Solvent- and halide-free synthesis of pyridine-2-yl substituted ureas through facile C–H functionalization of pyridine N-oxides
Rassadin, Valentin A.; Zimin, Dmitry P.; Raskil'dina, Gulnara Z.; Ivanov, Alexander Yu.; Boyarskiy, Vadim P.; Zlotskii, Semen S.; Kukushkin, Vadim Yu.; Green Chem. 18 (2016) 6630–; doi:10.1039/C6GC02556K

data_7226749
_publ_section_title
;
 Solvent- and halide-free synthesis of pyridine-2-yl substituted ureas
 through facile C--H functionalization of pyridine N-oxides
;
_journal_issue                   24
_journal_name_full               'Green Chem.'
_journal_page_first              6630
_journal_paper_doi               10.1039/C6GC02556K
_journal_volume                  18
_journal_year                    2016
_chemical_formula_moiety         'C9 H13 N3 O2'
_chemical_formula_sum            'C9 H13 N3 O2'
_chemical_formula_weight         195.22
_chemical_name_systematic        3-(2-methoxypyridin-3-yl)-1,1-dimethylurea
_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
_audit_creation_date             2016-04-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-04-12 deposited with the CCDC.
2016-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.555(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.3261(5)
_cell_length_b                   20.1659(12)
_cell_length_c                   13.1676(8)
_cell_measurement_reflns_used    6716
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.9359
_cell_measurement_theta_min      2.8428
_cell_volume                     1898.8(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_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_temperature      100.01(10)
_diffrn_detector_area_resol_mean 16.2096
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.885
_diffrn_measurement_details
;
  1 omega  -93.00  -44.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339 -178.0000 -120.0000 49

  2 omega  -90.00    3.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339  -38.0000 -180.0000 93

  3 omega    3.00   92.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1277    0.0000   30.0000 89

  4 omega  -25.00   24.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339  -99.0000  -30.0000 49

  5 omega  -25.00   61.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1277  -99.0000   90.0000 86

  6 omega   32.00   96.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1277 -178.0000  -30.0000 64

  7 omega   -2.00   27.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1277   57.0000 -180.0000 29

  8 omega   -6.00   92.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       19.1277   38.0000  120.0000 98

  9 omega  -75.00  -48.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.4031  -57.0000 -180.0000 27

 10 omega  -20.00    7.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       21.4968  -99.0000  120.0000 27

 11 omega   10.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       21.4968  -99.0000  120.0000 53

 12 omega   64.00   91.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       21.4968   77.0000    0.0000 27

 13 omega    0.00   83.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       21.4968   57.0000  -60.0000 83
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0015949000
_diffrn_orient_matrix_UB_12      -0.0183443000
_diffrn_orient_matrix_UB_13      0.0457489000
_diffrn_orient_matrix_UB_21      0.0670250000
_diffrn_orient_matrix_UB_22      0.0219210000
_diffrn_orient_matrix_UB_23      0.0293291000
_diffrn_orient_matrix_UB_31      -0.0732140000
_diffrn_orient_matrix_UB_32      0.0204759000
_diffrn_orient_matrix_UB_33      0.0095243000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0493
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.885
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            29572
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.885
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.002
_diffrn_reflns_theta_min         2.849
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.099
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67511
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       prism
_exptl_crystal_F_000             832
_exptl_crystal_preparation       'See experimental part.'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.318
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     259
_refine_ls_number_reflns         4907
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0737
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0465P)^2^+1.2110P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1212
_refine_ls_wR_factor_ref         0.1325
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3779
_reflns_number_total             4907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6gc02556k2.cif
_cod_data_source_block           0var306
_cod_depositor_comments
'Adding full bibliography for 7226749--7226751.cif.'
_cod_database_code               7226749
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C9 H13 O2 N3'
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.50
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N2A(H2A), N2B(H2B), C3B(H3B), C3A(H3A), C4A(H4A), C5A(H5A), C4B(H4B), C5B(H5B)
2.b Idealised Me refined as rotating group:
 C6B(H6BA,H6BB,H6BC), C8B(H8BA,H8BB,H8BC), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,
 H8AC), C9B(H9BA,H9BB,H9BC), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              99110
_olex2_submission_special_instructions 'No special instructions were received'
_solvent_exptl_crystal_recrystallization_method EtOAc/hexane