How intramolecular hydrogen bonding (IHB) controls the C–ON bond homolysis in alkoxyamines
Audran, Gérard; Bikanga, Raphael; Brémond, Paul; Edeleva, Mariya; Joly, Jean-Patrick; Marque, Sylvain R. A.; Nkolo, Paulin; Roubaud, Valérie; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB02223A

data_7155898
_publ_section_title
;
 How intramolecular hydrogen bonding (IHB) controls the C--ON bond
 homolysis in alkoxyamines
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB02223A
_journal_year                    2017
_chemical_formula_moiety         'C20 H37 N2 O5 P'
_chemical_formula_sum            'C20 H37 N2 O5 P'
_chemical_formula_weight         416.48
_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             2015-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2017-05-18 deposited with the CCDC.
2017-09-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.598(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3358(4)
_cell_length_b                   8.9190(3)
_cell_length_c                   19.7702(8)
_cell_measurement_reflns_used    4982
_cell_measurement_temperature    293
_cell_measurement_theta_max      25.5260
_cell_measurement_theta_min      3.8680
_cell_volume                     2340.29(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.874
_diffrn_measurement_details
;
  1 omega  -31.00   -5.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9721   77.0000 -180.0000 26

  2 omega   23.00   78.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9721   77.0000  -30.0000 55

  3 omega    4.00   86.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.0658   77.0000    0.0000 82

  4 omega  -16.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.0658   77.0000  120.0000 128

  5 omega  -25.00   71.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.0658   77.0000  -90.0000 96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0348580000
_diffrn_orient_matrix_UB_12      0.0598160000
_diffrn_orient_matrix_UB_13      -0.0010446000
_diffrn_orient_matrix_UB_21      -0.0402722000
_diffrn_orient_matrix_UB_22      0.0499987000
_diffrn_orient_matrix_UB_23      -0.0096034000
_diffrn_orient_matrix_UB_31      -0.0046640000
_diffrn_orient_matrix_UB_32      0.0156396000
_diffrn_orient_matrix_UB_33      0.0347210000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0272
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.874
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            15918
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.874
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.705
_diffrn_reflns_theta_min         3.532
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.148
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86944
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       plate
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.614
_refine_diff_density_min         -0.483
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         4783
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0852
_refine_ls_R_factor_gt           0.0621
_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^)+(0.0645P)^2^+1.7132P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1501
_refine_ls_wR_factor_ref         0.1665
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3474
_reflns_number_total             4783
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02223a3.cif
_cod_data_source_block           pnk16f1
_cod_original_cell_volume        2340.28(14)
_cod_database_code               7155898
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'c20 h37 n2 o5 p1'
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.66
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C17(H17A,H17B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C20(H20A,
 H20B,H20C)
2.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_olex2_submission_special_instructions 'No special instructions were received'