#------------------------------------------------------------------------------
#$Date: 2021-01-01 02:17:07 +0200 (Fri, 01 Jan 2021) $
#$Revision: 260316 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/13/54/4135475.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4135475
loop_
_publ_author_name
'Ito, Tsubasa'
'Harada, Shingo'
'Homma, Haruka'
'Takenaka, Hiroki'
'Hirose, Shumpei'
'Nemoto, Tetsuhiro'
_publ_section_title
;
 Asymmetric Intramolecular Dearomatization of Nonactivated Arenes with
 Ynamides for Rapid Assembly of Fused Ring System under Silver Catalysis
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c10682
_journal_year                    2020
_chemical_absolute_configuration 'CHOOSE rm ad rmad syn or unk'
_chemical_formula_moiety         'C21 H15 Br2 N O3 S'
_chemical_formula_sum            'C21 H15 Br2 N O3 S'
_chemical_formula_weight         521.22
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90.0000
_cell_angle_beta                 90.0000
_cell_angle_gamma                90.0000
_cell_formula_units_Z            4
_cell_length_a                   6.75499(15)
_cell_length_b                   10.0036(2)
_cell_length_c                   28.9000(7)
_cell_measurement_reflns_used    17170
_cell_measurement_temperature    93
_cell_measurement_theta_max      68.22
_cell_measurement_theta_min      3.06
_cell_volume                     1952.89(8)
_computing_cell_refinement       'RAPID AUTO'
_computing_data_collection       'RAPID AUTO (Rigaku, ????)'
_computing_data_reduction        'RAPID AUTO'
_computing_molecular_graphics    'CrystalStructure 4.3'
_computing_publication_material  'CrystalStructure 4.3 (Rigaku, 2019)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 2008)'
_computing_structure_solution    'SIR2014 (Burla, et al., 2014)'
_diffrn_ambient_temperature      93
_diffrn_detector_area_resol_mean 10.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       ω
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 0.000
_diffrn_reflns_Laue_measured_fraction_max 0.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            22758
_diffrn_reflns_point_group_measured_fraction_full 0.000
_diffrn_reflns_point_group_measured_fraction_max 0.000
_diffrn_reflns_theta_full        68.230
_diffrn_reflns_theta_max         68.230
_diffrn_reflns_theta_min         3.058
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.466
_exptl_absorpt_correction_T_max  0.524
_exptl_absorpt_correction_T_min  0.381
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.773
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1032.00
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.75
_refine_diff_density_min         -0.24
_refine_ls_abs_structure_details
'Flack, H. D. (1983), Acta Cryst. A39, 876-881.  1483 Friedel Pairs'
_refine_ls_abs_structure_Flack   -0.014(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_parameters     253
_refine_ls_number_reflns         3571
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0246
_refine_ls_R_factor_gt           0.0237
_refine_ls_shift/su_max          0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w = 1/[σ²(Fo²)+(0.0281P)²+0.6204P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0575
_refine_ls_wR_factor_ref         0.0579
_reflns_number_gt                3487
_reflns_number_total             3571
_reflns_threshold_expression     F²>2.0σ(F²)
_cod_data_source_file            ja0c10682_si_002.cif
_cod_data_source_block           20200304ito
_cod_database_code               4135475
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 +X,+Y,+Z
2 1/2-X,-Y,1/2+Z
3 1/2+X,1/2-Y,-Z
4 -X,1/2+Y,1/2-Z
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.37893(5) 0.07765(3) 0.109144(10) 0.02847(9) Uani 1 1 d . . .
Br2 Br 1.15775(5) -0.20483(3) 0.463424(11) 0.03111(9) Uani 1 1 d . . .
S1 S 0.90752(9) 0.39937(6) 0.25484(2) 0.01693(14) Uani 1 1 d . . .
O1 O 1.0915(3) 0.42967(18) 0.23237(6) 0.0202(4) Uani 1 1 d . . .
O2 O 0.6589(3) 0.26636(19) 0.32884(6) 0.0235(4) Uani 1 1 d . . .
O4 O 0.7883(3) 0.50444(19) 0.27324(6) 0.0211(4) Uani 1 1 d . . .
N22 N 0.9708(3) 0.2983(2) 0.29821(7) 0.0175(5) Uani 1 1 d . . .
C1 C 0.4450(4) 0.2592(3) 0.18350(9) 0.0195(6) Uani 1 1 d . . .
H1 H 0.3067 0.2754 0.1814 0.023 Uiso 1 1 calc R . .
C2 C 1.2936(4) 0.0680(3) 0.35735(9) 0.0185(6) Uani 1 1 d . . .
H2 H 1.4121 0.0695 0.3397 0.022 Uiso 1 1 calc R . .
C3 C 1.2891(4) -0.0239(3) 0.39597(9) 0.0191(6) Uani 1 1 d . . .
H3 H 1.4126 -0.0472 0.4094 0.023 Uiso 1 1 calc R . .
C5 C 0.8374(4) 0.2489(3) 0.33043(9) 0.0195(6) Uani 1 1 d . . .
C6 C 1.1512(4) 0.1505(2) 0.34376(8) 0.0160(5) Uani 1 1 d . . .
C7 C 0.9698(4) 0.2615(3) 0.41031(9) 0.0211(6) Uani 1 1 d . . .
C8 C 0.7601(4) 0.3021(3) 0.21754(9) 0.0172(5) Uani 1 1 d . . .
C9 C 1.1260(4) -0.0794(3) 0.41459(9) 0.0214(6) Uani 1 1 d . . .
C10 C 1.1733(4) 0.2456(3) 0.30338(9) 0.0169(5) Uani 1 1 d . . .
H10A H 1.2687 0.3178 0.3105 0.020 Uiso 1 1 calc R . .
H10B H 1.2168 0.1980 0.2751 0.020 Uiso 1 1 calc R . .
C11 C 0.7363(4) 0.1393(3) 0.15704(10) 0.0221(6) Uani 1 1 d . . .
H11 H 0.7952 0.0744 0.1374 0.027 Uiso 1 1 calc R . .
C12 C 0.8065(5) 0.2749(3) 0.43906(10) 0.0301(7) Uani 1 1 d . . .
H12 H 0.6899 0.2247 0.4331 0.036 Uiso 1 1 calc R . .
C13 C 1.1411(5) 0.3327(3) 0.41976(9) 0.0256(6) Uani 1 1 d . . .
H13 H 1.2542 0.3225 0.4005 0.031 Uiso 1 1 calc R . .
C14 C 0.5346(4) 0.1660(3) 0.15439(10) 0.0198(6) Uani 1 1 d . . .
C15 C 0.9252(4) -0.0644(3) 0.39847(9) 0.0219(6) Uani 1 1 d . . .
H15 H 0.8372 -0.1363 0.4045 0.026 Uiso 1 1 calc R . .
C16 C 1.1473(5) 0.4196(3) 0.45760(10) 0.0342(7) Uani 1 1 d . . .
H16 H 1.2642 0.4691 0.4639 0.041 Uiso 1 1 calc R . .
C17 C 0.5570(4) 0.3271(3) 0.21515(9) 0.0179(6) Uani 1 1 d . . .
H17 H 0.4974 0.3904 0.2353 0.022 Uiso 1 1 calc R . .
C18 C 0.9543(4) 0.1715(3) 0.36694(9) 0.0173(6) Uani 1 1 d . . .
C19 C 0.8513(4) 0.0397(3) 0.37609(9) 0.0246(6) Uani 1 1 d . . .
H19 H 0.7202 0.0308 0.3646 0.030 Uiso 1 1 calc R . .
C20 C 0.9849(6) 0.4334(3) 0.48552(11) 0.0405(9) Uani 1 1 d . . .
H20 H 0.9897 0.4926 0.5112 0.049 Uiso 1 1 calc R . .
C21 C 0.8131(6) 0.3616(3) 0.47662(11) 0.0395(9) Uani 1 1 d . . .
H21 H 0.7007 0.3717 0.4961 0.047 Uiso 1 1 calc R . .
C23 C 0.8489(4) 0.2082(3) 0.18862(9) 0.0198(6) Uani 1 1 d . . .
H23 H 0.9872 0.1919 0.1907 0.024 Uiso 1 1 calc R . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
H H 0.0000 0.0000
;
International Tables for Crystallography
(Vol. C, Table 6.1.1.4)
;
Br Br -0.6763 1.2805
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
O O 0.0492 0.0322
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
N N 0.0311 0.0180
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
S S 0.3331 0.5567
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O4 S1 O1 120.14(12) . . ?
O4 S1 N22 108.15(11) . . ?
O1 S1 N22 104.26(11) . . ?
O4 S1 C8 108.41(12) . . ?
O1 S1 C8 109.26(12) . . ?
N22 S1 C8 105.68(12) . . ?
C5 N22 C10 114.1(2) . . ?
C5 N22 S1 123.67(19) . . ?
C10 N22 S1 122.13(17) . . ?
C17 C1 C14 119.7(3) . . ?
C17 C1 H1 120.2 . . ?
C14 C1 H1 120.2 . . ?
C6 C2 C3 127.5(3) . . ?
C6 C2 H2 116.3 . . ?
C3 C2 H2 116.3 . . ?
C9 C3 C2 126.0(3) . . ?
C9 C3 H3 117.0 . . ?
C2 C3 H3 117.0 . . ?
O2 C5 N22 124.5(2) . . ?
O2 C5 C18 127.5(2) . . ?
N22 C5 C18 108.0(2) . . ?
C2 C6 C18 126.6(2) . . ?
C2 C6 C10 123.2(2) . . ?
C18 C6 C10 110.1(2) . . ?
C13 C7 C12 119.7(3) . . ?
C13 C7 C18 121.0(2) . . ?
C12 C7 C18 119.2(3) . . ?
C23 C8 C17 121.0(3) . . ?
C23 C8 S1 119.7(2) . . ?
C17 C8 S1 119.1(2) . . ?
C3 C9 C15 126.7(2) . . ?
C3 C9 Br2 118.5(2) . . ?
C15 C9 Br2 114.5(2) . . ?
N22 C10 C6 102.2(2) . . ?
N22 C10 H10A 111.3 . . ?
C6 C10 H10A 111.3 . . ?
N22 C10 H10B 111.3 . . ?
C6 C10 H10B 111.3 . . ?
H10A C10 H10B 109.2 . . ?
C23 C11 C14 118.9(3) . . ?
C23 C11 H11 120.6 . . ?
C14 C11 H11 120.6 . . ?
C7 C12 C21 120.1(3) . . ?
C7 C12 H12 119.9 . . ?
C21 C12 H12 119.9 . . ?
C7 C13 C16 119.9(3) . . ?
C7 C13 H13 120.0 . . ?
C16 C13 H13 120.0 . . ?
C11 C14 C1 121.4(3) . . ?
C11 C14 Br1 119.4(2) . . ?
C1 C14 Br1 119.1(2) . . ?
C19 C15 C9 126.5(3) . . ?
C19 C15 H15 116.7 . . ?
C9 C15 H15 116.7 . . ?
C20 C16 C13 120.0(3) . . ?
C20 C16 H16 120.0 . . ?
C13 C16 H16 120.0 . . ?
C1 C17 C8 119.2(3) . . ?
C1 C17 H17 120.4 . . ?
C8 C17 H17 120.4 . . ?
C6 C18 C19 111.2(2) . . ?
C6 C18 C5 102.7(2) . . ?
C19 C18 C5 108.9(2) . . ?
C6 C18 C7 112.5(2) . . ?
C19 C18 C7 113.4(2) . . ?
C5 C18 C7 107.4(2) . . ?
C15 C19 C18 126.6(3) . . ?
C15 C19 H19 116.7 . . ?
C18 C19 H19 116.7 . . ?
C16 C20 C21 120.6(3) . . ?
C16 C20 H20 119.7 . . ?
C21 C20 H20 119.7 . . ?
C20 C21 C12 119.6(3) . . ?
C20 C21 H21 120.2 . . ?
C12 C21 H21 120.2 . . ?
C11 C23 C8 119.9(3) . . ?
C11 C23 H23 120.1 . . ?
C8 C23 H23 120.1 . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 C14 1.896(3) . ?
Br2 C9 1.900(3) . ?
S1 O4 1.4272(19) . ?
S1 O1 1.4346(18) . ?
S1 N22 1.666(2) . ?
S1 C8 1.761(3) . ?
O2 C5 1.219(3) . ?
N22 C5 1.387(3) . ?
N22 C10 1.473(3) . ?
C1 C17 1.368(4) . ?
C1 C14 1.394(4) . ?
C1 H1 0.9500 . ?
C2 C6 1.327(4) . ?
C2 C3 1.446(4) . ?
C2 H2 0.9500 . ?
C3 C9 1.346(4) . ?
C3 H3 0.9500 . ?
C5 C18 1.529(4) . ?
C6 C18 1.504(4) . ?
C6 C10 1.513(3) . ?
C7 C13 1.386(4) . ?
C7 C12 1.388(4) . ?
C7 C18 1.547(4) . ?
C8 C23 1.393(4) . ?
C8 C17 1.396(4) . ?
C9 C15 1.442(4) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C23 1.374(4) . ?
C11 C14 1.390(4) . ?
C11 H11 0.9500 . ?
C12 C21 1.390(4) . ?
C12 H12 0.9500 . ?
C13 C16 1.398(4) . ?
C13 H13 0.9500 . ?
C15 C19 1.324(4) . ?
C15 H15 0.9500 . ?
C16 C20 1.369(5) . ?
C16 H16 0.9500 . ?
C17 H17 0.9500 . ?
C18 C19 1.514(4) . ?
C19 H19 0.9500 . ?
C20 C21 1.389(5) . ?
C20 H20 0.9500 . ?
C21 H21 0.9500 . ?
C23 H23 0.9500 . ?
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O4 S1 N22 C5 48.2(2) . . . . ?
O1 S1 N22 C5 177.1(2) . . . . ?
C8 S1 N22 C5 -67.8(2) . . . . ?
O4 S1 N22 C10 -136.5(2) . . . . ?
O1 S1 N22 C10 -7.6(2) . . . . ?
C8 S1 N22 C10 107.5(2) . . . . ?
C6 C2 C3 C9 26.1(5) . . . . ?
C10 N22 C5 O2 -170.5(3) . . . . ?
S1 N22 C5 O2 5.2(4) . . . . ?
C10 N22 C5 C18 9.6(3) . . . . ?
S1 N22 C5 C18 -174.76(18) . . . . ?
C3 C2 C6 C18 2.9(5) . . . . ?
C3 C2 C6 C10 178.4(2) . . . . ?
O4 S1 C8 C23 168.3(2) . . . . ?
O1 S1 C8 C23 35.7(3) . . . . ?
N22 S1 C8 C23 -76.0(2) . . . . ?
O4 S1 C8 C17 -7.3(3) . . . . ?
O1 S1 C8 C17 -139.9(2) . . . . ?
N22 S1 C8 C17 108.5(2) . . . . ?
C2 C3 C9 C15 3.5(5) . . . . ?
C2 C3 C9 Br2 176.9(2) . . . . ?
C5 N22 C10 C6 1.2(3) . . . . ?
S1 N22 C10 C6 -174.48(17) . . . . ?
C2 C6 C10 N22 172.0(2) . . . . ?
C18 C6 C10 N22 -11.9(3) . . . . ?
C13 C7 C12 C21 1.4(4) . . . . ?
C18 C7 C12 C21 -176.1(3) . . . . ?
C12 C7 C13 C16 -1.3(4) . . . . ?
C18 C7 C13 C16 176.1(2) . . . . ?
C23 C11 C14 C1 -1.1(4) . . . . ?
C23 C11 C14 Br1 177.2(2) . . . . ?
C17 C1 C14 C11 0.6(4) . . . . ?
C17 C1 C14 Br1 -177.7(2) . . . . ?
C3 C9 C15 C19 -28.4(5) . . . . ?
Br2 C9 C15 C19 158.0(2) . . . . ?
C7 C13 C16 C20 0.6(4) . . . . ?
C14 C1 C17 C8 0.3(4) . . . . ?
C23 C8 C17 C1 -0.8(4) . . . . ?
S1 C8 C17 C1 174.7(2) . . . . ?
C2 C6 C18 C19 -50.5(4) . . . . ?
C10 C6 C18 C19 133.6(2) . . . . ?
C2 C6 C18 C5 -166.9(3) . . . . ?
C10 C6 C18 C5 17.2(3) . . . . ?
C2 C6 C18 C7 78.0(3) . . . . ?
C10 C6 C18 C7 -98.0(3) . . . . ?
O2 C5 C18 C6 164.0(3) . . . . ?
N22 C5 C18 C6 -16.0(3) . . . . ?
O2 C5 C18 C19 46.0(4) . . . . ?
N22 C5 C18 C19 -134.1(2) . . . . ?
O2 C5 C18 C7 -77.2(3) . . . . ?
N22 C5 C18 C7 102.8(2) . . . . ?
C13 C7 C18 C6 11.5(4) . . . . ?
C12 C7 C18 C6 -171.0(2) . . . . ?
C13 C7 C18 C19 138.8(3) . . . . ?
C12 C7 C18 C19 -43.7(3) . . . . ?
C13 C7 C18 C5 -100.8(3) . . . . ?
C12 C7 C18 C5 76.7(3) . . . . ?
C9 C15 C19 C18 -7.0(5) . . . . ?
C6 C18 C19 C15 53.7(4) . . . . ?
C5 C18 C19 C15 166.3(3) . . . . ?
C7 C18 C19 C15 -74.2(4) . . . . ?
C13 C16 C20 C21 0.0(5) . . . . ?
C16 C20 C21 C12 0.1(5) . . . . ?
C7 C12 C21 C20 -0.8(5) . . . . ?
C14 C11 C23 C8 0.6(4) . . . . ?
C17 C8 C23 C11 0.3(4) . . . . ?
S1 C8 C23 C11 -175.1(2) . . . . ?
