data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Dr Yoshihiko Yamamoto' _publ_contact_author_address ; Department of Applied Chemistry, Graduate School of Engineering Nagoya University Chikusa Nagoya 464-8603 JAPAN ; _publ_contact_author_email YAMAMOTO@APCHEM.NAGOYA-U.AC.JP _publ_section_title ; Synthesis of benzo-fused lactams and lactones via Ru(II)-catalyzed cycloaddition of amide- and ester-tethered a,w-diynes with terminal alkynes: Electronic directing effect of internal conjugated carbonyl group ; loop_ _publ_author_name 'Yoshihiko Yamamoto' 'Jun-ichi Ishii' 'Kenji Itoh' 'Keisuke Kinpara' 'Hisao Nishiyama' 'Tomoaki Saigoku' data_ykin31 _database_code_depnum_ccdc_archive 'CCDC 224127' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C21 H17 N O' _chemical_formula_weight 299.36 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 8.3987(6) _cell_length_b 5.7449(4) _cell_length_c 15.9653(12) _cell_angle_alpha 90.00 _cell_angle_beta 90.7740(10) _cell_angle_gamma 90.00 _cell_volume 770.25(10) _cell_formula_units_Z 2 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour colorless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.4 _exptl_crystal_size_min 0.8 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.291 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 316 _exptl_absorpt_coefficient_mu 0.079 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.518165 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5753 _diffrn_reflns_av_R_equivalents 0.0236 _diffrn_reflns_av_sigmaI/netI 0.0199 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.43 _diffrn_reflns_theta_max 29.14 _reflns_number_total 3608 _reflns_number_gt 3456 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1515P)^2^+0.1588P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -2.4(15) _refine_ls_number_reflns 3608 _refine_ls_number_parameters 208 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0506 _refine_ls_R_factor_gt 0.0493 _refine_ls_wR_factor_ref 0.1349 _refine_ls_wR_factor_gt 0.1318 _refine_ls_goodness_of_fit_ref 0.719 _refine_ls_restrained_S_all 0.719 _refine_ls_shift/su_max 0.077 _refine_ls_shift/su_mean 0.012 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 C1 C 0.2718(2) 0.9190(3) 0.38698(10) 0.0394(4) Uani 1 1 d . . . H1 H 0.3358 1.0279 0.4144 0.047 Uiso 1 1 calc R . . C2 C 0.23028(19) 0.9553(3) 0.30327(10) 0.0404(4) Uani 1 1 d . . . H2 H 0.2658 1.0863 0.2749 0.048 Uiso 1 1 calc R . . C3 C 0.13476(15) 0.7915(3) 0.26321(8) 0.0284(3) Uani 1 1 d . . . C4 C 0.07161(15) 0.7877(3) 0.17522(9) 0.0312(3) Uani 1 1 d . . . C5 C -0.0160(2) 0.4474(3) 0.24574(10) 0.0399(4) Uani 1 1 d . . . H5A H 0.0310 0.2949 0.2377 0.048 Uiso 1 1 calc R . . H5B H -0.1238 0.4290 0.2658 0.048 Uiso 1 1 calc R . . C6 C 0.08343(15) 0.5938(2) 0.30518(9) 0.0293(3) Uani 1 1 d . . . C7 C 0.12387(17) 0.5571(3) 0.38915(9) 0.0328(3) Uani 1 1 d . . . H7 H 0.0880 0.4251 0.4169 0.039 Uiso 1 1 calc R . . C8 C 0.21946(15) 0.7213(2) 0.43152(8) 0.0266(3) Uani 1 1 d . . . C9 C 0.26785(15) 0.6901(3) 0.52172(9) 0.0274(3) Uani 1 1 d . . . C10 C 0.3669(2) 0.8515(3) 0.56255(11) 0.0417(4) Uani 1 1 d . . . H10 H 0.4018 0.9814 0.5333 0.050 Uiso 1 1 calc R . . C11 C 0.4147(2) 0.8224(4) 0.64607(11) 0.0450(4) Uani 1 1 d . . . H11 H 0.4808 0.9321 0.6715 0.054 Uiso 1 1 calc R . . C12 C 0.36431(17) 0.6318(3) 0.69085(9) 0.0380(3) Uani 1 1 d . . . H12 H 0.3954 0.6126 0.7466 0.046 Uiso 1 1 calc R . . C13 C 0.2666(2) 0.4687(4) 0.65181(11) 0.0484(4) Uani 1 1 d . . . H13 H 0.2331 0.3386 0.6814 0.058 Uiso 1 1 calc R . . C14 C 0.2179(2) 0.4981(4) 0.56825(11) 0.0453(4) Uani 1 1 d . . . H14 H 0.1513 0.3881 0.5433 0.054 Uiso 1 1 calc R . . C15 C -0.08571(17) 0.4986(3) 0.09090(9) 0.0369(3) Uani 1 1 d . . . H15A H -0.0317 0.3572 0.0740 0.044 Uiso 1 1 calc R . . H15B H -0.0717 0.6133 0.0470 0.044 Uiso 1 1 calc R . . C16 C -0.26205(15) 0.4483(3) 0.10021(8) 0.0284(3) Uani 1 1 d . . . C17 C -0.36181(17) 0.6125(3) 0.13739(9) 0.0337(3) Uani 1 1 d . . . H17 H -0.3193 0.7515 0.1575 0.040 Uiso 1 1 calc R . . C18 C -0.52436(19) 0.5693(3) 0.14458(10) 0.0411(4) Uani 1 1 d . . . H18 H -0.5898 0.6798 0.1691 0.049 Uiso 1 1 calc R . . C19 C -0.58930(18) 0.3608(4) 0.11509(10) 0.0412(4) Uani 1 1 d . . . H19 H -0.6976 0.3316 0.1203 0.049 Uiso 1 1 calc R . . C20 C -0.49072(19) 0.1964(3) 0.07774(10) 0.0386(3) Uani 1 1 d . . . H20 H -0.5336 0.0578 0.0575 0.046 Uiso 1 1 calc R . . C21 C -0.32755(18) 0.2397(3) 0.07069(9) 0.0331(3) Uani 1 1 d . . . H21 H -0.2622 0.1289 0.0462 0.040 Uiso 1 1 calc R . . N1 N -0.01306(15) 0.5848(3) 0.16845(8) 0.0345(3) Uani 1 1 d . . . O1 O 0.09042(16) 0.9337(3) 0.12026(8) 0.0475(3) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0420(7) 0.0401(9) 0.0358(7) 0.0033(7) -0.0059(5) -0.0179(6) C2 0.0449(8) 0.0398(8) 0.0363(7) 0.0088(7) -0.0044(6) -0.0193(7) C3 0.0234(5) 0.0310(7) 0.0307(6) 0.0026(6) 0.0014(4) -0.0031(5) C4 0.0242(5) 0.0380(8) 0.0314(6) 0.0004(6) 0.0015(4) -0.0035(5) C5 0.0486(8) 0.0350(8) 0.0359(7) 0.0029(7) -0.0087(6) -0.0158(6) C6 0.0280(6) 0.0259(6) 0.0340(6) -0.0003(5) -0.0011(4) -0.0035(5) C7 0.0372(6) 0.0263(7) 0.0348(7) 0.0029(6) -0.0020(5) -0.0061(5) C8 0.0218(5) 0.0279(6) 0.0302(6) -0.0008(5) 0.0013(4) 0.0002(4) C9 0.0229(5) 0.0287(6) 0.0305(6) -0.0004(5) 0.0028(4) 0.0037(4) C10 0.0513(9) 0.0362(8) 0.0373(7) 0.0024(7) -0.0068(6) -0.0085(7) C11 0.0524(9) 0.0450(10) 0.0374(8) -0.0039(7) -0.0088(6) -0.0060(7) C12 0.0342(7) 0.0504(10) 0.0293(6) -0.0003(7) 0.0009(5) 0.0067(6) C13 0.0553(9) 0.0530(11) 0.0369(8) 0.0117(8) -0.0008(7) -0.0129(9) C14 0.0504(9) 0.0487(10) 0.0367(7) 0.0069(7) -0.0045(6) -0.0200(8) C15 0.0313(6) 0.0482(9) 0.0313(6) -0.0069(6) 0.0006(5) -0.0053(6) C16 0.0303(6) 0.0295(6) 0.0254(5) -0.0013(5) -0.0026(4) -0.0005(5) C17 0.0378(7) 0.0295(7) 0.0337(6) -0.0040(6) -0.0014(5) 0.0010(5) C18 0.0358(7) 0.0470(9) 0.0405(7) 0.0010(7) 0.0031(6) 0.0101(7) C19 0.0290(6) 0.0553(10) 0.0393(7) 0.0109(7) -0.0029(5) -0.0034(6) C20 0.0433(8) 0.0348(8) 0.0372(7) 0.0046(6) -0.0103(6) -0.0106(6) C21 0.0386(7) 0.0292(7) 0.0314(6) -0.0039(6) -0.0040(5) 0.0004(5) N1 0.0325(5) 0.0384(7) 0.0324(6) -0.0003(5) -0.0029(4) -0.0083(5) O1 0.0547(7) 0.0521(8) 0.0357(5) 0.0116(6) -0.0047(5) -0.0167(6) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; 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 C1 C2 1.392(2) . ? C1 C8 1.413(2) . ? C2 C3 1.387(2) . ? C3 C6 1.3903(18) . ? C3 C4 1.4951(18) . ? C4 O1 1.2256(19) . ? C4 N1 1.369(2) . ? C5 N1 1.465(2) . ? C5 C6 1.511(2) . ? C6 C7 1.395(2) . ? C7 C8 1.4062(18) . ? C8 C9 1.5018(17) . ? C9 C14 1.398(2) . ? C9 C10 1.401(2) . ? C10 C11 1.397(2) . ? C11 C12 1.378(3) . ? C12 C13 1.388(3) . ? C13 C14 1.400(2) . ? C15 N1 1.4595(19) . ? C15 C16 1.5182(19) . ? C16 C21 1.398(2) . ? C16 C17 1.3991(19) . ? C17 C18 1.394(2) . ? C18 C19 1.395(3) . ? C19 C20 1.395(3) . ? C20 C21 1.399(2) . ? 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 C2 C1 C8 121.84(13) . . ? C3 C2 C1 118.49(14) . . ? C2 C3 C6 120.87(13) . . ? C2 C3 C4 129.71(13) . . ? C6 C3 C4 109.42(12) . . ? O1 C4 N1 126.73(14) . . ? O1 C4 C3 127.96(14) . . ? N1 C4 C3 105.31(12) . . ? N1 C5 C6 102.32(12) . . ? C3 C6 C7 120.93(13) . . ? C3 C6 C5 108.93(13) . . ? C7 C6 C5 130.14(13) . . ? C6 C7 C8 119.39(13) . . ? C7 C8 C1 118.47(12) . . ? C7 C8 C9 121.78(12) . . ? C1 C8 C9 119.74(12) . . ? C14 C9 C10 117.11(13) . . ? C14 C9 C8 121.63(13) . . ? C10 C9 C8 121.25(13) . . ? C11 C10 C9 121.75(16) . . ? C12 C11 C10 120.26(16) . . ? C11 C12 C13 119.18(14) . . ? C12 C13 C14 120.64(17) . . ? C9 C14 C13 121.06(16) . . ? N1 C15 C16 112.26(11) . . ? C21 C16 C17 119.07(12) . . ? C21 C16 C15 120.66(13) . . ? C17 C16 C15 120.26(13) . . ? C18 C17 C16 120.51(15) . . ? C17 C18 C19 120.27(15) . . ? C20 C19 C18 119.59(14) . . ? C19 C20 C21 120.12(15) . . ? C20 C21 C16 120.44(14) . . ? C4 N1 C5 114.01(12) . . ? C4 N1 C15 124.53(13) . . ? C5 N1 C15 121.32(14) . . ? _diffrn_measured_fraction_theta_max 0.973 _diffrn_reflns_theta_full 29.14 _diffrn_measured_fraction_theta_full 0.973 _refine_diff_density_max 0.329 _refine_diff_density_min -0.289 _refine_diff_density_rms 0.074