Ruthenium(ii)-catalysed direct synthesis of ketazines using secondary alcohols
Kishore, Jugal; Thiyagarajan, Subramanian; Gunanathan, Chidambaram; Chemical Communications  (2019) –; doi:10.1039/C9CC01383K

data_7123234
_publ_section_title
;
 Ruthenium(ii)-catalysed direct synthesis of ketazines using secondary
 alcohols
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC01383K
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C54 H88 N2'
_chemical_formula_sum            'C54 H88 N2'
_chemical_formula_weight         765.26
_chemical_name_systematic
(1Z,2Z)-1,2-bis((8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-ylidene)hydrazine
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-20
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2019-03-20 deposited with the CCDC.    2019-03-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.130(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.5019(4)
_cell_length_b                   10.2070(3)
_cell_length_c                   17.0548(5)
_cell_measurement_reflns_used    11284
_cell_measurement_temperature    194
_cell_measurement_theta_max      29.0150
_cell_measurement_theta_min      3.0370
_cell_volume                     2340.97(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.41b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.41b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.41b (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      194
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -68.00 -42.00   0.50   25.00    --    7.10 -29.00   1.00   52
  2  \w    -51.00 -26.00   0.50   25.00    --   -7.50 -29.00   1.00   50
  3  \w    -10.00  16.00   0.50   25.00    --   -7.50  29.00 162.00   52
  4  \w     50.00  88.00   0.50   25.00    --    7.10  77.00-180.00   76
  5  \w     63.00  96.00   0.50   25.00    --    7.10  77.00  30.00   66
  6  \w    -46.00 -17.00   0.50   25.00    --   -7.50  38.00  90.00   58
  7  \w    -13.00  35.00   0.50   25.00    --   -7.50 -82.00 -30.00   96
  8  \w    -63.00 -17.00   0.50   25.00    --   -7.50 -82.00 -30.00   92
  9  \w     20.00  79.00   0.50   25.00    --   -7.50  38.00  90.00  118
 10  \w    -59.00  23.00   0.50   25.00    --   -7.50 -82.00 120.00  164
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Supernova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0415523000
_diffrn_orient_matrix_UB_12      -0.0039505000
_diffrn_orient_matrix_UB_13      0.0225506000
_diffrn_orient_matrix_UB_21      0.0309447000
_diffrn_orient_matrix_UB_22      -0.0257662000
_diffrn_orient_matrix_UB_23      0.0321269000
_diffrn_orient_matrix_UB_31      0.0098441000
_diffrn_orient_matrix_UB_32      0.0644278000
_diffrn_orient_matrix_UB_33      0.0142519000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0525
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25355
_diffrn_reflns_point_group_measured_fraction_full 0.919
_diffrn_reflns_point_group_measured_fraction_max 0.904
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         2.835
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.061
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35027
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction,'
_exptl_crystal_colour            'metallic yellowish yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.086
_exptl_crystal_description       block
_exptl_crystal_F_000             852
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 2629 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.3(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         8342
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0534
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0766P)^2^+0.5956P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1368
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.712
_reflns_Friedel_fraction_full    0.829
_reflns_Friedel_fraction_max     0.799
_reflns_number_gt                7253
_reflns_number_total             8342
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc01383k2.cif
_cod_data_source_block           try1
_cod_database_code               7123234
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C54 H88 N2 '
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C003(H003), C005(H005), C007(H007), C00B(H00B), C00D(H00D), C00G(H00G),
 C00L(H00L), C00T(H00y), C00U(H00z), C00Y(H2aa), C01B(H01z), C01G(H7aa)
2.b Secondary CH2 refined with riding coordinates:
 C00C(H00a,H00c), C00F(H00e,H00f), C00K(H00i,H00k), C00M(H00m,H00n), C00N(H00o,
 H00p), C00O(H00q,H00r), C00P(H00s,H00t), C00R(H00u,H00v), C00S(H00w,H00x),
 C00V(H00,H), C00W(H0aa,Ha), C00X(H1aa,Hb), C00Z(H3aa,Hc), C011(H01d,H01e),
 C012(H01f,H01g), C014(H01k,H01l), C016(H01p,H01q), C018(H01u,H01v), C019(H01w,
 H01x), C01D(H4aa,Hh), C01H(H8aa,Hm), C01I(H9aa,Hn)
2.c Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00J(H00J)
2.d Idealised Me refined as rotating group:
 C010(H01a,H01b,H01c), C013(H01h,H01i,H01j), C015(H01m,H01n,H01o), C017(H01r,
 H01s,H01t), C01A(H01y,Hd,He), C01C(H01,Hf,Hg), C01E(H5aa,Hi,Hj), C01F(H6aa,Hk,
 Hl), C01J(H0ba,Ho,Hp), C01K(H1ba,Hq,Hr)
;
_olex2_submission_original_sample_id JK_206
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.212
_oxdiff_exptl_absorpt_empirical_full_min 0.741