Intramolecular CH⋯π attraction mediated conformational polymorphism of constrained helical peptides.
Sun, Jinming; Tian, Zi-You; Liu, Jianbo; Wan, Chuan; Dai, Chuan; Liu, Zhihong; Xing, Yun; Wu, Yujie; Hou, Zhanfeng; Han, Wei; Yin, Feng; Ye, Yuxin; Li, Zigang; Chemical science 15 (2024) 14264–14272; doi:10.1039/d4sc02545h

data_1572784
_publ_section_title
;
 Intramolecular CH&#x22ef;&#x3c0; attraction mediated conformational
 polymorphism of constrained helical peptides.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              14264
_journal_page_last               14272
_journal_paper_doi               10.1039/d4sc02545h
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C30 H46 N6 O6 S, 4(H2 O)'
_chemical_formula_sum            'C30 H54 N6 O10 S'
_chemical_formula_weight         690.85
_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
_audit_creation_date             2023-02-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-09-01 deposited with the CCDC.	2024-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8076(2)
_cell_length_b                   16.1235(3)
_cell_length_c                   22.4399(4)
_cell_measurement_reflns_used    11373
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.1420
_cell_measurement_theta_min      3.3860
_cell_volume                     3548.49(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9992
_diffrn_measured_fraction_theta_max 0.9342
_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    122.00 174.00   0.50    1.93    --  105.63  87.00 -87.00  104
  2  \w     99.00 158.00   0.50    1.93    --  105.63  61.00-120.00  118
  3  \w     34.00  60.00   0.50    1.93    --  105.63 -61.00 -90.00   52
  4  \w     38.00  63.00   0.50    1.93    --  105.63 -61.00-120.00   50
  5  \w    -16.00  54.00   0.50    0.48    --   46.30 -48.00 -88.00  140
  6  \w     36.00  69.00   0.50    1.93    --  105.63 -61.00  30.00   66
  7  \w     41.00  71.00   0.50    1.93    --  105.63 -61.00  60.00   60
  8  \w     85.00 142.00   0.50    1.93    --  105.63  91.00 168.00  114
  9  \w    -22.00  26.00   0.50    0.48    --  -46.30  19.00 120.00   96
 10  \w    -17.00  13.00   0.50    0.48    --  -46.30  19.00-120.00   60
 11  \w    -13.00  26.00   0.50    0.48    --  -46.30  19.00-180.00   78
 12  \w    -60.00 -35.00   0.50    1.93    -- -104.00  61.00-150.00   50
 13  \w    -67.00 -35.00   0.50    1.93    -- -104.00  61.00-180.00   64
 14  \w    -62.00 -36.00   0.50    1.93    -- -104.00  61.00-120.00   52
 15  \w    -65.00 -35.00   0.50    1.93    -- -104.00  61.00 150.00   60
 16  \w   -112.00 -37.00   0.50    1.93    -- -104.00 125.00   0.00  150
 17  \w   -100.00 -38.00   0.50    0.48    --  -46.30 -37.00-180.00  124
 18  \w   -175.00-150.00   0.50    1.93    -- -104.00 -48.00 -88.00   50
 19  \w   -174.00 -82.00   0.50    1.93    -- -104.00 -77.00 120.00  184
 20  \w   -102.00 -77.00   0.50    1.93    -- -104.00  91.00 168.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0904318000
_diffrn_orient_matrix_UB_12      0.0321861000
_diffrn_orient_matrix_UB_13      0.0511389000
_diffrn_orient_matrix_UB_21      0.0236587000
_diffrn_orient_matrix_UB_22      -0.0814107000
_diffrn_orient_matrix_UB_23      0.0343814000
_diffrn_orient_matrix_UB_31      0.1262623000
_diffrn_orient_matrix_UB_32      0.0383755000
_diffrn_orient_matrix_UB_33      0.0301830000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0442
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            19530
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.169
_diffrn_reflns_theta_min         3.375
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.328
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71065
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.902
_refine_diff_density_min         -0.610
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 2635 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.032(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     450
_refine_ls_number_reflns         7110
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0551
_refine_ls_R_factor_gt           0.0522
_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^)+(0.0989P)^2^+0.9023P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1399
_refine_ls_wR_factor_ref         0.1419
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.908
_reflns_number_gt                6711
_reflns_number_total             7110
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02545h2.cif
_cod_data_source_block           aadi-bang-2_auto
_cod_database_code               1572784
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.750
_diffrn_oxdiff_digest_frames
;
01b562960755372977652ac7ade63ff126000299742
;
_diffrn_oxdiff_digest_hkl
;
012e7dffb316be84ae7a0eb55b664c13228b91
;
_olex2_refinement_description
;
1. Restrained distances
 O44-H44A = O44-H44B
 0.87 with sigma of 0.02
 O45-H45A = O45-H45B
 0.87 with sigma of 0.02
 O46-H46A = O46-H46B
 0.87 with sigma of 0.02
 H45A-H45B
 1.38 with sigma of 0.04
 H44A-H44B
 1.38 with sigma of 0.04
 H46A-H46B
 1.38 with sigma of 0.04
2.a Free rotating group:
 O47(H47A,H47B)
2.b Ternary CH refined with riding coordinates:
 C19(H19), C16(H16), C10(H10), C38(H38), C1(H1), C7(H7), C13(H13)
2.c Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C6(H6A,H6B), C39(H39A,H39B), C4(H4A,H4B), C3(H3A,H3B), C2(H2A,
 H2B)
2.d Aromatic/amide H refined with riding coordinates:
 N18(H18), N9(H9), N12(H12), N15(H15), N27(H27), C22(H22), C26(H26), C25(H25),
 C24(H24), C23(H23)
2.e X=CH2 refined with riding coordinates:
 N32(H32A,H32B)
2.f Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C40(H40A,H40B,H40C), C41(H41A,H41B,
 H41C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              37912
_shelx_hkl_checksum              17910
_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 1.611
_oxdiff_exptl_absorpt_empirical_full_min 0.427