Synthesis of Functionalized Azacalix[1]arene[3]pyridine Macrocycles from Cu(II)-Mediated Direct Amination Reactions of Arene through High Valent Arylcopper(III) Intermediates.
Liu, Yang; Zhang, Qian; Guo, Qing-Hui; Wang, Mei-Xiang; The Journal of organic chemistry 81 (2016) 10404–10410; doi:10.1021/acs.joc.6b01448

data_4037093
_publ_section_title
;
 Synthesis of Functionalized Azacalix[1]arene[3]pyridine Macrocycles from
 Cu(II)-Mediated Direct Amination Reactions of Arene through High Valent
 Arylcopper(III) Intermediates.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10404
_journal_page_last               10410
_journal_paper_doi               10.1021/acs.joc.6b01448
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C32 H28 N8 O3 S'
_chemical_formula_sum            'C32 H28 N8 O3 S'
_chemical_formula_weight         604.68
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                103.785(3)
_cell_angle_beta                 96.266(3)
_cell_angle_gamma                98.736(3)
_cell_formula_units_Z            4
_cell_length_a                   14.185(3)
_cell_length_b                   15.666(4)
_cell_length_c                   16.155(4)
_cell_measurement_reflns_used    11284
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4841
_cell_measurement_theta_min      1.4694
_cell_volume                     3406.4(14)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 8.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 90.0000
	             XTD: 40.0976
	          2theta: -19.8341
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 8.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 0.0000
	             XTD: 40.0976
	          2theta: -19.8341
scan:
	Number of images: 330
	           Slice: -110.0000 - 55.0000
	     Image width: 0.5000
	        Exp time: 8.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 270.0000
	             XTD: 40.0976
	          2theta: -19.8341
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.0695
_diffrn_orient_matrix_UB_12      -0.0172
_diffrn_orient_matrix_UB_13      -0.0092
_diffrn_orient_matrix_UB_21      -0.0047
_diffrn_orient_matrix_UB_22      -0.0662
_diffrn_orient_matrix_UB_23      -0.0085
_diffrn_orient_matrix_UB_31      -0.0005
_diffrn_orient_matrix_UB_32      -0.0086
_diffrn_orient_matrix_UB_33      -0.0639
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0350
_diffrn_reflns_av_unetI/netI     0.0370
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            42424
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         1.628
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.138
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8724
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.179
_exptl_crystal_description       block
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.292
_exptl_crystal_size_mid          0.287
_exptl_crystal_size_min          0.193
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     801
_refine_ls_number_reflns         15521
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0683
_refine_ls_R_factor_gt           0.0610
_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^)+(0.0712P)^2^+1.7633P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1560
_refine_ls_wR_factor_ref         0.1622
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13937
_reflns_number_total             15521
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01448_si_006.cif
_cod_data_source_block           y_sq
_cod_original_cell_volume        3406.3(13)
_cod_database_code               4037093
_shelxl_version_number           2013-4
_diffrn_number_total             15541
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C15(H15), C16(H16),
 C17(H17), C21(H21), C22(H22), C23(H23), C28(H28), C29(H29), C30(H30), C31(H31),
  C4A(H4A), C5A(H5A), C6A(H6A), C9A(H9A), C10A(H10A), C11A(H11A), C15A(H15A),
 C16A(H16A), C17A(H17A), C21A(H21A), C22A(H22A), C23A(H23A), C28A(H28A),
 C29A(H29A), C30A(H30A), C31A(H31A)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C25(H25A,H25B,
 H25C), C7A(H7AA,H7AB,H7AC), C13A(H13D,H13E,H13F), C19A(H19D,H19E,H19F),
 C25A(H25D,H25E,H25F)
;
_shelx_res_checksum              77332
_shelx_hkl_checksum              993
_shelx_fab_checksum              20462
_olex2_submission_special_instructions 'No special instructions were received'