Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2002 data_2,3,12,13-tetrabutoxy-21,23-dithiaporphyrin _database_code_CSD 191919 _journal_coden_Cambridge 182 loop_ _publ_author_name 'Ravikanth Mangalampalli' 'Neeraj Agarwal' 'C.-H. Hung' 'Anil Kumar' 'Sarada Mishra' _publ_contact_author_name 'Prof Ravikanth Mangalampalli' _publ_contact_author_address ; Department of chemistry Indian Institute of Technology, Bombay Mumbai Maharashtra 400076 INDIA ; _publ_contact_author_email 'RAVIKANTH@CHEM.IITB.AC.IN' _publ_requested_journal 'Chemical Communications' _publ_section_title ; Synthesis and crystal structure of 2,3,12,13-tetraalkoxy-21, 23-dithiaporphyrins ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H30 N O2 S' _chemical_formula_weight 468.61 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'S' 'S' 0.1246 0.1234 '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' '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' _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 8.6153(9) _cell_length_b 12.0456(13) _cell_length_c 12.2567(14) _cell_angle_alpha 97.985(2) _cell_angle_beta 90.840(2) _cell_angle_gamma 97.106(2) _cell_volume 1249.3(2) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description Block _exptl_crystal_colour 'Dark Brown' _exptl_crystal_size_max 0.47 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.246 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 498 _exptl_absorpt_coefficient_mu 0.157 _exptl_absorpt_correction_type 'Empirical Used SADABS' _exptl_absorpt_correction_T_min 0.6485 _exptl_absorpt_correction_T_max 0.9486 _exptl_absorpt_process_details ? _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 graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7923 _diffrn_reflns_av_R_equivalents 0.0394 _diffrn_reflns_av_sigmaI/netI 0.1258 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.68 _diffrn_reflns_theta_max 27.53 _reflns_number_total 5514 _reflns_number_gt 2757 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1104P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5514 _refine_ls_number_parameters 349 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1264 _refine_ls_R_factor_gt 0.0694 _refine_ls_wR_factor_ref 0.2127 _refine_ls_wR_factor_gt 0.1761 _refine_ls_goodness_of_fit_ref 0.918 _refine_ls_restrained_S_all 0.918 _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 S1 S 0.13262(10) 0.98474(7) 0.08137(8) 0.0261(3) Uani 1 1 d . A . N1 N -0.1305(3) 0.8296(2) 0.0281(2) 0.0271(7) Uani 1 1 d . . . O1 O 0.5366(3) 1.04942(19) 0.2461(2) 0.0299(6) Uani 1 1 d . . . O2 O 0.3691(3) 0.83530(19) 0.28126(19) 0.0283(6) Uani 1 1 d . . . C1 C 0.2689(4) 1.2209(3) 0.0194(3) 0.0279(8) Uani 1 1 d . . . C2 C 0.3579(4) 1.1718(3) 0.0941(3) 0.0234(8) Uani 1 1 d . A . C3 C 0.5070(4) 1.2412(3) 0.1398(3) 0.0279(9) Uani 1 1 d . . . C4 C 0.5107(6) 1.3054(4) 0.2425(4) 0.0619(15) Uani 1 1 d . . . H4 H 0.4218 1.3014 0.2846 0.074 Uiso 1 1 calc R . . C5 C 0.6423(7) 1.3747(4) 0.2837(5) 0.0727(18) Uani 1 1 d . . . H5 H 0.6430 1.4171 0.3533 0.087 Uiso 1 1 calc R . . C6 C 0.7755(7) 1.3813(4) 0.2204(5) 0.074(2) Uani 1 1 d . . . H6 H 0.8656 1.4280 0.2479 0.089 Uiso 1 1 calc R . . C7 C 0.7739(6) 1.3216(6) 0.1223(5) 0.087(2) Uani 1 1 d . . . H7 H 0.8621 1.3277 0.0795 0.104 Uiso 1 1 calc R . . C8 C 0.6399(5) 1.2489(5) 0.0817(4) 0.0632(15) Uani 1 1 d . . . H8 H 0.6420 1.2047 0.0133 0.076 Uiso 1 1 calc R . . C9 C 0.3094(4) 1.0651(3) 0.1274(3) 0.0247(8) Uani 1 1 d . . . C10 C 0.3911(4) 1.0085(3) 0.1994(3) 0.0251(8) Uani 1 1 d . A . C11 C 0.3120(4) 0.9054(3) 0.2164(3) 0.0247(8) Uani 1 1 d . A . C12 C 0.1632(4) 0.8776(3) 0.1580(3) 0.0247(8) Uani 1 1 d . . . C13 C 0.0599(4) 0.7781(3) 0.1562(3) 0.0262(8) Uani 1 1 d . A . C14 C 0.0946(4) 0.6892(3) 0.2242(3) 0.0275(8) Uani 1 1 d . . . C15 C 0.1719(6) 0.6002(4) 0.1799(4) 0.0563(14) Uani 1 1 d . A . H15 H 0.2030 0.5953 0.1072 0.068 Uiso 1 1 calc R . . C16 C 0.2033(7) 0.5182(4) 0.2434(4) 0.0683(16) Uani 1 1 d . . . H16 H 0.2562 0.4591 0.2130 0.082 Uiso 1 1 calc R A . C17 C 0.1572(5) 0.5236(3) 0.3500(4) 0.0422(12) Uani 1 1 d . A . H17 H 0.1772 0.4676 0.3916 0.051 Uiso 1 1 calc R . . C18 C 0.0819(5) 0.6110(4) 0.3951(4) 0.0495(12) Uani 1 1 d . . . H18 H 0.0529 0.6160 0.4682 0.059 Uiso 1 1 calc R A . C19 C 0.0486(5) 0.6929(3) 0.3319(3) 0.0439(11) Uani 1 1 d . A . H19 H -0.0057 0.7511 0.3627 0.053 Uiso 1 1 calc R . . C20 C -0.0832(4) 0.7569(3) 0.0932(3) 0.0277(8) Uani 1 1 d . . . C21 C -0.1959(5) 0.6563(3) 0.0875(3) 0.0376(11) Uani 1 1 d . A . H21 H -0.1899 0.5947 0.1248 0.045 Uiso 1 1 calc R . . C22 C -0.3106(4) 0.6702(3) 0.0177(3) 0.0349(10) Uani 1 1 d . . . H22 H -0.4001 0.6196 -0.0032 0.042 Uiso 1 1 calc R A . C27 C 0.3976(6) 0.8836(4) 0.3992(4) 0.0311(12) Uani 0.742(4) 1 d P A . H27A H 0.3016 0.9050 0.4314 0.037 Uiso 0.742(4) 1 calc PR . . H27B H 0.4751 0.9500 0.4063 0.037 Uiso 0.742(4) 1 calc PR . . C28 C 0.4561(6) 0.7924(4) 0.4563(4) 0.0320(13) Uani 0.742(4) 1 d P . . H28A H 0.4786 0.8220 0.5333 0.038 Uiso 0.742(4) 1 calc PR A . H28B H 0.3735 0.7295 0.4530 0.038 Uiso 0.742(4) 1 calc PR . . C29 C 0.6007(6) 0.7494(4) 0.4074(4) 0.0518(13) Uani 1 1 d . A . C30 C 0.6417(7) 0.6539(4) 0.4626(5) 0.0752(18) Uani 1 1 d . . . H30A H 0.5681 0.5879 0.4392 0.113 Uiso 1 1 calc R A . H30B H 0.6383 0.6737 0.5411 0.113 Uiso 1 1 calc R . . H30C H 0.7452 0.6383 0.4431 0.113 Uiso 1 1 calc R . . C31 C 0.6627(6) 0.9882(5) 0.2020(4) 0.0386(14) Uani 0.742(4) 1 d P A . C32 C 0.8021(7) 1.0122(5) 0.2855(6) 0.0516(17) Uani 0.742(4) 1 d P . . C33 C 0.8746(9) 1.1282(6) 0.2966(7) 0.074(2) Uani 0.742(4) 1 d P A 2 C34 C 1.0259(6) 1.1342(6) 0.3724(5) 0.095(2) Uani 1 1 d . . . H34A H 1.0983 1.1209 0.3147 0.143 Uiso 1 1 calc R A 1 H34B H 1.0713 1.1216 0.4410 0.143 Uiso 1 1 calc R A 1 H34C H 1.0030 1.2107 0.3784 0.143 Uiso 1 1 calc R A 1 C27A C 0.4974(18) 0.7730(13) 0.2252(13) 0.039(4) Uani 0.258(4) 1 d P A 1 H27C H 0.4577 0.7298 0.1555 0.046 Uiso 0.258(4) 1 calc PR A 1 H27D H 0.5855 0.8267 0.2108 0.046 Uiso 0.258(4) 1 calc PR A 1 C28A C 0.5483(18) 0.6948(13) 0.3012(13) 0.038(4) Uani 0.258(4) 1 d P A 1 H28C H 0.4611 0.6376 0.3089 0.045 Uiso 0.258(4) 1 calc PR A 1 H28D H 0.6320 0.6567 0.2674 0.045 Uiso 0.258(4) 1 calc PR A 1 C32A C 0.7275(17) 1.1221(15) 0.3810(14) 0.047(5) Uani 0.258(4) 1 d P A 1 C33A C 0.8509(17) 1.0404(12) 0.3415(12) 0.024(3) Uiso 0.258(4) 1 d P A 1 C31A C 0.5564(17) 1.0591(15) 0.3587(13) 0.046(5) Uani 0.258(4) 1 d P A 1 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 0.0245(5) 0.0248(5) 0.0298(5) 0.0112(4) -0.0063(4) -0.0013(3) N1 0.0222(16) 0.0278(15) 0.0317(17) 0.0108(13) -0.0056(14) -0.0019(12) O1 0.0202(13) 0.0330(13) 0.0360(15) 0.0085(12) -0.0053(12) -0.0020(11) O2 0.0256(13) 0.0292(13) 0.0320(14) 0.0131(11) -0.0074(11) 0.0021(10) C1 0.029(2) 0.0270(18) 0.0270(19) 0.0063(15) -0.0036(16) -0.0005(15) C2 0.0217(18) 0.0244(17) 0.0231(18) 0.0017(14) 0.0020(15) 0.0008(14) C3 0.031(2) 0.0254(18) 0.029(2) 0.0114(15) -0.0080(17) -0.0001(15) C4 0.049(3) 0.060(3) 0.067(3) -0.031(3) -0.021(3) 0.017(2) C5 0.065(4) 0.047(3) 0.095(4) -0.019(3) -0.034(4) -0.003(3) C6 0.078(4) 0.061(3) 0.078(4) 0.046(3) -0.049(3) -0.047(3) C7 0.044(3) 0.154(6) 0.056(3) 0.036(4) -0.014(3) -0.033(4) C8 0.025(2) 0.119(4) 0.037(2) 0.005(3) 0.000(2) -0.018(3) C9 0.0232(18) 0.0274(17) 0.0234(18) 0.0043(15) 0.0002(15) 0.0026(14) C10 0.0227(18) 0.0292(18) 0.0238(18) 0.0056(15) -0.0039(15) 0.0033(15) C11 0.0198(18) 0.0288(18) 0.0275(19) 0.0096(15) 0.0000(15) 0.0050(14) C12 0.0256(19) 0.0241(17) 0.0257(18) 0.0086(15) -0.0028(16) 0.0032(14) C13 0.0273(19) 0.0251(17) 0.0280(19) 0.0102(15) -0.0024(16) 0.0037(15) C14 0.028(2) 0.0253(17) 0.029(2) 0.0096(15) -0.0065(17) -0.0012(15) C15 0.097(4) 0.041(2) 0.040(3) 0.017(2) 0.013(3) 0.029(3) C16 0.111(5) 0.047(3) 0.061(3) 0.024(3) 0.016(3) 0.044(3) C17 0.040(2) 0.036(2) 0.056(3) 0.029(2) -0.011(2) 0.0001(19) C18 0.055(3) 0.059(3) 0.042(3) 0.030(2) 0.005(2) 0.007(2) C19 0.051(3) 0.044(2) 0.044(3) 0.022(2) 0.008(2) 0.018(2) C20 0.0261(19) 0.0275(18) 0.0304(19) 0.0114(16) -0.0041(16) -0.0006(15) C21 0.040(2) 0.0280(19) 0.046(2) 0.0203(18) -0.012(2) -0.0075(17) C22 0.030(2) 0.0301(19) 0.044(2) 0.0180(18) -0.0094(19) -0.0114(16) C27 0.035(3) 0.038(3) 0.021(2) 0.008(2) -0.002(2) 0.005(2) C28 0.035(3) 0.034(3) 0.028(3) 0.011(2) -0.008(2) 0.003(2) C29 0.053(3) 0.056(3) 0.055(3) 0.027(2) -0.007(2) 0.022(2) C30 0.085(4) 0.064(3) 0.084(4) 0.023(3) -0.018(3) 0.025(3) C31 0.023(3) 0.054(3) 0.035(3) -0.010(3) -0.003(2) 0.011(2) C32 0.027(3) 0.062(4) 0.061(4) -0.003(3) -0.004(3) 0.001(3) C33 0.055(5) 0.074(5) 0.088(6) -0.012(5) -0.006(4) 0.011(4) C34 0.031(3) 0.150(6) 0.090(4) -0.030(4) -0.013(3) 0.007(3) C27A 0.036(9) 0.040(9) 0.044(9) 0.011(7) 0.008(8) 0.015(7) C28A 0.032(8) 0.044(9) 0.046(10) 0.023(8) 0.019(7) 0.020(7) C32A 0.014(7) 0.072(12) 0.049(10) -0.006(9) 0.000(7) -0.003(8) C31A 0.019(8) 0.078(12) 0.032(9) 0.004(8) -0.007(7) -0.022(8) _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 C12 1.741(3) . ? S1 C9 1.742(3) . ? N1 C1 1.354(4) 2_575 ? N1 C20 1.357(4) . ? O1 C10 1.375(4) . ? O1 C31A 1.375(15) . ? O1 C31 1.456(6) . ? O2 C11 1.366(4) . ? O2 C27 1.486(5) . ? O2 C27A 1.531(16) . ? C1 N1 1.354(4) 2_575 ? C1 C2 1.420(4) . ? C1 C22 1.452(4) 2_575 ? C2 C9 1.419(4) . ? C2 C3 1.499(4) . ? C3 C8 1.357(6) . ? C3 C4 1.381(6) . ? C4 C5 1.367(6) . ? C5 C6 1.395(8) . ? C6 C7 1.312(8) . ? C7 C8 1.400(6) . ? C9 C10 1.416(4) . ? C10 C11 1.384(4) . ? C11 C12 1.438(4) . ? C12 C13 1.399(4) . ? C13 C20 1.422(4) . ? C13 C14 1.501(4) . ? C14 C19 1.380(6) . ? C14 C15 1.383(6) . ? C15 C16 1.388(5) . ? C16 C17 1.367(7) . ? C17 C18 1.362(6) . ? C18 C19 1.389(5) . ? C20 C21 1.449(5) . ? C21 C22 1.339(5) . ? C22 C1 1.452(4) 2_575 ? C27 C28 1.513(6) . ? C28 C29 1.508(7) . ? C29 C28A 1.415(16) . ? C29 C30 1.489(6) . ? C31 C32 1.539(7) . ? C32 C33A 0.809(13) . ? C32 C33 1.446(10) . ? C32 C32A 1.827(19) . ? C33 C34 1.579(8) . ? C34 C33A 1.771(16) . ? C27A C28A 1.510(19) . ? C32A C33A 1.57(2) . ? C32A C31A 1.574(19) . ? 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 C12 S1 C9 92.90(15) . . ? C1 N1 C20 105.9(3) 2_575 . ? C10 O1 C31A 118.5(7) . . ? C10 O1 C31 114.6(3) . . ? C31A O1 C31 105.0(8) . . ? C11 O2 C27 115.1(3) . . ? C11 O2 C27A 112.1(6) . . ? C27 O2 C27A 116.9(6) . . ? N1 C1 C2 123.6(3) 2_575 . ? N1 C1 C22 110.2(3) 2_575 2_575 ? C2 C1 C22 126.2(3) . 2_575 ? C9 C2 C1 123.2(3) . . ? C9 C2 C3 120.7(3) . . ? C1 C2 C3 116.0(3) . . ? C8 C3 C4 117.3(4) . . ? C8 C3 C2 122.6(4) . . ? C4 C3 C2 120.0(4) . . ? C5 C4 C3 121.4(6) . . ? C4 C5 C6 119.3(5) . . ? C7 C6 C5 120.2(5) . . ? C6 C7 C8 120.1(6) . . ? C3 C8 C7 121.6(5) . . ? C10 C9 C2 127.3(3) . . ? C10 C9 S1 110.5(2) . . ? C2 C9 S1 122.2(2) . . ? O1 C10 C11 122.7(3) . . ? O1 C10 C9 123.9(3) . . ? C11 C10 C9 113.5(3) . . ? O2 C11 C10 123.8(3) . . ? O2 C11 C12 122.6(3) . . ? C10 C11 C12 113.6(3) . . ? C13 C12 C11 126.7(3) . . ? C13 C12 S1 123.7(2) . . ? C11 C12 S1 109.5(2) . . ? C12 C13 C20 122.6(3) . . ? C12 C13 C14 120.7(3) . . ? C20 C13 C14 116.7(3) . . ? C19 C14 C15 118.2(3) . . ? C19 C14 C13 121.1(4) . . ? C15 C14 C13 120.7(3) . . ? C14 C15 C16 120.3(4) . . ? C17 C16 C15 120.6(5) . . ? C18 C17 C16 119.8(4) . . ? C17 C18 C19 120.0(4) . . ? C14 C19 C18 121.1(4) . . ? N1 C20 C13 123.4(3) . . ? N1 C20 C21 110.9(3) . . ? C13 C20 C21 125.7(3) . . ? C22 C21 C20 106.0(3) . . ? C21 C22 C1 107.1(3) . 2_575 ? O2 C27 C28 106.6(4) . . ? C29 C28 C27 114.1(4) . . ? C28A C29 C30 102.4(7) . . ? C28A C29 C28 103.6(7) . . ? C30 C29 C28 110.2(4) . . ? O1 C31 C32 109.0(4) . . ? C33A C32 C33 60.0(11) . . ? C33A C32 C31 156.9(13) . . ? C33 C32 C31 112.3(6) . . ? C33A C32 C32A 59.1(12) . . ? C33 C32 C32A 59.1(6) . . ? C31 C32 C32A 97.9(6) . . ? C32 C33 C34 105.6(6) . . ? C33 C34 C33A 43.5(5) . . ? C28A C27A O2 108.1(12) . . ? C29 C28A C27A 114.3(12) . . ? C33A C32A C31A 110.4(13) . . ? C33A C32A C32 26.2(6) . . ? C31A C32A C32 90.0(10) . . ? C32 C33A C32A 94.8(14) . . ? C32 C33A C34 135.0(16) . . ? C32A C33A C34 99.8(10) . . ? O1 C31A C32A 103.3(12) . . ? _diffrn_measured_fraction_theta_max 0.957 _diffrn_reflns_theta_full 27.53 _diffrn_measured_fraction_theta_full 0.957 _refine_diff_density_max 0.763 _refine_diff_density_min -0.498 _refine_diff_density_rms 0.107