Aza-Knoevenagel-type condensation of secondary amides: direct access to N-monosubstituted β,β-difunctionalized enamines
Huang, Pei-Qiang; Ou, Wei; Ye, Jian-Liang; Organic Chemistry Frontiers 2 (2015) 1094–; doi:10.1039/C5QO00191A

data_1553161
_publ_section_title
;
 Aza-Knoevenagel-type condensation of secondary amides: direct access to
 N-monosubstituted \b,\b-difunctionalized enamines
;
_journal_issue                   9
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1094
_journal_paper_doi               10.1039/C5QO00191A
_journal_volume                  2
_journal_year                    2015
_chemical_formula_moiety         'C15 H18 N2 O2'
_chemical_formula_sum            'C15 H18 N2 O2'
_chemical_formula_weight         258.32
_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             2015-06-15
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Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
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_audit_update_record
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2015-06-14 deposited with the CCDC.
2015-07-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.5295(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   18.06936(19)
_cell_length_b                   17.8020(2)
_cell_length_c                   18.2203(2)
_cell_measurement_reflns_used    8561
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      60.2130
_cell_measurement_theta_min      4.2340
_cell_volume                     5860.69(11)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_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
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Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      173.00(14)
_diffrn_detector_area_resol_mean 16.1903
_diffrn_measured_fraction_theta_full 0.9958
_diffrn_measured_fraction_theta_max 0.9958
_diffrn_measurement_details
;
  1 omega    2.00  104.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       32.3584   77.0000  -90.0000 102

  2 omega   40.00  112.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       32.3584  178.0000  -90.0000 72

  3 omega   49.00   94.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       32.3584   38.0000   30.0000 45

  4 omega -130.00 -103.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      -75.0000  -92.0000    0.0000 27

  5 omega  113.00  139.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000   50.0000   60.0000 26

  6 omega   56.00   82.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000 -112.0000 -120.0000 26

  7 omega   34.00   90.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000 -112.0000  -30.0000 56

  8 omega   18.00   51.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -38.0000  -30.0000 33

  9 omega   19.00   65.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000 -112.0000 -180.0000 46

 10 omega   29.00  115.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -92.0000 -180.0000 86

 11 omega   71.00   98.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -92.0000  150.0000 27

 12 omega   18.00   68.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -38.0000    0.0000 50

 13 omega   60.00  163.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000   38.0000  -60.0000 103

 14 omega   65.00  138.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000   64.0000 -150.0000 73

 15 omega   67.00   92.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000 -117.0000  168.0000 25

 16 omega   25.00   53.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000 -117.0000  168.0000 28

 17 omega  113.00  158.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  112.0000   90.0000 45

 18 omega   21.00   49.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -50.0000 -150.0000 28

 19 omega   53.00   79.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -50.0000 -150.0000 26

 20 omega  138.00  163.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  112.0000    0.0000 25

 21 omega   35.00   66.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  -25.0000    0.0000 31

 22 omega   50.00  100.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -       90.5000  178.0000 -180.0000 50
;
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0094170000
_diffrn_orient_matrix_UB_12      0.0724616000
_diffrn_orient_matrix_UB_13      0.0453974000
_diffrn_orient_matrix_UB_21      0.0089599000
_diffrn_orient_matrix_UB_22      0.0455427000
_diffrn_orient_matrix_UB_23      -0.0712663000
_diffrn_orient_matrix_UB_31      -0.0842450000
_diffrn_orient_matrix_UB_32      0.0128998000
_diffrn_orient_matrix_UB_33      -0.0033224000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0214
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            24519
_diffrn_reflns_theta_full        60.12
_diffrn_reflns_theta_max         60.12
_diffrn_reflns_theta_min         3.43
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.632
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89330
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.1710
_exptl_crystal_F_000             2214.9335
_refine_diff_density_max         0.6430
_refine_diff_density_min         -0.4965
_refine_diff_density_rms         0.0441
_refine_ls_d_res_high            0.8891
_refine_ls_d_res_low             12.8891
_refine_ls_goodness_of_fit_ref   1.0616
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    116
_refine_ls_number_parameters     696
_refine_ls_number_reflns         8700
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0616
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0498
_refine_ls_shift/su_max          0.0002
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0681P)^2^+2.4663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1319
_refine_ls_wR_factor_ref         0.1382
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -20
_reflns_limit_k_max              19
_reflns_limit_k_min              0
_reflns_limit_l_max              20
_reflns_limit_l_min              -13
_reflns_number_gt                7578
_reflns_number_total             8700
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            c5qo00191a2.cif
_cod_data_source_block           exp_9816
_cod_depositor_comments
;

2022-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        5860.69(12)
_cod_original_sg_symbol_Hall     '-P 2ybc (x-z,y,z)'
_cod_original_formula_moiety     '4(C15 H18 N2 O2)'
_cod_original_formula_sum        'C60 H72 N8 O8'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     1033.29
_cod_database_code               1553161
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     59.94
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C28(H28), C43(H43), C44(H44), C50(H50)
2.b Secondary CH2 refined with riding coordinates:
 C35(H35a,H35b), C37(H37a,H37b), C47(H47a,H47b), C52(H52a,H52b)
2.c Aromatic/amide H refined with riding coordinates:
 N9(H9), N10(H10), N11(H11), N12(H12), C1(H1), C13(H13), C19(H19), C21(H21),
 C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C29(H29), C33(H33),
  C34(H34), C38(H38), C39(H39), C40(H40), C41(H41), C46(H46), C49(H49), C51(H51)
2.d Idealised Me refined as rotating group:
 C5(H5a,H5b,H5c), C6(H6a,H6b,H6c), C7(H7a,H7b,H7c), C1A(H1Aa,H1Ab,H1Ac),
 C1B(H1Ba,H1Bb,H1Bc), C1C(H1Ca,H1Cb,H1Cc), C1D(H1Da,H1Db,H1Dc), C1E(H1Ea,H1Eb,
 H1Ec), C1F(H1Fa,H1Fb,H1Fc), C1G(H1Ga,H1Gb,H1Gc), C1H(H1Ha,H1Hb,H1Hc), C1I(H1Ia,
 H1Ib,H1Ic)
;
_olex2_submission_special_instructions 'No special instructions were received'