Deactivation of Secondary Amine Catalysts via Aldol Reaction-Amine Catalysis under Solvent-Free Conditions.
Schnitzer, Tobias; Wennemers, Helma; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00665

data_4038329
_publ_section_title
;
 Deactivation of Secondary Amine Catalysts via Aldol Reaction-Amine
 Catalysis under Solvent-Free Conditions.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00665
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H15 N O3'
_chemical_formula_sum            'C12 H15 N O3'
_chemical_formula_weight         221.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.47770(10)
_cell_length_b                   8.3194(2)
_cell_length_c                   25.6879(5)
_cell_measurement_reflns_used    5578
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.3380
_cell_measurement_theta_min      5.5760
_cell_volume                     1170.63(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_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      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   -116.00 -78.00   0.50    0.10    --  -49.37 -77.00 -30.00   76
  2  \w    -65.00  22.00   0.50    0.10    --  -49.37  57.00  90.00  174
  3  \w    -26.00  49.00   0.50    0.10    --   49.37 -38.00 150.00  150
  4  \w    -83.00   6.00   0.50    0.30    --  -70.00  38.00-150.00  178
  5  \w     94.00 123.00   0.50    0.30    --  110.00 -19.00  30.00   58
  6  \w     38.00  84.00   0.50    0.30    --  110.00 -57.00 -60.00   92
  7  \w     94.00 123.00   0.50    0.30    --  110.00 -19.00 -30.00   58
  8  \w     94.00 123.00   0.50    0.30    --  110.00 -19.00   0.00   58
  9  \w     94.00 123.00   0.50    0.30    --  110.00 -19.00-120.00   58
 10  \w     38.00  84.00   0.50    0.30    --  110.00 -57.00-180.00   92
 11  \w     40.00 110.00   0.50    0.30    --  110.00 -99.00 150.00  140
 12  \w     40.00 110.00   0.50    0.30    --  110.00 -99.00-150.00  140
 13  \w     94.00 123.00   0.50    0.30    --  110.00 -19.00-150.00   58
 14  \w     38.00  84.00   0.50    0.30    --  110.00 -57.00 120.00   92
 15  \w     34.00 117.00   0.50    0.10    --   49.37  57.00-120.00  166
 16  \w     37.00 125.00   0.50    0.10    --   49.37  34.00 135.00  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0679473000
_diffrn_orient_matrix_UB_12      0.1696931000
_diffrn_orient_matrix_UB_13      0.0190942000
_diffrn_orient_matrix_UB_21      0.1034650000
_diffrn_orient_matrix_UB_22      0.0402560000
_diffrn_orient_matrix_UB_23      -0.0542324000
_diffrn_orient_matrix_UB_31      -0.2525395000
_diffrn_orient_matrix_UB_32      0.0622519000
_diffrn_orient_matrix_UB_33      -0.0170556000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            6939
_diffrn_reflns_point_group_measured_fraction_full 0.945
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        66.529
_diffrn_reflns_theta_max         66.529
_diffrn_reflns_theta_min         3.441
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.743
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.758
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       block
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.146
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.121
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 646 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     146
_refine_ls_number_reflns         1953
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0352
_refine_ls_R_factor_gt           0.0335
_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^)+(0.0447P)^2^+0.1222P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0834
_refine_ls_wR_factor_ref         0.0844
_reflns_Friedel_coverage         0.571
_reflns_Friedel_fraction_full    0.863
_reflns_Friedel_fraction_max     0.863
_reflns_number_gt                1846
_reflns_number_total             1953
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00665_si_002.cif
_cod_data_source_block           w360817_1_1
_cod_database_code               4038329
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C12H15NO3
_reflns_odcompleteness_completeness 99.92
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              13515
_shelx_hkl_checksum              41080
_olex2_date_sample_data_collection 2017-10-02
_olex2_date_sample_submission    2017-10-02
_olex2_submission_original_sample_id w360817_1_1
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.294
_oxdiff_exptl_absorpt_empirical_full_min 0.801