Four-Electron Oxidation of Phenols to p-Benzoquinone Imines by a (Salen)ruthenium(VI) Nitrido Complex.
Xie, Jianhui; Man, Wai-Lun; Wong, Chun-Yuen; Chang, Xiaoyong; Che, Chi-Ming; Lau, Tai-Chu; Journal of the American Chemical Society 138 (2016) 5817–5820; doi:10.1021/jacs.6b02923

data_4130400
_publ_section_title
;
 Four-Electron Oxidation of Phenols to p-Benzoquinone Imines by a
 (Salen)ruthenium(VI) Nitrido Complex.
;
_journal_issue                   18
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5817
_journal_page_last               5820
_journal_paper_doi               10.1021/jacs.6b02923
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety
'C31 H28 Cl2 N4 O3 Ru, 0.75(C5 H5 N), 0.5(C H4 O)'
_chemical_formula_sum            'C35.25 H33.75 Cl2 N4.75 O3.5 Ru'
_chemical_formula_weight         751.89
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-12-21
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   24.8814(6)
_cell_length_b                   20.0338(5)
_cell_length_c                   29.5126(7)
_cell_measurement_reflns_used    9936
_cell_measurement_temperature    100
_cell_measurement_theta_max      62.71
_cell_measurement_theta_min      3.00
_cell_volume                     14711.1(6)
_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      100.0
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0496
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            114477
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.771
_diffrn_reflns_theta_min         2.995
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.118
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.3948
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1152 before and 0.0659 after correction.
The Ratio of minimum to maximum transmission is 0.5243.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_description       block
_exptl_crystal_F_000             6152
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.904
_refine_diff_density_min         -0.662
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     838
_refine_ls_number_reflns         13237
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0477
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0664P)^2^+46.6384P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1329
_refine_ls_wR_factor_ref         0.1361
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12430
_reflns_number_total             13237
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b02923_si_002.cif
_cod_data_source_block           cxy346_o_sq
_cod_original_formula_sum        'C35.25 H33.75 Cl2 N4.75 O3.50 Ru'
_cod_database_code               4130400
_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, All O(H) groups
2. Restrained distances
 C42A-C43A = C44A-C43A
 1.53 with sigma of 0.02
 C74-O8
 1.42 with sigma of 0.02
 C43A-C41A
 2.52 with sigma of 0.04
 C43A-C39A
 2.52 with sigma of 0.04
 C43A-C40A
 2.98 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C39A \\sim C40A \\sim C41A \\sim C42A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
N11 \\sim C72A \\sim C71A \\sim C70A \\sim C69A \\sim C68A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
N9 \\sim C67 \\sim C66 \\sim C65 \\sim C64 \\sim C63: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(Cl2A) = Uanis(Cl2)
Uanis(Cl4) = Uanis(Cl4A)
Uanis(C10) = Uanis(C10A)
Uanis(C8) = Uanis(C8A)
Uanis(C11) = Uanis(C11A)
Uanis(C13) = Uanis(C13A)
Uanis(C42) = Uanis(C42A)
Uanis(C44) = Uanis(C44A)
Uanis(C41) = Uanis(C41A)
Uanis(C39) = Uanis(C39A)
Uanis(C40) = Uanis(C40A)
Uanis(C43) = Uanis(C43A)
Uiso(N10) = Uiso(N11)
Uiso(C72) = Uiso(C68A)
Uiso(C71) = Uiso(C69A)
Uiso(C70) = Uiso(C70A)
Uiso(C69) = Uiso(C71A)
Uiso(C68) = Uiso(C72A)
4. Others
 Sof(Cl2)=1-FVAR(1)
 Sof(Cl2A)=FVAR(1)
 Sof(Cl4A)=1-FVAR(2)
 Sof(Cl4)=FVAR(2)
 Sof(C8A)=Sof(H8A)=Sof(H9BC)=Sof(H9BD)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(C11A)=
 Sof(H11A)=Sof(H11B)=Sof(H12C)=Sof(H12D)=Sof(C13A)=Sof(H13A)=1-FVAR(3)
 Sof(H9AA)=Sof(H9AB)=Sof(H12A)=Sof(H12B)=Sof(C8)=Sof(H8)=Sof(C10)=Sof(H10C)=
 Sof(H10D)=Sof(C11)=Sof(H11C)=Sof(H11D)=Sof(C13)=Sof(H13)=FVAR(3)
 Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(C41A)=Sof(H41A)=
 Sof(H41B)=Sof(C42A)=Sof(H42A)=Sof(H42B)=Sof(C43A)=Sof(H43A)=Sof(H43B)=
 Sof(C44A)=Sof(H44A)=1-FVAR(4)
 Sof(C39)=Sof(H39)=Sof(C41)=Sof(H41C)=Sof(H41D)=Sof(C42)=Sof(H42C)=Sof(H42D)=
 Sof(C43)=Sof(H43C)=Sof(H43D)=Sof(C44)=Sof(H44)=Sof(C40)=Sof(H40C)=Sof(H40D)=
 FVAR(4)
 Sof(N11)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70A)=
 Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72A)=1-FVAR(5)
 Sof(C72)=Sof(H72)=Sof(N10)=Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=Sof(C70)=
 Sof(H70)=Sof(C71)=Sof(H71)=FVAR(5)
 Fixed Sof: N9(0.5) C63(0.5) H63(0.5) C64(0.5) H64(0.5) C65(0.5) H65(0.5)
 C66(0.5) H66(0.5) C67(0.5) H67(0.5) O8(0.5) H8B(0.5) C74(0.5) H74A(0.5)
 H74B(0.5) H74C(0.5) O7(0.5) H7B(0.5) C73(0.5) H73A(0.5) H73B(0.5) H73C(0.5)
5.a Ternary CH refined with riding coordinates:
 C39A(H39A), C44A(H44A), C8A(H8A), C13A(H13A), C8(H8), C13(H13), C39(H39),
 C44(H44)
5.b Secondary CH2 refined with riding coordinates:
 C40A(H40A,H40B), C41A(H41A,H41B), C42A(H42A,H42B), C43A(H43A,H43B), C9(H9AA,
 H9AB), C9(H9BC,H9BD), C10A(H10A,H10B), C11A(H11A,H11B), C12(H12A,H12B),
 C12(H12C,H12D), C10(H10C,H10D), C11(H11C,H11D), C41(H41C,H41D), C42(H42C,H42D),
  C43(H43C,H43D), C40(H40C,H40D)
5.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C45(H45), C47(H47),
 C48(H48), C49(H49), C50(H50), C53(H53), C57(H57), C58(H58), C59(H59), C60(H60),
  C61(H61), C62(H62), C2(H2), C3(H3A), C4(H4), C5(H5), C7(H7A), C14(H14),
 C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C26(H26), C27(H27), C28(H28),
  C29(H29), C30(H30), C31(H31), C68A(H68A), C69A(H69A), C70A(H70A), C71A(H71A),
 C72A(H72A), C63(H63), C64(H64), C65(H65), C66(H66), C67(H67), C72(H72),
 C68(H68), C69(H69), C70(H70), C71(H71)
5.d Fitted hexagon refined as free rotating group:
 N11(C68A,C69A,C70A,C71A,C72A), N9(C63,C64,C65,C66,C67), C72(N10,C68,C69,C70,
 C71)
5.e Idealised Me refined as rotating group:
 C74(H74A,H74B,H74C), C73(H73A,H73B,H73C)
5.f Idealised tetrahedral OH refined as rotating group:
 O8(H8B), O7(H7B)
;
_shelx_fab_checksum              91240
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
_platon_squeeze_void_probe_radius 1.20