Supplementary Material (ESI) for Perkin Transactions This journal is © The Royal Society of Chemistry 2002 data_CRYSTALS_cif _database_code_CSD 172908 _audit_creation_date 01-09-07 _audit_creation_method CRYSTALS _journal_coden_Cambridge 188 loop_ _publ_author_name _publ_author_address 'Lomas, John S.' ; ITODYS, Université de Paris 7, associé au C.N.R.S., 1 rue Guy de la Brosse, 75005 Paris, France ; 'Adenier, Alain' ; ITODYS, Université de Paris 7, associé au C.N.R.S., 1 rue Guy de la Brosse, 75005 Paris, France ; 'Gao, Kun' ; ITODYS, Université de Paris 7, associé au C.N.R.S., 1 rue Guy de la Brosse, 75005 Paris, France ; 'Maurel, François' ; ITODYS, Université de Paris 7, associé au C.N.R.S., 1 rue Guy de la Brosse, 75005 Paris, France' ; 'Vaissermann, Jacqueline' ; Laboratoire de Chimie des Métaux de Transition, Université de Paris 6, associé au C.N.R.S., Case 42, 4 place Jussieu, 75252 Paris Cedex 05, France' ; # 1. SUBMISSION DETAILS _publ_contact_author_name 'Dr J Lomas' _publ_contact_author_address ; I T O D Y S Universite de Paris VII 1 Rue Guy de la Brosse Paris Cedex 75005 FRANCE ; _publ_contact_author_phone '33 1 4427 6838' _publ_contact_author_fax '33 1 4427 6814' _publ_contact_author_email 'lomas@itodys.jussieu.fr' _publ_requested_journal 'J. Chem. Soc., Perkin Trans. 2 ' _publ_requested_coeditor_name ' ? ' #==================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Hydrogen bonding and steric effects on rotamerization in 3,4-alkylenedioxy-, 3-alkoxy- and 3,4-dialkoxy-2-thienyldi(tert-butyl)methanols: an NMR, IR and X-ray crystallographic study ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. #==================================================================== _computing_data_collection 'CAD-4 software (Enraf-Nonius, 1989)' _computing_cell_refinement 'CAD-4 software (Enraf-Nonius, 1989)' _computing_data_reduction ; RC93 (Watkin, D.J., Prout, C.K., Lilley, P.M.deQ. 1994) ; _computing_structure_refinement ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_publication_material ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_molecular_graphics ; CAMERON (Watkin, Prout & Pearce, 1996) ; # _computing_structure_solution 'SHELXS86 (Sheldrick, 1986)' #==================================================================== _chemical_melting_point '101 °C' _diffrn_radiation_monochromator 'graphite' _diffrn_measurement_device 'Enraf-Nonius MACH-3' _refine_ls_matrix_type 'full' _refine_ls_weighting_scheme ; Chebychev polynomial (Carruthers & Watkin, 1979) ; _atom_sites_solution_primary 'Direct methods' _atom_sites_solution_hydrogens 'placed in geometrically calculated positions' _refine_ls_hydrogen_treatment ; H coordinates refined with one overall isotropic thermal parameter ; #**************************************************************************** _chemical_name_systematic '3,4-diethoxy-2-thienyldi(tert-butyl)methanol' #; # IUPAC name, in full '3,4-diethoxy-2-thienyldi(tert-butyl)methanol' #; _cell_length_a 12.367(3) _cell_angle_alpha 90 _cell_length_b 11.139(2) _cell_angle_beta 112.72(2) _cell_length_c 14.127(3) _cell_angle_gamma 90 _cell_volume 1795.0(7) _symmetry_cell_setting 'Monoclinic' _symmetry_space_group_name_H-M 'P 1 21/c 1' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' '-x,-y,-z' '-x,y+1/2,-z+1/2' 'x,-y+1/2,z+1/2' loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source 'C ' 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International_Tables_Vol_IV_Table_2.2B' 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 'International_Tables_Vol_IV_Table_2.2B' 'O ' 0.0080 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International_Tables_Vol_IV_Table_2.2B' 'S ' 0.1100 0.1240 6.9053 1.4679 5.2034 22.2151 1.4379 0.2536 1.5863 56.1720 0.8669 'International_Tables_Vol_IV_Table_2.2B' _chemical_formula_sum 'C17 H30 O3 S1' _chemical_formula_moiety '(C2H5O)2(C4SH)C(C4H9)2 OH' _chemical_compound_source ; Prepared by the reaction of 3,4-diethoxy-2-thienyl-lithium with di(tert-butyl) ketone' ; _chemical_formula_weight 314.48 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 13 _cell_measurement_theta_max 13.3 _cell_measurement_temperature 295K _cell_formula_units_Z 4 _exptl_crystal_description 'block' _exptl_crystal_colour 'none' _exptl_crystal_size_min 0.6 _exptl_crystal_size_mid 0.6 _exptl_crystal_size_max 0.6 _exptl_crystal_density_diffrn 1.16 _exptl_crystal_density_meas ? _exptl_crystal_F_000 688.60 _exptl_absorpt_coefficient_mu 0.18 _exptl_absorpt_correction_type DIFABS _exptl_absorpt_process_details 'refined from delta-F' _exptl_absorpt_correction_T_min 0.62 _exptl_absorpt_correction_T_max 1.00 _diffrn_standards_interval_time 3600 _diffrn_standards_number 2 _diffrn_standards_decay_% 2.76 _diffrn_ambient_temperature 295K _diffrn_reflns_number 3898 _reflns_number_total 3523 _diffrn_reflns_av_R_equivalents 0.02 _reflns_number_observed 2271 _diffrn_reflns_theta_min 1 _diffrn_reflns_theta_max 26 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _reflns_observed_criterion >3.00\s(I) _refine_diff_density_min -0.25 _refine_diff_density_max 0.45 _refine_ls_number_reflns 2271 _refine_ls_number_parameters 192 _refine_ls_R_factor_obs 0.0547 _refine_ls_wR_factor_obs 0.0742 _refine_ls_goodness_of_fit_obs 1.23 _refine_ls_shift/esd_max 0.1805 _refine_ls_structure_factor_coef 'F' _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71069 _diffrn_measurement_method 2\q/\w loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_thermal_displace_type S1 0.88176(7) 0.23716(7) 0.36279(7) 0.0631 1.0000 Uani O1 0.6393(2) 0.5027(2) 0.2773(2) 0.0536 1.0000 Uani O3 0.8084(2) 0.5326(2) 0.2068(1) 0.0496 1.0000 Uani O4 0.9961(2) 0.4107(2) 0.1845(2) 0.0686 1.0000 Uani C2 0.8026(2) 0.3681(2) 0.3163(2) 0.0453 1.0000 Uani C3 0.8477(2) 0.4239(2) 0.2546(2) 0.0450 1.0000 Uani C4 0.9444(2) 0.3613(3) 0.2445(2) 0.0540 1.0000 Uani C5 0.9704(3) 0.2581(3) 0.2974(3) 0.0618 1.0000 Uani C6 0.7471(3) 0.5207(4) 0.0958(2) 0.0691 1.0000 Uani C7 0.6852(4) 0.6322(5) 0.0546(3) 0.0908 1.0000 Uani C8 1.0949(3) 0.3424(4) 0.1826(3) 0.0778 1.0000 Uani C9 1.1431(4) 0.4029(4) 0.1173(5) 0.0983 1.0000 Uani C10 0.6988(2) 0.4057(2) 0.3440(2) 0.0454 1.0000 Uani C11 0.6014(3) 0.3034(3) 0.3131(3) 0.0601 1.0000 Uani C12 0.5874(3) 0.2529(4) 0.2072(3) 0.0809 1.0000 Uani C13 0.4801(3) 0.3540(4) 0.3004(4) 0.0812 1.0000 Uani C14 0.6275(4) 0.1973(4) 0.3883(3) 0.0792 1.0000 Uani C15 0.7470(3) 0.4587(3) 0.4575(2) 0.0551 1.0000 Uani C16 0.6491(4) 0.5007(4) 0.4901(3) 0.0770 1.0000 Uani C17 0.8264(4) 0.3747(4) 0.5413(3) 0.0813 1.0000 Uani C18 0.8203(4) 0.5703(4) 0.4584(3) 0.0829 1.0000 Uani H1 0.6883 0.5506 0.2593 0.126(3) 1.0000 Uiso H51 1.0333 0.2012 0.2982 0.126(3) 1.0000 Uiso H61 0.8051 0.5041 0.0639 0.126(3) 1.0000 Uiso H62 0.6897 0.4531 0.0802 0.126(3) 1.0000 Uiso H71 0.6431 0.6246 -0.0214 0.126(3) 1.0000 Uiso H72 0.7428 0.6997 0.0703 0.126(3) 1.0000 Uiso H73 0.6274 0.6486 0.0866 0.126(3) 1.0000 Uiso H81 1.1562 0.3360 0.2537 0.126(3) 1.0000 Uiso H82 1.0683 0.2601 0.1551 0.126(3) 1.0000 Uiso H91 1.2114 0.3563 0.1156 0.126(3) 1.0000 Uiso H92 1.1695 0.4852 0.1449 0.126(3) 1.0000 Uiso H93 1.0816 0.4093 0.0463 0.126(3) 1.0000 Uiso H121 0.5264 0.1884 0.1866 0.126(3) 1.0000 Uiso H122 0.6638 0.2187 0.2112 0.126(3) 1.0000 Uiso H123 0.5629 0.3189 0.1552 0.126(3) 1.0000 Uiso H131 0.4212 0.2875 0.2811 0.126(3) 1.0000 Uiso H132 0.4851 0.3907 0.3666 0.126(3) 1.0000 Uiso H133 0.4556 0.4165 0.2454 0.126(3) 1.0000 Uiso H141 0.5618 0.1381 0.3627 0.126(3) 1.0000 Uiso H142 0.7022 0.1577 0.3938 0.126(3) 1.0000 Uiso H143 0.6354 0.2273 0.4574 0.126(3) 1.0000 Uiso H161 0.6839 0.5330 0.5616 0.126(3) 1.0000 Uiso H162 0.6027 0.5652 0.4424 0.126(3) 1.0000 Uiso H163 0.5966 0.4315 0.4876 0.126(3) 1.0000 Uiso H171 0.8520 0.4158 0.6094 0.126(3) 1.0000 Uiso H172 0.8968 0.3533 0.5264 0.126(3) 1.0000 Uiso H173 0.7823 0.2999 0.5428 0.126(3) 1.0000 Uiso H181 0.8521 0.6060 0.5289 0.126(3) 1.0000 Uiso H182 0.8868 0.5470 0.4386 0.126(3) 1.0000 Uiso H183 0.7699 0.6307 0.4085 0.126(3) 1.0000 Uiso 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 0.0634(5) 0.0568(5) 0.0744(6) 0.0133(4) 0.0249(4) 0.0158(4) O1 0.053(1) 0.062(1) 0.057(1) 0.023(1) 0.0233(9) 0.0141(9) O3 0.061(1) 0.052(1) 0.041(1) 0.0006(8) 0.0236(8) -0.0008(9) O4 0.072(1) 0.079(2) 0.084(2) -0.007(1) 0.050(1) 0.004(1) C2 0.044(1) 0.046(1) 0.043(1) 0.001(1) 0.012(1) 0.004(1) C3 0.047(1) 0.047(1) 0.042(1) -0.006(1) 0.015(1) 0.001(1) C4 0.049(1) 0.066(2) 0.054(2) -0.015(1) 0.022(1) -0.004(1) C5 0.055(2) 0.063(2) 0.071(2) -0.006(2) 0.023(1) 0.009(1) C6 0.096(2) 0.085(2) 0.041(2) 0.006(2) 0.023(2) 0.010(2) C7 0.108(3) 0.129(4) 0.062(2) 0.026(2) 0.027(2) 0.043(3) C8 0.079(2) 0.084(3) 0.110(3) -0.013(2) 0.061(2) 0.005(2) C9 0.105(3) 0.092(3) 0.150(4) 0.002(3) 0.084(3) 0.009(3) C10 0.046(1) 0.050(1) 0.042(1) 0.009(1) 0.016(1) 0.004(1) C11 0.051(2) 0.064(2) 0.065(2) 0.008(2) 0.018(1) -0.006(1) C12 0.077(2) 0.099(3) 0.072(2) -0.022(2) 0.014(2) -0.028(2) C13 0.047(2) 0.105(3) 0.109(3) 0.013(3) 0.026(2) -0.006(2) C14 0.084(3) 0.069(2) 0.107(3) 0.025(2) 0.042(2) -0.009(2) C15 0.061(2) 0.065(2) 0.043(1) 0.000(1) 0.019(1) 0.006(1) C16 0.092(3) 0.103(3) 0.066(2) 0.001(2) 0.046(2) 0.020(2) C17 0.098(3) 0.110(3) 0.047(2) 0.004(2) 0.007(2) 0.028(2) C18 0.106(3) 0.089(3) 0.077(2) -0.032(2) 0.039(2) -0.030(2) _refine_ls_extinction_coef 319.9 _refine_ls_extinction_method 'Larson 1970 Crystallographic Computing eq 22' loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag S1 . C2 . 1.738(3) yes S1 . C5 . 1.701(3) yes O1 . C10 . 1.436(3) no O1 . H1 . 0.914(2) no O3 . C3 . 1.381(3) yes O3 . C6 . 1.460(4) no O4 . C4 . 1.360(4) yes O4 . C8 . 1.449(4) no C2 . C3 . 1.354(4) yes C2 . C10 . 1.537(4) yes C3 . C4 . 1.438(4) yes C4 . C5 . 1.341(5) yes C5 . H51 . 1.000(3) no C6 . C7 . 1.457(6) no C6 . H61 . 1.000(4) no C6 . H62 . 1.000(4) no C7 . H71 . 1.001(4) no C7 . H72 . 1.000(6) no C7 . H73 . 0.999(5) no C8 . C9 . 1.444(6) no C8 . H81 . 1.000(5) no C8 . H82 . 1.000(4) no C9 . H91 . 1.000(4) no C9 . H92 . 1.000(5) no C9 . H93 . 0.999(6) no C10 . C11 . 1.592(4) yes C10 . C15 . 1.593(4) yes C11 . C12 . 1.544(5) no C11 . C13 . 1.546(5) no C11 . C14 . 1.537(5) no C12 . H121 . 1.000(4) no C12 . H122 . 1.000(4) no C12 . H123 . 1.000(5) no C13 . H131 . 1.000(4) no C13 . H132 . 1.000(5) no C13 . H133 . 1.000(4) no C14 . H141 . 1.000(4) no C14 . H142 . 1.000(4) no C14 . H143 . 1.001(5) no C15 . C16 . 1.525(4) no C15 . C17 . 1.531(5) no C15 . C18 . 1.536(5) no C16 . H161 . 1.000(4) no C16 . H162 . 1.000(4) no C16 . H163 . 1.000(5) no C17 . H171 . 1.000(4) no C17 . H172 . 1.000(4) no C17 . H173 . 1.000(5) no C18 . H181 . 1.000(4) no C18 . H182 . 1.000(4) no C18 . H183 . 1.000(5) no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C2 . S1 . C5 . 93.8(1) yes C10 . O1 . H1 . 113.2(2) no C3 . O3 . C6 . 112.6(2) no C4 . O4 . C8 . 113.7(3) no S1 . C2 . C3 . 108.4(2) yes S1 . C2 . C10 . 122.4(2) yes C3 . C2 . C10 . 129.1(2) no O3 . C3 . C2 . 124.3(2) yes O3 . C3 . C4 . 121.7(2) yes C2 . C3 . C4 . 114.0(3) yes O4 . C4 . C3 . 118.4(3) yes O4 . C4 . C5 . 128.7(3) yes C3 . C4 . C5 . 113.0(3) yes S1 . C5 . C4 . 110.7(2) yes S1 . C5 . H51 . 124.6(3) no C4 . C5 . H51 . 124.6(3) no O3 . C6 . C7 . 109.0(3) no O3 . C6 . H61 . 109.6(3) no C7 . C6 . H61 . 109.6(3) no O3 . C6 . H62 . 109.6(3) no C7 . C6 . H62 . 109.6(4) no H61 . C6 . H62 . 109.5(4) no C6 . C7 . H71 . 109.4(4) no C6 . C7 . H72 . 109.4(4) no H71 . C7 . H72 . 109.5(4) no C6 . C7 . H73 . 109.5(4) no H71 . C7 . H73 . 109.5(4) no H72 . C7 . H73 . 109.6(5) no O4 . C8 . C9 . 109.0(4) no O4 . C8 . H81 . 109.6(3) no C9 . C8 . H81 . 109.6(4) no O4 . C8 . H82 . 109.6(3) no C9 . C8 . H82 . 109.6(4) no H81 . C8 . H82 . 109.5(4) no C8 . C9 . H91 . 109.4(4) no C8 . C9 . H92 . 109.4(4) no H91 . C9 . H92 . 109.5(5) no C8 . C9 . H93 . 109.4(4) no H91 . C9 . H93 . 109.6(5) no H92 . C9 . H93 . 109.5(5) no O1 . C10 . C2 . 107.8(2) no O1 . C10 . C11 . 102.5(2) no C2 . C10 . C11 . 110.7(2) yes O1 . C10 . C15 . 106.2(2) no C2 . C10 . C15 . 109.4(2) yes C11 . C10 . C15 . 119.4(2) yes C10 . C11 . C12 . 108.4(3) no C10 . C11 . C13 . 111.6(3) no C12 . C11 . C13 . 106.2(3) no C10 . C11 . C14 . 115.3(3) no C12 . C11 . C14 . 107.7(3) no C13 . C11 . C14 . 107.2(3) no C11 . C12 . H121 . 109.5(4) no C11 . C12 . H122 . 109.5(3) no H121 . C12 . H122 . 109.5(4) no C11 . C12 . H123 . 109.5(4) no H121 . C12 . H123 . 109.5(4) no H122 . C12 . H123 . 109.4(4) no C11 . C13 . H131 . 109.5(4) no C11 . C13 . H132 . 109.5(3) no H131 . C13 . H132 . 109.5(4) no C11 . C13 . H133 . 109.5(3) no H131 . C13 . H133 . 109.5(4) no H132 . C13 . H133 . 109.4(4) no C11 . C14 . H141 . 109.5(4) no C11 . C14 . H142 . 109.5(3) no H141 . C14 . H142 . 109.5(4) no C11 . C14 . H143 . 109.5(4) no H141 . C14 . H143 . 109.4(3) no H142 . C14 . H143 . 109.4(4) no C10 . C15 . C16 . 112.7(3) no C10 . C15 . C17 . 115.5(3) no C16 . C15 . C17 . 107.5(3) no C10 . C15 . C18 . 107.4(2) no C16 . C15 . C18 . 106.5(3) no C17 . C15 . C18 . 106.8(3) no C15 . C16 . H161 . 109.5(3) no C15 . C16 . H162 . 109.4(3) no H161 . C16 . H162 . 109.4(4) no C15 . C16 . H163 . 109.5(3) no H161 . C16 . H163 . 109.5(3) no H162 . C16 . H163 . 109.5(4) no C15 . C17 . H171 . 109.5(4) no C15 . C17 . H172 . 109.5(3) no H171 . C17 . H172 . 109.5(4) no C15 . C17 . H173 . 109.5(3) no H171 . C17 . H173 . 109.5(4) no H172 . C17 . H173 . 109.4(4) no C15 . C18 . H181 . 109.5(4) no C15 . C18 . H182 . 109.5(4) no H181 . C18 . H182 . 109.5(4) no C15 . C18 . H183 . 109.5(3) no H181 . C18 . H183 . 109.5(4) no H182 . C18 . H183 . 109.5(4) no