The Effect of Base and Nucleophile on the Nucleophilic Substitution of Methoxytropone Derivatives: An Easy Access to 4- and 5-Substituted Multifunctional Azulenes.
Kumar, Neha; Agrawal, Abhijeet R.; Choudhury, Aditya; Zade, Sanjio S.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00951

data_4038501
_publ_section_title
;
 The Effect of Base and Nucleophile on the Nucleophilic Substitution of
 Methoxytropone Derivatives: An Easy Access to 4- and 5-Substituted
 Multifunctional Azulenes.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00951
_journal_year                    2020
_chemical_formula_moiety         'C15 H13 N3'
_chemical_formula_sum            'C15 H13 N3'
_chemical_formula_weight         235.29
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.001(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0220(11)
_cell_length_b                   11.2016(17)
_cell_length_c                   15.789(2)
_cell_measurement_reflns_used    2412
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      65.9630
_cell_measurement_theta_min      4.7800
_cell_volume                     1226.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9580
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9999
_diffrn_measured_fraction_theta_max 0.9999
_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    -14.00 100.00   1.00    2.00    --   24.08  57.00  30.00  114
  2  \w    -14.00 100.00   1.00    2.00    --   24.08  57.00 -60.00  114
  3  \w      1.00  79.00   1.00    2.00    --   24.08 -99.00   0.00   78
  4  \w     -4.00 108.00   1.00    8.00    --   66.04 -94.00-180.00  112
  5  \w     19.00 146.00   1.00    8.00    --   66.04  45.00 -60.00  127
  6  \w    100.00 153.00   1.00    8.00    --   66.04  87.00 -54.00   53
  7  \w     29.00 143.00   1.00    8.00    --   66.04  61.00-120.00  114
  8  \w     57.00 150.00   1.00    8.00    --   66.04 178.00-180.00   93
  9  \w    100.00 151.00   1.00    8.00    --   66.04 111.00 150.00   51
 10  \w     21.00 113.00   1.00   16.00    --  108.00-104.00-180.00   92
 11  \w    101.00 178.00   1.00   16.00    --  108.00 104.00 -30.00   77
 12  \w    101.00 178.00   1.00   16.00    --  108.00 104.00-150.00   77
 13  \w     31.00 147.00   1.00   16.00    --  108.00 -54.00 150.00  116
 14  \w     99.00 178.00   1.00   16.00    --  108.00  87.00 -54.00   79
 15  \w     71.00 178.00   1.00   16.00    --  108.00  65.00  60.00  107
 16  \w     70.00 178.00   1.00   16.00    --  108.00  67.00-129.88  108
 17  \w     65.00 178.00   1.00   16.00    --  108.00  77.00-120.00  113
 18  \w     26.00 120.00   1.00   16.00    --  108.00-123.00  49.59   94
 19  \w     71.00 178.00   1.00   16.00    --  108.00  65.00 -60.00  107
 20  \w     21.00 113.00   1.00   16.00    --  108.00-104.00  60.00   92
 21  \w     69.00 178.00   1.00   16.00    --  108.00  54.00 -90.00  109
 22  \w    -19.00 109.00   1.00    2.00    --   24.08  77.00-120.00  128
 23  \w    -63.00 108.00   1.00    2.00    --   24.08 -19.00-120.00  171
 24  \w    -14.00 100.00   1.00    2.00    --   24.08  57.00 150.00  114
 25  \w     57.00 118.00   1.00    2.00    --   24.08 178.00 -90.00   61
 26  \w     29.00 143.00   1.00    8.00    --   66.04  61.00  30.00  114
 27  \w     29.00 143.00   1.00    8.00    --   66.04  61.00-180.00  114
 28  \w     29.00 143.00   1.00    8.00    --   66.04  61.00 120.00  114
 29  \w     23.00 151.00   1.00    8.00    --   66.04  77.00 -30.00  128
 30  \w     23.00  84.00   1.00    8.00    --   66.04  77.00  60.00   61
 31  \w    100.00 151.00   1.00    8.00    --   66.04 111.00  60.00   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0952684000
_diffrn_orient_matrix_UB_12      -0.1174820000
_diffrn_orient_matrix_UB_13      0.0352407000
_diffrn_orient_matrix_UB_21      0.0961556000
_diffrn_orient_matrix_UB_22      0.0656744000
_diffrn_orient_matrix_UB_23      0.0812779000
_diffrn_orient_matrix_UB_31      -0.1762613000
_diffrn_orient_matrix_UB_32      -0.0276191000
_diffrn_orient_matrix_UB_33      0.0438335000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0878
_diffrn_reflns_av_unetI/netI     0.0659
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8024
_diffrn_reflns_theta_full        66.3872
_diffrn_reflns_theta_max         66.39
_diffrn_reflns_theta_min         5.67
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.612
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76217
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.2740
_exptl_crystal_description       block
_exptl_crystal_F_000             497.4284
_refine_diff_density_max         0.5580
_refine_diff_density_min         -0.5326
_refine_diff_density_rms         0.1379
_refine_ls_d_res_high            0.8414
_refine_ls_d_res_low             7.7973
_refine_ls_goodness_of_fit_ref   1.1139
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    21
_refine_ls_number_parameters     165
_refine_ls_number_reflns         1822
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.1139
_refine_ls_R_factor_all          0.1379
_refine_ls_R_factor_gt           0.0821
_refine_ls_shift/su_max          0.0014
_refine_ls_shift/su_mean         0.0003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1705
_refine_ls_wR_factor_ref         0.1987
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              7
_reflns_limit_h_min              -8
_reflns_limit_k_max              13
_reflns_limit_k_min              0
_reflns_limit_l_max              18
_reflns_limit_l_min              -6
_reflns_number_gt                1199
_reflns_number_total             1822
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jo0c00951_si_002.cif
_cod_data_source_block           CNPRAZ_100K
_cod_depositor_comments
;

2025-09-07
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C1.714 H1.486 N0.343'
_cod_original_formula_weight         26.89
_cod_original_formula_moiety         '0.11(C15 H13 N3)'
_cod_original_formula_units_Z            35
_cod_original_sg_symbol_H-M      'P 21/n'
_cod_database_code               4038501
_chemical_oxdiff_formula         'C H N'
_reflns_odcompleteness_completeness 97.24
_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, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Rotating group:
 N001(H00a,H00b)
2.b Secondary CH2 refined with riding coordinates:
 C00G(H00g,H00h), C00H(H00i,H00j)
2.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00D(H00D), C00E(H00E), C00F(H00F)
2.d Idealised Me refined as rotating group:
 C00I(H00k,H00l,H00m)
;
_olex2_date_sample_data_collection 2019-09-04
_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 1.910
_oxdiff_exptl_absorpt_empirical_full_min 0.322