Supplementary Material (ESI) for Perkin Transactions This journal is © The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 188 _publ_requested_journal 'Perkin Transactions 2' loop_ _publ_author_name 'Guccione, Salvatore' 'Balzano, Federica' 'Barretta, Gloria Uccello' 'Luque, F Javier' 'Pignatello, Rosario' 'Wouters, Johan' _publ_contact_author_name 'Prof Salvatore Guccione' _publ_contact_author_address ; Dipartimento di Scienze Farmaceutiche, Universita degli Studi di Catania Viale A Doria 6 Ed 2 Citta Univeristria I 95125 ITALY ; _publ_contact_author_email 'GUCCIONE@MBOX.UNICT.IT' _publ_section_title ; Crystallographic, NMR and ab initio calculation studies of tautomerism among substituted thiazol-2-yl-hydrazines. ; data_3a _database_code_CSD 174656 _chemical_formula_sum 'C21 H25 N3 O4 S' _chemical_formula_weight 415.50 _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21/c' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,1/2+y,1/2-z -x,-y,-z x,1/2-y,1/2+z _cell_length_a 5.8940(10) _cell_length_b 37.138(6) _cell_length_c 9.730(2) _cell_angle_alpha 90.00 _cell_angle_beta 91.827(16) _cell_angle_gamma 90.00 _cell_volume 2128.7(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 25 _cell_measurement_theta_max 45 _exptl_crystal_description 'needle' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.06 _exptl_crystal_density_diffrn 1.296 _exptl_crystal_F_000 880 _exptl_absorpt_coefficient_mu 1.618 _exptl_absorpt_correction_type 'analytical' _exptl_absorpt_correction_T_min 0.422 _exptl_absorpt_correction_T_max 0.944 _exptl_absorpt_process_details 'HELENA (Spek, 1997)' _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius CAD-4' _diffrn_measurement_method 'q/2q' _diffrn_standards_number 3 _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 1 _diffrn_reflns_number 6512 _diffrn_reflns_av_R_equivalents 0.0643 _diffrn_reflns_av_sigmaI/netI 0.0753 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -45 _diffrn_reflns_limit_k_max 39 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 4.70 _diffrn_reflns_theta_max 71.97 _reflns_number_total 4184 _reflns_number_gt 2222 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Enraf-Nonius (1989). CAD-4 Software' _computing_cell_refinement 'Enraf-Nonius (1989). CAD-4 Software' _computing_data_reduction 'HELENA (Spek, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 1990)' _computing_publication_material 'PLATON (Spek, 1990)' _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^)+(0.0578P)^2^+0.1810P] 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_number_reflns 4184 _refine_ls_number_parameters 274 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1144 _refine_ls_R_factor_gt 0.0490 _refine_ls_wR_factor_ref 0.1508 _refine_ls_wR_factor_gt 0.1227 _refine_ls_goodness_of_fit_ref 1.024 _refine_ls_restrained_S_all 1.024 _refine_ls_shift/su_max 2.046 _refine_ls_shift/su_mean 0.055 _refine_special_details ; The refine_ls_shift/su_max remains very large, even with additional refinement cycles. The maximum shifts are applied to the position of H18A of the methylene C18 position. All other coordinates have converged to their minimal values. ; loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags S5 S Uani 0.49108(15) 0.04800(2) 0.32960(8) 1.000 0.0877(3) . . O15 O Uani 1.0555(4) 0.21375(6) 0.8342(2) 1.000 0.0894(9) . . O17 O Uani 0.6983(4) 0.24372(6) 0.7084(2) 1.000 0.0863(8) . . O20 O Uani 0.4335(4) 0.20776(6) 0.5328(2) 1.000 0.0951(9) . . O36 O Uani 0.8319(4) -0.11858(6) -0.1415(2) 1.000 0.0854(8) . . N3 N Uani 0.7898(4) -0.00285(6) 0.3494(2) 1.000 0.0653(8) . . N6 N Uani 0.8649(4) 0.04548(6) 0.4961(2) 1.000 0.0662(8) . . N7 N Uani 0.7806(4) 0.07979(6) 0.5208(2) 1.000 0.0677(8) . . C1 C Uani 0.4619(7) 0.01014(10) 0.2134(4) 1.000 0.0941(14) . . C2 C Uani 0.6004(5) -0.02069(8) 0.2761(3) 1.000 0.0702(10) . . C4 C Uani 0.7406(4) 0.02944(8) 0.4027(2) 1.000 0.0626(10) . . C8 C Uani 0.8990(5) 0.09921(8) 0.6027(3) 1.000 0.0698(10) . . C9 C Uani 0.8384(5) 0.13638(8) 0.6335(3) 1.000 0.0680(10) . . C10 C Uani 0.9754(5) 0.15585(8) 0.7254(3) 1.000 0.0730(11) . . C11 C Uani 0.9300(6) 0.19188(8) 0.7493(3) 1.000 0.0719(11) . . C12 C Uani 0.7467(5) 0.20843(8) 0.6830(3) 1.000 0.0719(11) . . C13 C Uani 0.6073(5) 0.18865(8) 0.5914(3) 1.000 0.0722(11) . . C14 C Uani 0.6535(5) 0.15287(8) 0.5675(3) 1.000 0.0732(11) . . C16 C Uani 1.2536(6) 0.19936(10) 0.9004(3) 1.000 0.0970(14) . . C18 C Uani 0.8110(8) 0.26764(10) 0.6168(4) 1.000 0.0986(16) . . C19 C Uani 0.7518(7) 0.30503(9) 0.6511(4) 1.000 0.1184(16) . . C21 C Uani 0.2870(6) 0.19065(10) 0.4345(3) 1.000 0.1012(16) . . C30 C Uani 0.6755(5) -0.04693(7) 0.1690(2) 1.000 0.0621(9) . . C31 C Uani 0.8664(5) -0.04166(8) 0.0926(3) 1.000 0.0706(11) . . C32 C Uani 0.9246(5) -0.06476(8) -0.0107(3) 1.000 0.0724(11) . . C33 C Uani 0.7913(5) -0.09424(7) -0.0418(3) 1.000 0.0669(10) . . C34 C Uani 0.6003(5) -0.10001(8) 0.0337(3) 1.000 0.0752(11) . . C35 C Uani 0.5451(5) -0.07695(8) 0.1371(3) 1.000 0.0728(11) . . C37 C Uani 1.0009(7) -0.10973(9) -0.2377(3) 1.000 0.0975(14) . . H1A H Uiso 0.304(6) 0.0032(9) 0.202(3) 1.000 0.1127 . . H1B H Uiso 0.518(6) 0.0164(9) 0.124(3) 1.000 0.1127 . . H2 H Uiso 0.50834 -0.03343 0.34263 1.000 0.0842 . . H3 H Uiso 0.87830 -0.01930 0.41420 1.000 0.0500 . . H8 H Uiso 1.02893 0.08943 0.64463 1.000 0.0839 . . H10 H Uiso 1.09750 0.14471 0.77095 1.000 0.0874 . . H14 H Uiso 0.56061 0.13971 0.50693 1.000 0.0877 . . H16A H Uiso 1.32518 0.21759 0.95666 1.000 0.1453 . . H16B H Uiso 1.35687 0.19142 0.83232 1.000 0.1453 . . H16C H Uiso 1.21272 0.17934 0.95687 1.000 0.1453 . . H18A H Uiso 0.764(6) 0.2624(9) 0.522(4) 1.000 0.1181 . . H18B H Uiso 0.974(7) 0.2643(10) 0.626(4) 1.000 0.1181 . . H19A H Uiso 0.82741 0.32122 0.59076 1.000 0.1776 . . H19B H Uiso 0.79882 0.31001 0.74458 1.000 0.1776 . . H19C H Uiso 0.59059 0.30824 0.64047 1.000 0.1776 . . H21A H Uiso 0.17314 0.20741 0.40236 1.000 0.1517 . . H21B H Uiso 0.21521 0.17037 0.47619 1.000 0.1517 . . H21C H Uiso 0.37338 0.18259 0.35836 1.000 0.1517 . . H31 H Uiso 0.95840 -0.02182 0.11167 1.000 0.0847 . . H32 H Uiso 1.05459 -0.06045 -0.05985 1.000 0.0869 . . H34 H Uiso 0.50799 -0.11978 0.01397 1.000 0.0902 . . H35 H Uiso 0.41666 -0.08157 0.18727 1.000 0.0876 . . H37A H Uiso 1.01385 -0.12899 -0.30282 1.000 0.1459 . . H37B H Uiso 1.14408 -0.10625 -0.18981 1.000 0.1459 . . H37C H Uiso 0.95833 -0.08799 -0.28535 1.000 0.1459 . . 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 S5 0.0759(5) 0.0950(6) 0.0908(5) -0.0133(4) -0.0211(4) 0.0155(4) O15 0.0975(17) 0.0835(14) 0.0868(14) -0.0191(11) -0.0030(12) -0.0135(13) O17 0.0943(15) 0.0753(14) 0.0908(14) -0.0109(11) 0.0251(12) -0.0064(12) O20 0.0860(16) 0.0877(15) 0.1108(16) -0.0071(13) -0.0083(13) 0.0053(13) O36 0.1042(16) 0.0780(14) 0.0748(12) -0.0044(11) 0.0131(12) -0.0049(12) N3 0.0689(14) 0.0664(14) 0.0596(12) -0.0011(11) -0.0155(10) -0.0030(12) N6 0.0731(15) 0.0625(14) 0.0623(13) -0.0005(11) -0.0066(11) -0.0035(12) N7 0.0753(15) 0.0652(14) 0.0625(12) -0.0019(11) 0.0020(11) -0.0053(12) C1 0.079(2) 0.105(3) 0.096(2) -0.021(2) -0.031(2) 0.010(2) C2 0.0671(18) 0.0809(19) 0.0620(15) -0.0012(14) -0.0069(13) -0.0125(16) C4 0.0632(18) 0.0698(18) 0.0544(14) 0.0043(13) -0.0044(12) -0.0039(14) C8 0.078(2) 0.0707(19) 0.0606(15) 0.0027(14) 0.0002(14) -0.0096(16) C9 0.079(2) 0.0657(18) 0.0597(15) 0.0013(13) 0.0103(14) -0.0130(15) C10 0.082(2) 0.075(2) 0.0621(16) -0.0014(14) 0.0062(14) -0.0116(16) C11 0.084(2) 0.071(2) 0.0616(16) -0.0102(14) 0.0142(15) -0.0172(17) C12 0.079(2) 0.0685(19) 0.0692(17) -0.0048(15) 0.0181(16) -0.0088(17) C13 0.075(2) 0.073(2) 0.0693(17) -0.0002(15) 0.0112(15) -0.0059(17) C14 0.075(2) 0.078(2) 0.0669(16) -0.0044(15) 0.0061(15) -0.0163(17) C16 0.084(2) 0.107(3) 0.100(2) -0.023(2) 0.0007(19) -0.020(2) C18 0.107(3) 0.075(2) 0.115(3) 0.005(2) 0.022(3) -0.003(2) C19 0.130(3) 0.073(2) 0.153(3) -0.006(2) 0.018(3) -0.002(2) C21 0.092(3) 0.115(3) 0.096(2) -0.006(2) -0.005(2) 0.005(2) C30 0.0584(16) 0.0733(18) 0.0540(13) 0.0035(13) -0.0076(12) -0.0112(14) C31 0.0667(19) 0.0749(19) 0.0696(17) 0.0029(15) -0.0054(14) -0.0198(15) C32 0.0637(18) 0.083(2) 0.0706(17) 0.0048(15) 0.0058(14) -0.0083(16) C33 0.0751(19) 0.0663(18) 0.0592(15) 0.0051(14) -0.0015(14) -0.0052(15) C34 0.077(2) 0.0753(19) 0.0731(17) -0.0029(15) -0.0005(16) -0.0224(16) C35 0.0655(18) 0.084(2) 0.0692(17) -0.0020(15) 0.0051(14) -0.0230(16) C37 0.114(3) 0.098(2) 0.082(2) 0.0013(18) 0.027(2) 0.010(2) _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All esds are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag S5 C1 1.809(4) . . yes S5 C4 1.754(3) . . yes O15 C11 1.360(4) . . yes O15 C16 1.420(4) . . yes O17 C12 1.366(4) . . yes O17 C18 1.436(5) . . yes O20 C13 1.357(4) . . yes O20 C21 1.418(4) . . yes O36 C33 1.353(3) . . yes O36 C37 1.427(4) . . yes N3 C2 1.464(4) . . yes N3 C4 1.342(4) . . yes N6 N7 1.391(3) . . yes N6 C4 1.294(3) . . yes N7 C8 1.268(4) . . yes N3 H3 1.0109 . . no C1 C2 1.522(5) . . no C2 C30 1.504(4) . . no C8 C9 1.459(4) . . no C9 C14 1.389(4) . . no C9 C10 1.389(4) . . no C10 C11 1.386(4) . . no C11 C12 1.384(4) . . no C12 C13 1.401(4) . . no C13 C14 1.378(4) . . no C18 C19 1.473(5) . . no C30 C35 1.384(4) . . no C30 C31 1.382(4) . . no C31 C32 1.373(4) . . no C32 C33 1.376(4) . . no C33 C34 1.380(4) . . no C34 C35 1.368(4) . . no C1 H1A 0.97(4) . . no C1 H1B 0.97(3) . . no C2 H2 0.9797 . . no C8 H8 0.9300 . . no C10 H10 0.9301 . . no C14 H14 0.9303 . . no C16 H16A 0.9598 . . no C16 H16B 0.9602 . . no C16 H16C 0.9598 . . no C18 H18A 0.97(4) . . no C18 H18B 0.97(4) . . no C19 H19A 0.9599 . . no C19 H19B 0.9603 . . no C19 H19C 0.9599 . . no C21 H21A 0.9603 . . no C21 H21B 0.9601 . . no C21 H21C 0.9601 . . no C31 H31 0.9300 . . no C32 H32 0.9299 . . no C34 H34 0.9302 . . no C35 H35 0.9297 . . no C37 H37A 0.9602 . . no C37 H37B 0.9597 . . no C37 H37C 0.9604 . . no loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 S5 C4 90.56(16) . . . yes C11 O15 C16 118.3(3) . . . yes C12 O17 C18 112.2(2) . . . yes C13 O20 C21 119.0(3) . . . yes C33 O36 C37 117.4(2) . . . yes C2 N3 C4 115.0(2) . . . yes N7 N6 C4 110.2(2) . . . yes N6 N7 C8 115.9(2) . . . yes C4 N3 H3 114.37 . . . no C2 N3 H3 113.62 . . . no S5 C1 C2 107.2(2) . . . yes N3 C2 C1 104.2(2) . . . yes C1 C2 C30 112.1(3) . . . no N3 C2 C30 113.2(2) . . . yes N3 C4 N6 123.9(2) . . . yes S5 C4 N6 123.5(2) . . . yes S5 C4 N3 112.53(17) . . . yes N7 C8 C9 122.3(3) . . . yes C10 C9 C14 120.0(3) . . . no C8 C9 C10 118.9(3) . . . no C8 C9 C14 121.0(3) . . . no C9 C10 C11 120.0(3) . . . no O15 C11 C12 114.8(3) . . . yes C10 C11 C12 120.2(3) . . . no O15 C11 C10 125.1(3) . . . yes C11 C12 C13 119.8(3) . . . no O17 C12 C11 120.4(3) . . . yes O17 C12 C13 119.8(3) . . . yes C12 C13 C14 119.9(3) . . . no O20 C13 C14 125.7(3) . . . yes O20 C13 C12 114.4(3) . . . yes C9 C14 C13 120.2(3) . . . no O17 C18 C19 109.0(3) . . . yes C31 C30 C35 116.7(2) . . . no C2 C30 C31 122.9(3) . . . no C2 C30 C35 120.3(3) . . . no C30 C31 C32 122.1(3) . . . no C31 C32 C33 120.3(3) . . . no O36 C33 C34 116.3(3) . . . yes O36 C33 C32 125.2(3) . . . yes C32 C33 C34 118.4(3) . . . no C33 C34 C35 120.7(3) . . . no C30 C35 C34 121.7(3) . . . no S5 C1 H1A 110.5(19) . . . no S5 C1 H1B 110(2) . . . no C2 C1 H1A 110(2) . . . no C2 C1 H1B 110(2) . . . no H1A C1 H1B 108(3) . . . no N3 C2 H2 109.06 . . . no C1 C2 H2 109.08 . . . no C30 C2 H2 109.05 . . . no N7 C8 H8 118.86 . . . no C9 C8 H8 118.87 . . . no C9 C10 H10 120.03 . . . no C11 C10 H10 120.01 . . . no C9 C14 H14 119.89 . . . no C13 C14 H14 119.88 . . . no O15 C16 H16A 109.48 . . . no O15 C16 H16B 109.44 . . . no O15 C16 H16C 109.48 . . . no H16A C16 H16B 109.47 . . . no H16A C16 H16C 109.49 . . . no H16B C16 H16C 109.47 . . . no O17 C18 H18A 110(2) . . . no O17 C18 H18B 110(2) . . . no C19 C18 H18A 110(2) . . . no C19 C18 H18B 110(2) . . . no H18A C18 H18B 108(3) . . . no C18 C19 H19A 109.51 . . . no C18 C19 H19B 109.45 . . . no C18 C19 H19C 109.48 . . . no H19A C19 H19B 109.45 . . . no H19A C19 H19C 109.48 . . . no H19B C19 H19C 109.44 . . . no O20 C21 H21A 109.47 . . . no O20 C21 H21B 109.49 . . . no O20 C21 H21C 109.49 . . . no H21A C21 H21B 109.46 . . . no H21A C21 H21C 109.46 . . . no H21B C21 H21C 109.46 . . . no C30 C31 H31 118.97 . . . no C32 C31 H31 118.90 . . . no C31 C32 H32 119.87 . . . no C33 C32 H32 119.87 . . . no C33 C34 H34 119.62 . . . no C35 C34 H34 119.64 . . . no C30 C35 H35 119.12 . . . no C34 C35 H35 119.16 . . . no O36 C37 H37A 109.46 . . . no O36 C37 H37B 109.51 . . . no O36 C37 H37C 109.47 . . . no H37A C37 H37B 109.48 . . . no H37A C37 H37C 109.43 . . . no H37B C37 H37C 109.47 . . . no loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C1 S5 C4 N3 -2.9(2) . . . . no C4 S5 C1 C2 20.9(2) . . . . no C1 S5 C4 N6 176.1(2) . . . . no C16 O15 C11 C12 -176.7(3) . . . . no C16 O15 C11 C10 2.5(4) . . . . no C18 O17 C12 C11 90.2(4) . . . . no C12 O17 C18 C19 -179.6(3) . . . . no C18 O17 C12 C13 -91.1(4) . . . . no C21 O20 C13 C14 -2.1(4) . . . . no C21 O20 C13 C12 177.7(3) . . . . no C37 O36 C33 C34 168.2(3) . . . . no C37 O36 C33 C32 -11.9(4) . . . . no C2 N3 C4 S5 -17.7(3) . . . . no C4 N3 C2 C30 154.6(2) . . . . no C4 N3 C2 C1 32.6(3) . . . . no C2 N3 C4 N6 163.4(2) . . . . no C4 N6 N7 C8 -174.6(2) . . . . no N7 N6 C4 N3 174.5(2) . . . . no N7 N6 C4 S5 -4.3(3) . . . . no N6 N7 C8 C9 177.0(2) . . . . no S5 C1 C2 C30 -154.9(2) . . . . no S5 C1 C2 N3 -32.1(3) . . . . no C1 C2 C30 C31 83.3(3) . . . . no C1 C2 C30 C35 -92.9(3) . . . . no N3 C2 C30 C31 -34.2(4) . . . . no N3 C2 C30 C35 149.6(2) . . . . no N7 C8 C9 C14 -3.8(4) . . . . no N7 C8 C9 C10 179.4(3) . . . . no C14 C9 C10 C11 -1.2(4) . . . . no C10 C9 C14 C13 0.9(4) . . . . no C8 C9 C14 C13 -175.9(3) . . . . no C8 C9 C10 C11 175.7(3) . . . . no C9 C10 C11 O15 -178.3(3) . . . . no C9 C10 C11 C12 0.8(5) . . . . no C10 C11 C12 C13 -0.1(5) . . . . no C10 C11 C12 O17 178.6(3) . . . . no O15 C11 C12 O17 -2.3(4) . . . . no O15 C11 C12 C13 179.0(3) . . . . no C11 C12 C13 C14 -0.1(4) . . . . no C11 C12 C13 O20 -180.0(3) . . . . no O17 C12 C13 O20 1.3(4) . . . . no O17 C12 C13 C14 -178.8(3) . . . . no C12 C13 C14 C9 -0.3(4) . . . . no O20 C13 C14 C9 179.5(3) . . . . no C31 C30 C35 C34 -0.9(4) . . . . no C35 C30 C31 C32 0.4(4) . . . . no C2 C30 C31 C32 -175.8(3) . . . . no C2 C30 C35 C34 175.4(3) . . . . no C30 C31 C32 C33 0.3(4) . . . . no C31 C32 C33 O36 179.7(3) . . . . no C31 C32 C33 C34 -0.5(4) . . . . no O36 C33 C34 C35 179.8(3) . . . . no C32 C33 C34 C35 -0.1(4) . . . . no C33 C34 C35 C30 0.8(5) . . . . no data_3b _journal_coden_Cambridge 188 _publ_requested_journal 'Perkin Transactions 2' loop_ _publ_author_name 'Guccione, Salvatore' 'Balzano, Federica' 'Barretta, Gloria Uccello' 'Luque, F Javier' 'Pignatello, Rosario' 'Wouters, Johan' _publ_contact_author_name 'Prof Salvatore Guccione' _publ_contact_author_address ; Dipartimento di Scienze Farmaceutiche, Universita degli Studi di Catania Viale A Doria 6 Ed 2 Citta Univeristria I 95125 ITALY ; _publ_contact_author_email 'GUCCIONE@MBOX.UNICT.IT' _publ_section_title ; Crystallographic, NMR and ab initio calculation studies of tautomerism among substituted thiazol-2-yl-hydrazines. ; _database_code_CSD 174657 _chemical_formula_moiety 'C18 H16 N3 O3 S' _chemical_formula_sum 'C18 H16 N3 O3 S' _chemical_formula_weight 354.41 _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 6.2610(13) _cell_length_b 8.4800(17) _cell_length_c 16.433(3) _cell_angle_alpha 86.75(3) _cell_angle_beta 82.94(3) _cell_angle_gamma 81.98(3) _cell_volume 856.7(3) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 96 _cell_measurement_theta_min 2.7 _cell_measurement_theta_max 22.7 _exptl_special_details ; The crystal was transferred in oil and flash frozen for data collection. The crystal degraded upon defreezing and could not be Measured precisely. See text of manuscript ; _exptl_crystal_description 'prism' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_diffrn 1.374 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 370 _exptl_absorpt_coefficient_mu 0.211 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Rotating Anode' _diffrn_measurement_device_type 'MAR345' _diffrn_measurement_method 'phi scan' _diffrn_detector_area_resol_mean 6.66 _diffrn_reflns_number 4268 _diffrn_reflns_av_R_equivalents 0.0226 _diffrn_reflns_av_sigmaI/netI 0.0466 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.69 _diffrn_reflns_theta_max 22.72 _diffrn_measured_fraction_theta_max 0.947 _diffrn_reflns_theta_full 22.72 _diffrn_measured_fraction_theta_full 0.947 _refine_diff_density_max 0.784 _refine_diff_density_min -0.346 _refine_diff_density_rms 0.074 _reflns_number_total 2189 _reflns_number_gt 1658 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'mar345' _computing_cell_refinement 'marFLM' _computing_data_reduction 'marHKL (Otwinowski, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON (Spek, 1990)' _computing_publication_material 'PLATON (Spek, 1990)' _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^)+(0.1852P)^2^+0.2803P] 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 SHELXL _refine_ls_extinction_coef 0.25(4) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2189 _refine_ls_number_parameters 227 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0994 _refine_ls_R_factor_gt 0.0838 _refine_ls_wR_factor_ref 0.2587 _refine_ls_wR_factor_gt 0.2375 _refine_ls_goodness_of_fit_ref 1.055 _refine_ls_restrained_S_all 1.055 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_thermal_displace_type _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_U_iso_or_equiv _atom_site_calc_flag _atom_site_refinement_flags S5 S Uani 0.3478(2) 0.20293(14) 0.35530(7) 1.000 0.0841(6) . . O12 O Uani 0.9099(7) 0.2116(5) 0.0132(2) 1.000 0.1189(17) . . O14 O Uani 1.2453(7) 0.2933(6) -0.0281(2) 1.000 0.1179(18) . . O24 O Uani -0.1684(7) 0.0477(6) 0.8178(3) 1.000 0.1287(19) . . N3 N Uani 0.3307(5) 0.3368(4) 0.4948(2) 1.000 0.0698(12) . . N6 N Uani 0.6075(6) 0.4082(4) 0.3958(2) 1.000 0.0774(12) . . N7 N Uani 0.6906(6) 0.3731(4) 0.3153(2) 1.000 0.0774(12) . . C1 C Uani 0.1566(8) 0.1451(6) 0.4390(3) 1.000 0.0849(17) . . C2 C Uani 0.1185(8) 0.2789(6) 0.4990(3) 1.000 0.0868(19) . . C4 C Uani 0.4435(7) 0.3304(5) 0.4193(3) 1.000 0.0676(14) . . C8 C Uani 0.8607(7) 0.4338(5) 0.2866(3) 1.000 0.0793(17) . . C9 C Uani 0.9630(7) 0.4040(5) 0.2039(3) 1.000 0.0745(17) . . C10 C Uani 0.8625(8) 0.3217(6) 0.1503(3) 1.000 0.0834(17) . . C11 C Uani 0.9703(8) 0.2927(6) 0.0753(3) 1.000 0.0848(19) . . C13 C Uani 1.0810(11) 0.2082(9) -0.0518(4) 1.000 0.119(3) . . C15 C Uani 1.1727(8) 0.3404(6) 0.0496(3) 1.000 0.0880(17) . . C16 C Uani 1.2729(9) 0.4226(7) 0.0996(3) 1.000 0.098(2) . . C17 C Uani 1.1622(8) 0.4534(6) 0.1778(3) 1.000 0.0896(17) . . C18 C Uani 0.0451(7) 0.2203(5) 0.5859(3) 1.000 0.0734(17) . . C19 C Uani 0.1755(9) 0.1296(7) 0.6351(4) 1.000 0.092(2) . . C20 C Uani 0.1028(9) 0.0756(7) 0.7073(4) 1.000 0.101(3) . . C21 C Uani -0.1046(11) 0.1064(7) 0.7390(3) 1.000 0.096(2) . . C22 C Uani -0.2543(8) 0.2045(7) 0.6938(4) 1.000 0.101(2) . . C23 C Uani -0.1683(9) 0.2611(5) 0.6151(3) 1.000 0.084(2) . . C25 C Uani -0.3869(10) 0.0676(11) 0.8509(4) 1.000 0.151(4) . . H1A H Uiso 0.02145 0.13037 0.41909 1.000 0.1017 . . H1B H Uiso 0.21492 0.04601 0.46543 1.000 0.1017 . . H2 H Uiso 0.01029 0.36430 0.48093 1.000 0.1041 . . H8 H Uiso 0.92012 0.49832 0.31923 1.000 0.0952 . . H10 H Uiso 0.72739 0.28880 0.16602 1.000 0.1001 . . H13A H Uiso 1.02679 0.25791 -0.10121 1.000 0.1426 . . H13B H Uiso 1.14151 0.09888 -0.06291 1.000 0.1426 . . H16 H Uiso 1.40712 0.45628 0.08272 1.000 0.1175 . . H17 H Uiso 1.22543 0.50928 0.21339 1.000 0.1074 . . H19 H Uiso 0.32224 0.10497 0.61666 1.000 0.1101 . . H20 H Uiso 0.19952 0.01270 0.73828 1.000 0.1208 . . H22 H Uiso -0.39945 0.23023 0.71427 1.000 0.1209 . . H23 H Uiso -0.25887 0.32701 0.58290 1.000 0.1005 . . H25A H Uiso -0.40027 0.01962 0.90527 1.000 0.2261 . . H25B H Uiso -0.47019 0.01750 0.81699 1.000 0.2261 . . H25C H Uiso -0.44016 0.17921 0.85302 1.000 0.2261 . . 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 S5 0.0919(10) 0.0840(10) 0.0836(10) -0.0201(6) -0.0024(7) -0.0375(7) O12 0.125(3) 0.143(3) 0.097(3) -0.039(2) -0.010(2) -0.036(3) O14 0.120(3) 0.148(4) 0.083(2) -0.023(2) 0.011(2) -0.021(3) O24 0.119(3) 0.156(4) 0.111(3) 0.008(3) -0.011(3) -0.026(3) N3 0.065(2) 0.066(2) 0.083(2) -0.0078(17) -0.0022(18) -0.0281(16) N6 0.078(2) 0.080(2) 0.081(2) -0.0129(19) -0.0060(19) -0.0329(19) N7 0.079(2) 0.082(2) 0.075(2) -0.0122(18) -0.0009(19) -0.0278(19) C1 0.090(3) 0.083(3) 0.091(3) -0.017(2) -0.006(3) -0.043(2) C2 0.083(3) 0.086(3) 0.098(4) -0.011(3) -0.011(3) -0.031(3) C4 0.067(2) 0.060(2) 0.079(3) -0.006(2) -0.009(2) -0.018(2) C8 0.077(3) 0.082(3) 0.085(3) -0.012(2) -0.007(2) -0.031(2) C9 0.075(3) 0.075(3) 0.076(3) -0.003(2) -0.006(2) -0.021(2) C10 0.082(3) 0.084(3) 0.088(3) -0.006(2) -0.006(3) -0.027(2) C11 0.099(4) 0.084(3) 0.074(3) -0.011(2) -0.012(3) -0.016(3) C13 0.128(5) 0.135(5) 0.093(4) -0.021(4) -0.001(4) -0.018(4) C15 0.089(3) 0.096(3) 0.078(3) -0.005(3) -0.002(3) -0.015(3) C16 0.091(3) 0.114(4) 0.090(4) 0.000(3) 0.007(3) -0.033(3) C17 0.094(3) 0.100(3) 0.081(3) -0.012(3) 0.000(3) -0.040(3) C18 0.070(3) 0.073(3) 0.084(3) -0.012(2) -0.005(2) -0.033(2) C19 0.076(3) 0.098(4) 0.104(4) -0.020(3) -0.008(3) -0.018(3) C20 0.085(4) 0.095(4) 0.124(5) -0.002(3) -0.018(4) -0.014(3) C21 0.129(5) 0.106(4) 0.066(3) 0.003(3) -0.010(3) -0.061(4) C22 0.062(3) 0.122(4) 0.125(5) -0.053(4) 0.010(3) -0.034(3) C23 0.092(4) 0.064(3) 0.101(4) -0.006(2) -0.031(3) -0.011(2) C25 0.090(4) 0.227(9) 0.131(6) -0.043(6) 0.037(4) -0.036(5) _geom_special_details ; Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All esds are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag S5 C1 1.802(5) . . yes S5 C4 1.760(5) . . yes O12 C11 1.380(6) . . yes O12 C13 1.415(8) . . yes O14 C13 1.438(8) . . yes O14 C15 1.364(6) . . yes O24 C21 1.393(7) . . yes O24 C25 1.400(8) . . yes N3 C2 1.472(6) . . yes N3 C4 1.350(6) . . yes N6 N7 1.393(5) . . yes N6 C4 1.304(6) . . yes N7 C8 1.274(6) . . yes C1 C2 1.520(7) . . no C2 C18 1.523(7) . . no C8 C9 1.449(7) . . no C9 C10 1.410(7) . . no C9 C17 1.382(7) . . no C10 C11 1.349(7) . . no C11 C15 1.393(7) . . no C15 C16 1.367(7) . . no C16 C17 1.403(7) . . no C18 C19 1.352(8) . . no C18 C23 1.367(7) . . no C19 C20 1.299(9) . . no C20 C21 1.334(9) . . no C21 C22 1.416(8) . . no C22 C23 1.422(8) . . no C1 H1A 0.9700 . . no C1 H1B 0.9696 . . no C2 H2 0.9797 . . no C8 H8 0.9297 . . no C10 H10 0.9296 . . no C13 H13A 0.9701 . . no C13 H13B 0.9698 . . no C16 H16 0.9303 . . no C17 H17 0.9295 . . no C19 H19 0.9299 . . no C20 H20 0.9302 . . no C22 H22 0.9298 . . no C23 H23 0.9304 . . no C25 H25A 0.9595 . . no C25 H25B 0.9608 . . no C25 H25C 0.9597 . . no loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 S5 C4 90.4(2) . . . yes C11 O12 C13 106.7(5) . . . yes C13 O14 C15 105.7(4) . . . yes C21 O24 C25 121.0(5) . . . yes C2 N3 C4 113.5(3) . . . yes N7 N6 C4 109.9(4) . . . yes N6 N7 C8 116.2(4) . . . yes S5 C1 C2 106.7(3) . . . yes N3 C2 C1 104.3(4) . . . yes N3 C2 C18 110.9(4) . . . yes C1 C2 C18 111.9(4) . . . no S5 C4 N3 112.7(3) . . . yes S5 C4 N6 123.1(4) . . . yes N3 C4 N6 124.2(4) . . . yes N7 C8 C9 121.1(4) . . . yes C8 C9 C10 120.3(4) . . . no C8 C9 C17 120.0(4) . . . no C10 C9 C17 119.6(4) . . . no C9 C10 C11 117.3(5) . . . no O12 C11 C10 128.4(5) . . . yes O12 C11 C15 108.7(4) . . . yes C10 C11 C15 122.9(5) . . . no O12 C13 O14 108.4(5) . . . yes O14 C15 C11 110.5(4) . . . yes O14 C15 C16 128.3(5) . . . yes C11 C15 C16 121.2(5) . . . no C15 C16 C17 116.3(5) . . . no C9 C17 C16 122.6(5) . . . no C2 C18 C19 124.5(5) . . . no C2 C18 C23 117.2(4) . . . no C19 C18 C23 118.3(5) . . . no C18 C19 C20 122.3(5) . . . no C19 C20 C21 122.9(6) . . . no O24 C21 C20 119.4(6) . . . yes O24 C21 C22 120.9(6) . . . yes C20 C21 C22 119.6(5) . . . no C21 C22 C23 115.7(5) . . . no C18 C23 C22 121.2(5) . . . no S5 C1 H1A 110.33 . . . no S5 C1 H1B 110.36 . . . no C2 C1 H1A 110.37 . . . no C2 C1 H1B 110.42 . . . no H1A C1 H1B 108.64 . . . no N3 C2 H2 109.87 . . . no C1 C2 H2 109.91 . . . no C18 C2 H2 109.87 . . . no N7 C8 H8 119.46 . . . no C9 C8 H8 119.46 . . . no C9 C10 H10 121.34 . . . no C11 C10 H10 121.37 . . . no O12 C13 H13A 109.99 . . . no O12 C13 H13B 110.03 . . . no O14 C13 H13A 110.02 . . . no O14 C13 H13B 110.05 . . . no H13A C13 H13B 108.39 . . . no C15 C16 H16 121.85 . . . no C17 C16 H16 121.82 . . . no C9 C17 H17 118.77 . . . no C16 C17 H17 118.66 . . . no C18 C19 H19 118.91 . . . no C20 C19 H19 118.84 . . . no C19 C20 H20 118.60 . . . no C21 C20 H20 118.51 . . . no C21 C22 H22 122.13 . . . no C23 C22 H22 122.17 . . . no C18 C23 H23 119.38 . . . no C22 C23 H23 119.46 . . . no O24 C25 H25A 109.47 . . . no O24 C25 H25B 109.45 . . . no O24 C25 H25C 109.47 . . . no H25A C25 H25B 109.45 . . . no H25A C25 H25C 109.54 . . . no H25B C25 H25C 109.44 . . . no loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C1 S5 C4 N3 -4.1(3) . . . . no C4 S5 C1 C2 23.2(4) . . . . no C1 S5 C4 N6 175.2(4) . . . . no C11 O12 C13 O14 -1.4(6) . . . . no C13 O12 C11 C15 0.6(6) . . . . no C13 O12 C11 C10 -177.8(6) . . . . no C13 O14 C15 C16 178.7(6) . . . . no C13 O14 C15 C11 -1.3(6) . . . . no C15 O14 C13 O12 1.6(7) . . . . no C25 O24 C21 C20 -175.3(6) . . . . no C25 O24 C21 C22 7.7(9) . . . . no C2 N3 C4 N6 162.9(4) . . . . no C2 N3 C4 S5 -17.8(5) . . . . no C4 N3 C2 C18 155.1(4) . . . . no C4 N3 C2 C1 34.5(5) . . . . no C4 N6 N7 C8 -175.7(4) . . . . no N7 N6 C4 S5 -0.5(5) . . . . no N7 N6 C4 N3 178.7(4) . . . . no N6 N7 C8 C9 179.3(4) . . . . no S5 C1 C2 N3 -35.2(4) . . . . no S5 C1 C2 C18 -155.1(3) . . . . no N3 C2 C18 C19 -43.2(6) . . . . no N3 C2 C18 C23 137.7(4) . . . . no C1 C2 C18 C19 72.7(6) . . . . no C1 C2 C18 C23 -106.3(5) . . . . no N7 C8 C9 C17 -171.5(4) . . . . no N7 C8 C9 C10 7.1(7) . . . . no C8 C9 C10 C11 -177.5(4) . . . . no C17 C9 C10 C11 1.1(7) . . . . no C10 C9 C17 C16 -1.1(7) . . . . no C8 C9 C17 C16 177.5(5) . . . . no C9 C10 C11 C15 -0.1(8) . . . . no C9 C10 C11 O12 178.1(5) . . . . no O12 C11 C15 C16 -179.5(5) . . . . no C10 C11 C15 C16 -1.0(8) . . . . no O12 C11 C15 O14 0.4(6) . . . . no C10 C11 C15 O14 179.0(5) . . . . no O14 C15 C16 C17 -179.0(5) . . . . no C11 C15 C16 C17 0.9(8) . . . . no C15 C16 C17 C9 0.1(8) . . . . no C2 C18 C19 C20 -176.4(5) . . . . no C23 C18 C19 C20 2.7(8) . . . . no C2 C18 C23 C22 176.5(5) . . . . no C19 C18 C23 C22 -2.6(7) . . . . no C18 C19 C20 C21 -0.7(10) . . . . no C19 C20 C21 C22 -1.3(10) . . . . no C19 C20 C21 O24 -178.2(6) . . . . no C20 C21 C22 C23 1.2(8) . . . . no O24 C21 C22 C23 178.1(5) . . . . no C21 C22 C23 C18 0.7(8) . . . . no