Nucleophile-intercepted Beckmann Fragmentation Reactions
Touchette, Samuel J.; Dunkley, Evan M.; Lowder, Leah L.; Wu, Jimmy; Chemical Science  (2019) –; doi:10.1039/C9SC00926D

data_1551983
_publ_section_title
;
 Nucleophile-intercepted Beckmann Fragmentation Reactions
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC00926D
_journal_year                    2019
_chemical_formula_moiety         'C15 H17 Cl N2'
_chemical_formula_sum            'C15 H17 Cl N2'
_chemical_formula_weight         260.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-09
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.02.24 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2019-02-22 deposited with the CCDC.    2019-06-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.993(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1576(5)
_cell_length_b                   8.6724(5)
_cell_length_c                   15.2277(8)
_cell_measurement_reflns_used    5359
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      71.96
_cell_measurement_theta_min      4.93
_cell_volume                     1328.39(12)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'COSMO (BRUKER, V1.61, 2009)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 8.36
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.947
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            7531
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.953
_diffrn_reflns_theta_min         4.934
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.393
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0654 before and 0.0368 after correction. The Ratio of minimum to maximum transmission is 0.7442. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       needle
_exptl_crystal_F_000             552
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.228
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.229
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         2478
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0340
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0465P)^2^+0.5436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0910
_refine_ls_wR_factor_ref         0.0926
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2308
_reflns_number_total             2478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00926d2.cif
_cod_data_source_block           jw616a
_cod_database_code               1551983
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.412
_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
2.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id SJT-05-809-Major
_olex2_submission_special_instructions 'No special instructions were received'