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_7226750
_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 Br N3 O'
_chemical_formula_sum            'C8 H10 Br N3 O'
_chemical_formula_weight         244.10
_chemical_name_systematic        3-(6-bromopyridin-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   mixed
_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                 95.814(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.18964(13)
_cell_length_b                   21.1953(8)
_cell_length_c                   10.4364(4)
_cell_measurement_reflns_used    6702
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      31.1027
_cell_measurement_theta_min      2.7409
_cell_volume                     921.99(6)
_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 0.995
_diffrn_measured_fraction_theta_max 0.842
_diffrn_measurement_details
;
  1 omega  -25.00   46.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339   77.0000 -180.0000 71

  2 omega   -9.00   87.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714   77.0000  -60.0000 96

  3 omega   13.00   60.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714   77.0000   60.0000 47

  4 omega   -2.00   88.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714   57.0000  150.0000 90

  5 omega   35.00   95.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714  178.0000 -150.0000 60

  6 omega   32.00   96.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714 -178.0000    0.0000 64

  7 omega   -2.00   39.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714   57.0000 -120.0000 41

  8 omega  -39.00   55.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714  -87.0000    7.0000 94

  9 omega  -41.00  -14.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339   77.0000   90.0000 27

 10 omega   20.00   47.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339   77.0000 -120.0000 27

 11 omega   19.00   44.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714   77.0000 -120.0000 25

 12 omega  -25.00   24.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.0339  -99.0000  -30.0000 49

 13 omega  -25.00   61.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714  -99.0000 -120.0000 86

 14 omega  -25.00   61.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714  -99.0000  150.0000 86

 15 omega   -2.00   88.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714   57.0000   60.0000 90

 16 omega   -2.00   45.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714   57.0000 -150.0000 47

 17 omega  -53.00   44.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       18.9714  -38.0000   30.0000 97

 18 omega  -86.00  -51.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4031  -57.0000 -120.0000 35

 19 omega  -38.00  -13.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4031  -87.0000 -124.0000 25

 20 omega  -82.00  -52.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4031 -178.0000  -90.0000 30

 21 omega  -18.00    9.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4031  -87.0000    7.0000 27

 22 omega  -86.00  -47.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4031  178.0000    0.0000 39

 23 omega   -6.00   26.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3406   87.0000  172.0000 32

 24 omega    4.00   37.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3406   87.0000  -55.0000 33
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1204397000
_diffrn_orient_matrix_UB_12      0.0120086000
_diffrn_orient_matrix_UB_13      0.0462586000
_diffrn_orient_matrix_UB_21      0.0119141000
_diffrn_orient_matrix_UB_22      0.0275082000
_diffrn_orient_matrix_UB_23      -0.0379377000
_diffrn_orient_matrix_UB_31      -0.1197589000
_diffrn_orient_matrix_UB_32      0.0148016000
_diffrn_orient_matrix_UB_33      0.0329046000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0817
_diffrn_reflns_av_unetI/netI     0.0532
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.842
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            23771
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.842
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.172
_diffrn_reflns_theta_min         2.746
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.421
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28560
_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    1.759
_exptl_crystal_description       prism
_exptl_crystal_F_000             488
_exptl_crystal_preparation       'See experimental part.'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.898
_refine_diff_density_min         -0.840
_refine_diff_density_rms         0.145
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     120
_refine_ls_number_reflns         2504
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0657
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0200P)^2^+3.5700P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0946
_refine_ls_wR_factor_ref         0.1016
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2148
_reflns_number_total             2504
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6gc02556k2.cif
_cod_data_source_block           var260
_cod_depositor_comments
'Adding full bibliography for 7226749--7226751.cif.'
_cod_database_code               7226750
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'br1 C8 H10 N2'
_reflns_odcompleteness_completeness 99.14
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.51
_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 Riding coordinates:
 N2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C2(H2A), C3(H3)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              96559
_olex2_submission_special_instructions 'No special instructions were received'
_solvent_exptl_crystal_recrystallization_method EtOAc/hexane