Modular o-Quinone Catalyst System for Dehydrogenation of Tetrahydroquinolines under Ambient Conditions.
Wendlandt, Alison E.; Stahl, Shannon S.; Journal of the American Chemical Society 136 (2014) 11910–; doi:10.1021/ja506546w

data_4122462
_publ_section_title
;
 Modular o-Quinone Catalyst System for Dehydrogenation of
 Tetrahydroquinolines under Ambient Conditions.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11910
_journal_paper_doi               10.1021/ja506546w
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C36 H18 N6 O6 Ru, 2(Cl O4), 2.5(C2 H3 N)'
_chemical_formula_sum            'C41 H25.5 Cl2 N8.5 O14 Ru'
_chemical_formula_weight         1033.17
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-01-16
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.744(5)
_cell_length_b                   14.024(6)
_cell_length_c                   20.665(8)
_cell_measurement_temperature    100(2)
_cell_volume                     3983(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS-2013 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            76925
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         30.522
_diffrn_reflns_theta_min         1.755
_exptl_absorpt_coefficient_mu    0.613
_exptl_absorpt_correction_T_max  0.8622
_exptl_absorpt_correction_T_min  0.7887
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1134 before and 0.0560 after correction.
The Ratio of minimum to maximum transmission is 0.9148.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.723
_exptl_crystal_F_000             2084
_exptl_crystal_size_max          0.274
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.998
_refine_diff_density_min         -0.731
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.37(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         12129
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0383
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0408P)^2^+4.3940P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0880
_refine_ls_wR_factor_ref         0.0934
_reflns_Friedel_coverage         0.821
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                10744
_reflns_number_total             12129
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja506546w_si_002.cif
_cod_data_source_block           stahl194
_cod_depositor_comments          'Adding full bibliography for 4122462.cif.'
_cod_original_formula_sum        'C41 H25.50 Cl2 N8.50 O14 Ru'
_cod_database_code               4122462
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.850
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O11-O12 = O11-O13 = O11-O14 = O12-O13 = O12-O14 = O13-O14
 2.383657 with sigma of 0.02
 O15-O16 = O15-O17 = O15-O18 = O16-O17 = O16-O18 = O17-O18
 2.295786 with sigma of 0.02
 Cl2-O11 = Cl2-O12 = Cl2-O13 = Cl2-O14
 1.45968 with sigma of 0.01
 Cl3-O15 = Cl3-O16 = Cl3-O17 = Cl3-O18
 1.40587 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C30A) \\sim Ueq, Uanis(O6A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C42) = Uanis(N9) = Uanis(C41)
4. Rigid body (RIGU) restrains
 O15, Cl3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30, O6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C42, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, N9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30A, O6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2, O11, O12, O13, O14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl3, O15, O16, O17, O18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C30A, O6A}
{C30, O6}
as
{C29, O5}
{N9, C41, C42}
as
{N7, C37, C38}
6. Others
 Sof(Cl3)=Sof(O15)=Sof(O16)=Sof(O17)=Sof(O18)=1-FVAR(1)
 Sof(Cl2)=Sof(O11)=Sof(O12)=Sof(O13)=Sof(O14)=FVAR(1)
 1(DFIX)=FVAR(2)
 1(DFIX)=1.633*FVAR(3)
 1(DFIX)=FVAR(3)
 1(DFIX)=1.633*FVAR(4)
 Sof(C30A)=Sof(O6A)=1-FVAR(4)
 Sof(C30)=Sof(O6)=FVAR(4)
 Fixed Sof: N9(0.5) C41(0.5) C42(0.5) H42A(0.5) H42B(0.5) H42C(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14),
 C15(H15), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C27(H27), C32(H32),
  C33(H33), C34(H34)
7.b Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              97781
_shelx_hkl_checksum              21925