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_7226751
_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         'C8 H10 Cl N3 O'
_chemical_formula_sum            'C8 H10 Cl N3 O'
_chemical_formula_weight         199.64
_chemical_name_systematic        3-(6-chloropyridin-2-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
_atom_sites_solution_primary     direct
_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                 95.909(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.1274(3)
_cell_length_b                   20.8167(12)
_cell_length_c                   10.4887(6)
_cell_measurement_reflns_used    1214
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.0358
_cell_measurement_theta_min      2.7587
_cell_volume                     896.39(10)
_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 0.999
_diffrn_measured_fraction_theta_max 0.860
_diffrn_measurement_details
;
  1 omega  -13.00   23.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339  -99.0000   60.0000 36

  2 omega  -44.00   -5.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339   98.0000  -65.0000 39

  3 omega  -53.00   72.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714    0.0000 -150.0000 125

  4 omega  -95.00  -70.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339  178.0000  -30.0000 25
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0039702000
_diffrn_orient_matrix_UB_12      0.0157269000
_diffrn_orient_matrix_UB_13      -0.0597842000
_diffrn_orient_matrix_UB_21      0.0622090000
_diffrn_orient_matrix_UB_22      0.0280433000
_diffrn_orient_matrix_UB_23      0.0321797000
_diffrn_orient_matrix_UB_31      0.1612530000
_diffrn_orient_matrix_UB_32      -0.0112249000
_diffrn_orient_matrix_UB_33      -0.0034216000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.860
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            4077
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.860
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.100
_diffrn_reflns_theta_min         2.764
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.387
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86823
_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    1.479
_exptl_crystal_description       prism
_exptl_crystal_F_000             416
_exptl_crystal_preparation       'See experimental part.'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.372
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     120
_refine_ls_number_reflns         2078
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0552
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0370P)^2^+0.4340P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0926
_refine_ls_wR_factor_ref         0.1028
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1696
_reflns_number_total             2078
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6gc02556k2.cif
_cod_data_source_block           var257
_cod_depositor_comments
'Adding full bibliography for 7226749--7226751.cif.'
_cod_original_cell_volume        896.38(9)
_cod_database_code               7226751
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'c8 n3 cl1 o1 H10'
_reflns_odcompleteness_completeness 95.82
_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:
 N2(H2), C2(H2A), C4(H4), C3(H3)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              33089
_olex2_submission_special_instructions 'No special instructions were received'
_solvent_exptl_crystal_recrystallization_method EtOAc/hexane