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_7155899
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-09-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.31 svn.r3340 for OlexSys, GUI svn.r5221)
;
_audit_update_record
;
2017-05-18 deposited with the CCDC.
2017-09-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.748(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4884(6)
_cell_length_b                   12.0955(4)
_cell_length_c                   14.1006(6)
_cell_measurement_reflns_used    6274
_cell_measurement_temperature    293
_cell_measurement_theta_max      27.1280
_cell_measurement_theta_min      4.1600
_cell_volume                     2339.94(17)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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 0.859
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -5.00  39.00   1.00   25.00    --   -8.76  38.00-180.00   44
  2  \w     -6.00  64.00   1.00   25.00    --   -8.76  38.00   0.00   70
  3  \w    -18.00  88.00   1.00   25.00    --    9.46  77.00  30.00  106
  4  \w      1.00  48.00   1.00   25.00    --    9.46 -99.00 -30.00   47
  5  \w    -20.00  50.00   1.00   25.00    --    9.46 -99.00-120.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0264864000
_diffrn_orient_matrix_UB_12      -0.0431917000
_diffrn_orient_matrix_UB_13      0.0134536000
_diffrn_orient_matrix_UB_21      -0.0272044000
_diffrn_orient_matrix_UB_22      0.0396371000
_diffrn_orient_matrix_UB_23      0.0169754000
_diffrn_orient_matrix_UB_31      -0.0350682000
_diffrn_orient_matrix_UB_32      0.0018821000
_diffrn_orient_matrix_UB_33      -0.0485135000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.859
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            18820
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.383
_diffrn_reflns_theta_min         3.369
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.148
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77700
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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       prism
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         5038
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0489
_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^)+(0.0593P)^2^+0.8550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1227
_refine_ls_wR_factor_ref         0.1359
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3760
_reflns_number_total             5038
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob02223a3.cif
_cod_data_source_block           jp297rrss
_cod_database_code               7155899
_chemical_oxdiff_formula         'c20 h37 n2 o5 p1'
_reflns_odcompleteness_completeness 99.64
_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:
 C11(H11A,H11B), 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:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), 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)
;
_shelx_shelxl_version_number     2016/4
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.420
_oxdiff_exptl_absorpt_empirical_full_min 0.642