One-Pot Synthesis of Spirocyclic or Fused Pyrazoles from Cyclic Ketones: Calcium Carbide as the Carbon Source in Ring Expansion.
Yu, Yue; Chen, Yang; Huang, Wei; Wu, Wanqing; Jiang, Huanfeng; The Journal of organic chemistry 82 (2017) 9479–9486; doi:10.1021/acs.joc.7b01496

data_4033092
_publ_section_title
;
 One-Pot Synthesis of Spirocyclic or Fused Pyrazoles from Cyclic Ketones:
 Calcium Carbide as the Carbon Source in Ring Expansion.
;
_journal_issue                   18
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9479
_journal_page_last               9486
_journal_paper_doi               10.1021/acs.joc.7b01496
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C14 H16 N2'
_chemical_formula_sum            'C14 H16 N2'
_chemical_formula_weight         212.29
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-07-03
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.58762(7)
_cell_length_b                   8.03454(8)
_cell_length_c                   25.9706(3)
_cell_measurement_reflns_used    7125
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.7580
_cell_measurement_theta_min      5.7490
_cell_volume                     1165.92(2)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.991
_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   -116.00 -18.00   1.00    1.00    --  -41.89 -37.00  60.00   98
  2  \w    -70.00  31.00   1.00    1.00    --  -41.89  57.00-180.00  101
  3  \w      1.00  83.00   1.00    1.00    --   41.89 -99.00 120.00   82
  4  \w     35.00 134.00   1.00    2.85    --  107.79 -45.00 120.00   99
  5  \w     94.00 178.00   1.00    2.85    --  107.79 125.00 -90.00   84
  6  \w     94.00 178.00   1.00    2.85    --  107.79 125.00  60.00   84
  7  \w     35.00 122.00   1.00    2.85    --  107.79-125.00-120.00   87
  8  \w     94.00 178.00   1.00    2.85    --  107.79 125.00-150.00   84
  9  \w     32.00 116.00   1.00    2.85    --  107.79-114.00 -71.00   84
 10  \w     94.00 178.00   1.00    2.85    --  107.79 125.00-120.00   84
 11  \w   -114.00 -63.00   1.00    1.00    --  -41.89-142.00-144.00   51
 12  \w   -118.00  -9.00   1.00    1.00    --  -41.89 -77.00-150.00  109
 13  \w   -115.00 -14.00   1.00    1.00    --  -41.89 -57.00 -30.00  101
 14  \w     80.00 178.00   1.00    2.85    --  107.79  30.00 -90.00   98
 15  \w     55.00 178.00   1.00    2.85    --  107.79  15.00  60.00  123
 16  \w     75.00 156.00   1.00    2.85    --  107.79  77.00 120.00   81
 17  \w     80.00 178.00   1.00    2.85    --  107.79  30.00-180.00   98
;
_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      -0.0482939000
_diffrn_orient_matrix_UB_12      -0.1684108000
_diffrn_orient_matrix_UB_13      0.0264087000
_diffrn_orient_matrix_UB_21      0.0090509000
_diffrn_orient_matrix_UB_22      0.0855988000
_diffrn_orient_matrix_UB_23      0.0530427000
_diffrn_orient_matrix_UB_31      -0.2712664000
_diffrn_orient_matrix_UB_32      0.0328019000
_diffrn_orient_matrix_UB_33      -0.0029334000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0181
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            11117
_diffrn_reflns_theta_full        74.10
_diffrn_reflns_theta_max         74.10
_diffrn_reflns_theta_min         5.76
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.554
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70883
_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    1.209
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             456
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.147
_refine_diff_density_min         -0.135
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.1(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     145
_refine_ls_number_reflns         2320
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0305
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0387P)^2^+0.1225P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0741
_refine_ls_wR_factor_ref         0.0750
_reflns_number_gt                2247
_reflns_number_total             2320
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo7b01496_si_002.cif
_cod_data_source_block           1606242
_cod_database_code               4033092
_chemical_oxdiff_formula         'C20 H20 N6'
_chemical_oxdiff_usercomment     YY0516
_reflns_odcompleteness_completeness 99.84
_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
2.a Ternary CH refined with riding coordinates:
 C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C10(H10A,H10B), C12(H12A,H12B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C11(H11), C13(H13), C14(H14), C16(H16)
;
_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 1.414
_oxdiff_exptl_absorpt_empirical_full_min 0.666