Synthesis of di/trifluoromethyl cyclopropane-dicarbonitriles via [2 + 1] annulation of fluoro-based diazoethanes with (alkylidene)malononitriles
Gao, Cheng-Feng; Chen, Yue-Ji; Nie, Jing; Zhang, Fa-Guang; Cheung, Chi Wai; Ma, Jun-An; Chemical Communications  (2023) –; doi:10.1039/D3CC03897A

data_7132081
_publ_section_title
;
 Synthesis of di/trifluoromethyl cyclopropane-dicarbonitriles via [2 + 1]
 annulation of fluoro-based diazoethanes with (alkylidene)malononitriles
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03897A
_journal_year                    2023
_chemical_formula_moiety         'C13 H6 F6 N2'
_chemical_formula_sum            'C13 H6 F6 N2'
_chemical_formula_weight         304.20
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-16
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2021.11.04 svn.r5db059d7 for OlexSys, GUI svn.r6419)
;
_audit_update_record
;
2022-03-31 deposited with the CCDC.	2023-08-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.388(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4191(9)
_cell_length_b                   12.5633(10)
_cell_length_c                   12.8164(12)
_cell_measurement_reflns_used    5068
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.5870
_cell_measurement_theta_min      2.4250
_cell_volume                     1293.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.850
_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    -71.00 -45.00   0.50   12.00    --   -9.80  35.00  63.00   52
  2  \w     55.00  81.00   0.50   12.00    --    5.00  55.00   0.00   52
  3  \w    -99.00  80.00   0.50   12.00    --   -9.80  55.00-180.00  358
  4  \w    -26.00  73.00   0.50   12.00    --   -9.80  35.00  63.00  198
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0736371000
_diffrn_orient_matrix_UB_12      -0.0304603000
_diffrn_orient_matrix_UB_13      -0.0085096000
_diffrn_orient_matrix_UB_21      0.0001281000
_diffrn_orient_matrix_UB_22      0.0108859000
_diffrn_orient_matrix_UB_23      0.0543318000
_diffrn_orient_matrix_UB_31      -0.0486235000
_diffrn_orient_matrix_UB_32      0.0463033000
_diffrn_orient_matrix_UB_33      -0.0184018000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.850
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10601
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.850
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.267
_diffrn_reflns_theta_min         2.324
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.155
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.738
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         2994
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0831
_refine_ls_R_factor_gt           0.0693
_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^)+(0.1157P)^2^+0.7300P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2150
_refine_ls_wR_factor_ref         0.2259
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2333
_reflns_number_total             2994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03897a2.cif
_cod_data_source_block           cyj20211116
_cod_database_code               7132081
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.952
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C008(H008), C00D(H00D)
2.b Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00F(H00F), C00H(H00H), C00K(H00K)
;
_shelx_res_checksum              91165
_shelx_hkl_checksum              35685
_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 1.416
_oxdiff_exptl_absorpt_empirical_full_min 0.542