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#$Date: 2025-08-19 23:06:29 +0300 (Tue, 19 Aug 2025) $
#$Revision: 301812 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/02/45/4024577.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4024577
loop_
_publ_author_name
'Nugzar Ghavtadze'
'Roland Fröhlich'
'Ernst-Ulrich Würthwein'
_publ_section_title
;
Acid-Mediated Electrocyclic Domino Transformations of 5,5-Disubstituted
1-Amino-1-azapenta-1,4-dien-3-ones into Dihydrospiroindenepyrazole and
Dihydroindenodiazepine Derivatives
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              4584
_journal_page_last               4591
_journal_paper_doi               10.1021/jo900270e
_journal_volume                  74
_journal_year                    2009
_chemical_formula_sum            'C16 H17 F3 N2 O2'
_chemical_formula_weight         326.32
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                75.02(1)
_cell_angle_beta                 84.11(1)
_cell_angle_gamma                61.97(1)
_cell_formula_units_Z            2
_cell_length_a                   9.075(1)
_cell_length_b                   9.616(1)
_cell_length_c                   10.500(1)
_cell_measurement_reflns_used    2374
_cell_measurement_temperature    198(2)
_cell_measurement_theta_max      28.28
_cell_measurement_theta_min      0.41
_cell_volume                     781.1(1)
_computing_cell_refinement       'Collect (Nonius B.V., 1998)'
_computing_data_collection       'Collect (Nonius B.V., 1998)'
_computing_data_reduction        'Denzo-SMN (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'SCHAKAL (Keller, 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      198(2)
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'rotating anode Nonius FR591'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0797
_diffrn_reflns_av_sigmaI/netI    0.0842
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8144
_diffrn_reflns_theta_full        28.11
_diffrn_reflns_theta_max         28.11
_diffrn_reflns_theta_min         2.01
_exptl_absorpt_coefficient_mu    0.116
_exptl_absorpt_correction_T_max  0.9965
_exptl_absorpt_correction_T_min  0.9716
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SORTAV (Blessing, 1995 & 1997)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             340
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    riding
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3733
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.1272
_refine_ls_R_factor_gt           0.0651
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0093P)²+0.6911P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1188
_refine_ls_wR_factor_ref         0.1419
_reflns_number_gt                2136
_reflns_number_total             3733
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo900270e_si_002.cif
_cod_data_source_block           wue3779
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               4024577
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.8046(3) 0.1322(2) -0.45406(19) 0.0427(5) Uani 1 1 d . . .
C2 C 0.7826(4) -0.0003(3) -0.3746(3) 0.0446(8) Uani 1 1 d . . .
H2A H 0.8918 -0.0992 -0.3605 0.054 Uiso 1 1 calc R . .
H2B H 0.7073 -0.0196 -0.4215 0.054 Uiso 1 1 calc R . .
C3 C 0.7100(4) 0.0299(3) -0.2422(3) 0.0385(7) Uani 1 1 d . . .
H3A H 0.5970 0.1237 -0.2550 0.046 Uiso 1 1 calc R . .
H3B H 0.7003 -0.0664 -0.1884 0.046 Uiso 1 1 calc R . .
N4 N 0.8197(3) 0.0628(2) -0.1733(2) 0.0309(5) Uani 1 1 d . . .
C5 C 0.8476(4) 0.1965(3) -0.2574(3) 0.0354(6) Uani 1 1 d . . .
H5A H 0.9280 0.2120 -0.2130 0.042 Uiso 1 1 calc R . .
H5B H 0.7411 0.2984 -0.2716 0.042 Uiso 1 1 calc R . .
C6 C 0.9148(4) 0.1588(3) -0.3882(3) 0.0400(7) Uani 1 1 d . . .
H6A H 0.9311 0.2503 -0.4444 0.048 Uiso 1 1 calc R . .
H6B H 1.0248 0.0609 -0.3740 0.048 Uiso 1 1 calc R . .
N7 N 0.7822(3) 0.0878(2) -0.0490(2) 0.0302(5) Uani 1 1 d . . .
C8 C 0.7466(3) -0.0075(3) 0.0450(3) 0.0313(6) Uani 1 1 d . . .
C9 C 0.7515(4) -0.1669(3) 0.0485(3) 0.0478(8) Uani 1 1 d . . .
H9A H 0.8441 -0.2263 -0.0046 0.072 Uiso 1 1 calc R . .
H9B H 0.6461 -0.1470 0.0124 0.072 Uiso 1 1 calc R . .
H9C H 0.7675 -0.2312 0.1398 0.072 Uiso 1 1 calc R . .
C10 C 0.7046(3) 0.0492(3) 0.1685(3) 0.0334(6) Uani 1 1 d . . .
O11 O 0.6500(3) -0.0161(2) 0.2629(2) 0.0464(5) Uani 1 1 d . . .
C12 C 0.7345(3) 0.1880(3) 0.1736(3) 0.0305(6) Uani 1 1 d . . .
H12A H 0.8349 0.1883 0.1376 0.037 Uiso 1 1 calc R . .
C13 C 0.6297(3) 0.3108(3) 0.2251(3) 0.0293(6) Uani 1 1 d . . .
C14 C 0.6758(3) 0.4407(3) 0.2283(3) 0.0365(7) Uani 1 1 d . . .
F1 F 0.8261(2) 0.4146(2) 0.1796(2) 0.0679(6) Uani 1 1 d . . .
F2 F 0.5684(2) 0.58525(19) 0.15611(17) 0.0469(4) Uani 1 1 d . . .
F3 F 0.6735(3) 0.4621(2) 0.34890(18) 0.0642(6) Uani 1 1 d . . .
C15 C 0.4585(3) 0.3412(3) 0.2715(2) 0.0270(6) Uani 1 1 d . . .
C16 C 0.4189(4) 0.3263(3) 0.4037(3) 0.0380(7) Uani 1 1 d . . .
H16A H 0.5020 0.2945 0.4682 0.046 Uiso 1 1 calc R . .
C17 C 0.2572(4) 0.3579(4) 0.4415(3) 0.0456(8) Uani 1 1 d . . .
H17A H 0.2309 0.3447 0.5324 0.055 Uiso 1 1 calc R . .
C18 C 0.1347(4) 0.4079(3) 0.3490(3) 0.0412(7) Uani 1 1 d . . .
H18A H 0.0239 0.4316 0.3757 0.049 Uiso 1 1 calc R . .
C19 C 0.1732(3) 0.4238(3) 0.2172(3) 0.0397(7) Uani 1 1 d . . .
H19A H 0.0890 0.4575 0.1530 0.048 Uiso 1 1 calc R . .
C20 C 0.3343(3) 0.3907(3) 0.1784(3) 0.0340(6) Uani 1 1 d . . .
H20A H 0.3603 0.4019 0.0875 0.041 Uiso 1 1 calc R . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C6 O1 C2 109.5(2) . . ?
O1 C2 C3 112.1(2) . . ?
N4 C3 C2 109.4(2) . . ?
N7 N4 C5 109.19(19) . . ?
N7 N4 C3 119.8(2) . . ?
C5 N4 C3 110.4(2) . . ?
N4 C5 C6 110.1(2) . . ?
O1 C6 C5 111.5(2) . . ?
C8 N7 N4 123.0(2) . . ?
N7 C8 C10 112.6(2) . . ?
N7 C8 C9 129.9(3) . . ?
C10 C8 C9 117.4(2) . . ?
O11 C10 C8 121.3(2) . . ?
O11 C10 C12 121.4(3) . . ?
C8 C10 C12 117.2(2) . . ?
C13 C12 C10 124.1(2) . . ?
C12 C13 C15 125.5(2) . . ?
C12 C13 C14 119.3(2) . . ?
C15 C13 C14 115.0(2) . . ?
F3 C14 F1 107.1(2) . . ?
F3 C14 F2 105.3(2) . . ?
F1 C14 F2 105.4(2) . . ?
F3 C14 C13 113.1(2) . . ?
F1 C14 C13 113.7(2) . . ?
F2 C14 C13 111.5(2) . . ?
C16 C15 C20 119.2(2) . . ?
C16 C15 C13 122.0(2) . . ?
C20 C15 C13 118.7(2) . . ?
C15 C16 C17 119.7(3) . . ?
C18 C17 C16 120.7(3) . . ?
C17 C18 C19 119.8(3) . . ?
C18 C19 C20 120.0(3) . . ?
C19 C20 C15 120.4(3) . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 C6 1.420(3) . ?
O1 C2 1.420(3) . ?
C2 C3 1.514(4) . ?
C3 N4 1.475(3) . ?
N4 N7 1.368(3) . ?
N4 C5 1.473(3) . ?
C5 C6 1.506(4) . ?
N7 C8 1.290(3) . ?
C8 C10 1.480(4) . ?
C8 C9 1.503(4) . ?
C10 O11 1.221(3) . ?
C10 C12 1.496(4) . ?
C12 C13 1.327(3) . ?
C13 C15 1.492(3) . ?
C13 C14 1.501(4) . ?
C14 F3 1.331(3) . ?
C14 F1 1.337(3) . ?
C14 F2 1.338(3) . ?
C15 C16 1.385(4) . ?
C15 C20 1.391(4) . ?
C16 C17 1.388(4) . ?
C17 C18 1.374(4) . ?
C18 C19 1.379(4) . ?
C19 C20 1.383(4) . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6 O1 C2 C3 59.8(3) . . . . ?
O1 C2 C3 N4 -57.4(3) . . . . ?
C2 C3 N4 N7 -177.6(2) . . . . ?
C2 C3 N4 C5 54.3(3) . . . . ?
N7 N4 C5 C6 171.3(2) . . . . ?
C3 N4 C5 C6 -55.0(3) . . . . ?
C2 O1 C6 C5 -59.8(3) . . . . ?
N4 C5 C6 O1 58.0(3) . . . . ?
C5 N4 N7 C8 177.8(2) . . . . ?
C3 N4 N7 C8 49.2(3) . . . . ?
N4 N7 C8 C10 -177.9(2) . . . . ?
N4 N7 C8 C9 6.0(4) . . . . ?
N7 C8 C10 O11 171.8(2) . . . . ?
C9 C8 C10 O11 -11.6(4) . . . . ?
N7 C8 C10 C12 -9.2(3) . . . . ?
C9 C8 C10 C12 167.5(2) . . . . ?
O11 C10 C12 C13 -43.1(4) . . . . ?
C8 C10 C12 C13 137.9(3) . . . . ?
C10 C12 C13 C15 -7.5(4) . . . . ?
C10 C12 C13 C14 178.2(3) . . . . ?
C12 C13 C14 F3 -124.2(3) . . . . ?
C15 C13 C14 F3 60.9(3) . . . . ?
C12 C13 C14 F1 -1.7(4) . . . . ?
C15 C13 C14 F1 -176.6(2) . . . . ?
C12 C13 C14 F2 117.3(3) . . . . ?
C15 C13 C14 F2 -57.6(3) . . . . ?
C12 C13 C15 C16 111.7(3) . . . . ?
C14 C13 C15 C16 -73.7(3) . . . . ?
C12 C13 C15 C20 -70.2(3) . . . . ?
C14 C13 C15 C20 104.3(3) . . . . ?
C20 C15 C16 C17 1.2(4) . . . . ?
C13 C15 C16 C17 179.2(2) . . . . ?
C15 C16 C17 C18 -1.7(4) . . . . ?
C16 C17 C18 C19 1.4(4) . . . . ?
C17 C18 C19 C20 -0.6(4) . . . . ?
C18 C19 C20 C15 0.1(4) . . . . ?
C16 C15 C20 C19 -0.4(4) . . . . ?
C13 C15 C20 C19 -178.5(2) . . . . ?
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 ChemSpider 30658963
2 PubChem 44196689
