# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'A J Canty' _publ_contact_author_email ALLAN.CANTY@UTAS.EDU.AU _publ_section_title ; A New Mechanistic Pathway under Sonogashira Reaction Protocol Involving Multiple Acetylene Insertions ; loop_ _publ_author_name 'A J Canty' 'Thomas Caradoc-Davies' 'Noel W Davies' 'Michael Guy Gardiner' 'Roderick C. Jone' ; P.Marriott ; 'Christian P. G. Ruhle' 'Vicki-Anne Tolhurst' # Attachment 'compound_5.cif' data_c:\1-(4-nitrophenyl)-2,4,6-triphenylbenzene _database_code_depnum_ccdc_archive 'CCDC 755775' #TrackingRef 'compound_5.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C30 H21 N O2' _chemical_formula_sum 'C30 H21 N O2' _chemical_formula_weight 427.48 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 triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.588(4) _cell_length_b 10.867(5) _cell_length_c 10.920(4) _cell_angle_alpha 87.032(11) _cell_angle_beta 77.218(13) _cell_angle_gamma 66.155(17) _cell_volume 1119.7(8) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4953 _cell_measurement_theta_min 2.20 _cell_measurement_theta_max 27.77 _exptl_crystal_description rod _exptl_crystal_colour yellow _exptl_crystal_size_max 0.05 _exptl_crystal_size_mid 0.01 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.268 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 448 _exptl_absorpt_coefficient_mu 0.079 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; Low data completion ratio is due to the limitations of the instrument available at the Australian Synchrotron operating under rotation data collection with a fixed detector and affects some high angle data. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.76207 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'Synchrotron ID' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-ID1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q315' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7122 _diffrn_reflns_av_R_equivalents 0.0579 _diffrn_reflns_av_sigmaI/netI 0.0834 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.20 _diffrn_reflns_theta_max 27.77 _reflns_number_total 3728 _reflns_number_gt 3084 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 2008)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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^)+(0.0913P)^2^+0.3139P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3728 _refine_ls_number_parameters 298 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0703 _refine_ls_R_factor_gt 0.0604 _refine_ls_wR_factor_ref 0.1678 _refine_ls_wR_factor_gt 0.1607 _refine_ls_goodness_of_fit_ref 1.055 _refine_ls_restrained_S_all 1.055 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 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 O1 O -0.21752(18) 0.80961(17) -0.49903(14) 0.0367(4) Uani 1 1 d . . . O2 O -0.36125(17) 1.00265(18) -0.40803(14) 0.0348(4) Uani 1 1 d . . . N1 N -0.26331(19) 0.89213(19) -0.41008(15) 0.0244(4) Uani 1 1 d . . . C1 C -0.0070(2) 0.7519(2) 0.01414(17) 0.0191(4) Uani 1 1 d . . . C2 C -0.0708(2) 0.7008(2) 0.11997(17) 0.0193(4) Uani 1 1 d . . . C3 C -0.0106(2) 0.6669(2) 0.22474(17) 0.0203(4) Uani 1 1 d . . . H3 H -0.0522 0.6289 0.2939 0.024 Uiso 1 1 calc R . . C4 C 0.1096(2) 0.6879(2) 0.22967(17) 0.0202(4) Uani 1 1 d . . . C5 C 0.1700(2) 0.7414(2) 0.12631(17) 0.0197(4) Uani 1 1 d . . . H5 H 0.2500 0.7589 0.1302 0.024 Uiso 1 1 calc R . . C6 C 0.1172(2) 0.7703(2) 0.01702(17) 0.0193(4) Uani 1 1 d . . . C11 C -0.0733(2) 0.7887(2) -0.09689(17) 0.0190(4) Uani 1 1 d . . . C12 C -0.2023(2) 0.6791(2) 0.12508(17) 0.0188(4) Uani 1 1 d . . . C14 C 0.17375(19) 0.6519(2) 0.34200(17) 0.0203(5) Uani 1 1 d . . . C16 C 0.1969(2) 0.8182(2) -0.09153(17) 0.0199(4) Uani 1 1 d . . . C21 C -0.0044(2) 0.7175(2) -0.21193(17) 0.0206(4) Uani 1 1 d . . . H21 H 0.0862 0.6456 -0.2198 0.025 Uiso 1 1 calc R . . C22 C -0.2153(2) 0.6044(2) 0.03135(18) 0.0224(5) Uani 1 1 d . . . H22 H -0.1410 0.5711 -0.0413 0.027 Uiso 1 1 calc R . . C24 C 0.1994(2) 0.5260(2) 0.39339(18) 0.0249(5) Uani 1 1 d . . . H24 H 0.1714 0.4649 0.3591 0.030 Uiso 1 1 calc R . . C26 C 0.3454(2) 0.7552(2) -0.12146(19) 0.0251(5) Uani 1 1 d . . . H26 H 0.3925 0.6805 -0.0754 0.030 Uiso 1 1 calc R . . C31 C -0.0664(2) 0.7502(2) -0.31453(18) 0.0216(4) Uani 1 1 d . . . H31 H -0.0202 0.7008 -0.3924 0.026 Uiso 1 1 calc R . . C32 C -0.3350(2) 0.5786(2) 0.04331(19) 0.0255(5) Uani 1 1 d . . . H32 H -0.3425 0.5282 -0.0213 0.031 Uiso 1 1 calc R . . C34 C 0.2656(2) 0.4892(2) 0.49442(19) 0.0293(5) Uani 1 1 d . . . H34 H 0.2844 0.4026 0.5277 0.035 Uiso 1 1 calc R . . C36 C 0.4243(2) 0.8003(2) -0.2172(2) 0.0299(5) Uani 1 1 d . . . H36 H 0.5246 0.7565 -0.2360 0.036 Uiso 1 1 calc R . . C41 C -0.1967(2) 0.8560(2) -0.30133(17) 0.0211(5) Uani 1 1 d . . . C42 C -0.4443(2) 0.6258(2) 0.1492(2) 0.0268(5) Uani 1 1 d . . . H42 H -0.5255 0.6061 0.1583 0.032 Uiso 1 1 calc R . . C44 C 0.3043(2) 0.5791(3) 0.54667(18) 0.0290(5) Uani 1 1 d . . . H44 H 0.3497 0.5539 0.6154 0.035 Uiso 1 1 calc R . . C46 C 0.3576(2) 0.9087(2) -0.28544(19) 0.0293(5) Uani 1 1 d . . . H46 H 0.4117 0.9399 -0.3508 0.035 Uiso 1 1 calc R . . C51 C -0.2683(2) 0.9310(2) -0.18884(18) 0.0223(5) Uani 1 1 d . . . H51 H -0.3573 1.0047 -0.1826 0.027 Uiso 1 1 calc R . . C52 C -0.4339(2) 0.7020(2) 0.24169(19) 0.0253(5) Uani 1 1 d . . . H52 H -0.5091 0.7360 0.3136 0.030 Uiso 1 1 calc R . . C54 C 0.2766(2) 0.7049(2) 0.49851(18) 0.0276(5) Uani 1 1 d . . . H54 H 0.3013 0.7670 0.5352 0.033 Uiso 1 1 calc R . . C56 C 0.2116(2) 0.9714(2) -0.25752(19) 0.0261(5) Uani 1 1 d . . . H56 H 0.1651 1.0455 -0.3045 0.031 Uiso 1 1 calc R . . C61 C -0.2058(2) 0.8947(2) -0.08664(17) 0.0211(4) Uani 1 1 d . . . H61 H -0.2538 0.9428 -0.0083 0.025 Uiso 1 1 calc R . . C62 C -0.3146(2) 0.7288(2) 0.22980(18) 0.0226(5) Uani 1 1 d . . . H62 H -0.3089 0.7815 0.2935 0.027 Uiso 1 1 calc R . . C64 C 0.2123(2) 0.7412(2) 0.39613(18) 0.0235(5) Uani 1 1 d . . . H64 H 0.1946 0.8277 0.3629 0.028 Uiso 1 1 calc R . . C66 C 0.1315(2) 0.9268(2) -0.16082(18) 0.0220(5) Uani 1 1 d . . . H66 H 0.0312 0.9713 -0.1423 0.026 Uiso 1 1 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 0.0485(10) 0.0453(11) 0.0201(8) -0.0038(7) -0.0114(7) -0.0203(9) O2 0.0334(9) 0.0450(11) 0.0255(8) 0.0068(7) -0.0118(7) -0.0133(9) N1 0.0259(9) 0.0353(11) 0.0175(9) 0.0046(8) -0.0052(7) -0.0181(9) C1 0.0187(9) 0.0222(11) 0.0131(9) -0.0012(7) 0.0008(8) -0.0069(9) C2 0.0166(9) 0.0268(11) 0.0129(9) -0.0026(8) 0.0016(7) -0.0092(9) C3 0.0191(9) 0.0291(11) 0.0119(9) -0.0004(8) 0.0005(7) -0.0107(9) C4 0.0180(9) 0.0267(11) 0.0136(9) -0.0016(8) -0.0003(7) -0.0081(9) C5 0.0154(9) 0.0261(11) 0.0175(9) -0.0002(8) -0.0016(8) -0.0091(9) C6 0.0173(9) 0.0249(11) 0.0138(9) -0.0015(8) 0.0006(7) -0.0083(9) C11 0.0191(9) 0.0268(11) 0.0137(9) 0.0006(8) 0.0006(8) -0.0140(9) C12 0.0182(9) 0.0247(11) 0.0141(9) 0.0041(8) -0.0034(7) -0.0097(9) C14 0.0120(9) 0.0349(12) 0.0116(9) -0.0005(8) 0.0019(7) -0.0093(9) C16 0.0220(10) 0.0277(11) 0.0138(9) 0.0009(8) -0.0022(8) -0.0146(9) C21 0.0181(9) 0.0282(11) 0.0149(9) -0.0012(8) 0.0007(7) -0.0106(9) C22 0.0216(10) 0.0275(12) 0.0165(9) -0.0006(8) -0.0028(8) -0.0089(9) C24 0.0238(10) 0.0319(12) 0.0191(10) 0.0004(9) -0.0038(8) -0.0118(10) C26 0.0218(10) 0.0349(13) 0.0202(10) 0.0058(9) -0.0020(8) -0.0149(10) C31 0.0216(10) 0.0317(12) 0.0137(9) -0.0011(8) 0.0004(8) -0.0148(9) C32 0.0256(11) 0.0286(12) 0.0251(11) 0.0016(9) -0.0086(9) -0.0122(10) C34 0.0249(11) 0.0381(13) 0.0218(11) 0.0065(9) -0.0046(9) -0.0105(10) C36 0.0223(10) 0.0455(14) 0.0247(11) 0.0037(10) 0.0002(9) -0.0196(11) C41 0.0247(10) 0.0329(12) 0.0128(9) 0.0039(8) -0.0046(8) -0.0189(10) C42 0.0184(10) 0.0338(13) 0.0318(11) 0.0073(9) -0.0091(9) -0.0128(10) C44 0.0185(10) 0.0535(16) 0.0136(9) 0.0039(9) -0.0025(8) -0.0138(11) C46 0.0358(12) 0.0436(14) 0.0187(10) 0.0070(9) -0.0029(9) -0.0286(11) C51 0.0212(10) 0.0281(12) 0.0179(10) 0.0024(8) -0.0026(8) -0.0113(9) C52 0.0186(10) 0.0338(13) 0.0215(10) 0.0054(9) -0.0007(8) -0.0110(10) C54 0.0229(10) 0.0477(14) 0.0165(10) -0.0017(9) -0.0009(8) -0.0201(11) C56 0.0360(12) 0.0317(12) 0.0176(10) 0.0035(8) -0.0057(9) -0.0213(11) C61 0.0210(10) 0.0303(12) 0.0125(9) -0.0016(8) -0.0005(8) -0.0123(9) C62 0.0226(10) 0.0317(12) 0.0153(9) 0.0023(8) -0.0025(8) -0.0138(10) C64 0.0198(10) 0.0364(13) 0.0161(9) 0.0016(8) -0.0004(8) -0.0149(10) C66 0.0231(10) 0.0275(12) 0.0176(9) -0.0010(8) -0.0035(8) -0.0127(9) _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 O1 N1 1.230(2) . ? O2 N1 1.226(2) . ? N1 C41 1.470(3) . ? C1 C2 1.412(3) . ? C1 C6 1.415(3) . ? C1 C11 1.491(3) . ? C2 C3 1.393(3) . ? C2 C12 1.492(3) . ? C3 C4 1.393(3) . ? C3 H3 0.9500 . ? C4 C5 1.391(3) . ? C4 C14 1.491(3) . ? C5 C6 1.396(3) . ? C5 H5 0.9500 . ? C6 C16 1.496(3) . ? C11 C61 1.395(3) . ? C11 C21 1.396(3) . ? C12 C62 1.398(3) . ? C12 C22 1.402(3) . ? C14 C64 1.394(3) . ? C14 C24 1.396(3) . ? C16 C66 1.387(3) . ? C16 C26 1.404(3) . ? C21 C31 1.382(3) . ? C21 H21 0.9500 . ? C22 C32 1.383(3) . ? C22 H22 0.9500 . ? C24 C34 1.392(3) . ? C24 H24 0.9500 . ? C26 C36 1.386(3) . ? C26 H26 0.9500 . ? C31 C41 1.375(3) . ? C31 H31 0.9500 . ? C32 C42 1.389(3) . ? C32 H32 0.9500 . ? C34 C44 1.390(3) . ? C34 H34 0.9500 . ? C36 C46 1.382(3) . ? C36 H36 0.9500 . ? C41 C51 1.393(3) . ? C42 C52 1.389(3) . ? C42 H42 0.9500 . ? C44 C54 1.379(3) . ? C44 H44 0.9500 . ? C46 C56 1.382(3) . ? C46 H46 0.9500 . ? C51 C61 1.382(3) . ? C51 H51 0.9500 . ? C52 C62 1.385(3) . ? C52 H52 0.9500 . ? C54 C64 1.394(3) . ? C54 H54 0.9500 . ? C56 C66 1.397(3) . ? C56 H56 0.9500 . ? C61 H61 0.9500 . ? C62 H62 0.9500 . ? C64 H64 0.9500 . ? C66 H66 0.9500 . ? 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 O2 N1 O1 123.22(18) . . ? O2 N1 C41 118.68(17) . . ? O1 N1 C41 118.10(18) . . ? C2 C1 C6 119.09(18) . . ? C2 C1 C11 119.62(17) . . ? C6 C1 C11 121.27(16) . . ? C3 C2 C1 120.23(17) . . ? C3 C2 C12 117.21(16) . . ? C1 C2 C12 122.55(17) . . ? C2 C3 C4 121.04(17) . . ? C2 C3 H3 119.5 . . ? C4 C3 H3 119.5 . . ? C5 C4 C3 118.43(18) . . ? C5 C4 C14 120.57(17) . . ? C3 C4 C14 121.00(17) . . ? C4 C5 C6 122.29(17) . . ? C4 C5 H5 118.9 . . ? C6 C5 H5 118.9 . . ? C5 C6 C1 118.79(17) . . ? C5 C6 C16 117.59(16) . . ? C1 C6 C16 123.62(17) . . ? C61 C11 C21 119.16(18) . . ? C61 C11 C1 120.19(17) . . ? C21 C11 C1 120.64(18) . . ? C62 C12 C22 118.26(17) . . ? C62 C12 C2 119.31(17) . . ? C22 C12 C2 122.35(17) . . ? C64 C14 C24 118.59(18) . . ? C64 C14 C4 121.12(18) . . ? C24 C14 C4 120.27(18) . . ? C66 C16 C26 118.00(18) . . ? C66 C16 C6 123.04(18) . . ? C26 C16 C6 118.89(19) . . ? C31 C21 C11 120.78(19) . . ? C31 C21 H21 119.6 . . ? C11 C21 H21 119.6 . . ? C32 C22 C12 120.79(18) . . ? C32 C22 H22 119.6 . . ? C12 C22 H22 119.6 . . ? C34 C24 C14 120.60(19) . . ? C34 C24 H24 119.7 . . ? C14 C24 H24 119.7 . . ? C36 C26 C16 121.0(2) . . ? C36 C26 H26 119.5 . . ? C16 C26 H26 119.5 . . ? C41 C31 C21 118.49(18) . . ? C41 C31 H31 120.8 . . ? C21 C31 H31 120.8 . . ? C22 C32 C42 120.36(19) . . ? C22 C32 H32 119.8 . . ? C42 C32 H32 119.8 . . ? C44 C34 C24 120.0(2) . . ? C44 C34 H34 120.0 . . ? C24 C34 H34 120.0 . . ? C46 C36 C26 120.3(2) . . ? C46 C36 H36 119.8 . . ? C26 C36 H36 119.8 . . ? C31 C41 C51 122.64(18) . . ? C31 C41 N1 118.95(17) . . ? C51 C41 N1 118.42(19) . . ? C52 C42 C32 119.41(18) . . ? C52 C42 H42 120.3 . . ? C32 C42 H42 120.3 . . ? C54 C44 C34 119.88(19) . . ? C54 C44 H44 120.1 . . ? C34 C44 H44 120.1 . . ? C56 C46 C36 119.30(19) . . ? C56 C46 H46 120.3 . . ? C36 C46 H46 120.3 . . ? C61 C51 C41 117.95(19) . . ? C61 C51 H51 121.0 . . ? C41 C51 H51 121.0 . . ? C62 C52 C42 120.43(18) . . ? C62 C52 H52 119.8 . . ? C42 C52 H52 119.8 . . ? C44 C54 C64 120.19(19) . . ? C44 C54 H54 119.9 . . ? C64 C54 H54 119.9 . . ? C46 C56 C66 120.6(2) . . ? C46 C56 H56 119.7 . . ? C66 C56 H56 119.7 . . ? C51 C61 C11 120.95(18) . . ? C51 C61 H61 119.5 . . ? C11 C61 H61 119.5 . . ? C52 C62 C12 120.73(18) . . ? C52 C62 H62 119.6 . . ? C12 C62 H62 119.6 . . ? C54 C64 C14 120.7(2) . . ? C54 C64 H64 119.7 . . ? C14 C64 H64 119.7 . . ? C16 C66 C56 120.68(19) . . ? C16 C66 H66 119.7 . . ? C56 C66 H66 119.7 . . ? 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 C6 C1 C2 C3 -1.1(3) . . . . ? C11 C1 C2 C3 -179.49(17) . . . . ? C6 C1 C2 C12 179.62(18) . . . . ? C11 C1 C2 C12 1.2(3) . . . . ? C1 C2 C3 C4 2.8(3) . . . . ? C12 C2 C3 C4 -177.90(18) . . . . ? C2 C3 C4 C5 -1.2(3) . . . . ? C2 C3 C4 C14 179.86(18) . . . . ? C3 C4 C5 C6 -2.2(3) . . . . ? C14 C4 C5 C6 176.81(18) . . . . ? C4 C5 C6 C1 3.8(3) . . . . ? C4 C5 C6 C16 -175.72(18) . . . . ? C2 C1 C6 C5 -2.1(3) . . . . ? C11 C1 C6 C5 176.28(18) . . . . ? C2 C1 C6 C16 177.38(18) . . . . ? C11 C1 C6 C16 -4.2(3) . . . . ? C2 C1 C11 C61 65.3(3) . . . . ? C6 C1 C11 C61 -113.1(2) . . . . ? C2 C1 C11 C21 -114.3(2) . . . . ? C6 C1 C11 C21 67.3(3) . . . . ? C3 C2 C12 C62 49.8(3) . . . . ? C1 C2 C12 C62 -130.9(2) . . . . ? C3 C2 C12 C22 -126.8(2) . . . . ? C1 C2 C12 C22 52.5(3) . . . . ? C5 C4 C14 C64 48.0(3) . . . . ? C3 C4 C14 C64 -133.1(2) . . . . ? C5 C4 C14 C24 -130.6(2) . . . . ? C3 C4 C14 C24 48.4(3) . . . . ? C5 C6 C16 C66 -134.5(2) . . . . ? C1 C6 C16 C66 46.0(3) . . . . ? C5 C6 C16 C26 42.3(3) . . . . ? C1 C6 C16 C26 -137.2(2) . . . . ? C61 C11 C21 C31 -0.5(3) . . . . ? C1 C11 C21 C31 179.11(17) . . . . ? C62 C12 C22 C32 -1.1(3) . . . . ? C2 C12 C22 C32 175.55(19) . . . . ? C64 C14 C24 C34 -1.7(3) . . . . ? C4 C14 C24 C34 176.83(17) . . . . ? C66 C16 C26 C36 0.1(3) . . . . ? C6 C16 C26 C36 -176.80(18) . . . . ? C11 C21 C31 C41 1.0(3) . . . . ? C12 C22 C32 C42 -0.4(3) . . . . ? C14 C24 C34 C44 1.3(3) . . . . ? C16 C26 C36 C46 -0.1(3) . . . . ? C21 C31 C41 C51 -0.1(3) . . . . ? C21 C31 C41 N1 179.70(16) . . . . ? O2 N1 C41 C31 -163.45(18) . . . . ? O1 N1 C41 C31 16.4(3) . . . . ? O2 N1 C41 C51 16.4(3) . . . . ? O1 N1 C41 C51 -163.76(18) . . . . ? C22 C32 C42 C52 1.5(3) . . . . ? C24 C34 C44 C54 0.2(3) . . . . ? C26 C36 C46 C56 -0.2(3) . . . . ? C31 C41 C51 C61 -1.2(3) . . . . ? N1 C41 C51 C61 178.94(16) . . . . ? C32 C42 C52 C62 -1.2(3) . . . . ? C34 C44 C54 C64 -1.2(3) . . . . ? C36 C46 C56 C66 0.5(3) . . . . ? C41 C51 C61 C11 1.7(3) . . . . ? C21 C11 C61 C51 -0.9(3) . . . . ? C1 C11 C61 C51 179.48(17) . . . . ? C42 C52 C62 C12 -0.4(3) . . . . ? C22 C12 C62 C52 1.5(3) . . . . ? C2 C12 C62 C52 -175.27(18) . . . . ? C44 C54 C64 C14 0.8(3) . . . . ? C24 C14 C64 C54 0.7(3) . . . . ? C4 C14 C64 C54 -177.83(17) . . . . ? C26 C16 C66 C56 0.1(3) . . . . ? C6 C16 C66 C56 176.93(17) . . . . ? C46 C56 C66 C16 -0.4(3) . . . . ? _diffrn_measured_fraction_theta_max 0.870 _diffrn_reflns_theta_full 27.77 _diffrn_measured_fraction_theta_full 0.870 _refine_diff_density_max 0.272 _refine_diff_density_min -0.322 _refine_diff_density_rms 0.057 # Attachment 'compound_7.cif' data_c:\PdI(4O2NC6H4)pyCH2SMe _database_code_depnum_ccdc_archive 'CCDC 755776' #TrackingRef 'compound_7.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C13 H13 I N2 O2 Pd S' _chemical_formula_sum 'C13 H13 I N2 O2 Pd S' _chemical_formula_weight 494.61 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 7.7510(10) _cell_length_b 11.9940(13) _cell_length_c 16.0450(12) _cell_angle_alpha 90.000 _cell_angle_beta 95.476(6) _cell_angle_gamma 90.000 _cell_volume 1484.8(3) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 14568 _cell_measurement_theta_min 2.32 _cell_measurement_theta_max 26.44 _exptl_crystal_description plate _exptl_crystal_colour orange _exptl_crystal_size_max 0.03 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.213 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 944 _exptl_absorpt_coefficient_mu 3.471 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.77487 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron BM' _diffrn_radiation_monochromator Si<111> _diffrn_measurement_device_type '3-BM1 Australian Synchrotron' _diffrn_measurement_method Rotation _diffrn_detector_area_resol_mean 'ADSC Q210' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15675 _diffrn_reflns_av_R_equivalents 0.0995 _diffrn_reflns_av_sigmaI/netI 0.0592 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.32 _diffrn_reflns_theta_max 26.44 _reflns_number_total 2262 _reflns_number_gt 2190 _reflns_threshold_expression >2sigma(I) _computing_data_collection BLU-ICE _computing_cell_refinement XDS _computing_data_reduction XDS _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; 'X-SEED (Barbour, 2008) and ORTEPIII (Farrugia, 1998)' ; _computing_publication_material 'WinGX (Farrugia, 1999)' _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^)+(0.0331P)^2^+5.6246P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2262 _refine_ls_number_parameters 184 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0370 _refine_ls_R_factor_gt 0.0363 _refine_ls_wR_factor_ref 0.0892 _refine_ls_wR_factor_gt 0.0887 _refine_ls_goodness_of_fit_ref 1.087 _refine_ls_restrained_S_all 1.087 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 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 I1 I 0.06554(4) 0.62363(3) 0.891982(18) 0.0151(9) Uani 1 1 d . . . Pd1 Pd 0.04008(4) 0.71002(3) 1.03991(2) 0.0098(9) Uani 1 1 d . . . S1 S 0.01956(15) 0.80076(10) 1.16377(7) 0.0134(9) Uani 1 1 d . . . N1 N 0.2558(5) 0.6258(3) 1.1070(3) 0.0132(12) Uani 1 1 d . . . C9 C -0.2799(7) 0.9555(4) 0.9111(3) 0.0170(14) Uani 1 1 d . . . H9 H -0.2626 1.0226 0.8815 0.020 Uiso 1 1 calc R . . C2 C 0.3118(6) 0.6625(4) 1.1840(3) 0.0115(13) Uani 1 1 d . . . C6 C 0.3327(6) 0.5348(4) 1.0780(3) 0.0155(13) Uani 1 1 d . . . H6 H 0.2904 0.5061 1.0248 0.019 Uiso 1 1 calc R . . C10 C -0.4452(6) 0.9170(4) 0.9193(3) 0.0126(13) Uani 1 1 d . . . C7 C -0.1626(6) 0.7956(4) 0.9893(3) 0.0127(13) Uani 1 1 d . . . C12 C -0.3333(6) 0.7605(4) 0.9981(3) 0.0143(13) Uani 1 1 d . . . H12 H -0.3515 0.6942 1.0285 0.017 Uiso 1 1 calc R . . C8 C -0.1393(7) 0.8946(4) 0.9466(3) 0.0172(14) Uani 1 1 d . . . H8 H -0.0251 0.9210 0.9416 0.021 Uiso 1 1 calc R . . C21 C 0.2285(6) 0.7644(4) 1.2175(3) 0.0160(14) Uani 1 1 d . . . H21A H 0.3080 0.8285 1.2140 0.019 Uiso 1 1 calc R . . H21B H 0.2139 0.7521 1.2775 0.019 Uiso 1 1 calc R . . C22 C -0.1245(8) 0.7159(5) 1.2186(3) 0.0259(15) Uani 1 1 d . . . H22A H -0.0857 0.6382 1.2186 0.039 Uiso 1 1 calc R . . H22B H -0.2422 0.7211 1.1906 0.039 Uiso 1 1 calc R . . H22C H -0.1239 0.7423 1.2764 0.039 Uiso 1 1 calc R . . O1 O -0.7404(5) 0.9437(3) 0.8864(2) 0.0262(12) Uani 1 1 d . . . O2 O -0.5655(5) 1.0651(3) 0.8396(2) 0.0274(13) Uani 1 1 d . . . N2 N -0.5945(5) 0.9804(4) 0.8798(2) 0.0163(13) Uani 1 1 d . . . C4 C 0.5304(6) 0.5207(4) 1.2006(3) 0.0143(13) Uani 1 1 d . . . H4 H 0.6259 0.4859 1.2318 0.017 Uiso 1 1 calc R . . C5 C 0.4688(6) 0.4817(4) 1.1219(3) 0.0159(13) Uani 1 1 d . . . H5 H 0.5207 0.4186 1.0987 0.019 Uiso 1 1 calc R . . C11 C -0.4765(6) 0.8209(4) 0.9632(3) 0.0160(14) Uani 1 1 d . . . H11 H -0.5914 0.7968 0.9693 0.019 Uiso 1 1 calc R . . C3 C 0.4485(6) 0.6121(4) 1.2323(3) 0.0153(14) Uani 1 1 d . . . H3 H 0.4855 0.6399 1.2865 0.018 Uiso 1 1 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 I1 0.0127(9) 0.0218(9) 0.0104(9) -0.00087(11) -0.00124(16) 0.00436(11) Pd1 0.0071(9) 0.0132(9) 0.0087(9) -0.00006(12) -0.00166(17) 0.00132(12) S1 0.0130(11) 0.0151(11) 0.0116(11) -0.0013(4) -0.0009(5) 0.0020(4) N1 0.011(2) 0.015(2) 0.014(2) 0.0027(15) 0.0021(17) -0.0028(15) C9 0.017(3) 0.019(3) 0.015(3) 0.0021(19) 0.0007(19) -0.001(2) C2 0.012(2) 0.011(3) 0.012(3) 0.0011(18) 0.0022(19) -0.0026(18) C6 0.013(3) 0.022(3) 0.010(2) 0.0006(19) -0.0014(18) 0.000(2) C10 0.011(3) 0.018(3) 0.009(2) -0.0031(19) -0.0022(18) 0.0023(19) C7 0.014(3) 0.018(3) 0.006(2) -0.0041(17) -0.0007(18) 0.0015(18) C12 0.012(3) 0.012(3) 0.019(3) 0.0000(19) -0.0008(19) -0.0006(18) C8 0.011(3) 0.024(3) 0.016(3) -0.001(2) -0.001(2) 0.001(2) C21 0.015(3) 0.017(3) 0.016(3) -0.002(2) -0.003(2) 0.004(2) C22 0.026(3) 0.036(4) 0.016(3) 0.003(2) 0.007(2) -0.007(2) O1 0.012(2) 0.040(3) 0.025(2) 0.0013(17) -0.0046(15) 0.0009(16) O2 0.021(2) 0.031(2) 0.029(2) 0.0117(17) -0.0031(16) 0.0073(16) N2 0.014(2) 0.026(3) 0.009(2) -0.0059(17) -0.0031(16) 0.0059(17) C4 0.007(2) 0.020(3) 0.015(3) 0.0055(19) -0.0007(18) -0.0009(18) C5 0.015(3) 0.014(3) 0.019(3) 0.0024(19) 0.005(2) 0.0004(19) C11 0.011(3) 0.020(3) 0.017(3) -0.004(2) 0.0017(19) -0.0014(19) C3 0.011(3) 0.022(3) 0.012(3) 0.0025(19) -0.0005(19) -0.0031(19) _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 I1 Pd1 2.6144(5) . ? Pd1 C7 1.984(5) . ? Pd1 N1 2.152(4) . ? Pd1 S1 2.2846(12) . ? S1 C22 1.801(5) . ? S1 C21 1.814(5) . ? N1 C2 1.344(6) . ? N1 C6 1.348(6) . ? C9 C10 1.380(7) . ? C9 C8 1.388(7) . ? C9 H9 0.9500 . ? C2 C3 1.390(7) . ? C2 C21 1.505(7) . ? C6 C5 1.368(7) . ? C6 H6 0.9500 . ? C10 C11 1.384(7) . ? C10 N2 1.476(6) . ? C7 C8 1.392(7) . ? C7 C12 1.408(7) . ? C12 C11 1.397(7) . ? C12 H12 0.9500 . ? C8 H8 0.9500 . ? C21 H21A 0.9900 . ? C21 H21B 0.9900 . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? O1 N2 1.228(6) . ? O2 N2 1.235(6) . ? C4 C3 1.387(7) . ? C4 C5 1.387(7) . ? C4 H4 0.9500 . ? C5 H5 0.9500 . ? C11 H11 0.9500 . ? C3 H3 0.9500 . ? 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 C7 Pd1 N1 173.94(17) . . ? C7 Pd1 S1 89.50(13) . . ? N1 Pd1 S1 84.46(11) . . ? C7 Pd1 I1 87.66(13) . . ? N1 Pd1 I1 98.40(11) . . ? S1 Pd1 I1 174.90(3) . . ? C22 S1 C21 101.5(3) . . ? C22 S1 Pd1 104.69(19) . . ? C21 S1 Pd1 99.57(16) . . ? C2 N1 C6 117.9(4) . . ? C2 N1 Pd1 118.3(3) . . ? C6 N1 Pd1 123.7(3) . . ? C10 C9 C8 119.0(5) . . ? C10 C9 H9 120.5 . . ? C8 C9 H9 120.5 . . ? N1 C2 C3 122.1(4) . . ? N1 C2 C21 118.8(4) . . ? C3 C2 C21 119.0(4) . . ? N1 C6 C5 122.9(5) . . ? N1 C6 H6 118.5 . . ? C5 C6 H6 118.5 . . ? C9 C10 C11 122.4(5) . . ? C9 C10 N2 118.9(4) . . ? C11 C10 N2 118.6(4) . . ? C8 C7 C12 118.2(4) . . ? C8 C7 Pd1 120.5(4) . . ? C12 C7 Pd1 121.3(4) . . ? C11 C12 C7 121.5(5) . . ? C11 C12 H12 119.2 . . ? C7 C12 H12 119.2 . . ? C9 C8 C7 121.1(5) . . ? C9 C8 H8 119.4 . . ? C7 C8 H8 119.4 . . ? C2 C21 S1 114.8(3) . . ? C2 C21 H21A 108.6 . . ? S1 C21 H21A 108.6 . . ? C2 C21 H21B 108.6 . . ? S1 C21 H21B 108.6 . . ? H21A C21 H21B 107.5 . . ? S1 C22 H22A 109.5 . . ? S1 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? S1 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? O1 N2 O2 123.7(4) . . ? O1 N2 C10 118.0(4) . . ? O2 N2 C10 118.3(4) . . ? C3 C4 C5 118.0(4) . . ? C3 C4 H4 121.0 . . ? C5 C4 H4 121.0 . . ? C6 C5 C4 119.5(5) . . ? C6 C5 H5 120.2 . . ? C4 C5 H5 120.2 . . ? C10 C11 C12 117.7(5) . . ? C10 C11 H11 121.1 . . ? C12 C11 H11 121.1 . . ? C4 C3 C2 119.4(5) . . ? C4 C3 H3 120.3 . . ? C2 C3 H3 120.3 . . ? 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 C7 Pd1 S1 C22 89.4(3) . . . . ? N1 Pd1 S1 C22 -90.2(2) . . . . ? I1 Pd1 S1 C22 145.5(4) . . . . ? C7 Pd1 S1 C21 -165.9(2) . . . . ? N1 Pd1 S1 C21 14.5(2) . . . . ? I1 Pd1 S1 C21 -109.8(4) . . . . ? C7 Pd1 N1 C2 -12.2(18) . . . . ? S1 Pd1 N1 C2 -8.6(3) . . . . ? I1 Pd1 N1 C2 167.1(3) . . . . ? C7 Pd1 N1 C6 164.4(15) . . . . ? S1 Pd1 N1 C6 168.0(4) . . . . ? I1 Pd1 N1 C6 -16.3(4) . . . . ? C6 N1 C2 C3 2.2(7) . . . . ? Pd1 N1 C2 C3 179.0(3) . . . . ? C6 N1 C2 C21 179.7(4) . . . . ? Pd1 N1 C2 C21 -3.5(6) . . . . ? C2 N1 C6 C5 -2.8(7) . . . . ? Pd1 N1 C6 C5 -179.4(4) . . . . ? C8 C9 C10 C11 1.2(7) . . . . ? C8 C9 C10 N2 -178.5(4) . . . . ? N1 Pd1 C7 C8 96.9(17) . . . . ? S1 Pd1 C7 C8 93.3(4) . . . . ? I1 Pd1 C7 C8 -82.4(4) . . . . ? N1 Pd1 C7 C12 -80.7(17) . . . . ? S1 Pd1 C7 C12 -84.3(4) . . . . ? I1 Pd1 C7 C12 99.9(4) . . . . ? C8 C7 C12 C11 1.8(7) . . . . ? Pd1 C7 C12 C11 179.5(4) . . . . ? C10 C9 C8 C7 0.6(8) . . . . ? C12 C7 C8 C9 -2.1(7) . . . . ? Pd1 C7 C8 C9 -179.8(4) . . . . ? N1 C2 C21 S1 18.1(6) . . . . ? C3 C2 C21 S1 -164.4(4) . . . . ? C22 S1 C21 C2 86.1(4) . . . . ? Pd1 S1 C21 C2 -21.2(4) . . . . ? C9 C10 N2 O1 178.5(4) . . . . ? C11 C10 N2 O1 -1.3(6) . . . . ? C9 C10 N2 O2 1.0(6) . . . . ? C11 C10 N2 O2 -178.8(4) . . . . ? N1 C6 C5 C4 1.3(7) . . . . ? C3 C4 C5 C6 1.0(7) . . . . ? C9 C10 C11 C12 -1.5(7) . . . . ? N2 C10 C11 C12 178.3(4) . . . . ? C7 C12 C11 C10 0.0(7) . . . . ? C5 C4 C3 C2 -1.5(7) . . . . ? N1 C2 C3 C4 -0.1(7) . . . . ? C21 C2 C3 C4 -177.5(4) . . . . ? _diffrn_measured_fraction_theta_max 0.960 _diffrn_reflns_theta_full 26.44 _diffrn_measured_fraction_theta_full 0.960 _refine_diff_density_max 0.748 _refine_diff_density_min -1.497 _refine_diff_density_rms 0.184