Instability of Amide Bond with Trifluoroacetic Acid (20%): Synthesis, Conformational Analysis, and Mechanistic Insights into Cleavable Amide Bond Comprising β-Troponylhydrazino Acid.
Dalabehera, Nihar Ranjan; Meher, Sagarika; Bhusana Palai, Bibhuti; Sharma, Nagendra K.; ACS omega 5 (2020) 26141–26152; doi:10.1021/acsomega.0c03729

data_4518104
_publ_section_title
;
 Instability of Amide Bond with Trifluoroacetic Acid (20%): Synthesis,
 Conformational Analysis, and Mechanistic Insights into Cleavable Amide
 Bond Comprising \b-Troponylhydrazino Acid.
;
_journal_issue                   40
_journal_name_full               'ACS omega'
_journal_page_first              26141
_journal_page_last               26152
_journal_paper_doi               10.1021/acsomega.0c03729
_journal_volume                  5
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C25 H33 N3 O5'
_chemical_formula_sum            'C25 H33 N3 O5'
_chemical_formula_weight         455.54
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-04-15
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_formula_units_Z            6
_cell_length_a                   13.8479(6)
_cell_length_b                   13.8479(6)
_cell_length_c                   22.9802(10)
_cell_measurement_reflns_used    4645
_cell_measurement_temperature    112.1(4)
_cell_measurement_theta_max      75.4360
_cell_measurement_theta_min      3.6850
_cell_volume                     3816.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      112.1(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_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      8.00  33.00   0.50   25.00    --    0.00  34.00 -80.00   50
  2  \w     45.00  70.00   0.50   25.00    --  102.08 -34.00 121.00   50
  3  \w    103.00 152.00   0.50   25.00    --  102.08  34.00 -80.00   98
  4  \w     -1.00  60.00   0.50   25.00    --    0.00  19.00   0.00  122
  5  \w    -36.00  -5.00   0.50   25.00    --    0.00 -57.00   0.00   62
  6  \w    -48.00   0.00   0.50   25.00    --    0.00 122.00  36.58   96
  7  \w    100.00 127.00   0.50   25.00    --  102.08  15.00  30.00   54
  8  \w     39.00 105.00   0.50   25.00    --  102.08 -45.00 150.00  132
  9  \w     87.00 112.00   0.50   25.00    --  102.08  66.00  23.76   50
 10  \w     76.00 112.00   0.50   25.00    --  102.08 -61.00 -60.00   72
 11  \w     91.00 116.00   0.50   25.00    --  102.08  61.00   0.00   50
 12  \w     34.00  93.00   0.50   25.00    --  102.08 -94.00 -90.00  118
 13  \w     80.00 106.00   0.50   25.00    --  102.08  77.00 -30.00   52
 14  \w     83.00 109.00   0.50   25.00    --  102.08  74.00  20.94   52
 15  \w    103.00 131.00   0.50   25.00    --  102.08  30.00  30.00   56
 16  \w    101.00 128.00   0.50   25.00    --  102.08  30.00   0.00   54
 17  \w     90.00 116.00   0.50   25.00    --  102.08  63.00  -7.10   52
 18  \w     80.00 105.00   0.50   25.00    --  102.08  77.00   0.00   50
 19  \w    102.00 128.00   0.50   25.00    --  102.08  45.00   0.00   52
 20  \w    115.00 141.00   0.50   25.00    --  102.08  15.00   0.00   52
 21  \w     91.00 117.00   0.50   25.00    --  102.08  60.00 -23.04   52
 22  \w     78.00 104.00   0.50   25.00    --  102.08 -45.00 -90.00   52
 23  \w     40.00  66.00   0.50   25.00    --  102.08 -45.00 -90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1173420000
_diffrn_orient_matrix_UB_12      -0.0618867000
_diffrn_orient_matrix_UB_13      0.0270866000
_diffrn_orient_matrix_UB_21      0.0128077000
_diffrn_orient_matrix_UB_22      -0.1030849000
_diffrn_orient_matrix_UB_23      0.0104324000
_diffrn_orient_matrix_UB_31      0.0503634000
_diffrn_orient_matrix_UB_32      0.0454037000
_diffrn_orient_matrix_UB_33      0.0604094000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1942
_diffrn_reflns_av_unetI/netI     0.1480
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            20076
_diffrn_reflns_theta_full        74.35
_diffrn_reflns_theta_max         74.35
_diffrn_reflns_theta_min         3.69
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.677
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34498
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light pink'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.0012
_exptl_crystal_size_mid          0.0012
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.427
_refine_diff_density_min         -0.568
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.3(5)
_refine_ls_extinction_coef       0.0044(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         4951
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.1417
_refine_ls_R_factor_gt           0.1121
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1940P)^2^+0.5190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2865
_refine_ls_wR_factor_ref         0.3197
_reflns_number_gt                3599
_reflns_number_total             4951
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ao0c03729_si_004.cif
_cod_data_source_block           nks_nrd_117
_cod_depositor_comments
'Adding full bibliography for 4518104--4518107.cif.'
_cod_database_code               4518104
_chemical_oxdiff_formula         'C150 H192 N12 O36 '
_reflns_odcompleteness_completeness 99.96
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3AA(H3AA)
2.b Secondary CH2 refined with riding coordinates:
 C5AA(H5AA,H5AB), C7AA(H7AA,H7AB), C4BA(H4BA,H4BB), C5BA(H5BA,H5BB)
2.c Aromatic/amide H refined with riding coordinates:
 N2AA(H2AA), N1AA(H1AA), C1AA(H1AB), C6AA(H6AA), C9AA(H9AA), C2BA(H2BA),
 C3BA(H3BA), C6BA(H6BA), C7BA(H7BA), C9BA(H9BA), C1CA(H1CA), C2CA(H2CA)
2.d Idealised Me refined as rotating group:
 C8BA(H8BA,H8BB,H8BC), C0CA(H0CA,H0CB,H0CC), C3CA(H3CA,H3CB,H3CC), C4CA(H4CA,
 H4CB,H4CC)
;
_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 2.597
_oxdiff_exptl_absorpt_empirical_full_min 0.140