Synthesis of Aza-Quaternary Centers via Pictet‒Spengler Reactions of Ketonitrones
Lynch-Colameta, Tessa; Greta, Sarah; Snyder, Scott A.; Chemical Science  (2021) –; doi:10.1039/D1SC00882J

data_1561051
_publ_section_title
;
 Synthesis of Aza-Quaternary Centers via Pictet--Spengler Reactions of
 Ketonitrones
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC00882J
_journal_year                    2021
_chemical_formula_moiety         'C22 H22 N2 O3, 0.15(H2 O)'
_chemical_formula_sum            'C22 H22.3 N2 O3.15'
_chemical_formula_weight         365.12
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-12-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-02-02 deposited with the CCDC.	2021-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.457(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.9936(14)
_cell_length_b                   10.3069(7)
_cell_length_c                   17.3090(11)
_cell_measurement_reflns_used    9992
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.44
_cell_measurement_theta_min      2.31
_cell_volume                     3694.4(4)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics
;
OLEX2: a complete structure solution, refinement and analysis program 
Dolomanov et al., 2009

Mercury: visualization and analysis of crystal structures
Macrae, et al., 2006

O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann.
J. Appl. Cryst. (2009). 42, 339-341;

C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
M. Towler and J. van de Streek, J. Appl. Cryst. (2006). 39, 453-457.
;
_computing_publication_material
;
 APEX3 v.2015.5-2 (Bruker AXS Inc., 2015)
 OLEX2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'XL-2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON 100'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            CMOS
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0519
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            96894
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.418
_diffrn_reflns_theta_min         2.207
_diffrn_source                   'micro-focus X-ray tube'
_diffrn_source_type              'INCOATEC ImuS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.088
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6670
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.1064 before and 0.0579 after correction. 
The Ratio of minimum to maximum transmission is 0.8948.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       block
_exptl_crystal_F_000             1548
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.304
_refine_diff_density_min         -0.373
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     504
_refine_ls_number_reflns         7298
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      8.967
_refine_ls_R_factor_all          0.0758
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0371P)^2^+2.2164P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0956
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5440
_reflns_number_total             7298
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00882j2.cif
_cod_data_source_block           0869_tessa_top
_cod_original_formula_sum        'C22 H22.30 N2 O3.15'
_cod_database_code               1561051
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.981
_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, All O(H,H) groups
2. Restrained distances
 N3-H3 = N1-H1
 0.88 with sigma of 0.02
3. Others
 Fixed Sof: O7(0.3) H7A(0.3) H7B(0.3)
4.a Free rotating group:
 O7(H7A,H7B)
4.b Ternary CH refined with riding coordinates:
 C18(H18), C20(H20), C40(H40), C42(H42)
4.c Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C19(H19A,H19B), C39(H39A,H39B), C41(H41A,H41B)
4.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C24(H24), C25(H25), C26(H26), C27(H27), C34(H34), C35(H35), C36(H36),
  C37(H37), C38(H38)
4.e Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C22(H22A,H22B,H22C), C32(H32A,H32B,H32C), C44(H44A,H44B,
 H44C)
;
_shelx_res_checksum              38419
_shelx_hkl_checksum              19193
_olex2_submission_special_instructions 'No special instructions were received'