Transition-Metal-Free [3+2] Cycloaddition of Dehydroaminophosphonates and N-Tosylhydrazones: Access to Aminocyclopropanephosphonates with Adjacent Quaternary-Tetrasubstituted Carbon Centers.
Wu, Wanqing; Lin, Zhiming; Zhu, Chuanle; Chen, Pengquan; Li, Jiawei; Jiang, Huanfeng; The Journal of organic chemistry 82 (2017) 12746–12756; doi:10.1021/acs.joc.7b01862

data_4033025
_publ_section_title
;
 Transition-Metal-Free [3+2] Cycloaddition of Dehydroaminophosphonates and
 N-Tosylhydrazones: Access to Aminocyclopropanephosphonates with Adjacent
 Quaternary-Tetrasubstituted Carbon Centers.
;
_journal_issue                   23
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12746
_journal_page_last               12756
_journal_paper_doi               10.1021/acs.joc.7b01862
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C17 H23 F3 N O4 P, 0.5(H2 O)'
_chemical_formula_sum            'C17 H24 F3 N O4.5 P'
_chemical_formula_weight         402.34
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-03-01
_audit_creation_method
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.550(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.3954(6)
_cell_length_b                   10.8878(4)
_cell_length_c                   19.5641(7)
_cell_measurement_reflns_used    7679
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.6310
_cell_measurement_theta_min      4.5350
_cell_volume                     3906.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.967
_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    -88.00 -21.00   1.00    1.00    --  -40.48 125.00 -90.00   67
  2  \w    -99.00 -21.00   1.00    1.00    --  -40.48 -37.00  60.00   78
  3  \w   -114.00 -16.00   1.00    1.00    --  -40.48 -37.00 -30.00   98
  4  \w     56.00  85.00   1.00    1.00    --   40.48-125.00-180.00   29
  5  \w     35.00 128.00   1.00    1.00    --  107.58 -45.00 -60.00   93
  6  \w     86.00 178.00   1.00    1.00    --  107.58  61.00  90.00   92
  7  \w     48.00 135.00   1.00    1.00    --  107.58 -61.00  30.00   87
  8  \w     45.00 109.00   1.00    1.00    --  107.58 -94.00 -30.00   64
  9  \w     26.00 108.00   1.00    1.00    --  107.58 -94.00-120.00   82
;
_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      -0.0067475000
_diffrn_orient_matrix_UB_12      0.0530179000
_diffrn_orient_matrix_UB_13      -0.0733866000
_diffrn_orient_matrix_UB_21      0.0818526000
_diffrn_orient_matrix_UB_22      0.0313737000
_diffrn_orient_matrix_UB_23      0.0066237000
_diffrn_orient_matrix_UB_31      0.0173889000
_diffrn_orient_matrix_UB_32      -0.1274418000
_diffrn_orient_matrix_UB_33      -0.0285802000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0283
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            14814
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.896
_diffrn_reflns_theta_min         3.437
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.732
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67672
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_description       block
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.955
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.070
_refine_ls_extinction_coef       0.00033(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     490
_refine_ls_number_reflns         7666
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0560
_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^)+(0.0740P)^2^+4.0705P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1429
_refine_ls_wR_factor_ref         0.1500
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6687
_reflns_number_total             7666
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01862_si_003.cif
_cod_data_source_block           exp_276
_cod_depositor_comments
'Adding full bibliography for 4033025--4033026.cif.'
_cod_original_formula_sum        'C17 H24 F3 N O4.50 P'
_cod_database_code               4033025
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.769
_shelx_estimated_absorpt_t_min   0.643
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2.a Free rotating group:
 O1W(H1WA,H1WB)
2.b Secondary CH2 refined with riding coordinates:
 C00U(H00A,H00B), C10(H10A,H10B), C12(H12A,H12B), C018(H01G,H01H), C019(H01I,
 H01J), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 N00F(H00F), N1(H1), C00M(H00M), C00T(H00T), C00X(H00X), C4(H4), C010(H010),
 C6(H6), C7(H7), C3(H3)
2.d Idealised Me refined as rotating group:
 C013(H01A,H01B,H01C), C015(H01D,H01E,H01F), C17(H17A,H17B,H17C), C8(H8A,H8B,
 H8C), C13(H13A,H13B,H13C), C01F(H01K,H01L,H01M), C01G(H01N,H01O,H01P),
 C14(H14A,H14B,H14C)
;
_shelx_res_checksum              93642
_shelx_hkl_checksum              55419
_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 1.435
_oxdiff_exptl_absorpt_empirical_full_min 0.719