Supplementary Material (ESI) for Journal of Materials Chemistry This journal is © The Royal Society of Chemistry 2001 data_azo4s _database_code_CSD 139879 _publ_contact_author_name 'Dr Stephane Parola' _publ_contact_author_address ; Laboratoire des Multimateriaux et Interfaces UMR CNRS 5615 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; _publ_contact_author_phone '33 4 72 44 81 67' _publ_contact_author_fax '33 4 72 43 15 68' _publ_contact_author_email 'Stephane.Parola@univ-lyon1.fr' _journal_coden_Cambridge 1145 _publ_requested_journal 'Journal of Materials Chemistry' _publ_section_title ; Synthesis, characterization and optical power limiting behaviour of phenylazo- and 4-nitrophenylazo-tetra-hydroxythiacalix[4]arene ; loop_ _publ_author_name _publ_author_address 'C. Desroches' ; Laboratoire des Multimateriaux et Interfaces UMR CNRS 5615 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; 'F. Vocanson' ; Laboratoire de Chimie Industrielle UMR 5078 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; 'S. Parola' ; Laboratoire des Multimateriaux et Interfaces UMR CNRS 5615 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; 'P. Miele' ; Laboratoire des Multimateriaux et Interfaces UMR CNRS 5615 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; 'N. Ehlinger' ; Laboratoire de Cristallographie UMR 5078 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; 'R. Lamartine' ; Laboratoire de Chimie Industrielle UMR 5078 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; 'J. Bouix' ; Laboratoire des Multimateriaux et Interfaces UMR CNRS 5615 Universite Claude Bernard LYON I 43, boulevard du 11 novembre 1918 69693 Villeurbanne Cedex France ; 'C. Lopes' ; Swedish Defense Research (FOA), Division of Sensor Technology Departement of Electromagnetic and Optic Materials (FOA 31) SE-581 11 Linkoping Sweden ; 'Eriksson, Anders' '?' 'Lindgren, Mikael' '?' _publ_section_abstract ; Calixarene are currently the most studied macrocycles. They present interesting complexing powers for neutral or ionic species and a potential as non-linear optical materal(second order). In the field of material science, a new class of macrocycle was recently reported, namely thiacalixarene, in which substitution of the original methylene bridges by sulfur was introduced between thephenolic units of the related calixarene. In this paper we report the synthesis and characterisation of new thiacalixarenes, namely p-tetrakis(4-nitrophenylazo)-tetrahydroxythiacalix[4]arene and p-tetrakis(phenylazo)-tetrahydroxythiacalix[4]arene and the first studies on the third order non-linear optical activities of such molecules ; _publ_section_exptl_refinement ; The macrocycle cristallyses with seven pyridine molecules. The asymmetric unit is represented by an half of calixarene molecule and by three and an half of pyridine molecules. The entire pyridine molecule with atoms C50, N50, C51, C52 is obtained by symmetry over inversion center. So, N50 and C50 atoms lie on the same site with each an occupation of 0.5 ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; p-tetrakis(4-nitrophenylazo)-tetrahydroxythiacalix[4]arene ; _chemical_name_common ; p-tetrakis(4-nitrophenylazo)-tetrahydroxythiacalix[4]arene ; _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C83 H63 N19 O12 S4' _chemical_formula_weight 1646.76 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' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.7076(5) _cell_length_b 13.6925(5) _cell_length_c 15.3195(6) _cell_angle_alpha 65.773(2) _cell_angle_beta 70.237(2) _cell_angle_gamma 88.749(2) _cell_volume 1909.62(14) _cell_formula_units_Z 1 _cell_measurement_temperature 123(2) _cell_measurement_reflns_used 21779 _cell_measurement_theta_min 0.998 _cell_measurement_theta_max 27.485 _exptl_crystal_description needle _exptl_crystal_colour red _exptl_crystal_size_max 0.56 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.432 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 854 _exptl_absorpt_coefficient_mu 0.203 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.8946 _exptl_absorpt_correction_T_max 0.9899 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 123(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 'Nonius CCD' _diffrn_measurement_method 'area detector' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 14905 _diffrn_reflns_av_R_equivalents 0.0464 _diffrn_reflns_av_sigmaI/netI 0.1015 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.71 _diffrn_reflns_theta_max 27.81 _reflns_number_total 8717 _reflns_number_gt 4437 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Denzo (Otwinowski & Minor 1997)' _computing_cell_refinement 'Denzo' _computing_data_reduction 'Denzo' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 1999)' _computing_publication_material 'SHELXL-97' _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^)+(0.1100P)^2^+0.7827P] 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_number_reflns 8717 _refine_ls_number_parameters 534 _refine_ls_number_restraints 54 _refine_ls_R_factor_all 0.1571 _refine_ls_R_factor_gt 0.0764 _refine_ls_wR_factor_ref 0.2409 _refine_ls_wR_factor_gt 0.1906 _refine_ls_goodness_of_fit_ref 1.012 _refine_ls_restrained_S_all 1.027 _refine_ls_shift/su_max 0.008 _refine_ls_shift/su_mean 0.001 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 S1 S 0.32926(9) 0.74403(8) 0.37973(9) 0.0542(3) Uani 1 1 d . . . S2 S 0.81784(9) 0.70447(8) 0.43019(11) 0.0692(4) Uani 1 1 d . . . O1 O 0.3756(2) 0.5099(2) 0.4248(2) 0.0563(7) Uani 1 1 d . . . H1 H 0.4301 0.5653 0.4024 0.084 Uiso 1 1 calc R . . O2 O -0.7876(4) 0.4700(3) 1.0131(3) 0.1009(13) Uani 1 1 d . . . O3 O -0.7130(4) 0.6354(3) 0.9626(3) 0.1000(12) Uani 1 1 d . . . O4 O 0.5844(2) 0.6523(2) 0.3700(2) 0.0601(8) Uani 1 1 d . . . H4O H 0.6589 0.6786 0.3221 0.090 Uiso 1 1 calc R . . O5 O 0.2779(5) 1.1837(3) 0.8759(3) 0.1021(13) Uani 1 1 d . . . O6 O 0.4331(4) 1.1284(3) 0.9366(3) 0.0941(12) Uani 1 1 d . . . N1 N -0.1209(3) 0.5620(3) 0.6639(3) 0.0595(9) Uani 1 1 d . . . N2 N -0.2076(3) 0.4801(3) 0.7191(3) 0.0613(9) Uani 1 1 d . . . N3 N -0.6993(5) 0.5468(4) 0.9628(3) 0.0786(12) Uani 1 1 d . . . N4 N 0.4399(3) 0.8684(2) 0.6181(3) 0.0507(8) Uani 1 1 d . . . N5 N 0.5186(3) 0.8788(2) 0.6602(3) 0.0525(8) Uani 1 1 d . . . N6 N 0.3682(5) 1.1283(3) 0.8845(3) 0.0771(12) Uani 1 1 d . . . C1 C 0.1619(4) 0.4299(3) 0.5532(4) 0.0552(11) Uani 1 1 d . . . C2 C 0.0365(4) 0.4401(3) 0.6135(3) 0.0555(10) Uani 1 1 d . . . H2 H -0.0264 0.3774 0.6611 0.067 Uiso 1 1 calc R . . C3 C 0.0021(4) 0.5424(3) 0.6049(4) 0.0559(10) Uani 1 1 d . . . C4 C 0.0933(4) 0.6337(3) 0.5350(3) 0.0525(10) Uani 1 1 d . . . H4 H 0.0707 0.7029 0.5296 0.063 Uiso 1 1 calc R . . C5 C 0.2181(3) 0.6249(3) 0.4725(3) 0.0508(10) Uani 1 1 d . . . C6 C 0.2548(3) 0.5220(3) 0.4817(3) 0.0507(10) Uani 1 1 d . . . C7 C -0.3300(4) 0.5026(3) 0.7789(3) 0.0570(10) Uani 1 1 d . . . C8 C -0.4370(5) 0.4217(4) 0.8292(4) 0.0742(13) Uani 1 1 d . . . H8 H -0.4270 0.3562 0.8217 0.089 Uiso 1 1 calc R . . C9 C -0.5596(5) 0.4345(4) 0.8909(4) 0.0781(14) Uani 1 1 d . . . H9 H -0.6338 0.3788 0.9257 0.094 Uiso 1 1 calc R . . C10 C -0.5696(5) 0.5310(3) 0.8995(3) 0.0619(12) Uani 1 1 d . . . C11 C -0.4651(5) 0.6122(4) 0.8511(3) 0.0647(12) Uani 1 1 d . . . H11 H -0.4760 0.6775 0.8591 0.078 Uiso 1 1 calc R . . C12 C -0.3433(5) 0.5990(3) 0.7904(3) 0.0632(11) Uani 1 1 d . . . H12 H -0.2693 0.6547 0.7569 0.076 Uiso 1 1 calc R . . C13 C 0.4352(3) 0.7494(3) 0.4453(3) 0.0450(9) Uani 1 1 d . . . C14 C 0.4019(3) 0.8019(3) 0.5073(3) 0.0443(9) Uani 1 1 d . . . H14 H 0.3201 0.8315 0.5177 0.053 Uiso 1 1 calc R . . C15 C 0.4869(4) 0.8122(3) 0.5555(3) 0.0484(9) Uani 1 1 d . . . C16 C 0.6104(3) 0.7718(3) 0.5364(3) 0.0505(10) Uani 1 1 d . . . H16 H 0.6691 0.7790 0.5688 0.061 Uiso 1 1 calc R . . C17 C 0.6470(3) 0.7222(3) 0.4715(3) 0.0503(10) Uani 1 1 d . . . C18 C 0.5593(3) 0.7057(3) 0.4251(3) 0.0478(9) Uani 1 1 d . . . C19 C 0.4704(4) 0.9398(3) 0.7192(3) 0.0521(9) Uani 1 1 d . . . C20 C 0.3652(4) 1.0005(3) 0.7130(3) 0.0587(10) Uani 1 1 d . . . H20 H 0.3173 0.9997 0.6712 0.070 Uiso 1 1 calc R . . C21 C 0.3304(5) 1.0625(3) 0.7685(3) 0.0606(11) Uani 1 1 d . . . H21 H 0.2596 1.1052 0.7646 0.073 Uiso 1 1 calc R . . C22 C 0.4010(5) 1.0599(3) 0.8285(3) 0.0619(11) Uani 1 1 d . . . C23 C 0.5061(5) 0.9993(3) 0.8365(3) 0.0683(12) Uani 1 1 d . . . H23 H 0.5527 0.9993 0.8794 0.082 Uiso 1 1 calc R . . C24 C 0.5407(5) 0.9390(3) 0.7805(3) 0.0599(11) Uani 1 1 d . . . H24 H 0.6124 0.8972 0.7841 0.072 Uiso 1 1 calc R . . N50 N -0.0384(5) 0.9353(3) 0.4620(3) 0.0684(11) Uani 0.50 1 d P . . C50 C -0.0384(5) 0.9353(3) 0.4620(3) 0.0684(11) Uani 0.50 1 d P . . H50 H -0.0653 0.8909 0.4357 0.082 Uiso 0.50 1 calc PR . . C51 C -0.1298(4) 0.9787(3) 0.5168(3) 0.0607(11) Uani 1 1 d . . . H51 H -0.2220 0.9636 0.5293 0.073 Uiso 1 1 calc R . . C52 C 0.0929(5) 0.9572(3) 0.4460(3) 0.0617(11) Uani 1 1 d . . . H52 H 0.1589 0.9273 0.4086 0.074 Uiso 1 1 calc R . . N60 N 0.8263(4) 0.8007(3) 0.8014(3) 0.0641(9) Uani 1 1 d . . . C61 C 0.9339(7) 0.8049(4) 0.9122(4) 0.0822(15) Uani 1 1 d . . . H61 H 0.9235 0.8029 0.9770 0.099 Uiso 1 1 calc R . . C62 C 1.0551(7) 0.8111(4) 0.8468(6) 0.0950(17) Uani 1 1 d . . . H62 H 1.1321 0.8134 0.8638 0.114 Uiso 1 1 calc R . . C63 C 1.0667(5) 0.8142(4) 0.7544(5) 0.0889(18) Uani 1 1 d . . . H63 H 1.1521 0.8210 0.7046 0.107 Uiso 1 1 calc R . . C64 C 0.9498(6) 0.8071(4) 0.7348(3) 0.0809(16) Uani 1 1 d . . . H64 H 0.9577 0.8068 0.6712 0.097 Uiso 1 1 calc R . . C65 C 0.8244(5) 0.8013(3) 0.8874(3) 0.0634(11) Uani 1 1 d . . . H65 H 0.7398 0.7990 0.9359 0.076 Uiso 1 1 calc R . . N40 N 0.7601(4) 0.5768(3) 0.2634(3) 0.0668(10) Uani 1 1 d . . . C41 C 0.8806(5) 0.6235(4) 0.1901(4) 0.0707(13) Uani 1 1 d . . . H41 H 0.9123 0.6956 0.1732 0.085 Uiso 1 1 calc R . . C42 C 0.9593(6) 0.5682(4) 0.1388(4) 0.0820(15) Uani 1 1 d . . . H42 H 1.0440 0.6018 0.0863 0.098 Uiso 1 1 calc R . . C43 C 0.9125(6) 0.4644(4) 0.1653(4) 0.0943(19) Uani 1 1 d . . . H43 H 0.9654 0.4243 0.1320 0.113 Uiso 1 1 calc R . . C44 C 0.7890(6) 0.4179(4) 0.2399(4) 0.0875(17) Uani 1 1 d . . . H44 H 0.7551 0.3460 0.2578 0.105 Uiso 1 1 calc R . . C45 C 0.7141(5) 0.4767(4) 0.2889(4) 0.0748(13) Uani 1 1 d . . . H45 H 0.6289 0.4446 0.3413 0.090 Uiso 1 1 calc R . . N70 N 0.7872(7) 0.1802(5) 0.9264(5) 0.1344(19) Uani 1 1 d U . . C72 C 0.8515(9) 0.1263(7) 0.7927(9) 0.172(4) Uani 1 1 d U . . H72 H 0.8347 0.1234 0.7367 0.206 Uiso 1 1 calc R . . C75 C 0.8935(6) 0.1241(7) 0.9527(5) 0.128(3) Uani 1 1 d U . . H75 H 0.9133 0.1195 1.0101 0.153 Uiso 1 1 calc R . . C71 C 0.7713(8) 0.1768(6) 0.8416(6) 0.127(3) Uani 1 1 d U . . H71 H 0.7029 0.2108 0.8186 0.152 Uiso 1 1 calc R . . C73 C 0.9489(7) 0.0813(4) 0.8136(6) 0.110(2) Uani 1 1 d U . . H73 H 1.0081 0.0509 0.7726 0.132 Uiso 1 1 calc R . . C74 C 0.9609(7) 0.0800(7) 0.8940(5) 0.130(3) Uani 1 1 d U . . H74 H 1.0288 0.0412 0.9137 0.156 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 S1 0.0430(6) 0.0548(6) 0.0984(8) -0.0534(6) -0.0404(5) 0.0247(4) S2 0.0303(5) 0.0594(6) 0.1527(11) -0.0753(7) -0.0373(6) 0.0198(4) O1 0.0330(14) 0.0592(16) 0.110(2) -0.0630(17) -0.0318(14) 0.0220(12) O2 0.104(3) 0.078(2) 0.072(2) -0.028(2) 0.019(2) 0.028(2) O3 0.109(3) 0.078(2) 0.094(2) -0.051(2) 0.000(2) 0.042(2) O4 0.0359(14) 0.0687(17) 0.112(2) -0.0707(18) -0.0296(15) 0.0217(13) O5 0.167(4) 0.094(2) 0.097(2) -0.071(2) -0.075(3) 0.092(3) O6 0.155(4) 0.093(2) 0.081(2) -0.065(2) -0.067(2) 0.068(2) N1 0.0425(19) 0.064(2) 0.102(3) -0.059(2) -0.0324(19) 0.0231(17) N2 0.053(2) 0.062(2) 0.093(3) -0.056(2) -0.0282(19) 0.0254(18) N3 0.097(3) 0.069(3) 0.047(2) -0.025(2) 0.000(2) 0.032(2) N4 0.0444(18) 0.0488(17) 0.079(2) -0.0404(17) -0.0295(17) 0.0150(14) N5 0.0459(18) 0.0465(17) 0.083(2) -0.0409(17) -0.0291(17) 0.0192(14) N6 0.130(4) 0.064(2) 0.056(2) -0.0388(19) -0.041(2) 0.051(2) C1 0.035(2) 0.057(2) 0.114(3) -0.064(2) -0.041(2) 0.0243(17) C2 0.037(2) 0.058(2) 0.107(3) -0.061(2) -0.037(2) 0.0215(17) C3 0.036(2) 0.064(2) 0.109(3) -0.066(2) -0.039(2) 0.0292(18) C4 0.039(2) 0.054(2) 0.106(3) -0.059(2) -0.045(2) 0.0261(17) C5 0.0345(19) 0.057(2) 0.101(3) -0.059(2) -0.042(2) 0.0234(16) C6 0.0299(19) 0.058(2) 0.103(3) -0.060(2) -0.037(2) 0.0220(16) C7 0.056(2) 0.060(2) 0.070(3) -0.043(2) -0.023(2) 0.027(2) C8 0.075(3) 0.058(3) 0.087(3) -0.045(2) -0.009(3) 0.021(2) C9 0.081(3) 0.061(3) 0.075(3) -0.035(2) -0.002(3) 0.026(2) C10 0.076(3) 0.062(3) 0.045(2) -0.031(2) -0.010(2) 0.036(2) C11 0.078(3) 0.066(3) 0.067(3) -0.046(2) -0.025(2) 0.034(3) C12 0.067(3) 0.064(3) 0.082(3) -0.051(2) -0.030(2) 0.029(2) C13 0.0357(19) 0.0413(18) 0.081(3) -0.0418(19) -0.0296(18) 0.0159(15) C14 0.0284(17) 0.0405(18) 0.081(3) -0.0403(18) -0.0227(17) 0.0154(14) C15 0.042(2) 0.0430(19) 0.082(3) -0.0434(19) -0.0276(19) 0.0166(16) C16 0.037(2) 0.0456(19) 0.095(3) -0.047(2) -0.035(2) 0.0157(16) C17 0.0326(19) 0.0453(19) 0.098(3) -0.050(2) -0.0296(19) 0.0162(15) C18 0.0355(19) 0.0443(19) 0.085(3) -0.047(2) -0.0243(19) 0.0167(15) C19 0.058(2) 0.0420(19) 0.070(2) -0.0353(19) -0.025(2) 0.0202(17) C20 0.065(3) 0.054(2) 0.074(3) -0.037(2) -0.034(2) 0.022(2) C21 0.078(3) 0.049(2) 0.068(3) -0.033(2) -0.033(2) 0.033(2) C22 0.099(3) 0.043(2) 0.058(2) -0.0330(19) -0.033(2) 0.033(2) C23 0.105(4) 0.056(2) 0.072(3) -0.041(2) -0.051(3) 0.041(2) C24 0.079(3) 0.050(2) 0.074(3) -0.039(2) -0.040(2) 0.034(2) N50 0.086(3) 0.045(2) 0.079(3) -0.0307(19) -0.030(2) 0.010(2) C50 0.086(3) 0.045(2) 0.079(3) -0.0307(19) -0.030(2) 0.010(2) C51 0.048(2) 0.050(2) 0.080(3) -0.027(2) -0.020(2) 0.0079(19) C52 0.064(3) 0.045(2) 0.072(3) -0.030(2) -0.013(2) 0.020(2) N60 0.081(3) 0.0514(19) 0.059(2) -0.0263(17) -0.022(2) 0.0167(18) C61 0.116(5) 0.068(3) 0.087(4) -0.047(3) -0.049(4) 0.032(3) C62 0.101(5) 0.060(3) 0.119(5) -0.022(3) -0.055(4) 0.025(3) C63 0.065(3) 0.051(3) 0.094(4) -0.003(3) 0.001(3) 0.032(2) C64 0.117(5) 0.066(3) 0.044(2) -0.022(2) -0.016(3) 0.043(3) C65 0.074(3) 0.053(2) 0.058(3) -0.027(2) -0.014(2) 0.013(2) N40 0.071(3) 0.069(2) 0.073(2) -0.039(2) -0.033(2) 0.043(2) C41 0.081(3) 0.064(3) 0.075(3) -0.038(2) -0.029(3) 0.044(2) C42 0.102(4) 0.058(3) 0.065(3) -0.023(2) -0.011(3) 0.044(3) C43 0.120(5) 0.063(3) 0.067(3) -0.026(2) 0.000(3) 0.050(3) C44 0.109(4) 0.054(3) 0.074(3) -0.030(2) -0.002(3) 0.041(3) C45 0.080(3) 0.068(3) 0.079(3) -0.043(3) -0.021(3) 0.044(3) N70 0.133(5) 0.105(4) 0.159(5) -0.045(4) -0.060(4) 0.001(3) C72 0.177(7) 0.189(7) 0.335(10) -0.210(8) -0.195(8) 0.132(6) C75 0.073(4) 0.251(9) 0.087(4) -0.083(5) -0.049(3) 0.064(5) C71 0.159(6) 0.137(5) 0.218(7) -0.133(5) -0.159(6) 0.101(5) C73 0.140(5) 0.065(3) 0.151(5) -0.043(4) -0.088(5) 0.038(3) C74 0.112(5) 0.178(7) 0.075(4) -0.020(4) -0.048(4) 0.061(5) _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 S1 C13 1.771(3) . ? S1 C5 1.770(4) . ? S2 C1 1.769(4) 2_666 ? S2 C17 1.769(4) . ? O1 C6 1.345(4) . ? O2 N3 1.216(5) . ? O3 N3 1.219(5) . ? O4 C18 1.289(4) . ? O5 N6 1.224(5) . ? O6 N6 1.224(5) . ? N1 N2 1.253(5) . ? N1 C3 1.416(5) . ? N2 C7 1.433(5) . ? N3 C10 1.471(5) . ? N4 N5 1.263(4) . ? N4 C15 1.425(5) . ? N5 C19 1.438(5) . ? N6 C22 1.474(5) . ? C1 C2 1.391(5) . ? C1 C6 1.401(6) . ? C1 S2 1.769(4) 2_666 ? C2 C3 1.404(5) . ? C3 C4 1.383(6) . ? C4 C5 1.393(5) . ? C5 C6 1.418(5) . ? C7 C8 1.375(6) . ? C7 C12 1.401(5) . ? C8 C9 1.391(6) . ? C9 C10 1.379(6) . ? C10 C11 1.362(6) . ? C11 C12 1.380(6) . ? C13 C14 1.366(5) . ? C13 C18 1.435(5) . ? C14 C15 1.392(5) . ? C15 C16 1.407(5) . ? C16 C17 1.373(5) . ? C17 C18 1.425(5) . ? C19 C24 1.386(5) . ? C19 C20 1.390(5) . ? C20 C21 1.395(6) . ? C21 C22 1.365(6) . ? C22 C23 1.393(6) . ? C23 C24 1.381(5) . ? C51 C52 1.353(6) 2_576 ? C52 C51 1.353(6) 2_576 ? N60 C65 1.314(5) . ? N60 C64 1.347(6) . ? C61 C62 1.323(8) . ? C61 C65 1.357(7) . ? C62 C63 1.361(8) . ? C63 C64 1.397(8) . ? N40 C45 1.317(6) . ? N40 C41 1.342(6) . ? C41 C42 1.384(6) . ? C42 C43 1.362(7) . ? C43 C44 1.371(7) . ? C44 C45 1.383(6) . ? N70 C71 1.385(8) . ? N70 C75 1.437(8) . ? C72 C73 1.267(8) . ? C72 C71 1.319(9) . ? C75 C74 1.298(10) . ? C73 C74 1.274(9) . ? 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 C13 S1 C5 100.53(17) . . ? C1 S2 C17 111.94(17) 2_666 . ? N2 N1 C3 114.3(3) . . ? N1 N2 C7 112.7(3) . . ? O2 N3 O3 123.3(4) . . ? O2 N3 C10 118.0(4) . . ? O3 N3 C10 118.7(4) . . ? N5 N4 C15 114.3(3) . . ? N4 N5 C19 112.7(3) . . ? O6 N6 O5 122.6(4) . . ? O6 N6 C22 118.8(4) . . ? O5 N6 C22 118.6(4) . . ? C2 C1 C6 120.2(3) . . ? C2 C1 S2 113.7(3) . 2_666 ? C6 C1 S2 125.9(3) . 2_666 ? C1 C2 C3 120.7(4) . . ? C4 C3 C2 119.6(4) . . ? C4 C3 N1 115.0(3) . . ? C2 C3 N1 125.4(4) . . ? C3 C4 C5 120.4(3) . . ? C4 C5 C6 120.4(4) . . ? C4 C5 S1 119.2(3) . . ? C6 C5 S1 120.4(3) . . ? O1 C6 C1 119.0(3) . . ? O1 C6 C5 122.3(3) . . ? C1 C6 C5 118.7(3) . . ? C8 C7 C12 119.9(4) . . ? C8 C7 N2 116.4(4) . . ? C12 C7 N2 123.6(4) . . ? C7 C8 C9 121.0(4) . . ? C10 C9 C8 117.5(5) . . ? C11 C10 C9 122.8(4) . . ? C11 C10 N3 119.0(4) . . ? C9 C10 N3 118.3(4) . . ? C10 C11 C12 119.6(4) . . ? C11 C12 C7 119.2(4) . . ? C14 C13 C18 121.8(3) . . ? C14 C13 S1 119.4(3) . . ? C18 C13 S1 118.6(3) . . ? C13 C14 C15 120.6(3) . . ? C14 C15 C16 119.3(3) . . ? C14 C15 N4 114.7(3) . . ? C16 C15 N4 125.9(3) . . ? C17 C16 C15 120.6(3) . . ? C16 C17 C18 121.3(3) . . ? C16 C17 S2 115.8(3) . . ? C18 C17 S2 121.8(3) . . ? O4 C18 C17 123.7(3) . . ? O4 C18 C13 120.0(3) . . ? C17 C18 C13 116.3(3) . . ? C24 C19 C20 121.0(3) . . ? C24 C19 N5 115.2(3) . . ? C20 C19 N5 123.6(4) . . ? C19 C20 C21 119.8(4) . . ? C22 C21 C20 118.0(4) . . ? C21 C22 C23 123.3(4) . . ? C21 C22 N6 118.4(4) . . ? C23 C22 N6 118.3(4) . . ? C24 C23 C22 118.3(4) . . ? C23 C24 C19 119.6(4) . . ? C65 N60 C64 114.3(4) . . ? C62 C61 C65 120.5(5) . . ? C61 C62 C63 118.3(6) . . ? C62 C63 C64 118.4(5) . . ? N60 C64 C63 123.3(5) . . ? N60 C65 C61 125.1(5) . . ? C45 N40 C41 120.8(4) . . ? N40 C41 C42 121.0(5) . . ? C43 C42 C41 118.5(5) . . ? C42 C43 C44 119.9(4) . . ? C43 C44 C45 119.4(5) . . ? N40 C45 C44 120.5(5) . . ? C71 N70 C75 113.7(6) . . ? C73 C72 C71 126.0(8) . . ? C74 C75 N70 116.5(6) . . ? C72 C71 N70 119.9(6) . . ? C72 C73 C74 114.5(8) . . ? C73 C74 C75 129.2(7) . . ? _diffrn_measured_fraction_theta_max 0.965 _diffrn_reflns_theta_full 27.81 _diffrn_measured_fraction_theta_full 0.965 _refine_diff_density_max 0.648 _refine_diff_density_min -0.435 _refine_diff_density_rms 0.062