00    --  -23.50 -99.00  60.00   52
  8  \w    -20.00  32.00   1.00   20.00    --  -23.50 -99.00 -90.00   52
  9  \w    -49.00  65.00   1.00   20.00    --   27.42 -57.00 -30.00  114
 10  \w    -16.00 112.00   1.00   20.00    --   27.42  77.00 -30.00  128
 11  \w    -28.00 109.00   1.00   20.00    --   27.42  38.00 120.00  137
 12  \w    -16.00  78.00   1.00   20.00    --   27.42  77.00  60.00   94
 13  \w    -16.00 112.00   1.00   20.00    --   27.42  77.00-180.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0003661500
_diffrn_orient_matrix_UB_12      0.0252084081
_diffrn_orient_matrix_UB_13      0.0016700622
_diffrn_orient_matrix_UB_21      -0.0573613880
_diffrn_orient_matrix_UB_22      0.0001475747
_diffrn_orient_matrix_UB_23      -0.0092461904
_diffrn_orient_matrix_UB_31      0.0012992046
_diffrn_orient_matrix_UB_32      -0.0004542139
_diffrn_orient_matrix_UB_33      0.0905676444
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0421
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            58568
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.123
_diffrn_reflns_theta_min         1.647
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.815
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.249
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.659
_exptl_crystal_description       plate
_exptl_crystal_F_000             1384
_exptl_crystal_size_max          0.283
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.945
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.38(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     752
_refine_ls_number_reflns         12395
_refine_ls_number_restraints     139
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0325
_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^)+(0.0402P)^2^+1.6010P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0791
_refine_ls_wR_factor_ref         0.0812
_reflns_Friedel_coverage         0.961
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.952
_reflns_number_gt                11581
_reflns_number_total             12395
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04873a2.cif
_cod_data_source_block           complex4c_18ma096c2_pk53
_cod_depositor_comments
'Adding full bibliography for 7703329--7703332.cif.'
_cod_original_cell_volume        2730.25(3)
_cod_database_code               7703330
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.802
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.62(3)
 0.38(3)
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. Uiso/Uaniso restraints and constraints
O6A \\sim O6 \\sim C32 \\sim O5 \\sim O5A \\sim C33A \\sim C33 \\sim C34A \\sim
C34: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 O6A, O6, C32, O5, O5A, C33A, C33, C34A, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O6A)=Sof(O5A)=Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=1-FVAR(1)
 Sof(O6)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(O5)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C20(H20), C42(H42)
6.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C33(H33A,H33B), C33A(H33C,H33D)
6.c Me refined with riding coordinates:
 C34(H34A,H34B,H34C), C34A(H34D,H34E,H34F)
6.d Aromatic/amide H refined with riding coordinates:
 C37(H37), C30(H30), C14(H14), C29(H29), C5(H5), C15(H15), C36(H36), C27(H27),
 C39(H39), C40(H40), C17(H17), C8(H8), C7(H7), C18(H18)
6.e Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C43(H43A,H43B,H43C), C9(H9A,H9B,H9C), C41(H41A,H41B,H41C),
 C22(H22A,H22B,H22C), C44(H44A,H44B,H44C), C19(H19A,H19B,H19C), C31(H31A,H31B,
 H31C), C25(H25A,H25B,H25C), C12(H12A,H12B,H12C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              91280
_olex2_submission_special_instructions 'No special instructions were received'