Construction of Natural-Product-Like Cyclophane-Braced Peptide Macrocycles via sp<sup>3</sup> C-H Arylation.
Li, Bo; Li, Xinghua; Han, Boyang; Chen, Zhijie; Zhang, Xuekai; He, Gang; Chen, Gong; Journal of the American Chemical Society 141 (2019) 9401–9407; doi:10.1021/jacs.9b04221

data_4128708
_publ_section_title
;
 Construction of Natural-Product-Like Cyclophane-Braced Peptide
 Macrocycles via sp<sup>3</sup> C-H Arylation.
;
_journal_issue                   23
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9401
_journal_page_last               9407
_journal_paper_doi               10.1021/jacs.9b04221
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(C H2 Cl2), C30 H35 N5 O6'
_chemical_formula_sum            'C30.5 H36 Cl N5 O6'
_chemical_formula_weight         604.09
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.35500(10)
_cell_length_b                   12.84090(10)
_cell_length_c                   11.14110(10)
_cell_measurement_reflns_used    17020
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      79.5000
_cell_measurement_theta_min      4.0280
_cell_volume                     3055.08(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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_temperature      293(2)
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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      7.00  32.00   0.50    0.50    --    5.00  23.00  94.00   50
  2  \w    -46.00 -21.00   0.50    0.50    --    5.00 -23.00 -70.00   50
  3  \w    -45.00  -7.00   0.50    0.50    --  -50.90  23.00  94.00   76
  4  \w   -101.00 -76.00   0.50    0.50    --  -50.90 -23.00 -70.00   50
  5  \w   -137.00-112.00   0.50    1.00    -- -110.00 -23.00 -70.00   50
  6  \w   -108.00 -83.00   0.50    1.00    -- -110.00  23.00  94.00   50
  7  \w    -22.00  16.00   0.50    0.50    --    5.00  38.00-180.00   76
  8  \w   -139.00 -24.00   0.50    0.50    --  -50.90 -42.00 147.95  230
  9  \w    -52.00 -26.00   0.50    1.00    -- -110.00  38.00  60.00   52
 10  \w   -137.00 -31.00   0.50    1.00    -- -110.00  72.00-120.00  212
 11  \w   -167.00-142.00   0.50    1.00    -- -110.00 -40.00  51.70   50
 12  \w   -127.00 -90.00   0.50    1.00    -- -110.00 -40.00  51.70   74
 13  \w   -141.00 -93.00   0.50    1.00    -- -110.00 -36.00 138.42   96
 14  \w   -165.00-139.00   0.50    1.00    -- -110.00 -44.00 -71.24   52
 15  \w    -88.00 -62.00   0.50    1.00    -- -110.00  72.00-180.00   52
 16  \w   -141.00-115.00   0.50    1.00    -- -110.00  72.00  30.00   52
 17  \w    -99.00 -68.00   0.50    1.00    -- -110.00  72.00  30.00   62
 18  \w   -183.00 -83.00   0.50    1.00    -- -110.00 -51.00 -14.20  200
 19  \w   -156.00-109.00   0.50    1.00    -- -110.00 -46.00 129.00   94
 20  \w    -93.00 -67.00   0.50    1.00    -- -110.00  65.00-154.04   52
 21  \w    -63.00 -21.00   0.50    1.00    -- -110.00  65.00-154.04   84
 22  \w   -199.00-148.00   0.50    1.00    -- -110.00 -36.00 138.42  102
 23  \w   -196.00 -84.00   0.50    1.00    -- -110.00 -47.00-161.17  224
 24  \w   -141.00 -89.00   0.50    1.00    -- -110.00  72.00-180.00  104
 25  \w   -129.00 -90.00   0.50    1.00    -- -110.00  38.00  60.00   78
 26  \w   -138.00 -59.00   0.50    1.00    -- -110.00  57.00-120.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0224468000
_diffrn_orient_matrix_UB_12      0.1080450000
_diffrn_orient_matrix_UB_13      0.0419381000
_diffrn_orient_matrix_UB_21      0.0685225000
_diffrn_orient_matrix_UB_22      0.0366603000
_diffrn_orient_matrix_UB_23      0.0093555000
_diffrn_orient_matrix_UB_31      -0.0022547000
_diffrn_orient_matrix_UB_32      0.0371100000
_diffrn_orient_matrix_UB_33      -0.1314250000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0237
_diffrn_reflns_av_unetI/netI     0.0212
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            26818
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.991
_diffrn_reflns_theta_min         3.968
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.531
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48272
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.313
_exptl_crystal_description       prism
_exptl_crystal_F_000             1276
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.305
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 2624 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(10)
_refine_ls_extinction_coef       0.0030(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         6542
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.0413
_refine_ls_R_factor_gt           0.0404
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0736P)^2^+0.2856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1199
_refine_ls_wR_factor_ref         0.1209
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                6321
_reflns_number_total             6542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04221_si_004.cif
_cod_data_source_block           p20190114a
_cod_original_formula_sum        'C30.50 H36 Cl N5 O6'
_cod_database_code               4128708
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H35N5O6
_reflns_odcompleteness_completeness 98.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_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. Restrained distances
 C31-Cl1 = C31-Cl2
 1.72 with sigma of 0.01
 Cl1-Cl2
 2.82 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: Cl1(0.5) Cl2(0.5) C31(0.5) H31A(0.5) H31B(0.5)
5.a Ternary CH refined with riding coordinates:
 C4(H4A), C8(H8), C18(H18), C19(H19), C23(H23)
5.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C6(H6A,H6B), C11(H11A,
 H11B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B)
5.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N3(H3), N4(H4), C13(H13), C14(H14), C16(H16), C17(H17), C27(H27),
 C28(H28), C29(H29), C30(H30)
5.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              17308
_shelx_hkl_checksum              17295
_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 1.583
_oxdiff_exptl_absorpt_empirical_full_min 0.630