Unexpected O-H Insertion of Rhodium-Azavinylcarbenes with N-Acylhydrazones: Divergent Synthesis of 3,6-Disubstituted- and 3,5,6-Trisubstituted-1,2,4-Triazines.
Meng, Jiang; Wen, Min; Zhang, Shiwei; Pan, Peiwen; Yu, Xingxin; Deng, Wei-Ping; The Journal of organic chemistry 82 (2017) 1676–1687; doi:10.1021/acs.joc.6b02846

data_4032153
_publ_section_title
;
 Unexpected O-H Insertion of Rhodium-Azavinylcarbenes with
 N-Acylhydrazones: Divergent Synthesis of 3,6-Disubstituted- and
 3,5,6-Trisubstituted-1,2,4-Triazines.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1676
_journal_page_last               1687
_journal_paper_doi               10.1021/acs.joc.6b02846
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C19 H15 N3 O3'
_chemical_formula_sum            'C19 H15 N3 O3'
_chemical_formula_weight         333.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-10
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.963(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.8797(11)
_cell_length_b                   10.6151(16)
_cell_length_c                   19.258(3)
_cell_measurement_reflns_used    4523
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      30.64
_cell_measurement_theta_min      2.604
_cell_volume                     1598.9(4)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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      130
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            15665
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.637
_diffrn_reflns_theta_min         2.131
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0716 before and 0.0454 after correction.
The Ratio of minimum to maximum transmission is 0.8999.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.394
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.861
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         4906
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.861
_refine_ls_R_factor_all          0.0784
_refine_ls_R_factor_gt           0.0628
_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^)+(0.0621P)^2^+4.4807P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1700
_refine_ls_wR_factor_ref         0.1797
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3832
_reflns_number_total             4906
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02846_si_002.cif
_cod_data_source_block           mo_dm15545_0m
_cod_depositor_comments          'Adding full bibliography for 4032153.cif.'
_cod_original_cell_volume        1599.0(4)
_cod_database_code               4032153
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.981
_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 Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.b Me refined with riding coordinates:
 C6(H6A,H6B,H6C)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19)
;
_shelx_res_checksum              64155
_shelx_hkl_checksum              39642
_olex2_submission_special_instructions 'No special instructions were received'