# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Manojit Pal' _publ_contact_author_address ; Discovery Chemistry Dr Reddys Lab Ltd Bollaram Road Miyapur Hyderabad 5000 49 INDIA ; _publ_contact_author_email MANOJITPAL@DRREDDYS.COM _publ_section_title ; Tandem C-C Coupling Intramolecular Acetylenic Schmidt Reaction Under Pd/C-Cu Catalysis ; loop_ _publ_author_name 'Manojit Pal' 'Dinesh Kumar' 'Deepak Kumar Barange' 'Venkateswara Rao Batchu ' 'E. Amarender Reddy' 'Bukkapattanam R. Sreekanth' ; K.Vyas ; data___DKB_006 _database_code_depnum_ccdc_archive 'CCDC 630060' #============================================================================== # CHEMICAL DATA _chemical_formula_sum 'C14 H14 N2 O2 ' _chemical_formula_moiety 'C14 H14 N2 O2 ' _chemical_formula_weight 242.28 _chemical_melting_point ? #============================================================================== # CRYSTAL DATA _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P c a 21' _symmetry_space_group_name_Hall 'P 2c -2ac' _symmetry_Int_Tables_number 29 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 +X,+Y,+Z 2 1/2-X,+Y,1/2+Z 3 1/2+X,-Y,+Z 4 -X,-Y,1/2+Z #------------------------------------------------------------------------------ _cell_length_a 23.78(1) _cell_length_b 4.560(3) _cell_length_c 11.134(7) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1207.3(12) _cell_formula_units_Z 4 _cell_measurement_reflns_used 4826 _cell_measurement_theta_min 1.8 _cell_measurement_theta_max 27.5 _cell_measurement_temperature 298 #------------------------------------------------------------------------------ _exptl_crystal_description platelet _exptl_crystal_colour colorless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.15 _exptl_crystal_density_diffrn 1.333 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 512.00 _exptl_absorpt_coefficient_mu 0.091 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'Jacobson, R. (1998) Private communication' _exptl_absorpt_correction_T_min 0.974 _exptl_absorpt_correction_T_max 0.986 #============================================================================== # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_measurement_device_type 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 7.31 _diffrn_reflns_number 13936 _diffrn_reflns_av_R_equivalents 0.035 _diffrn_reflns_theta_max 27.46 _diffrn_measured_fraction_theta_max 0.9635 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.9801 _diffrn_reflns_limit_h_min -30 _diffrn_reflns_limit_h_max 30 _diffrn_reflns_limit_k_min -3 _diffrn_reflns_limit_k_max 5 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 #============================================================================== # REFINEMENT DATA _refine_special_details ; Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F^2^. R-factor (gt) are based on F. The threshold expression of F^2^ > 2.0 sigma(F^2^) is used only for calculating R-factor (gt). ; _reflns_number_total 1401 _reflns_number_gt 917 _reflns_threshold_expression F^2^>2.0\s(F^2^) _refine_ls_structure_factor_coef Fsqd _refine_ls_R_factor_gt 0.0560 _refine_ls_wR_factor_ref 0.0650 _refine_ls_hydrogen_treatment constr _refine_ls_number_reflns 1231 _refine_ls_number_parameters 178 _refine_ls_goodness_of_fit_ref 1.120 _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Chebychev polynomial with 3 parameters (Carruthers & Watkin, 1979) 3861.1500 5318.8000 1509.9700 ; _refine_ls_shift/su_max 0.0000 _refine_diff_density_max 0.33 _refine_diff_density_min -0.37 _refine_ls_extinction_method 'Larson (1970) Crystallographic Computing eq. 22' _refine_ls_extinction_coef 275.7(20) _refine_ls_abs_structure_details ? _refine_ls_abs_structure_Flack ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.003 0.002 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; H H 0.000 0.000 ; International Tables for Crystallography (1992, Vol. C, Table 6.1.1.4) ; N N 0.006 0.003 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; O O 0.011 0.006 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; #============================================================================== # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags O1 O Uani 0.35992(11) -0.0544(7) 0.3052(2) 1.000 0.0673(8) . . O2 O Uani 0.54862(9) 0.5287(6) 0.0515(2) 1.000 0.0594(10) . . N1 N Uani 0.35389(9) 0.2670(5) 0.1579(2) 1.000 0.0378(6) . . N2 N Uani 0.2861(2) 0.8568(11) -0.3099(3) 1.000 0.0877(18) . . C1 C Uani 0.38530(10) 0.1032(8) 0.2346(3) 1.000 0.0500(12) . . C2 C Uani 0.44615(13) 0.1327(8) 0.2282(3) 1.000 0.0450(12) . . C3 C Uani 0.48020(10) -0.0256(9) 0.3089(3) 1.000 0.0547(12) . . C4 C Uani 0.53760(10) 0.0013(9) 0.3000(3) 1.000 0.0557(12) . . C5 C Uani 0.5620(2) 0.1859(8) 0.2149(3) 1.000 0.0517(12) . . C6 C Uani 0.52865(13) 0.3411(7) 0.1369(3) 1.000 0.0457(12) . . C7 C Uani 0.46951(13) 0.3176(7) 0.1427(3) 1.000 0.0413(12) . . C8 C Uani 0.43364(13) 0.4782(8) 0.0638(3) 1.000 0.0440(12) . . C9 C Uani 0.37800(10) 0.4503(8) 0.0736(3) 1.000 0.0470(12) . . C10 C Uani 0.33400(10) 0.6066(7) 0.0004(3) 1.000 0.0537(12) . . C11 C Uani 0.2925(2) 0.3947(8) -0.0609(4) 1.000 0.0650(14) . . C12 C Uani 0.2465(2) 0.5532(8) -0.1292(4) 1.000 0.0680(14) . . C13 C Uani 0.2687(2) 0.7245(10) -0.2341(4) 1.000 0.0657(16) . . C14 C Uani 0.60840(10) 0.5672(10) 0.0443(4) 1.000 0.0690(16) . . H1 H Uiso 0.31410 0.25610 0.16320 1.000 0.0460 calc R H2 H Uiso 0.46360 -0.15190 0.36680 1.000 0.0650 calc R H3 H Uiso 0.56100 -0.10970 0.35220 1.000 0.0670 calc R H4 H Uiso 0.60170 0.20860 0.21280 1.000 0.0620 calc R H5 H Uiso 0.44920 0.60310 0.00420 1.000 0.0530 calc R H6 H Uiso 0.31310 0.73010 0.05280 1.000 0.0640 calc R H7 H Uiso 0.35200 0.72260 -0.05910 1.000 0.0640 calc R H8 H Uiso 0.27540 0.27390 -0.00170 1.000 0.0780 calc R H9 H Uiso 0.31310 0.27590 -0.11540 1.000 0.0780 calc R H10 H Uiso 0.22080 0.41120 -0.15890 1.000 0.0820 calc R H11 H Uiso 0.22750 0.68270 -0.07620 1.000 0.0820 calc R H12 H Uiso 0.61940 0.72630 0.09420 1.000 0.0830 calc R H13 H Uiso 0.61870 0.60740 -0.03650 1.000 0.0830 calc R H14 H Uiso 0.62730 0.39410 0.06930 1.000 0.0830 calc R 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 O1 0.0590(10) 0.086(2) 0.0570(10) 0.014(2) 0.0014(13) -0.0210(10) O2 0.0441(13) 0.079(2) 0.055(2) 0.008(2) 0.0047(12) -0.0062(13) N1 0.0240(10) 0.0500(10) 0.0394(13) 0.0029(12) -0.0019(12) -0.0049(10) N2 0.061(2) 0.131(4) 0.071(3) 0.012(3) 0.002(2) 0.005(2) C1 0.048(2) 0.060(2) 0.042(2) -0.003(2) 0.002(2) -0.008(2) C2 0.044(2) 0.049(2) 0.042(2) -0.004(2) -0.002(2) -0.0060(10) C3 0.059(2) 0.054(2) 0.051(2) 0.007(2) -0.006(2) -0.005(2) C4 0.050(2) 0.061(2) 0.056(2) 0.004(2) -0.012(2) 0.002(2) C5 0.046(2) 0.059(2) 0.050(2) -0.004(2) -0.005(2) 0.001(2) C6 0.039(2) 0.051(2) 0.047(2) -0.005(2) 0.003(2) -0.0040(10) C7 0.044(2) 0.045(2) 0.035(2) -0.003(2) 0.0000(10) -0.0004(13) C8 0.044(2) 0.050(2) 0.038(2) -0.003(2) 0.0000(10) 0.0010(10) C9 0.047(2) 0.052(2) 0.042(2) -0.005(2) 0.001(2) 0.002(2) C10 0.050(2) 0.053(2) 0.058(2) 0.000(2) -0.011(2) 0.008(2) C11 0.060(2) 0.058(2) 0.077(3) 0.000(2) -0.019(2) 0.001(2) C12 0.045(2) 0.078(2) 0.081(3) 0.002(3) -0.014(2) -0.002(2) C13 0.046(2) 0.081(3) 0.070(3) -0.011(2) -0.013(2) 0.012(2) C14 0.045(2) 0.089(3) 0.073(3) 0.007(3) 0.008(2) -0.007(2) #=============================================================================== # 10. MOLECULAR GEOMETRY _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag O1 C1 1.224(4) . . yes O2 C6 1.364(4) . . yes O2 C14 1.435(3) . . yes N1 C1 1.358(4) . . yes N1 C9 1.381(4) . . yes N2 C13 1.117(6) . . yes N1 H1 0.9500 . . no C1 C2 1.455(4) . . no C2 C3 1.409(5) . . no C2 C7 1.388(5) . . no C3 C4 1.374(4) . . no C4 C5 1.394(5) . . no C5 C6 1.373(5) . . no C6 C7 1.412(4) . . no C7 C8 1.427(5) . . no C8 C9 1.334(4) . . no C9 C10 1.506(4) . . no C10 C11 1.541(5) . . no C11 C12 1.516(6) . . no C12 C13 1.501(6) . . no C3 H2 0.9500 . . no C4 H3 0.9500 . . no C5 H4 0.9500 . . no C8 H5 0.9500 . . no C10 H6 0.9500 . . no C10 H7 0.9500 . . no C11 H8 0.9500 . . no C11 H9 0.9500 . . no C12 H10 0.9500 . . no C12 H11 0.9500 . . no C14 H12 0.9500 . . no C14 H13 0.9500 . . no C14 H14 0.9500 . . no 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 O2 C14 117.4(3) . . . yes C1 N1 C9 122.1(2) . . . yes C1 N1 H1 119.00 . . . no C9 N1 H1 119.00 . . . no O1 C1 N1 117.1(2) . . . yes N1 C1 C2 117.7(3) . . . yes O1 C1 C2 125.2(3) . . . yes C1 C2 C7 119.2(3) . . . no C1 C2 C3 119.5(3) . . . no C3 C2 C7 121.3(3) . . . no C2 C3 C4 118.6(3) . . . no C3 C4 C5 121.1(3) . . . no C4 C5 C6 120.1(4) . . . no C5 C6 C7 120.5(3) . . . no O2 C6 C7 115.2(3) . . . yes O2 C6 C5 124.3(3) . . . yes C2 C7 C6 118.4(3) . . . no C2 C7 C8 119.7(3) . . . no C6 C7 C8 121.9(3) . . . no C7 C8 C9 119.6(3) . . . no C8 C9 C10 126.9(3) . . . no N1 C9 C8 121.7(3) . . . yes N1 C9 C10 111.5(2) . . . yes C9 C10 C11 112.8(3) . . . no C10 C11 C12 112.7(3) . . . no C11 C12 C13 112.6(4) . . . no N2 C13 C12 178.0(5) . . . yes C2 C3 H2 120.00 . . . no C4 C3 H2 121.00 . . . no C3 C4 H3 119.00 . . . no C5 C4 H3 120.00 . . . no C4 C5 H4 120.00 . . . no C6 C5 H4 120.00 . . . no C7 C8 H5 120.00 . . . no C9 C8 H5 120.00 . . . no C9 C10 H6 108.00 . . . no C9 C10 H7 109.00 . . . no C11 C10 H6 108.00 . . . no C11 C10 H7 109.00 . . . no H6 C10 H7 109.00 . . . no C10 C11 H8 109.00 . . . no C10 C11 H9 108.00 . . . no C12 C11 H8 108.00 . . . no C12 C11 H9 109.00 . . . no H8 C11 H9 109.00 . . . no C11 C12 H10 108.00 . . . no C11 C12 H11 109.00 . . . no C13 C12 H10 108.00 . . . no C13 C12 H11 109.00 . . . no H10 C12 H11 110.00 . . . no O2 C14 H12 109.00 . . . no O2 C14 H13 109.00 . . . no O2 C14 H14 111.00 . . . no H12 C14 H13 110.00 . . . no H12 C14 H14 109.00 . . . no H13 C14 H14 108.00 . . . no 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 C14 O2 C6 C5 -0.7(5) . . . . no C14 O2 C6 C7 178.2(3) . . . . no C9 N1 C1 O1 -179.3(3) . . . . no C9 N1 C1 C2 1.9(5) . . . . no C1 N1 C9 C8 -0.6(5) . . . . no C1 N1 C9 C10 -179.9(3) . . . . no O1 C1 C2 C3 -0.9(6) . . . . no O1 C1 C2 C7 179.3(3) . . . . no N1 C1 C2 C3 177.8(3) . . . . no N1 C1 C2 C7 -2.0(5) . . . . no C1 C2 C3 C4 178.9(3) . . . . no C7 C2 C3 C4 -1.4(5) . . . . no C1 C2 C7 C6 -179.3(3) . . . . no C1 C2 C7 C8 0.8(5) . . . . no C3 C2 C7 C6 0.9(5) . . . . no C3 C2 C7 C8 -179.0(3) . . . . no C2 C3 C4 C5 1.4(6) . . . . no C3 C4 C5 C6 -1.0(6) . . . . no C4 C5 C6 O2 179.4(3) . . . . no C4 C5 C6 C7 0.6(5) . . . . no O2 C6 C7 C2 -179.4(3) . . . . no O2 C6 C7 C8 0.4(5) . . . . no C5 C6 C7 C2 -0.5(5) . . . . no C5 C6 C7 C8 179.3(3) . . . . no C2 C7 C8 C9 0.4(5) . . . . no C6 C7 C8 C9 -179.4(3) . . . . no C7 C8 C9 N1 -0.6(5) . . . . no C7 C8 C9 C10 178.6(3) . . . . no N1 C9 C10 C11 -55.5(4) . . . . no C8 C9 C10 C11 125.3(4) . . . . no C9 C10 C11 C12 177.0(3) . . . . no C10 C11 C12 C13 65.3(5) . . . . no loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A _geom_hbond_publ_flag # #D H A D - H H...A D...A D - H...A symm(A) # C11 H8 N1 0.9500 2.5800 2.899(5) 100.00 . yes #============================================================================== # End of CIF #==============================================================================