Difluoroketenimine: Generation from Difluorocarbene and Isocyanide, and Its [3+2] Cycloadditions with Alkenes or Alkynes.
Zhang, Rui; Zhang, Zhikun; Wang, Kang; Wang, Jianbo; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01120

data_4038580
_publ_section_title
;
 Difluoroketenimine: Generation from Difluorocarbene and Isocyanide, and
 Its [3+2] Cycloadditions with Alkenes or Alkynes.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01120
_journal_year                    2020
_chemical_formula_moiety         'C15 H18 F2 N2'
_chemical_formula_sum            'C15 H18 F2 N2'
_chemical_formula_weight         264.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-05-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.852(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.9761(3)
_cell_length_b                   9.3925(2)
_cell_length_c                   25.5523(6)
_cell_measurement_reflns_used    17337
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      28.4160
_cell_measurement_theta_min      3.9190
_cell_volume                     2802.26(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7e (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      100.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -50.00 -11.00   0.50    3.01    --   -9.40  77.00 150.00   78
  2  \w    -70.00  88.00   0.50    3.01    --    9.60  19.00 120.00  316
  3  \w    -34.00  24.00   0.50    3.01    --   -9.40 -82.00 120.00  116
  4  \w    -99.00 -14.00   0.50    3.01    --   -9.40 -57.00-120.00  170
  5  \w    -99.00  36.00   0.50    3.01    --   -9.40 -57.00 -60.00  270
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0309030000
_diffrn_orient_matrix_UB_12      -0.0454715000
_diffrn_orient_matrix_UB_13      -0.0138370000
_diffrn_orient_matrix_UB_21      -0.0351696000
_diffrn_orient_matrix_UB_22      0.0218318000
_diffrn_orient_matrix_UB_23      -0.0248204000
_diffrn_orient_matrix_UB_31      0.0387433000
_diffrn_orient_matrix_UB_32      0.0562001000
_diffrn_orient_matrix_UB_33      -0.0015768000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            30343
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.021
_diffrn_reflns_theta_min         3.420
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91001
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         5509
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.184
_refine_ls_R_factor_all          0.0478
_refine_ls_R_factor_gt           0.0453
_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^)+(0.0267P)^2^+2.7104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1150
_refine_ls_wR_factor_ref         0.1160
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5162
_reflns_number_total             5509
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01120_si_002.cif
_cod_data_source_block           exp_523
_cod_depositor_comments
;

2025-07-29
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C15 H18 F2 N2)'
_cod_original_formula_sum        'C30 H36 F4 N4'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     528.63
_cod_database_code               4038580
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C1 O1 N1'
_chemical_oxdiff_usercomment     mengxiao
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_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:
 C00H(H00H), C00M(H00M), C00O(H00O), C00S(H00V)
2.b Secondary CH2 refined with riding coordinates:
 C00W(H00A,H00C), C00X(H00Z,H)
2.c Aromatic/amide H refined with riding coordinates:
 C00A(H00G), C00B(H00B), C00E(H00I), C00G(H00J), C00I(H00K), C00L(H00L),
 C00N(H00N), C00Q(H00Q), C00R(H00U), C00T(H00T)
2.d Idealised Me refined as rotating group:
 C00P(H00P,H00R,H00S), C00V(H00W,H00X,H00Y), C00Z(H00D,H00E,H00F), C010(H01G,
 H01H,H01I), C011(H01A,H01B,H01C), C012(H01D,H01E,H01F)
;
_shelx_res_checksum              23913
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.129
_oxdiff_exptl_absorpt_empirical_full_min 0.873