Synthesis of trifluoromethylthiolated azacalix[1]arene[3]pyridines from the Cu(ii)-mediated direct trifluoromethylthiolation reaction of arenes via reactive arylcopper(iii) intermediates
Wang, Fei; Zhao, Liang; You, Jingsong; Wang, Mei-Xiang; Organic Chemistry Frontiers 3 (2016) 880–; doi:10.1039/C6QO00161K

data_1553460
_publ_section_title
;
 Synthesis of trifluoromethylthiolated azacalix[1]arene[3]pyridines from
 the Cu(ii)-mediated direct trifluoromethylthiolation reaction of arenes
 via reactive arylcopper(iii) intermediates
;
_journal_issue                   7
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              880
_journal_paper_doi               10.1039/C6QO00161K
_journal_volume                  3
_journal_year                    2016
_chemical_formula_moiety         'C26 H24 F3 N7 S, C H2 Cl2'
_chemical_formula_sum            'C27 H26 Cl2 F3 N7 S'
_chemical_formula_weight         608.51
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-12-02
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-04-15 deposited with the CCDC.
2016-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.558(3)
_cell_length_b                   17.307(4)
_cell_length_c                   19.571(4)
_cell_measurement_reflns_used    15440
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4600
_cell_measurement_theta_min      1.1766
_cell_volume                     5608(2)
_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., 2013)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2013)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2013)'
_computing_structure_solution
;
 'XS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 7.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 270.0000
	             XTD: 45.1241
	          2theta: -19.7988
scan:
	Number of images: 300
	           Slice: -80.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 7.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 90.0000
	             XTD: 45.1241
	          2theta: -19.7988
;
_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      0.0448
_diffrn_orient_matrix_UB_12      -0.0074
_diffrn_orient_matrix_UB_13      0.0398
_diffrn_orient_matrix_UB_21      0.0017
_diffrn_orient_matrix_UB_22      0.0571
_diffrn_orient_matrix_UB_23      0.0087
_diffrn_orient_matrix_UB_31      -0.0342
_diffrn_orient_matrix_UB_32      -0.0047
_diffrn_orient_matrix_UB_33      0.0377
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0483
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            37998
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.459
_diffrn_reflns_theta_min         1.995
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.358
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7445
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.441
_exptl_crystal_description       block
_exptl_crystal_F_000             2512
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.44
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.820
_refine_diff_density_min         -0.874
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.243
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     405
_refine_ls_number_reflns         6385
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.248
_refine_ls_R_factor_all          0.0947
_refine_ls_R_factor_gt           0.0895
_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^)+(0.0904P)^2^+9.5479P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2241
_refine_ls_wR_factor_ref         0.2349
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6224
_reflns_number_total             6385
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6qo00161k2.cif
_cod_data_source_block           sa4447
_cod_original_cell_volume        5608.3(19)
_cod_database_code               1553460
_shelxl_version_number           2013-4
_diffrn_number_total             7032
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F2-C1 = F2A-C1 = F3-C1 = F3A-C1 = F1-C1 = F1A-C1
 1.34 with sigma of 0.01
 Cl2-C27 = Cl2A-C27
 1.74 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F2A \\sim F1A \\sim F3A: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.04
Cl2 \\sim Cl2A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(F1A) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F3)
\\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F2) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(Cl2) \\sim Ueq, Uanis(Cl2A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(F2A)=1-FVAR(1)
 Sof(F2)=FVAR(1)
 Sof(F3A)=1-FVAR(2)
 Sof(F3)=FVAR(2)
 Sof(F1A)=1-FVAR(3)
 Sof(F1)=FVAR(3)
 Sof(H27C)=Sof(H27D)=Sof(Cl2A)=1-FVAR(4)
 Sof(H27A)=Sof(H27B)=Sof(Cl2)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C27(H27C,H27D)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C17(H17), C18(H18),
 C19(H19), C22(H22), C23(H23), C24(H24)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C14(H14A,H14B,H14C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              86388
_shelx_hkl_checksum              45542
_olex2_submission_special_instructions 'No special instructions were received'