A novel strategy for the functionalization and design of 4-methylene-4<i>H</i>-pyran merocyanines <i>via</i> enamination and 1,8-conjugate addition.
Obydennov, Dmitrii L.; Simbirtseva, Alena E.; Shirinkin, Alexander S.; Kornev, Mikhail Y.; Sosnovskikh, Vyacheslav Y.; Organic & biomolecular chemistry 21 (2023) 600–620; doi:10.1039/d2ob01862d

data_7159047
_publ_section_title
;
 A novel strategy for the functionalization and design of
 4-methylene-4<i>H</i>-pyran merocyanines <i>via</i> enamination and
 1,8-conjugate addition.
;
_journal_issue                   3
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              600
_journal_page_last               620
_journal_paper_doi               10.1039/d2ob01862d
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C13 H13 N3 O'
_chemical_formula_sum            'C13 H13 N3 O'
_chemical_formula_weight         227.26
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-08-10 deposited with the CCDC.	2022-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.260(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3597(8)
_cell_length_b                   18.0931(15)
_cell_length_c                   7.4440(8)
_cell_measurement_reflns_used    1963
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      26.4110
_cell_measurement_theta_min      4.0280
_cell_volume                     1253.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      295(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.5253
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.884
_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     33.00  67.00   1.00   30.00    --   21.45  25.00  60.00   34
  2  \w    -50.00  52.00   1.00   30.00    --   21.45 -25.00-103.00  102
  3  \w    -26.00  -1.00   1.00   30.00    --  -23.01  25.00  60.00   25
  4  \w    -73.00 -47.00   1.00   30.00    --  -23.01 -25.00-103.00   26
  5  \w     40.00  95.00   1.00   30.00    --   21.45 178.00-120.00   55
  6  \w    -91.00 -37.00   1.00   30.00    --  -23.01 -57.00-150.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0604768000
_diffrn_orient_matrix_UB_12      -0.0121611000
_diffrn_orient_matrix_UB_13      0.0417423000
_diffrn_orient_matrix_UB_21      0.0390521000
_diffrn_orient_matrix_UB_22      0.0049028000
_diffrn_orient_matrix_UB_23      0.0862844000
_diffrn_orient_matrix_UB_31      -0.0251487000
_diffrn_orient_matrix_UB_32      0.0369192000
_diffrn_orient_matrix_UB_33      0.0022818000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0464
_diffrn_reflns_av_unetI/netI     0.0500
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.884
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            7993
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.884
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.472
_diffrn_reflns_theta_min         3.868
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'greenish brown'
_exptl_crystal_colour_modifier   green
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_description       block
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.27
_refine_diff_density_max         0.272
_refine_diff_density_min         -0.196
_refine_diff_density_rms         0.051
_refine_ls_extinction_coef       0.004(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     174
_refine_ls_number_reflns         3371
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1391
_refine_ls_R_factor_gt           0.0694
_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^)+(0.1100P)^2^+0.0250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1681
_refine_ls_wR_factor_ref         0.2367
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1608
_reflns_number_total             3371
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01862d2.cif
_cod_data_source_block           exp_22
_cod_depositor_comments          'Adding full bibliography for 7159047.cif.'
_cod_database_code               7159047
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.962
_reflns_odcompleteness_completeness 98.23
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2.a Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C)
;
_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 1.379
_oxdiff_exptl_absorpt_empirical_full_min 0.818