# Electronic Supplementary Material (ESI) for Green Chemistry # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Green Chemistry' _journal_coden_cambridge 1048 #TrackingRef '- 3_9b.cif' #=============================================================================== # 1. SUBMISSION DETAILS _publ_contact_author # Name and address of author for correspondence ; Josefina D\'iez Departamento de Qu\'imica Org\'anica e Inorg\'anica Facultad de Qu\'imica Universidad de Oviedo Avda. Juli\'an Claver\'ia, 8 33006 Oviedo Spain ; _publ_contact_author_phone '0034 98 5102960' _publ_contact_author_fax '0034 98 5103446' _publ_contact_author_email jdv@uniovi.es _publ_requested_coeditor_name ? _publ_contact_letter ; Oviedo 25/07/2012 Please receive the CIF for compounds 3 and 7a submitted to be published in Green Chemistry. Thank you very much. J. D\'iez. ; #============================================================================== # 2. PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_date_printers_first ? _journal_date_printers_final ? _journal_date_proofs_out ? _journal_date_proofs_in ? _journal_coeditor_name ? _journal_coeditor_code ? _journal_coeditor_notes ? _journal_techeditor_code ? _journal_techeditor_notes ? _journal_coden_ASTM ? _journal_year ? _journal_volume ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? #============================================================================== # 3. TITLE, ABSTRACT AND AUTHOR LIST _publ_section_title ; Pd(II)-Catalyzed Cycloisomerisation of \g-Alkynoic Acids and One-Pot Tandem Cycloisomerisation/CuAAC Reactions in Water. ; _publ_section_abstract ; Cycloisomerisation reactions of \g-alkynoic acids into cyclic enol-lactones can be conveniently performed in pure water as solvent and under aerobic conditions by using a novel iminophosphorane-Pd(II) complex trans-[PdCl2{\m^2^-N,S-(PTA)=NP(=S)(OEt)2}]2 as catalyst. It is important to note that the catalytic system could be recycled up to 10 consecutive runs. In addition and for the first time, a one-pot tandem orthogonal reaction involving the fast cycloisomerisation of \g-alkynoic acids, followed by an intermolecular atom economically process, i.e. the 1,3-dipolar cycloaddition of azides with terminal alkynes (CuAAC), is reported. This new tandem cycloisomerisation/click chemistry reaction proceeds also in water, at room temperature and under aerobic conditions, giving rise to unprecedented bicyclic triazol-enol-lactones under the principles of the so called ^"^Green Chemistry^"^. ; # The loop structure below should contain the names and addresses of all #authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address J.Garcia-Alvarez ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Facultad de Qu\'imica Universidad de Oviedo Avda. Juli\'an Claver\'ia, 8 33006 Oviedo Spain ; J.Diez ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Facultad de Qu\'imica Universidad de Oviedo Avda. Juli\'an Claver\'ia, 8 33006 Oviedo Spain ; 'Cristian Vidal' ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Facultad de Qu\'imica Universidad de Oviedo Avda. Juli\'an Claver\'ia, 8 33006 Oviedo Spain ; _publ_contact_author_name 'Josefina Diez' #=============================================================================== data_3 _database_code_depnum_ccdc_archive 'CCDC 894082' #TrackingRef '- 3_9b.cif' #=============================================================================== _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C20 H44 Cl4 N8 O4 P4 Pd2 S2, C4 H10 O, C H2 Cl2' _chemical_formula_sum 'C25 H56 Cl6 N8 O5 P4 Pd2 S2' _chemical_formula_weight 1162.28 _chemical_compound_source synthesis 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' P P 0.1023 0.0942 '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' Cl Cl 0.1484 0.1585 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 12.8415(5) _cell_length_b 13.0797(5) _cell_length_c 28.1381(12) _cell_angle_alpha 90.00 _cell_angle_beta 109.006(1) _cell_angle_gamma 90.00 _cell_volume 4468.5(3) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 7473 _cell_measurement_theta_min 0.407 _cell_measurement_theta_max 25.350 _exptl_crystal_description Prism _exptl_crystal_colour Orange _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.728 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2352 _exptl_absorpt_coefficient_mu 1.444 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.778 _exptl_absorpt_correction_T_max 0.916 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'horizonally mounted graphite crystal' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 9 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 31922 _diffrn_reflns_av_R_equivalents 0.051 _diffrn_reflns_av_sigmaI/netI 0.1137 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -34 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.53 _diffrn_reflns_theta_max 25.45 _reflns_number_total 8114 _reflns_number_gt 5223 _reflns_threshold_expression >2\s(I) _computing_data_collection 'Collect (Bruker, 2004)' _computing_cell_refinement 'HKL Scalepack (Otwinowki & Minor 1997)' _computing_data_reduction 'HKL Denzo and scalepack (Otwinowski & Minor 1997)' _computing_structure_solution 'SIR-92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 2007)' _computing_publication_material 'WinGX publication routines (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^ > 2\s(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^)+(0.0813P)^2^+0.0000P] 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 8114 _refine_ls_number_parameters 414 _refine_ls_number_restraints 5 _refine_ls_R_factor_all 0.0826 _refine_ls_R_factor_gt 0.0459 _refine_ls_wR_factor_ref 0.1580 _refine_ls_wR_factor_gt 0.1290 _refine_ls_goodness_of_fit_ref 0.946 _refine_ls_restrained_S_all 0.958 _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 C1 C 0.9592(6) 0.2161(5) 0.3263(3) 0.0196(18) Uani 1 1 d . . . H1A H 0.9868 0.2050 0.3623 0.024 Uiso 1 1 calc R . . H1B H 0.8819 0.2343 0.3172 0.024 Uiso 1 1 calc R . . C2 C 0.9802(6) 0.3157(6) 0.2427(3) 0.0200(18) Uani 1 1 d . . . H2A H 0.9035 0.3363 0.2313 0.024 Uiso 1 1 calc R . . H2B H 1.0209 0.3624 0.2285 0.024 Uiso 1 1 calc R . . C3 C 1.1698(6) 0.2625(6) 0.3233(3) 0.025(2) Uani 1 1 d . . . H3A H 1.2175 0.3079 0.3125 0.030 Uiso 1 1 calc R . . H3B H 1.2029 0.2504 0.3591 0.030 Uiso 1 1 calc R . . C4 C 0.9273(6) 0.1364(6) 0.2437(3) 0.0198(18) Uani 1 1 d . . . H4A H 0.9278 0.0719 0.2267 0.024 Uiso 1 1 calc R . . H4B H 0.8515 0.1594 0.2344 0.024 Uiso 1 1 calc R . . C5 C 1.1064(6) 0.1788(6) 0.2415(3) 0.025(2) Uani 1 1 d . . . H5A H 1.1112 0.1151 0.2247 0.030 Uiso 1 1 calc R . . H5B H 1.1483 0.2299 0.2304 0.030 Uiso 1 1 calc R . . C6 C 1.0916(6) 0.0903(6) 0.3128(4) 0.025(2) Uani 1 1 d . . . H6A H 1.1233 0.0834 0.3490 0.030 Uiso 1 1 calc R . . H6B H 1.0969 0.0243 0.2980 0.030 Uiso 1 1 calc R . . C7 C 1.0255(8) 0.3695(7) 0.4724(4) 0.0427(13) Uani 1 1 d . . . H7A H 0.9529 0.3905 0.4722 0.051 Uiso 1 1 calc R . . H7B H 1.0789 0.4189 0.4918 0.051 Uiso 1 1 calc R . . C8 C 1.0521(11) 0.2651(9) 0.4950(4) 0.0712(19) Uani 1 1 d . . . H8A H 0.9986 0.2170 0.4756 0.107 Uiso 1 1 calc R . . H8B H 1.0508 0.2661 0.5289 0.107 Uiso 1 1 calc R . . H8C H 1.1241 0.2452 0.4950 0.107 Uiso 1 1 calc R . . C9 C 1.0916(8) 0.6392(7) 0.3986(4) 0.0427(13) Uani 1 1 d . . . H9A H 1.0225 0.6758 0.3914 0.051 Uiso 1 1 calc R . . H9B H 1.1114 0.6370 0.3681 0.051 Uiso 1 1 calc R . . C10 C 1.1802(10) 0.6916(9) 0.4399(5) 0.0712(19) Uani 1 1 d . . . H10A H 1.1549 0.7027 0.4681 0.107 Uiso 1 1 calc R . . H10B H 1.1974 0.7561 0.4280 0.107 Uiso 1 1 calc R . . H10C H 1.2450 0.6495 0.4501 0.107 Uiso 1 1 calc R . . C11 C 0.4387(6) 0.1168(6) 0.3273(3) 0.0217(18) Uani 1 1 d . . . H11A H 0.3738 0.0740 0.3147 0.026 Uiso 1 1 calc R . . H11B H 0.4586 0.1206 0.3636 0.026 Uiso 1 1 calc R . . C12 C 0.6528(6) 0.1643(5) 0.3307(3) 0.0162(17) Uani 1 1 d . . . H12A H 0.6772 0.1685 0.3671 0.019 Uiso 1 1 calc R . . H12B H 0.7165 0.1488 0.3206 0.019 Uiso 1 1 calc R . . C13 C 0.5047(6) 0.0802(6) 0.2419(3) 0.0207(19) Uani 1 1 d . . . H13A H 0.5630 0.0631 0.2284 0.025 Uiso 1 1 calc R . . H13B H 0.4420 0.0364 0.2262 0.025 Uiso 1 1 calc R . . C14 C 0.3822(6) 0.2151(6) 0.2505(3) 0.0222(19) Uani 1 1 d . . . H14A H 0.3528 0.2811 0.2369 0.027 Uiso 1 1 calc R . . H14B H 0.3238 0.1650 0.2382 0.027 Uiso 1 1 calc R . . C15 C 0.5060(6) 0.2904(5) 0.3258(3) 0.0186(18) Uani 1 1 d . . . H15A H 0.5287 0.2887 0.3622 0.022 Uiso 1 1 calc R . . H15B H 0.4808 0.3591 0.3150 0.022 Uiso 1 1 calc R . . C16 C 0.5647(6) 0.2581(6) 0.2524(3) 0.0187(18) Uani 1 1 d . . . H16A H 0.5422 0.3257 0.2387 0.022 Uiso 1 1 calc R . . H16B H 0.6252 0.2366 0.2412 0.022 Uiso 1 1 calc R . . C17 C 0.6748(8) -0.2934(7) 0.3953(4) 0.0427(13) Uani 1 1 d . . . H17A H 0.7530 -0.3018 0.4013 0.051 Uiso 1 1 calc R . . H17B H 0.6353 -0.3183 0.3618 0.051 Uiso 1 1 calc R . . C18 C 0.6418(11) -0.3526(9) 0.4329(4) 0.0712(19) Uani 1 1 d . . . H18A H 0.6796 -0.3265 0.4659 0.107 Uiso 1 1 calc R . . H18B H 0.6607 -0.4232 0.4313 0.107 Uiso 1 1 calc R . . H18C H 0.5637 -0.3466 0.4259 0.107 Uiso 1 1 calc R . . C19 C 0.7946(8) -0.0119(7) 0.4636(4) 0.0427(13) Uani 1 1 d . . . H19A H 0.8674 -0.0199 0.4607 0.051 Uiso 1 1 calc R . . H19B H 0.7797 -0.0704 0.4816 0.051 Uiso 1 1 calc R . . C20 C 0.7879(11) 0.0856(9) 0.4907(4) 0.0712(19) Uani 1 1 d . . . H20A H 0.7940 0.1429 0.4705 0.107 Uiso 1 1 calc R . . H20B H 0.8469 0.0876 0.5222 0.107 Uiso 1 1 calc R . . H20C H 0.7186 0.0885 0.4967 0.107 Uiso 1 1 calc R . . C22 C 0.6176(9) 0.3353(9) 0.1318(5) 0.061(3) Uani 1 1 d . . . H22A H 0.6001 0.3649 0.1599 0.074 Uiso 1 1 calc R . . H22B H 0.5506 0.3352 0.1031 0.074 Uiso 1 1 calc R . . C23 C 0.4950(11) 0.2359(10) 0.4728(6) 0.087(4) Uiso 1 1 d D . . H23A H 0.5254 0.2655 0.5060 0.104 Uiso 1 1 calc R . . H23B H 0.5537 0.2242 0.4588 0.104 Uiso 1 1 calc R . . C24 C 0.4432(9) 0.3943(8) 0.4446(4) 0.057(3) Uiso 1 1 d D . . H24A H 0.4513 0.4209 0.4778 0.068 Uiso 1 1 calc R . . H24B H 0.5137 0.4017 0.4393 0.068 Uiso 1 1 calc R . . C25 C 0.4376(16) 0.1480(13) 0.4736(8) 0.160(9) Uiso 1 1 d D . . H25A H 0.3954 0.1567 0.4959 0.240 Uiso 1 1 calc R . . H25B H 0.4882 0.0923 0.4851 0.240 Uiso 1 1 calc R . . H25C H 0.3888 0.1334 0.4404 0.240 Uiso 1 1 calc R . . C26 C 0.3692(12) 0.4520(12) 0.4106(6) 0.110(6) Uiso 1 1 d D . . H26A H 0.3459 0.4174 0.3788 0.165 Uiso 1 1 calc R . . H26B H 0.4021 0.5164 0.4072 0.165 Uiso 1 1 calc R . . H26C H 0.3067 0.4637 0.4215 0.165 Uiso 1 1 calc R . . N1 N 0.9705(5) 0.1189(4) 0.2997(3) 0.0187(15) Uani 1 1 d . . . N2 N 0.9906(5) 0.2110(5) 0.2263(3) 0.0216(16) Uani 1 1 d . . . N3 N 1.1557(5) 0.1646(5) 0.2955(3) 0.0259(17) Uani 1 1 d . . . N4 N 1.0264(5) 0.4280(5) 0.3350(3) 0.0272(17) Uani 1 1 d . . . N5 N 0.4153(5) 0.2192(4) 0.3055(3) 0.0182(15) Uani 1 1 d . . . N6 N 0.6058(5) 0.2653(4) 0.3089(2) 0.0164(14) Uani 1 1 d . . . N7 N 0.4733(5) 0.1883(5) 0.2320(2) 0.0168(14) Uani 1 1 d . . . N8 N 0.5900(5) -0.0517(5) 0.3279(3) 0.0201(15) Uani 1 1 d . . . O1 O 1.0290(5) 0.3638(4) 0.4206(2) 0.0312(14) Uani 1 1 d . . . O2 O 1.0811(5) 0.5421(5) 0.4146(3) 0.0400(17) Uani 1 1 d . . . O3 O 0.7117(4) -0.0040(4) 0.4139(2) 0.0254(13) Uani 1 1 d . . . O4 O 0.6494(4) -0.1849(4) 0.3992(2) 0.0280(14) Uani 1 1 d . . . O5 O 0.4192(11) 0.2915(9) 0.4441(5) 0.135(4) Uiso 1 1 d D . . P1 P 0.99939(17) 0.45823(16) 0.38402(9) 0.0245(5) Uani 1 1 d . . . P2 P 1.03408(16) 0.32037(15) 0.31031(9) 0.0210(5) Uani 1 1 d . . . P3 P 0.68915(16) -0.09181(15) 0.37381(9) 0.0207(5) Uani 1 1 d . . . P4 P 0.55209(15) 0.06180(15) 0.31006(8) 0.0171(5) Uani 1 1 d . . . S1 S 0.84842(16) 0.51520(15) 0.37460(9) 0.0249(5) Uani 1 1 d . . . S2 S 0.82486(16) -0.14091(15) 0.35989(9) 0.0237(5) Uani 1 1 d . . . Cl1 Cl 0.72674(18) 0.34411(17) 0.41830(8) 0.0323(5) Uani 1 1 d . . . Cl2 Cl 0.73998(15) 0.42549(15) 0.26098(8) 0.0227(5) Uani 1 1 d . . . Cl3 Cl 0.76238(15) -0.03133(14) 0.24901(8) 0.0227(5) Uani 1 1 d . . . Cl4 Cl 1.00906(19) 0.02773(19) 0.40690(9) 0.0413(6) Uani 1 1 d . . . Cl5 Cl 0.7150(3) 0.4124(3) 0.11817(16) 0.0900(12) Uani 1 1 d . . . Cl6 Cl 0.6598(3) 0.2106(3) 0.14640(12) 0.0683(9) Uani 1 1 d . . . Pd1 Pd 0.72937(5) 0.38269(4) 0.33918(2) 0.01695(17) Uani 1 1 d . . . Pd2 Pd 0.88954(5) -0.00123(4) 0.32758(2) 0.01920(17) 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 0.012(4) 0.015(4) 0.034(5) 0.002(4) 0.010(4) 0.001(3) C2 0.016(4) 0.015(4) 0.035(5) -0.001(4) 0.016(4) 0.000(3) C3 0.011(4) 0.019(4) 0.045(6) 0.001(4) 0.008(4) -0.004(3) C4 0.017(4) 0.014(4) 0.031(5) 0.001(3) 0.010(4) -0.001(3) C5 0.022(4) 0.016(4) 0.046(6) -0.004(4) 0.022(4) -0.001(3) C6 0.011(4) 0.016(4) 0.047(6) 0.001(4) 0.010(4) 0.001(3) C7 0.047(3) 0.042(3) 0.038(3) 0.002(2) 0.012(3) -0.003(2) C8 0.094(5) 0.060(4) 0.052(4) -0.001(3) 0.012(4) -0.014(4) C9 0.047(3) 0.042(3) 0.038(3) 0.002(2) 0.012(3) -0.003(2) C10 0.094(5) 0.060(4) 0.052(4) -0.001(3) 0.012(4) -0.014(4) C11 0.013(4) 0.020(4) 0.036(5) -0.001(4) 0.012(4) -0.005(3) C12 0.013(4) 0.011(4) 0.024(5) 0.003(3) 0.005(3) 0.003(3) C13 0.008(4) 0.021(4) 0.031(5) -0.003(4) 0.002(4) -0.001(3) C14 0.011(4) 0.020(4) 0.034(6) 0.002(4) 0.006(4) 0.005(3) C15 0.016(4) 0.010(4) 0.033(5) 0.000(3) 0.012(4) 0.003(3) C16 0.015(4) 0.016(4) 0.026(5) 0.005(3) 0.007(4) 0.005(3) C17 0.047(3) 0.042(3) 0.038(3) 0.002(2) 0.012(3) -0.003(2) C18 0.094(5) 0.060(4) 0.052(4) -0.001(3) 0.012(4) -0.014(4) C19 0.047(3) 0.042(3) 0.038(3) 0.002(2) 0.012(3) -0.003(2) C20 0.094(5) 0.060(4) 0.052(4) -0.001(3) 0.012(4) -0.014(4) C22 0.042(6) 0.067(8) 0.072(9) -0.007(7) 0.013(6) 0.002(6) N1 0.012(3) 0.010(3) 0.036(4) -0.003(3) 0.010(3) -0.002(3) N2 0.017(3) 0.015(3) 0.036(5) 0.000(3) 0.013(3) 0.000(3) N3 0.016(3) 0.015(3) 0.050(5) -0.001(3) 0.015(4) -0.001(3) N4 0.024(4) 0.015(3) 0.050(5) -0.008(3) 0.023(4) -0.007(3) N5 0.012(3) 0.015(3) 0.030(4) 0.006(3) 0.009(3) 0.003(3) N6 0.011(3) 0.012(3) 0.028(4) -0.003(3) 0.009(3) -0.001(2) N7 0.014(3) 0.017(3) 0.019(4) 0.004(3) 0.005(3) 0.003(3) N8 0.014(3) 0.013(3) 0.031(4) 0.001(3) 0.004(3) -0.003(3) O1 0.027(3) 0.029(3) 0.036(4) -0.004(3) 0.007(3) 0.003(3) O2 0.040(4) 0.033(4) 0.052(5) -0.021(3) 0.021(3) -0.018(3) O3 0.030(3) 0.018(3) 0.026(3) 0.003(2) 0.006(3) 0.008(2) O4 0.032(3) 0.017(3) 0.045(4) 0.012(3) 0.026(3) 0.006(2) P1 0.0173(11) 0.0199(11) 0.0375(15) -0.0089(10) 0.0106(10) -0.0041(9) P2 0.0150(10) 0.0147(10) 0.0378(15) -0.0023(9) 0.0145(10) -0.0021(8) P3 0.0183(10) 0.0138(10) 0.0310(14) 0.0047(9) 0.0096(10) 0.0024(8) P4 0.0115(9) 0.0126(10) 0.0269(13) 0.0023(9) 0.0058(9) 0.0000(8) S1 0.0206(10) 0.0158(10) 0.0412(14) -0.0082(9) 0.0142(10) -0.0022(8) S2 0.0183(10) 0.0165(10) 0.0391(14) 0.0058(9) 0.0132(10) 0.0026(8) Cl1 0.0368(12) 0.0370(12) 0.0241(13) -0.0029(10) 0.0113(10) -0.0140(10) Cl2 0.0177(9) 0.0226(10) 0.0301(13) 0.0060(9) 0.0111(9) -0.0002(8) Cl3 0.0154(9) 0.0227(10) 0.0305(12) -0.0024(9) 0.0083(9) -0.0034(8) Cl4 0.0383(13) 0.0446(14) 0.0323(14) 0.0079(11) -0.0006(11) -0.0162(11) Cl5 0.088(3) 0.091(3) 0.109(3) -0.030(2) 0.057(2) -0.033(2) Cl6 0.072(2) 0.075(2) 0.063(2) -0.0055(17) 0.0294(18) 0.0181(17) Pd1 0.0139(3) 0.0132(3) 0.0254(4) 0.0002(3) 0.0086(3) 0.0000(2) Pd2 0.0137(3) 0.0147(3) 0.0299(4) 0.0017(3) 0.0080(3) -0.0008(2) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 N1 1.507(9) . ? C1 P2 1.808(7) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C2 N2 1.466(9) . ? C2 P2 1.800(9) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 N3 1.482(10) . ? C3 P2 1.824(7) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 N2 1.454(9) . ? C4 N1 1.509(10) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 N3 1.456(11) . ? C5 N2 1.468(9) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 N3 1.456(10) . ? C6 N1 1.523(9) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 O1 1.475(11) . ? C7 C8 1.499(14) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 H8A 0.9600 . ? C8 H8B 0.9600 . ? C8 H8C 0.9600 . ? C9 O2 1.369(11) . ? C9 C10 1.503(14) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C11 N5 1.463(9) . ? C11 P4 1.826(7) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 N6 1.498(9) . ? C12 P4 1.822(7) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 N7 1.472(9) . ? C13 P4 1.828(8) . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 N5 1.468(10) . ? C14 N7 1.470(9) . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C15 N5 1.455(9) . ? C15 N6 1.539(9) . ? C15 H15A 0.9700 . ? C15 H15B 0.9700 . ? C16 N7 1.449(9) . ? C16 N6 1.507(10) . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C17 O4 1.468(10) . ? C17 C18 1.480(14) . ? C17 H17A 0.9700 . ? C17 H17B 0.9700 . ? C18 H18A 0.9600 . ? C18 H18B 0.9600 . ? C18 H18C 0.9600 . ? C19 O3 1.459(11) . ? C19 C20 1.502(14) . ? C19 H19A 0.9700 . ? C19 H19B 0.9700 . ? C20 H20A 0.9600 . ? C20 H20B 0.9600 . ? C20 H20C 0.9600 . ? C22 Cl6 1.726(12) . ? C22 Cl5 1.745(11) . ? C22 H22A 0.9700 . ? C22 H22B 0.9700 . ? C23 O5 1.270(13) . ? C23 C25 1.370(15) . ? C23 H23A 0.9700 . ? C23 H23B 0.9700 . ? C24 C26 1.340(13) . ? C24 O5 1.378(12) . ? C24 H24A 0.9700 . ? C24 H24B 0.9700 . ? C25 H25A 0.9600 . ? C25 H25B 0.9600 . ? C25 H25C 0.9600 . ? C26 H26A 0.9600 . ? C26 H26B 0.9600 . ? C26 H26C 0.9600 . ? N1 Pd2 2.167(6) . ? N4 P1 1.579(7) . ? N4 P2 1.587(7) . ? N6 Pd1 2.173(6) . ? N8 P3 1.579(7) . ? N8 P4 1.592(6) . ? O1 P1 1.573(6) . ? O2 P1 1.567(6) . ? O3 P3 1.570(6) . ? O4 P3 1.578(5) . ? P1 S1 2.012(3) . ? P3 S2 2.012(3) . ? S1 Pd1 2.311(2) . ? S2 Pd2 2.312(2) . ? Cl1 Pd1 2.294(2) . ? Cl2 Pd1 2.317(2) . ? Cl3 Pd2 2.315(2) . ? Cl4 Pd2 2.291(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 N1 C1 P2 111.6(5) . . ? N1 C1 H1A 109.3 . . ? P2 C1 H1A 109.3 . . ? N1 C1 H1B 109.3 . . ? P2 C1 H1B 109.3 . . ? H1A C1 H1B 108.0 . . ? N2 C2 P2 108.8(5) . . ? N2 C2 H2A 109.9 . . ? P2 C2 H2A 109.9 . . ? N2 C2 H2B 109.9 . . ? P2 C2 H2B 109.9 . . ? H2A C2 H2B 108.3 . . ? N3 C3 P2 108.0(5) . . ? N3 C3 H3A 110.1 . . ? P2 C3 H3A 110.1 . . ? N3 C3 H3B 110.1 . . ? P2 C3 H3B 110.1 . . ? H3A C3 H3B 108.4 . . ? N2 C4 N1 113.4(6) . . ? N2 C4 H4A 108.9 . . ? N1 C4 H4A 108.9 . . ? N2 C4 H4B 108.9 . . ? N1 C4 H4B 108.9 . . ? H4A C4 H4B 107.7 . . ? N3 C5 N2 113.3(7) . . ? N3 C5 H5A 108.9 . . ? N2 C5 H5A 108.9 . . ? N3 C5 H5B 108.9 . . ? N2 C5 H5B 108.9 . . ? H5A C5 H5B 107.7 . . ? N3 C6 N1 113.5(6) . . ? N3 C6 H6A 108.9 . . ? N1 C6 H6A 108.9 . . ? N3 C6 H6B 108.9 . . ? N1 C6 H6B 108.9 . . ? H6A C6 H6B 107.7 . . ? O1 C7 C8 107.3(8) . . ? O1 C7 H7A 110.3 . . ? C8 C7 H7A 110.3 . . ? O1 C7 H7B 110.3 . . ? C8 C7 H7B 110.3 . . ? H7A C7 H7B 108.5 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? O2 C9 C10 107.4(9) . . ? O2 C9 H9A 110.2 . . ? C10 C9 H9A 110.2 . . ? O2 C9 H9B 110.2 . . ? C10 C9 H9B 110.2 . . ? H9A C9 H9B 108.5 . . ? C9 C10 H10A 109.5 . . ? C9 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C9 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N5 C11 P4 108.8(5) . . ? N5 C11 H11A 109.9 . . ? P4 C11 H11A 109.9 . . ? N5 C11 H11B 109.9 . . ? P4 C11 H11B 109.9 . . ? H11A C11 H11B 108.3 . . ? N6 C12 P4 111.6(5) . . ? N6 C12 H12A 109.3 . . ? P4 C12 H12A 109.3 . . ? N6 C12 H12B 109.3 . . ? P4 C12 H12B 109.3 . . ? H12A C12 H12B 108.0 . . ? N7 C13 P4 107.6(5) . . ? N7 C13 H13A 110.2 . . ? P4 C13 H13A 110.2 . . ? N7 C13 H13B 110.2 . . ? P4 C13 H13B 110.2 . . ? H13A C13 H13B 108.5 . . ? N5 C14 N7 113.1(6) . . ? N5 C14 H14A 109.0 . . ? N7 C14 H14A 109.0 . . ? N5 C14 H14B 109.0 . . ? N7 C14 H14B 109.0 . . ? H14A C14 H14B 107.8 . . ? N5 C15 N6 112.5(6) . . ? N5 C15 H15A 109.1 . . ? N6 C15 H15A 109.1 . . ? N5 C15 H15B 109.1 . . ? N6 C15 H15B 109.1 . . ? H15A C15 H15B 107.8 . . ? N7 C16 N6 114.7(6) . . ? N7 C16 H16A 108.6 . . ? N6 C16 H16A 108.6 . . ? N7 C16 H16B 108.6 . . ? N6 C16 H16B 108.6 . . ? H16A C16 H16B 107.6 . . ? O4 C17 C18 109.4(9) . . ? O4 C17 H17A 109.8 . . ? C18 C17 H17A 109.8 . . ? O4 C17 H17B 109.8 . . ? C18 C17 H17B 109.8 . . ? H17A C17 H17B 108.3 . . ? C17 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C17 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? O3 C19 C20 106.3(8) . . ? O3 C19 H19A 110.5 . . ? C20 C19 H19A 110.5 . . ? O3 C19 H19B 110.5 . . ? C20 C19 H19B 110.5 . . ? H19A C19 H19B 108.7 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? Cl6 C22 Cl5 114.0(6) . . ? Cl6 C22 H22A 108.8 . . ? Cl5 C22 H22A 108.8 . . ? Cl6 C22 H22B 108.8 . . ? Cl5 C22 H22B 108.8 . . ? H22A C22 H22B 107.7 . . ? O5 C23 C25 100.7(14) . . ? O5 C23 H23A 111.6 . . ? C25 C23 H23A 111.6 . . ? O5 C23 H23B 111.6 . . ? C25 C23 H23B 111.6 . . ? H23A C23 H23B 109.4 . . ? C26 C24 O5 116.0(12) . . ? C26 C24 H24A 108.3 . . ? O5 C24 H24A 108.3 . . ? C26 C24 H24B 108.3 . . ? O5 C24 H24B 108.3 . . ? H24A C24 H24B 107.4 . . ? C23 C25 H25A 109.5 . . ? C23 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? C23 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? C24 C26 H26A 109.5 . . ? C24 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C24 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? C1 N1 C4 109.2(6) . . ? C1 N1 C6 110.1(6) . . ? C4 N1 C6 106.8(6) . . ? C1 N1 Pd2 107.3(4) . . ? C4 N1 Pd2 115.6(4) . . ? C6 N1 Pd2 107.9(4) . . ? C4 N2 C2 113.8(6) . . ? C4 N2 C5 109.5(6) . . ? C2 N2 C5 111.3(6) . . ? C5 N3 C6 109.5(6) . . ? C5 N3 C3 112.2(6) . . ? C6 N3 C3 112.6(7) . . ? P1 N4 P2 131.9(5) . . ? C15 N5 C11 113.1(6) . . ? C15 N5 C14 110.9(6) . . ? C11 N5 C14 111.0(6) . . ? C12 N6 C16 109.5(6) . . ? C12 N6 C15 109.1(6) . . ? C16 N6 C15 107.4(6) . . ? C12 N6 Pd1 108.5(4) . . ? C16 N6 Pd1 114.7(4) . . ? C15 N6 Pd1 107.7(4) . . ? C16 N7 C14 110.2(6) . . ? C16 N7 C13 113.2(6) . . ? C14 N7 C13 111.2(6) . . ? P3 N8 P4 130.6(4) . . ? C7 O1 P1 121.9(5) . . ? C9 O2 P1 126.1(6) . . ? C19 O3 P3 122.8(5) . . ? C17 O4 P3 126.9(5) . . ? C23 O5 C24 115.4(13) . . ? O2 P1 O1 102.4(4) . . ? O2 P1 N4 110.9(3) . . ? O1 P1 N4 107.4(3) . . ? O2 P1 S1 104.9(3) . . ? O1 P1 S1 113.2(2) . . ? N4 P1 S1 117.0(3) . . ? N4 P2 C2 115.8(4) . . ? N4 P2 C1 116.5(4) . . ? C2 P2 C1 100.7(4) . . ? N4 P2 C3 118.1(4) . . ? C2 P2 C3 102.2(4) . . ? C1 P2 C3 100.8(4) . . ? O3 P3 O4 104.5(3) . . ? O3 P3 N8 104.8(3) . . ? O4 P3 N8 109.4(3) . . ? O3 P3 S2 113.9(2) . . ? O4 P3 S2 105.7(2) . . ? N8 P3 S2 117.8(3) . . ? N8 P4 C12 118.2(3) . . ? N8 P4 C11 118.1(3) . . ? C12 P4 C11 99.8(3) . . ? N8 P4 C13 114.6(4) . . ? C12 P4 C13 101.4(4) . . ? C11 P4 C13 101.8(4) . . ? P1 S1 Pd1 104.64(10) . . ? P3 S2 Pd2 105.62(10) . . ? N6 Pd1 Cl1 89.13(18) . . ? N6 Pd1 S1 174.27(16) . . ? Cl1 Pd1 S1 87.89(8) . . ? N6 Pd1 Cl2 93.46(18) . . ? Cl1 Pd1 Cl2 177.29(8) . . ? S1 Pd1 Cl2 89.61(8) . . ? N1 Pd2 Cl4 89.11(18) . . ? N1 Pd2 S2 172.46(16) . . ? Cl4 Pd2 S2 87.71(8) . . ? N1 Pd2 Cl3 92.86(18) . . ? Cl4 Pd2 Cl3 177.38(8) . . ? S2 Pd2 Cl3 90.53(8) . . ? 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 P2 C1 N1 C4 -59.1(6) . . . . ? P2 C1 N1 C6 57.9(7) . . . . ? P2 C1 N1 Pd2 175.0(3) . . . . ? N2 C4 N1 C1 64.3(7) . . . . ? N2 C4 N1 C6 -54.7(7) . . . . ? N2 C4 N1 Pd2 -174.7(4) . . . . ? N3 C6 N1 C1 -64.0(9) . . . . ? N3 C6 N1 C4 54.4(8) . . . . ? N3 C6 N1 Pd2 179.3(6) . . . . ? N1 C4 N2 C2 -68.5(8) . . . . ? N1 C4 N2 C5 56.8(8) . . . . ? P2 C2 N2 C4 62.7(7) . . . . ? P2 C2 N2 C5 -61.6(7) . . . . ? N3 C5 N2 C4 -57.2(8) . . . . ? N3 C5 N2 C2 69.4(8) . . . . ? N2 C5 N3 C6 56.9(8) . . . . ? N2 C5 N3 C3 -68.9(8) . . . . ? N1 C6 N3 C5 -56.3(9) . . . . ? N1 C6 N3 C3 69.3(9) . . . . ? P2 C3 N3 C5 59.9(7) . . . . ? P2 C3 N3 C6 -64.2(8) . . . . ? N6 C15 N5 C11 69.7(8) . . . . ? N6 C15 N5 C14 -55.7(8) . . . . ? P4 C11 N5 C15 -64.4(7) . . . . ? P4 C11 N5 C14 61.0(7) . . . . ? N7 C14 N5 C15 56.3(8) . . . . ? N7 C14 N5 C11 -70.4(7) . . . . ? P4 C12 N6 C16 -57.3(7) . . . . ? P4 C12 N6 C15 59.9(7) . . . . ? P4 C12 N6 Pd1 176.9(3) . . . . ? N7 C16 N6 C12 64.7(7) . . . . ? N7 C16 N6 C15 -53.5(7) . . . . ? N7 C16 N6 Pd1 -173.1(4) . . . . ? N5 C15 N6 C12 -65.4(8) . . . . ? N5 C15 N6 C16 53.2(8) . . . . ? N5 C15 N6 Pd1 177.1(5) . . . . ? N6 C16 N7 C14 55.2(8) . . . . ? N6 C16 N7 C13 -70.1(8) . . . . ? N5 C14 N7 C16 -55.0(8) . . . . ? N5 C14 N7 C13 71.3(8) . . . . ? P4 C13 N7 C16 62.7(7) . . . . ? P4 C13 N7 C14 -62.0(7) . . . . ? C8 C7 O1 P1 176.9(7) . . . . ? C10 C9 O2 P1 -179.5(7) . . . . ? C20 C19 O3 P3 -178.3(7) . . . . ? C18 C17 O4 P3 168.1(7) . . . . ? C25 C23 O5 C24 165.3(14) . . . . ? C26 C24 O5 C23 172.9(15) . . . . ? C9 O2 P1 O1 177.8(7) . . . . ? C9 O2 P1 N4 63.4(8) . . . . ? C9 O2 P1 S1 -63.8(8) . . . . ? C7 O1 P1 O2 56.3(7) . . . . ? C7 O1 P1 N4 173.1(6) . . . . ? C7 O1 P1 S1 -56.1(7) . . . . ? P2 N4 P1 O2 135.6(6) . . . . ? P2 N4 P1 O1 24.5(7) . . . . ? P2 N4 P1 S1 -104.1(6) . . . . ? P1 N4 P2 C2 141.2(6) . . . . ? P1 N4 P2 C1 23.2(8) . . . . ? P1 N4 P2 C3 -97.1(6) . . . . ? N2 C2 P2 N4 -178.3(5) . . . . ? N2 C2 P2 C1 -51.8(5) . . . . ? N2 C2 P2 C3 51.9(6) . . . . ? N1 C1 P2 N4 178.6(5) . . . . ? N1 C1 P2 C2 52.6(6) . . . . ? N1 C1 P2 C3 -52.2(6) . . . . ? N3 C3 P2 N4 -178.8(5) . . . . ? N3 C3 P2 C2 -50.5(6) . . . . ? N3 C3 P2 C1 53.0(6) . . . . ? C19 O3 P3 O4 62.0(7) . . . . ? C19 O3 P3 N8 177.1(6) . . . . ? C19 O3 P3 S2 -52.8(7) . . . . ? C17 O4 P3 O3 -142.9(7) . . . . ? C17 O4 P3 N8 105.4(7) . . . . ? C17 O4 P3 S2 -22.4(8) . . . . ? P4 N8 P3 O3 26.8(6) . . . . ? P4 N8 P3 O4 138.4(5) . . . . ? P4 N8 P3 S2 -101.0(5) . . . . ? P3 N8 P4 C12 21.2(7) . . . . ? P3 N8 P4 C11 -99.2(6) . . . . ? P3 N8 P4 C13 140.7(5) . . . . ? N6 C12 P4 N8 177.5(5) . . . . ? N6 C12 P4 C11 -53.0(6) . . . . ? N6 C12 P4 C13 51.3(6) . . . . ? N5 C11 P4 N8 -177.9(5) . . . . ? N5 C11 P4 C12 52.5(6) . . . . ? N5 C11 P4 C13 -51.4(6) . . . . ? N7 C13 P4 N8 -179.9(4) . . . . ? N7 C13 P4 C12 -51.3(5) . . . . ? N7 C13 P4 C11 51.4(5) . . . . ? O2 P1 S1 Pd1 -172.6(3) . . . . ? O1 P1 S1 Pd1 -61.7(3) . . . . ? N4 P1 S1 Pd1 64.1(3) . . . . ? O3 P3 S2 Pd2 -62.2(3) . . . . ? O4 P3 S2 Pd2 -176.3(3) . . . . ? N8 P3 S2 Pd2 61.1(3) . . . . ? C12 N6 Pd1 Cl1 -61.3(5) . . . . ? C16 N6 Pd1 Cl1 176.0(4) . . . . ? C15 N6 Pd1 Cl1 56.6(4) . . . . ? C12 N6 Pd1 S1 -120.0(17) . . . . ? C16 N6 Pd1 S1 117.4(18) . . . . ? C15 N6 Pd1 S1 -2(2) . . . . ? C12 N6 Pd1 Cl2 117.8(5) . . . . ? C16 N6 Pd1 Cl2 -4.8(4) . . . . ? C15 N6 Pd1 Cl2 -124.3(4) . . . . ? P1 S1 Pd1 N6 155.7(18) . . . . ? P1 S1 Pd1 Cl1 97.01(13) . . . . ? P1 S1 Pd1 Cl2 -81.94(12) . . . . ? C1 N1 Pd2 Cl4 -60.1(4) . . . . ? C4 N1 Pd2 Cl4 177.9(5) . . . . ? C6 N1 Pd2 Cl4 58.5(5) . . . . ? C1 N1 Pd2 S2 -125.2(13) . . . . ? C4 N1 Pd2 S2 112.8(14) . . . . ? C6 N1 Pd2 S2 -6.6(18) . . . . ? C1 N1 Pd2 Cl3 118.2(4) . . . . ? C4 N1 Pd2 Cl3 -3.8(5) . . . . ? C6 N1 Pd2 Cl3 -123.2(5) . . . . ? P3 S2 Pd2 N1 162.1(14) . . . . ? P3 S2 Pd2 Cl4 96.94(13) . . . . ? P3 S2 Pd2 Cl3 -81.12(12) . . . . ? _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 25.45 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 1.870 _refine_diff_density_min -1.208 _refine_diff_density_rms 0.347 #===END #=============================================================================== data_9b _database_code_depnum_ccdc_archive 'CCDC 894083' #TrackingRef '- 3_9b.cif' #=============================================================================== _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H17 N3 O4' _chemical_formula_sum 'C17 H17 N3 O4' _chemical_formula_weight 327.34 _chemical_compound_source synthesis 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 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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/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 11.6784(2) _cell_length_b 5.6853(1) _cell_length_c 23.4754(3) _cell_angle_alpha 90.00 _cell_angle_beta 96.479(1) _cell_angle_gamma 90.00 _cell_volume 1548.70(4) _cell_formula_units_Z 4 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 6338 _cell_measurement_theta_min 3.7869 _cell_measurement_theta_max 74.3176 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.146 _exptl_crystal_size_mid 0.078 _exptl_crystal_size_min 0.062 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.404 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 688 _exptl_absorpt_coefficient_mu 0.846 _exptl_absorpt_correction_T_min 0.82139 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 1.54184 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'Nova (Cu) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Onyx, Nova' _diffrn_measurement_device ; 165 mm Onyx CCD detector in \k-geometry diffractometer ; _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.2640 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10719 _diffrn_reflns_av_R_equivalents 0.0487 _diffrn_reflns_av_sigmaI/netI 0.0346 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 3.79 _diffrn_reflns_theta_max 74.48 _reflns_number_total 3079 _reflns_number_gt 2636 _reflns_threshold_expression >2\s(I) _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) ; _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) ; _computing_structure_solution 'SIR-92 (Altomare, 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 2007)' _computing_publication_material 'WinGX publication routines (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^ > 2\s(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^)+(0.0545P)^2^+0.3672P] 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 3079 _refine_ls_number_parameters 218 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0460 _refine_ls_R_factor_gt 0.0389 _refine_ls_wR_factor_ref 0.1055 _refine_ls_wR_factor_gt 0.0984 _refine_ls_goodness_of_fit_ref 1.045 _refine_ls_restrained_S_all 1.045 _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 C1 C 0.58814(13) 0.2204(3) 0.53133(6) 0.0267(3) Uani 1 1 d . . . H1A H 0.6038 0.3623 0.5141 0.032 Uiso 1 1 calc R . . H1B H 0.6119 0.0795 0.5163 0.032 Uiso 1 1 calc R . . C2 C 0.53249(12) 0.2189(2) 0.57679(6) 0.0219(3) Uani 1 1 d . . . C3 C 0.49676(12) 0.0204(2) 0.61318(6) 0.0212(3) Uani 1 1 d . . . H3A H 0.5557 -0.1004 0.6180 0.025 Uiso 1 1 calc R . . H3B H 0.4250 -0.0495 0.5964 0.025 Uiso 1 1 calc R . . C4 C 0.48194(12) 0.1408(2) 0.67067(5) 0.0207(3) Uani 1 1 d . . . C5 C 0.46608(12) 0.3989(2) 0.65319(6) 0.0217(3) Uani 1 1 d . . . C6 C 0.37665(12) 0.0622(2) 0.69864(6) 0.0215(3) Uani 1 1 d . . . C7 C 0.17573(13) 0.0023(3) 0.68321(7) 0.0295(3) Uani 1 1 d . . . H7A H 0.1791 -0.1618 0.6930 0.044 Uiso 1 1 calc R . . H7B H 0.1117 0.0299 0.6546 0.044 Uiso 1 1 calc R . . H7C H 0.1662 0.0933 0.7168 0.044 Uiso 1 1 calc R . . C8 C 0.59033(12) 0.1199(3) 0.71490(6) 0.0236(3) Uani 1 1 d . . . H8A H 0.5829 0.2273 0.7464 0.028 Uiso 1 1 calc R . . H8B H 0.5947 -0.0385 0.7303 0.028 Uiso 1 1 calc R . . C9 C 0.69932(12) 0.1736(2) 0.68977(5) 0.0220(3) Uani 1 1 d . . . C10 C 0.74438(12) 0.3839(2) 0.67427(6) 0.0223(3) Uani 1 1 d . . . H10 H 0.7150 0.5338 0.6790 0.027 Uiso 1 1 calc R . . C11 C 0.91515(12) 0.4794(3) 0.62087(6) 0.0250(3) Uani 1 1 d . . . H11A H 0.9940 0.4234 0.6274 0.030 Uiso 1 1 calc R . . H11B H 0.9130 0.6377 0.6361 0.030 Uiso 1 1 calc R . . C12 C 0.87644(12) 0.4833(2) 0.55716(6) 0.0233(3) Uani 1 1 d . . . C13 C 0.81648(12) 0.6759(3) 0.53220(6) 0.0263(3) Uani 1 1 d . . . H13 H 0.8007 0.8039 0.5547 0.032 Uiso 1 1 calc R . . C14 C 0.78006(13) 0.6773(3) 0.47365(6) 0.0286(3) Uani 1 1 d . . . H14 H 0.7406 0.8069 0.4572 0.034 Uiso 1 1 calc R . . C15 C 0.80224(13) 0.4870(3) 0.43973(6) 0.0293(3) Uani 1 1 d . . . H15 H 0.7774 0.4880 0.4007 0.035 Uiso 1 1 calc R . . C16 C 0.86190(13) 0.2947(3) 0.46458(6) 0.0296(3) Uani 1 1 d . . . H16 H 0.8771 0.1662 0.4421 0.035 Uiso 1 1 calc R . . C17 C 0.89894(13) 0.2936(3) 0.52292(6) 0.0266(3) Uani 1 1 d . . . H17 H 0.9392 0.1646 0.5392 0.032 Uiso 1 1 calc R . . N1 N 0.76998(11) -0.0017(2) 0.67509(5) 0.0258(3) Uani 1 1 d . . . N2 N 0.85633(11) 0.0922(2) 0.65116(5) 0.0262(3) Uani 1 1 d . . . N3 N 0.84049(10) 0.3260(2) 0.65070(5) 0.0225(3) Uani 1 1 d . . . O1 O 0.43543(10) 0.55782(18) 0.68103(4) 0.0305(3) Uani 1 1 d . . . O3 O 0.37848(9) 0.00733(18) 0.74816(4) 0.0270(2) Uani 1 1 d . . . O2 O 0.49641(9) 0.43218(16) 0.59958(4) 0.0232(2) Uani 1 1 d . . . O4 O 0.28186(8) 0.07078(18) 0.66095(4) 0.0254(2) 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 0.0304(7) 0.0288(8) 0.0215(6) -0.0005(5) 0.0049(5) -0.0048(6) C2 0.0243(7) 0.0215(7) 0.0192(6) -0.0005(5) -0.0005(5) -0.0009(5) C3 0.0245(7) 0.0204(7) 0.0189(6) -0.0007(5) 0.0030(5) -0.0011(5) C4 0.0248(7) 0.0190(7) 0.0184(6) 0.0008(5) 0.0027(5) -0.0005(5) C5 0.0248(7) 0.0206(7) 0.0196(6) 0.0007(5) 0.0022(5) -0.0014(5) C6 0.0289(7) 0.0156(6) 0.0203(6) -0.0011(5) 0.0048(5) 0.0004(5) C7 0.0281(7) 0.0326(8) 0.0291(7) -0.0022(6) 0.0091(6) -0.0051(6) C8 0.0284(7) 0.0246(7) 0.0174(6) 0.0018(5) 0.0012(5) -0.0005(5) C9 0.0253(7) 0.0228(7) 0.0169(6) 0.0002(5) -0.0022(5) 0.0010(5) C10 0.0244(7) 0.0226(7) 0.0195(6) -0.0010(5) 0.0001(5) 0.0015(5) C11 0.0236(7) 0.0255(7) 0.0259(7) 0.0014(5) 0.0024(5) -0.0033(5) C12 0.0202(6) 0.0252(7) 0.0249(7) 0.0020(5) 0.0035(5) -0.0036(5) C13 0.0252(7) 0.0240(7) 0.0298(7) -0.0003(6) 0.0036(6) -0.0007(5) C14 0.0260(7) 0.0294(8) 0.0301(7) 0.0064(6) 0.0013(6) 0.0009(6) C15 0.0276(7) 0.0368(8) 0.0233(7) 0.0020(6) 0.0016(6) -0.0046(6) C16 0.0326(8) 0.0296(8) 0.0278(7) -0.0044(6) 0.0089(6) -0.0028(6) C17 0.0269(7) 0.0243(7) 0.0292(7) 0.0037(6) 0.0051(6) 0.0010(5) N1 0.0300(6) 0.0229(6) 0.0244(6) 0.0019(5) 0.0033(5) 0.0012(5) N2 0.0291(6) 0.0225(6) 0.0274(6) 0.0029(5) 0.0042(5) 0.0026(5) N3 0.0246(6) 0.0215(6) 0.0206(5) 0.0002(4) -0.0001(4) -0.0002(5) O1 0.0438(6) 0.0197(5) 0.0299(5) -0.0020(4) 0.0120(5) 0.0015(4) O3 0.0364(6) 0.0262(5) 0.0191(5) 0.0017(4) 0.0065(4) -0.0004(4) O2 0.0307(5) 0.0193(5) 0.0201(5) 0.0022(4) 0.0049(4) 0.0002(4) O4 0.0236(5) 0.0298(5) 0.0235(5) 0.0037(4) 0.0051(4) -0.0015(4) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.311(2) . ? C1 H1A 0.9300 . ? C1 H1B 0.9300 . ? C2 O2 1.4091(17) . ? C2 C3 1.5024(18) . ? C3 C4 1.5403(18) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C4 C6 1.5247(19) . ? C4 C5 1.5295(19) . ? C4 C8 1.5486(19) . ? C5 O1 1.1934(18) . ? C5 O2 1.3585(16) . ? C6 O3 1.2016(17) . ? C6 O4 1.3377(17) . ? C7 O4 1.4516(17) . ? C7 H7A 0.9600 . ? C7 H7B 0.9600 . ? C7 H7C 0.9600 . ? C8 C9 1.4935(19) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C9 N1 1.3628(18) . ? C9 C10 1.372(2) . ? C10 N3 1.3472(18) . ? C10 H10 0.9300 . ? C11 N3 1.4660(18) . ? C11 C12 1.513(2) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 C17 1.388(2) . ? C12 C13 1.393(2) . ? C13 C14 1.392(2) . ? C13 H13 0.9300 . ? C14 C15 1.385(2) . ? C14 H14 0.9300 . ? C15 C16 1.389(2) . ? C15 H15 0.9300 . ? C16 C17 1.389(2) . ? C16 H16 0.9300 . ? C17 H17 0.9300 . ? N1 N2 1.3212(18) . ? N2 N3 1.3418(17) . ? 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 H1A 120.0 . . ? C2 C1 H1B 120.0 . . ? H1A C1 H1B 120.0 . . ? C1 C2 O2 120.03(13) . . ? C1 C2 C3 131.52(13) . . ? O2 C2 C3 108.44(11) . . ? C2 C3 C4 103.32(11) . . ? C2 C3 H3A 111.1 . . ? C4 C3 H3A 111.1 . . ? C2 C3 H3B 111.1 . . ? C4 C3 H3B 111.1 . . ? H3A C3 H3B 109.1 . . ? C6 C4 C5 108.52(11) . . ? C6 C4 C3 115.01(11) . . ? C5 C4 C3 102.33(10) . . ? C6 C4 C8 109.07(11) . . ? C5 C4 C8 108.58(11) . . ? C3 C4 C8 112.91(11) . . ? O1 C5 O2 121.86(12) . . ? O1 C5 C4 127.88(12) . . ? O2 C5 C4 110.22(11) . . ? O3 C6 O4 124.91(13) . . ? O3 C6 C4 124.44(13) . . ? O4 C6 C4 110.61(11) . . ? O4 C7 H7A 109.5 . . ? O4 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? O4 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C9 C8 C4 112.83(11) . . ? C9 C8 H8A 109.0 . . ? C4 C8 H8A 109.0 . . ? C9 C8 H8B 109.0 . . ? C4 C8 H8B 109.0 . . ? H8A C8 H8B 107.8 . . ? N1 C9 C10 108.00(12) . . ? N1 C9 C8 121.19(12) . . ? C10 C9 C8 130.70(13) . . ? N3 C10 C9 104.95(12) . . ? N3 C10 H10 127.5 . . ? C9 C10 H10 127.5 . . ? N3 C11 C12 110.69(11) . . ? N3 C11 H11A 109.5 . . ? C12 C11 H11A 109.5 . . ? N3 C11 H11B 109.5 . . ? C12 C11 H11B 109.5 . . ? H11A C11 H11B 108.1 . . ? C17 C12 C13 119.10(13) . . ? C17 C12 C11 120.42(13) . . ? C13 C12 C11 120.47(13) . . ? C14 C13 C12 120.19(14) . . ? C14 C13 H13 119.9 . . ? C12 C13 H13 119.9 . . ? C15 C14 C13 120.47(14) . . ? C15 C14 H14 119.8 . . ? C13 C14 H14 119.8 . . ? C14 C15 C16 119.40(14) . . ? C14 C15 H15 120.3 . . ? C16 C15 H15 120.3 . . ? C15 C16 C17 120.21(14) . . ? C15 C16 H16 119.9 . . ? C17 C16 H16 119.9 . . ? C12 C17 C16 120.63(14) . . ? C12 C17 H17 119.7 . . ? C16 C17 H17 119.7 . . ? N2 N1 C9 108.96(12) . . ? N1 N2 N3 107.02(12) . . ? N2 N3 C10 111.06(12) . . ? N2 N3 C11 120.28(12) . . ? C10 N3 C11 128.22(12) . . ? C5 O2 C2 110.63(10) . . ? C6 O4 C7 115.38(11) . . ? 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 C1 C2 C3 C4 157.46(15) . . . . ? O2 C2 C3 C4 -21.99(14) . . . . ? C2 C3 C4 C6 138.13(12) . . . . ? C2 C3 C4 C5 20.70(13) . . . . ? C2 C3 C4 C8 -95.81(13) . . . . ? C6 C4 C5 O1 46.48(19) . . . . ? C3 C4 C5 O1 168.46(14) . . . . ? C8 C4 C5 O1 -71.95(18) . . . . ? C6 C4 C5 O2 -135.73(11) . . . . ? C3 C4 C5 O2 -13.75(14) . . . . ? C8 C4 C5 O2 105.84(12) . . . . ? C5 C4 C6 O3 -113.96(15) . . . . ? C3 C4 C6 O3 132.16(14) . . . . ? C8 C4 C6 O3 4.15(19) . . . . ? C5 C4 C6 O4 63.92(14) . . . . ? C3 C4 C6 O4 -49.96(15) . . . . ? C8 C4 C6 O4 -177.97(11) . . . . ? C6 C4 C8 C9 175.02(11) . . . . ? C5 C4 C8 C9 -66.90(15) . . . . ? C3 C4 C8 C9 45.84(16) . . . . ? C4 C8 C9 N1 -101.56(15) . . . . ? C4 C8 C9 C10 74.33(18) . . . . ? N1 C9 C10 N3 0.14(14) . . . . ? C8 C9 C10 N3 -176.16(13) . . . . ? N3 C11 C12 C17 -75.44(16) . . . . ? N3 C11 C12 C13 103.75(15) . . . . ? C17 C12 C13 C14 -0.1(2) . . . . ? C11 C12 C13 C14 -179.33(13) . . . . ? C12 C13 C14 C15 0.5(2) . . . . ? C13 C14 C15 C16 -0.4(2) . . . . ? C14 C15 C16 C17 0.0(2) . . . . ? C13 C12 C17 C16 -0.3(2) . . . . ? C11 C12 C17 C16 178.92(13) . . . . ? C15 C16 C17 C12 0.4(2) . . . . ? C10 C9 N1 N2 -0.11(15) . . . . ? C8 C9 N1 N2 176.62(11) . . . . ? C9 N1 N2 N3 0.02(15) . . . . ? N1 N2 N3 C10 0.07(15) . . . . ? N1 N2 N3 C11 -173.03(11) . . . . ? C9 C10 N3 N2 -0.14(15) . . . . ? C9 C10 N3 C11 172.28(12) . . . . ? C12 C11 N3 N2 80.71(15) . . . . ? C12 C11 N3 C10 -91.09(16) . . . . ? O1 C5 O2 C2 178.18(13) . . . . ? C4 C5 O2 C2 0.23(15) . . . . ? C1 C2 O2 C5 -165.36(13) . . . . ? C3 C2 O2 C5 14.16(14) . . . . ? O3 C6 O4 C7 -1.4(2) . . . . ? C4 C6 O4 C7 -179.25(11) . . . . ? _diffrn_measured_fraction_theta_max 0.974 _diffrn_reflns_theta_full 74.48 _diffrn_measured_fraction_theta_full 0.974 _refine_diff_density_max 0.180 _refine_diff_density_min -0.292 _refine_diff_density_rms 0.055 #===END