#------------------------------------------------------------------------------
#$Date: 2025-08-19 22:06:29 +0200 (Tue 19 de Aug de 2025) $
#$Revision: 301812 $
#$URL: svn://www.crystallography.net/cod/cif/4/02/53/4025300.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_4025300
loop_
_publ_author_name
'Perla Y. López-Camacho'
'Pedro Joseph-Nathan'
'Bárbara Gordillo-Román'
'Oscar R. Suárez-Castillo'
'Martha S. Morales-Ríos'
_publ_section_title
;
 Cascade [1,3]-Sigmatropic Rearrangements of Ketene O,O-Acetals: Kinetic
 and DFT Level Mechanistic Studies
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              1898
_journal_page_last               1910
_journal_paper_doi               10.1021/jo902520z
_journal_volume                  75
_journal_year                    2010
_chemical_formula_moiety         'C21 H18 N2 O4'
_chemical_formula_sum            'C21 H18 N2 O4'
_chemical_formula_weight         362.37
_chemical_name_systematic
;
1a-Benzyl-1-cyano-1a,6a-dihydro-1H-6-aza-cyclopropa
[alpha]indene-1,6-dicarboxylic acid dimethyl ester.
;
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 111.248(1)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.5591(4)
_cell_length_b                   19.9752(7)
_cell_length_c                   10.3978(4)
_cell_measurement_reflns_used    600
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.00
_cell_measurement_theta_min      1.99
_cell_volume                     1850.44(12)
_computing_cell_refinement       'Bruker Smart'
_computing_data_collection       'Bruker Smart'
_computing_data_reduction        'Bruker Smart'
_computing_molecular_graphics    'Ortep-3 for Windows (Farrugia, 1997)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXL-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Smart 6000 CCD'
_diffrn_measurement_method       'Phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_sigmaI/netI    0.0464
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            12483
_diffrn_reflns_theta_full        26.01
_diffrn_reflns_theta_max         26.01
_diffrn_reflns_theta_min         2.04
_diffrn_standards_decay_%        <1
_exptl_absorpt_coefficient_mu    0.091
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.025(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.931
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3633
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.931
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0428
_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)+(0.0655P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1196
_reflns_number_gt                2276
_reflns_number_total             3633
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo902520z_si_002_2.cif
_cod_data_source_block           3c
_cod_database_code               4025300
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
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
C2 C 1.0910(2) 0.94989(9) 0.2618(2) 0.0457(5) Uani 1 1 d . . .
C3 C 0.9320(2) 0.93388(9) 0.24016(18) 0.0404(4) Uani 1 1 d . . .
C3A C 0.8270(2) 0.90348(8) 0.09701(18) 0.0385(4) Uani 1 1 d . . .
C3B C 0.6845(2) 0.87377(9) 0.09929(18) 0.0391(4) Uani 1 1 d . . .
C4 C 0.6294(2) 0.80901(9) 0.07077(19) 0.0462(5) Uani 1 1 d . . .
H4 H 0.6888 0.7747 0.0505 0.080 Uiso 1 1 d R . .
C5 C 0.4881(2) 0.79514(11) 0.0720(2) 0.0555(5) Uani 1 1 d . . .
H5 H 0.4489 0.7505 0.0529 0.080 Uiso 1 1 d R . .
C6 C 0.4033(2) 0.84489(11) 0.1013(2) 0.0559(6) Uani 1 1 d . . .
H6 H 0.3058 0.8340 0.1022 0.080 Uiso 1 1 d R . .
C7 C 0.4551(2) 0.91013(10) 0.12852(19) 0.0483(5) Uani 1 1 d . . .
H7 H 0.3968 0.9446 0.1497 0.080 Uiso 1 1 d R . .
C7A C 0.5961(2) 0.92362(9) 0.12577(17) 0.0403(4) Uani 1 1 d . . .
C8A C 0.8147(2) 0.97555(9) 0.12735(19) 0.0416(5) Uani 1 1 d . . .
H8A H 0.8483 1.0086 0.0780 0.080 Uiso 1 1 d R . .
C9 C 0.6395(2) 1.04287(10) 0.19952(19) 0.0471(5) Uani 1 1 d . . .
C10 C 0.7397(3) 1.14881(10) 0.2865(3) 0.0736(7) Uani 1 1 d . . .
H10A H 0.8288 1.1749 0.3027 0.080 Uiso 1 1 d R . .
H10B H 0.7251 1.1419 0.3722 0.080 Uiso 1 1 d R . .
H10C H 0.6547 1.1722 0.2234 0.080 Uiso 1 1 d R . .
C11 C 0.8997(2) 0.91633(10) 0.3611(2) 0.0481(5) Uani 1 1 d . . .
C12 C 1.3368(3) 0.95381(17) 0.4243(3) 0.0941(10) Uani 1 1 d . . .
H12A H 1.3777 0.9318 0.3637 0.080 Uiso 1 1 d R . .
H12B H 1.3931 0.9412 0.5180 0.080 Uiso 1 1 d R . .
H12C H 1.3427 1.0014 0.4148 0.080 Uiso 1 1 d R . .
C13 C 0.8940(2) 0.87833(9) -0.00524(19) 0.0453(5) Uani 1 1 d . . .
H13A H 0.9630 0.9115 -0.0133 0.080 Uiso 1 1 d R . .
H13B H 0.8151 0.8743 -0.0939 0.080 Uiso 1 1 d R . .
C14 C 0.9754(2) 0.81185(9) 0.02895(19) 0.0417(4) Uani 1 1 d . . .
C15 C 1.0112(2) 0.77914(11) -0.0728(2) 0.0561(5) Uani 1 1 d . . .
H15 H 0.9795 0.7984 -0.1635 0.080 Uiso 1 1 d R . .
C16 C 1.0919(3) 0.71997(12) -0.0454(2) 0.0671(6) Uani 1 1 d . . .
H16 H 1.1166 0.6984 -0.1170 0.080 Uiso 1 1 d R . .
C17 C 1.1371(3) 0.69190(11) 0.0837(3) 0.0652(6) Uani 1 1 d . . .
H17 H 1.1929 0.6508 0.1027 0.080 Uiso 1 1 d R . .
C18 C 1.1010(3) 0.72299(11) 0.1846(2) 0.0654(6) Uani 1 1 d . . .
H18 H 1.1315 0.7034 0.2749 0.080 Uiso 1 1 d R . .
C19 C 1.0208(2) 0.78261(10) 0.1580(2) 0.0553(6) Uani 1 1 d . . .
H19 H 0.9957 0.8039 0.2296 0.080 Uiso 1 1 d R . .
N8 N 0.67319(17) 0.98535(7) 0.14350(16) 0.0427(4) Uani 1 1 d . . .
N11 N 0.8728(2) 0.90220(12) 0.4559(2) 0.0784(6) Uani 1 1 d . . .
O1 O 1.13076(15) 0.97370(8) 0.17438(15) 0.0630(4) Uani 1 1 d . . .
O2 O 1.18138(15) 0.93552(8) 0.38900(14) 0.0634(4) Uani 1 1 d . . .
O9 O 0.52419(17) 1.05243(7) 0.21797(15) 0.0627(4) Uani 1 1 d . . .
O10 O 0.75532(16) 1.08500(6) 0.22887(14) 0.0594(4) Uani 1 1 d . . .
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'
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
O1 C2 O2 124.75(18) . . ?
O1 C2 C3 123.75(17) . . ?
O2 C2 C3 111.49(16) . . ?
C11 C3 C2 116.69(16) . . ?
C11 C3 C8A 117.97(16) . . ?
C2 C3 C8A 114.87(15) . . ?
C11 C3 C3A 117.61(15) . . ?
C2 C3 C3A 119.29(15) . . ?
C8A C3 C3A 56.85(11) . . ?
C8A C3A C3B 103.81(14) . . ?
C8A C3A C13 123.83(15) . . ?
C3B C3A C13 120.01(16) . . ?
C8A C3A C3 60.10(12) . . ?
C3B C3A C3 114.09(14) . . ?
C13 C3A C3 120.17(15) . . ?
C4 C3B C7A 119.84(17) . . ?
C4 C3B C3A 130.11(17) . . ?
C7A C3B C3A 109.88(15) . . ?
C5 C4 C3B 118.72(18) . . ?
C4 C5 C6 120.65(19) . . ?
C5 C6 C7 121.69(19) . . ?
C7A C7 C6 117.20(18) . . ?
C7 C7A C3B 121.89(17) . . ?
C7 C7A N8 129.20(17) . . ?
C3B C7A N8 108.89(15) . . ?
N8 C8A C3A 107.87(15) . . ?
N8 C8A C3 116.17(14) . . ?
C3A C8A C3 63.05(12) . . ?
O9 C9 O10 126.63(19) . . ?
O9 C9 N8 124.66(19) . . ?
O10 C9 N8 108.71(16) . . ?
N11 C11 C3 179.3(2) . . ?
C3A C13 C14 116.02(15) . . ?
C19 C14 C15 117.66(18) . . ?
C19 C14 C13 123.53(16) . . ?
C15 C14 C13 118.78(17) . . ?
C16 C15 C14 121.3(2) . . ?
C17 C16 C15 120.3(2) . . ?
C18 C17 C16 119.2(2) . . ?
C17 C18 C19 120.8(2) . . ?
C14 C19 C18 120.81(19) . . ?
C9 N8 C7A 126.28(15) . . ?
C9 N8 C8A 122.51(16) . . ?
C7A N8 C8A 109.54(14) . . ?
C2 O2 C12 116.07(16) . . ?
C9 O10 C10 116.79(17) . . ?
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
C2 O1 1.204(2) . ?
C2 O2 1.323(2) . ?
C2 C3 1.488(3) . ?
C3 C11 1.442(3) . ?
C3 C8A 1.540(2) . ?
C3 C3A 1.584(3) . ?
C3A C8A 1.487(2) . ?
C3A C3B 1.494(2) . ?
C3A C13 1.512(2) . ?
C3B C4 1.387(3) . ?
C3B C7A 1.396(2) . ?
C4 C5 1.384(3) . ?
C5 C6 1.384(3) . ?
C6 C7 1.386(3) . ?
C7 C7A 1.385(2) . ?
C7A N8 1.414(2) . ?
C8A N8 1.435(2) . ?
C9 O9 1.201(2) . ?
C9 O10 1.335(2) . ?
C9 N8 1.378(2) . ?
C10 O10 1.439(2) . ?
C11 N11 1.141(2) . ?
C12 O2 1.442(3) . ?
C13 C14 1.515(2) . ?
C14 C19 1.381(3) . ?
C14 C15 1.387(3) . ?
C15 C16 1.384(3) . ?
C16 C17 1.372(3) . ?
C17 C18 1.366(3) . ?
C18 C19 1.389(3) . ?
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 PubChem 139091433
