Preparation, X-ray Structure, and Reactivity of 2-Iodylpyridines: Recyclable Hypervalent Iodine(V) Reagents
Akira Yoshimura; Christopher T. Banek; Mekhman S. Yusubov; Victor N. Nemykin; Viktor V. Zhdankin; Journal of Organic Chemistry 76 (2011) 3812–3819; doi:10.1021/jo200163m

data_4026289
_publ_contact_author_address
; 
 Department of Chemistry, 
 University of Minnesota Duluth, 
 1039 University Drive
 Duluth, MN 55812, USA. 
;
_publ_contact_author_email       vnemykin@d.umn.edu
_publ_contact_author_fax         '+1 218 726 7394'
_publ_contact_author_name        'Victor Nemykin'
_publ_contact_author_phone       '+1 218 726 6729'
_publ_section_title
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 Preparation, X-ray Structure, and Reactivity of 2-Iodylpyridines:
 Recyclable Hypervalent Iodine(V) Reagents
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              3812
_journal_page_last               3819
_journal_paper_doi               10.1021/jo200163m
_journal_volume                  76
_journal_year                    2011
_chemical_formula_moiety         'C8 H14 I1 N1 O5'
_chemical_formula_sum            'C8 H14 I N O5'
_chemical_formula_weight         331.10
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             11-01-06
_audit_creation_method           CRYSTALS_ver_14.11
_cell_angle_alpha                82.634(6)
_cell_angle_beta                 85.041(6)
_cell_angle_gamma                82.063(6)
_cell_formula_units_Z            4
_cell_length_a                   9.1841(3)
_cell_length_b                   10.3130(5)
_cell_length_c                   12.2949(8)
_cell_measurement_reflns_used    5201
_cell_measurement_temperature    123
_cell_measurement_theta_max      27
_cell_measurement_theta_min      3
_cell_volume                     1141.04(10)
_computing_cell_refinement       'CrystalClear 2.0'
_computing_data_collection       'CrystalClear 2.0'
_computing_data_reduction        'Crystal Structure 4.0'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SHELXS 86 (Sheldrick, 1986)'
_diffrn_ambient_temperature      123
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'RAPID II'
_diffrn_measurement_device_type  'RAPID II image plate'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.059
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            32057
_diffrn_reflns_theta_full        27.472
_diffrn_reflns_theta_max         27.472
_diffrn_reflns_theta_min         3.066
_diffrn_standards_decay_%        0.00
_diffrn_standards_interval_time  8
_diffrn_standards_number         5201
_exptl_absorpt_coefficient_mu    2.809
_exptl_absorpt_correction_T_max  0.67
_exptl_absorpt_correction_T_min  0.60
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.927
_exptl_crystal_description       block
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.290
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.140
_refine_diff_density_max         2.20
_refine_diff_density_min         -1.41
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9781
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         5191
_refine_ls_number_restraints     86
_refine_ls_R_factor_all          0.0573
_refine_ls_R_factor_gt           0.0432
_refine_ls_shift/su_max          0.0034532
_refine_ls_shift/su_mean         0.0000916
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= Modified Sheldrick 
 w=1/[\s^2^(F^2^) + ( 0.01P)^2^ +22.43P] 
 ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1031
_refine_ls_wR_factor_gt          0.0926
_refine_ls_wR_factor_ref         0.1031
_reflns_limit_h_max              11
_reflns_limit_h_min              -11
_reflns_limit_k_max              13
_reflns_limit_k_min              -13
_reflns_limit_l_max              15
_reflns_limit_l_min              0
_reflns_number_gt                4267
_reflns_number_total             5201
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00
_oxford_refine_ls_r_factor_ref   0.0573
_oxford_refine_ls_scale          0.949(2)
_oxford_reflns_number_all        5191
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title '_082610_VN1'
_cod_data_source_file            jo200163m_si_002.cif
_cod_data_source_block           1
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C8 H14 I1 N1 O5'
_cod_database_code               4026289
_iucr_refine_instruction_details_constraints
;
BLOCK 
CONT SCALE 
CONT I    (    1 ,X'S,U'S)  UNTIL O    (   30 ) 
CONT H    (   61 ,X'S)  UNTIL H    (  262 ) 
RIDE O   (  27,X'S) H   ( 271,X'S) H   ( 272,X'S) 
RIDE O   (  28,X'S) H   ( 281,X'S) H   ( 282,X'S) 
RIDE O   (  29,X'S) H   (  92,X'S) H   ( 292,X'S) 
RIDE O   (  30,X'S) H   (  24,X'S) H   (  64,X'S) 
END                                                                             
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_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM NO H   NO #H U MULT DIST 
REM C-H 
REM >4           1.5    .96 DISORDER 
REM 1      1     1.2    .93 C C-H (ACETYLENE) 
REM 1      2     1.2    .93 C-C(H)-C 
REM 1      3     1.2    .98 (C)3-C-H 
REM 2      1     1.2    .93 C=C-H(2) 
REM 2      2     1.2    .97 (C)2-C-(H)2 
REM 3      1     1.5    .96 C-C-(H)3 
REM N-H 
REM >4           1.5    .89 DISORDER 
REM 1      1     1.2    .86 N-N/H 
REM 1      2     1.2    .86 (C)2-N-H 
REM 1      3     1.2    .89 (C)3-N-H 
REM 2      1     1.2    .86 C-N-(H)2 
REM 2      2     1.2    .89 (C)2-N-(H)2 
REM 3      1     1.2    .89 C-H-(H)3 
REM O-H 
REM 1      1     1.5    .82 O-H 
REM 
REM DIST      ESD = 0.02 
REM VIB       ESD = 0.002 
REM ANGLE     ESD = 2.0 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 6) TO H(61) 
REST 0.022, 0.002 = H(61,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(61) TO C ( 6) TO N(5) 
CONT H(61) TO C ( 6) TO C(7) 
PLANAR C ( 6) N(5) C(7) H(61) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 7) TO H(71) 
REST 0.029, 0.002 = H(71,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(71) TO C ( 7) TO C(6) 
CONT H(71) TO C ( 7) TO C(8) 
PLANAR C ( 7) C(6) C(8) H(71) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 8) TO H(81) 
REST 0.029, 0.002 = H(81,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(81) TO C ( 8) TO C(7) 
CONT H(81) TO C ( 8) TO C(9) 
PLANAR C ( 8) C(7) C(9) H(81) 
REM            1 H ON SP 3 
DIST 0.98, 0.02 = 
CONT C ( 11) TO H(111) 
REST 0.027, 0.002 = H(111,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(111) TO C ( 11) TO O(10) 
CONT H(111) TO C ( 11) TO C(12) 
CONT H(111) TO C ( 11) TO C(13) 
REM            3 H ON SP 3 
DIST 0.96, 0.02 = 
CONT C ( 12) TO H(121) 
CONT C ( 12) TO H(122) 
CONT C ( 12) TO H(123) 
REST 0.049, 0.002 = H(121,U[ISO]) 
REST 0.049, 0.002 = H(122,U[ISO]) 
REST 0.049, 0.002 = H(123,U[ISO]) 
ANGLE 109.54, 2.0 = 
CONT C(11) TO C ( 12) TO H(121) 
CONT C(11) TO C ( 12) TO H(122) 
CONT C(11) TO C ( 12) TO H(123) 
ANGLE 0.0, 2.0 = MEAN H(121) TO C ( 12) TO H(122) 
CONT H(121) TO C ( 12) TO H(123) 
CONT H(122) TO C ( 12) TO H(123) 
REM            3 H ON SP 3 
DIST 0.96, 0.02 = 
CONT C ( 13) TO H(132) 
CONT C ( 13) TO H(133) 
CONT C ( 13) TO H(131) 
REST 0.042, 0.002 = H(132,U[ISO]) 
REST 0.042, 0.002 = H(133,U[ISO]) 
REST 0.042, 0.002 = H(131,U[ISO]) 
ANGLE 109.54, 2.0 = 
CONT C(11) TO C ( 13) TO H(132) 
CONT C(11) TO C ( 13) TO H(133) 
CONT C(11) TO C ( 13) TO H(131) 
ANGLE 0.0, 2.0 = MEAN H(132) TO C ( 13) TO H(133) 
CONT H(132) TO C ( 13) TO H(131) 
CONT H(133) TO C ( 13) TO H(131) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 19) TO H(191) 
REST 0.026, 0.002 = H(191,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(191) TO C ( 19) TO N(18) 
CONT H(191) TO C ( 19) TO C(20) 
PLANAR C ( 19) N(18) C(20) H(191) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 20) TO H(201) 
REST 0.024, 0.002 = H(201,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(201) TO C ( 20) TO C(19) 
CONT H(201) TO C ( 20) TO C(21) 
PLANAR C ( 20) C(19) C(21) H(201) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 21) TO H(211) 
REST 0.024, 0.002 = H(211,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(211) TO C ( 21) TO C(20) 
CONT H(211) TO C ( 21) TO C(22) 
PLANAR C ( 21) C(20) C(22) H(211) 
REM            1 H ON SP 3 
DIST 0.98, 0.02 = 
CONT C ( 24) TO H(241) 
REST 0.023, 0.002 = H(241,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(241) TO C ( 24) TO O(23) 
CONT H(241) TO C ( 24) TO C(25) 
CONT H(241) TO C ( 24) TO C(26) 
REM            3 H ON SP 3 
DIST 0.96, 0.02 = 
CONT C ( 25) TO H(252) 
CONT C ( 25) TO H(251) 
CONT C ( 25) TO H(253) 
REST 0.048, 0.002 = H(252,U[ISO]) 
REST 0.048, 0.002 = H(251,U[ISO]) 
REST 0.048, 0.002 = H(253,U[ISO]) 
ANGLE 109.54, 2.0 = 
CONT C(24) TO C ( 25) TO H(252) 
CONT C(24) TO C ( 25) TO H(251) 
CONT C(24) TO C ( 25) TO H(253) 
ANGLE 0.0, 2.0 = MEAN H(252) TO C ( 25) TO H(251) 
CONT H(252) TO C ( 25) TO H(253) 
CONT H(251) TO C ( 25) TO H(253) 
REM            3 H ON SP 3 
DIST 0.96, 0.02 = 
CONT C ( 26) TO H(263) 
CONT C ( 26) TO H(261) 
CONT C ( 26) TO H(262) 
REST 0.045, 0.002 = H(263,U[ISO]) 
REST 0.045, 0.002 = H(261,U[ISO]) 
REST 0.045, 0.002 = H(262,U[ISO]) 
ANGLE 109.54, 2.0 = 
CONT C(24) TO C ( 26) TO H(263) 
CONT C(24) TO C ( 26) TO H(261) 
CONT C(24) TO C ( 26) TO H(262) 
ANGLE 0.0, 2.0 = MEAN H(263) TO C ( 26) TO H(261) 
CONT H(263) TO C ( 26) TO H(262) 
CONT H(261) TO C ( 26) TO H(262) 
REM       H ON O-HETRO ATOM 
DIST 0.82, 0.02 = 
CONT O ( 27) TO H(271) 
CONT O ( 27) TO H(272) 
REST 0.043, 0.002 = H(271,U[ISO]) 
REST 0.043, 0.002 = H(272,U[ISO]) 
REM       H ON O-HETRO ATOM 
DIST 0.82, 0.02 = 
CONT O ( 28) TO H(281) 
CONT O ( 28) TO H(282) 
REST 0.053, 0.002 = H(281,U[ISO]) 
REST 0.053, 0.002 = H(282,U[ISO]) 
REM       H ON O-HETRO ATOM 
DIST 0.82, 0.02 = 
CONT O ( 29) TO H(92) 
CONT O ( 29) TO H(292) 
REST 0.058, 0.002 = H(92,U[ISO]) 
REST 0.058, 0.002 = H(292,U[ISO]) 
REM       H ON O-HETRO ATOM 
DIST 0.82, 0.02 = 
CONT O ( 30) TO H(24) 
CONT O ( 30) TO H(64) 
REST 0.056, 0.002 = H(24,U[ISO]) 
REST 0.056, 0.002 = H(64,U[ISO]) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;