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_4038502
_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         'C22 H13 N3'
_chemical_formula_sum            'C22 H13 N3'
_chemical_formula_weight         319.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.2830(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   23.9762(3)
_cell_length_b                   11.8933(2)
_cell_length_c                   22.7987(3)
_cell_measurement_reflns_used    26046
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      66.1600
_cell_measurement_theta_min      2.7310
_cell_volume                     6490.52(16)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 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 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -29.00 108.00   1.00    2.00    --   26.33  38.00-120.00  137
  2  \w    -12.00 102.00   1.00    2.00    --   26.33  57.00   0.00  114
  3  \w      1.00  81.00   1.00    2.00    --   26.33 -99.00  60.00   80
  4  \w     25.00  52.00   1.00    2.82    --  108.00 -21.00 -30.00   27
  5  \w     30.00 144.00   1.00    2.82    --   67.17  61.00-180.00  114
  6  \w     12.00 116.00   1.00    2.82    --   67.17-111.00 120.00  104
  7  \w    100.00 153.00   1.00    2.82    --   67.17 111.00 -30.00   53
  8  \w     57.00 150.00   1.00    2.82    --   67.17 178.00-150.00   93
  9  \w    100.00 153.00   1.00    2.82    --   67.17 111.00-180.00   53
 10  \w    100.00 153.00   1.00    2.82    --   67.17 111.00 120.00   53
 11  \w    100.00 153.00   1.00    2.82    --   67.17 111.00  30.00   53
 12  \w    100.00 153.00   1.00    2.82    --   67.17 111.00 150.00   53
 13  \w     21.00 113.00   1.00    2.82    --  108.00-104.00  30.00   92
 14  \w     21.00 113.00   1.00    2.82    --  108.00-104.00  90.00   92
 15  \w     28.00 158.00   1.00    2.82    --  108.00 -43.00  60.00  130
 16  \w     69.00 178.00   1.00    2.82    --  108.00  54.00 120.00  109
 17  \w    101.00 178.00   1.00    2.82    --  108.00 104.00 150.00   77
 18  \w     24.00 117.00   1.00    2.82    --  108.00-116.00 -90.09   93
 19  \w     21.00 113.00   1.00    2.82    --  108.00-104.00   0.00   92
 20  \w     21.00 113.00   1.00    2.82    --  108.00-104.00 -30.00   92
 21  \w    101.00 178.00   1.00    2.82    --  108.00 104.00  90.00   77
 22  \w     71.00 178.00   1.00    2.82    --  108.00  65.00-180.00  107
 23  \w     86.00 178.00   1.00    2.82    --  108.00 138.00  30.00   92
 24  \w     66.00 178.00   1.00    2.82    --  108.00  75.00-143.58  112
 25  \w     67.00 178.00   1.00    2.82    --  108.00  73.00 -66.22  111
 26  \w     69.00 178.00   1.00    2.82    --  108.00  69.00 155.72  109
 27  \w     28.00 158.00   1.00    2.82    --  108.00 -43.00 -60.00  130
 28  \w     66.00 178.00   1.00    2.82    --  108.00  74.00-150.06  112
 29  \w     25.00 178.00   1.00    2.82    --  108.00  21.00 -60.00  153
 30  \w     69.00 178.00   1.00    2.82    --  108.00  54.00-120.00  109
 31  \w     69.00 178.00   1.00    2.82    --  108.00  54.00 -30.00  109
 32  \w     21.00 113.00   1.00    2.82    --  108.00-104.00 120.00   92
 33  \w     25.00 174.00   1.00    2.82    --  108.00 -21.00 -30.00  149
 34  \w    130.00 174.00   1.00    2.82    --  108.00 -21.00 -30.00   44
;
_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      -0.0118587000
_diffrn_orient_matrix_UB_12      0.0092206000
_diffrn_orient_matrix_UB_13      0.0655154000
_diffrn_orient_matrix_UB_21      0.0494363000
_diffrn_orient_matrix_UB_22      -0.0792804000
_diffrn_orient_matrix_UB_23      0.0157143000
_diffrn_orient_matrix_UB_31      0.0394984000
_diffrn_orient_matrix_UB_32      0.1020340000
_diffrn_orient_matrix_UB_33      0.0062295000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            59031
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.286
_diffrn_reflns_theta_max         66.286
_diffrn_reflns_theta_min         3.884
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.618
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96260
_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    1.307
_exptl_crystal_description       block
_exptl_crystal_F_000             2656
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.145
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     901
_refine_ls_number_reflns         11323
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0569
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0387P)^2^+6.1313P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1351
_refine_ls_wR_factor_ref         0.1370
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10415
_reflns_number_total             11323
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00951_si_002.cif
_cod_data_source_block           npcnaz
_cod_database_code               4038502
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N'
_reflns_odcompleteness_completeness 97.76
_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 N(H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C019(H019), C01A(H01A), C01D(H01D), C01J(H01J), C01K(H01K), C01M(H01M),
 C01Q(H01Q), C01R(H01R), C01S(H01S), C01T(H01T), C01V(H01V), C01W(H01W),
 C01X(H01X), C01Y(H01Y), C01Z(H01Z), C020(H020), C021(H021), C022(H022),
 C023(H023), C024(H024), C025(H025), C026(H026), C027(H027), C028(H028),
 C029(H029), C02A(H02A), C02B(H02B), C02C(H02C), C02D(H02D), C02E(H02E),
 C02F(H02F), C02G(H02G), C02H(H02H), C02I(H02I), C02J(H02J), C02K(H02K),
 C02L(H02L), C02M(H02M), C02N(H02N), C02O(H02O), C02P(H02P), C02Q(H02Q),
 C02R(H02R), C02S(H02S)
2.b X=CH2 refined with riding coordinates:
 N001(H00A,H00B), N002(H00C,H00D), N003(H00E,H00F), N004(H00G,H00H)
;
_shelx_res_checksum              57713
_shelx_hkl_checksum              36764
_olex2_date_sample_data_collection 2019-12-10
_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 1.255
_oxdiff_exptl_absorpt_empirical_full_min 0.881