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_4518106
_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 syn
_chemical_formula_moiety         'C31 H42 N4 O7'
_chemical_formula_sum            'C31 H42 N4 O7'
_chemical_formula_weight         582.70
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-04
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.02.24 svn.r3390 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5951(2)
_cell_length_b                   15.3645(3)
_cell_length_c                   18.9752(5)
_cell_measurement_reflns_used    14077
_cell_measurement_temperature    296.54(18)
_cell_measurement_theta_max      79.4510
_cell_measurement_theta_min      4.4560
_cell_volume                     3380.49(13)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296.54(18)
_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     37.00 119.00   0.50    2.00    --   51.98-151.00 -46.00  164
  2  \w     21.00  72.00   0.50    2.00    --   51.98-122.00 114.00  102
  3  \w    104.00 136.00   0.50    7.00    --  111.00-151.00 -46.00   64
  4  \w     57.00  82.00   0.50    7.00    --  111.00-122.00 114.00   50
  5  \w    100.00 125.00   0.50    7.00    --  111.00 151.00  -3.00   50
  6  \w     96.00 151.00   0.50    7.00    --  111.00 122.00-163.00  110
  7  \w     39.00  69.00   0.50    2.00    --   51.98  77.00   0.00   60
  8  \w     83.00 114.00   0.50    2.00    --   51.98  77.00   0.00   62
  9  \w     85.00 110.00   0.50    2.00    --   51.98  37.00-180.00   50
 10  \w    -10.00  21.00   0.50    2.00    --   51.98 -77.00  90.00   62
 11  \w    -15.00  42.00   0.50    2.00    --   51.98 -19.00 -60.00  114
 12  \w     27.00  72.00   0.50    2.00    --   51.98 -77.00  90.00   90
 13  \w     -6.00  51.00   0.50    2.00    --   51.98 -37.00  30.00  114
 14  \w      6.00  53.00   0.50    2.00    --   51.98 -37.00-180.00   94
 15  \w     88.00 113.00   0.50    7.00    --  111.00 -15.00-150.00   50
 16  \w    110.00 167.00   0.50    7.00    --  111.00  15.00 120.00  114
 17  \w     43.00  68.00   0.50    7.00    --  111.00 -15.00-150.00   50
 18  \w     58.00  88.00   0.50    7.00    --  111.00 178.00-120.00   60
 19  \w     43.00 111.00   0.50    7.00    --  111.00-111.00 120.00  136
 20  \w     49.00 110.00   0.50    7.00    --  111.00 -61.00 -60.00  122
 21  \w     58.00  84.00   0.50    7.00    --  111.00 -77.00 120.00   52
 22  \w     56.00 114.00   0.50    7.00    --  111.00 -45.00 -60.00  116
 23  \w     44.00  83.00   0.50    7.00    --  111.00 -30.00-120.00   78
 24  \w     91.00 122.00   0.50    7.00    --  111.00 -77.00 120.00   62
 25  \w     44.00  78.00   0.50    7.00    --  111.00 -94.00-120.00   68
 26  \w     48.00  87.00   0.50    7.00    --  111.00 -45.00-180.00   78
 27  \w     64.00 109.00   0.50    7.00    --  111.00 -94.00 -60.00   90
 28  \w    117.00 142.00   0.50    7.00    --  111.00 178.00-120.00   50
 29  \w    117.00 142.00   0.50    7.00    --  111.00  45.00 -90.00   50
 30  \w     52.00 114.00   0.50    7.00    --  111.00 -45.00-120.00  124
;
_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      0.0220890000
_diffrn_orient_matrix_UB_12      -0.0389682000
_diffrn_orient_matrix_UB_13      -0.0736490000
_diffrn_orient_matrix_UB_21      0.0148871000
_diffrn_orient_matrix_UB_22      -0.0908371000
_diffrn_orient_matrix_UB_23      0.0331651000
_diffrn_orient_matrix_UB_31      -0.1300432000
_diffrn_orient_matrix_UB_32      -0.0169698000
_diffrn_orient_matrix_UB_33      -0.0087507000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0852
_diffrn_reflns_av_unetI/netI     0.0553
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            25955
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.474
_diffrn_reflns_theta_min         3.702
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.667
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31601
_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 brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.145
_exptl_crystal_description       needle
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.002
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1895 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         6767
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0811
_refine_ls_R_factor_gt           0.0683
_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^)+(0.1525P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2023
_refine_ls_wR_factor_ref         0.2176
_reflns_Friedel_coverage         0.751
_reflns_Friedel_fraction_full    0.967
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                5317
_reflns_number_total             6767
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao0c03729_si_003.cif
_cod_data_source_block           nks_nrd-tr-tptd
_cod_depositor_comments
;
Adding full bibliography for 4518104--4518107.cif.

2025-09-07
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C1.97 H2.67 N0.25 O0.44'
_cod_original_formula_weight         37.00
_cod_original_formula_moiety         '0.06(C31 H42 N4 O7)'
_cod_original_formula_units_Z            63
_cod_database_code               4518106
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'C H N O '
_diffrn_oxdiff_ac3_digest_frames
;
01433cd7ff60f9cc606e500f6d8362dd3700031320e
;
_diffrn_oxdiff_ac3_digest_hkl
;
0148191c00b5ffc464cf6bf7b7e141abd1f2b6
;
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C00I(H00I), C00K(H00K), C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C00J(H00A,H00B), C00M(H00C,H00D), C00N(H00E,H00F), C00W(H00P,H00Q)
2.c Aromatic/amide H refined with riding coordinates:
 N004(H004), N008(H008), N009(H009), C00L(H00L), C00S(H00S), C00T(H00T),
 C00U(H00U), C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011), C012(H012)
2.d Idealised Me refined as rotating group:
 C00Q(H00G,H00H,H00J), C00V(H00M,H00N,H00O), C00X(H00V,H00W,H00X), C013(H01A,
 H01B,H01C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C)
;
_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 5.829
_oxdiff_exptl_absorpt_empirical_full_min 0.180