# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 182/1483 # CIF for ms 9/08476B # # Steric constraint generating large through-space 1H-203.205 # Tl coupling in a dithallium(I) cryptate # data_tlr3bm _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C38 H54 F6 N8 O6 S2 Tl2' _chemical_formula_weight 1305.75 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' 'F' 'F' 0.0171 0.0103 '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' 'Tl' 'Tl' -2.8358 9.6688 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M 'P 6(3)/m' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' '-x, -y, z+1/2' 'y, -x+y, z+1/2' 'x-y, x, z+1/2' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' 'x, y, -z-1/2' '-y, x-y, -z-1/2' '-x+y, -x, -z-1/2' _cell_length_a 9.5074(2) _cell_length_b 9.5074(2) _cell_length_c 29.7005(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 2324.97(8) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 5467 _cell_measurement_theta_min 3 _cell_measurement_theta_max 54 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.16 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.865 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1268 _exptl_absorpt_coefficient_mu 7.088 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.3968 _exptl_absorpt_correction_T_max 0.7647 _exptl_absorpt_process_details ? _exptl_special_details ; Data collected at the CLRC Daresbury Lab on line 9.8 of the SRS ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.68850 _diffrn_radiation_type Synchrotron _diffrn_radiation_source 'synchrotron' _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 16580 _diffrn_reflns_av_R_equivalents 0.0346 _diffrn_reflns_av_sigmaI/netI 0.0219 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -41 _diffrn_reflns_limit_l_max 41 _diffrn_reflns_theta_min 2.49 _diffrn_reflns_theta_max 29.33 _reflns_number_total 2277 _reflns_number_gt 1694 _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 'SHELXL-97 (Sheldrick, 1997)' _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. The only significant residual electron density peak and hole lie on the threefold axis. ; _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^)+(0.0400P)^2^+4.5453P] 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 2277 _refine_ls_number_parameters 100 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0542 _refine_ls_R_factor_gt 0.0357 _refine_ls_wR_factor_ref 0.0835 _refine_ls_wR_factor_gt 0.0788 _refine_ls_goodness_of_fit_ref 1.060 _refine_ls_restrained_S_all 1.060 _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_multiplicit _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Tl Tl 0.0000 0.0000 0.176340(7) 0.02918(9) Uani 1 3 d S . . N1 N 0.0000 0.0000 0.08450(18) 0.0252(10) Uani 1 3 d S . . C1 C 0.0198(5) -0.1362(5) 0.06763(12) 0.0283(8) Uani 1 1 d . . . H1A H 0.1360 -0.1044 0.0693 0.034 Uiso 1 1 calc R . . H1B H -0.0134 -0.1564 0.0356 0.034 Uiso 1 1 calc R . . C2 C -0.0787(5) -0.2913(5) 0.09397(13) 0.0301(8) Uani 1 1 d . . . H2A H -0.1928 -0.3160 0.0959 0.036 Uiso 1 1 calc R . . H2B H -0.0776 -0.3822 0.0780 0.036 Uiso 1 1 calc R . . N11 N -0.0131(4) -0.2772(4) 0.13973(11) 0.0257(6) Uani 1 1 d . .. . H11 H 0.082(5) -0.270(5) 0.1386(15) 0.030 Uiso 1 1 d . . . C3 C -0.1178(5) -0.4274(5) 0.16499(14) 0.0319(9) Uani 1 1 d . . . H3A H -0.1414 -0.5213 0.1455 0.038 Uiso 1 1 calc R . . H3B H -0.2223 -0.4320 0.1713 0.038 Uiso 1 1 calc R . . C4 C -0.0494(4) -0.4462(4) 0.20892(12) 0.0243(7) Uani 1 1 d . . . C5 C 0.0610(5) -0.5027(4) 0.20926(13) 0.0265(8) Uani 1 1 d . . . H5 H 0.0986 -0.5222 0.1816 0.032 Uiso 1 1 calc R . . C6 C 0.1164(7) -0.5308(6) 0.2500 0.0274(11) Uani 1 2 d S . . H6 H 0.1917 -0.5689 0.2500 0.033 Uiso 1 2 calc SR . . C9 C -0.1022(6) -0.4185(6) 0.2500 0.0238(10) Uani 1 2 d S . . H9 H -0.1767 -0.3794 0.2500 0.029 Uiso 1 2 calc SR . . S1 S 0.3333 -0.3333 0.08636(6) 0.0279(3) Uani 1 3 d S . . O1 O 0.3463(4) -0.1795(4) 0.09777(10) 0.0405(7) Uani 1 1 d . . . C10 C 0.3333 -0.3333 0.0249(3) 0.049(2) Uani 1 3 d S . . F1 F 0.2118(5) -0.3162(6) 0.00860(10) 0.0761(12) 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 Tl 0.03378(11) 0.03378(11) 0.01996(13) 0.000 0.000 0.01689(5) N1 0.0266(14) 0.0266(14) 0.023(2) 0.000 0.000 0.0133(7) C1 0.037(2) 0.0294(19) 0.0202(16) -0.0043(14) -0.0006(15) 0.0175(18) C2 0.036(2) 0.030(2) 0.0228(17) -0.0007(15) -0.0042(16) 0.0161(17) N11 0.0246(15) 0.0271(16) 0.0227(14) 0.0024(12) -0.0002(12) 0.0109(13) C3 0.0249(19) 0.031(2) 0.0309(19) 0.0048(16) -0.0072(15) 0.0075(16) C4 0.0223(16) 0.0165(16) 0.0281(17) 0.0029(14) -0.0029(14) 0.0053(14) C5 0.0285(18) 0.0182(17) 0.0275(18) -0.0032(14) 0.0019(15) 0.0078(15) C6 0.025(3) 0.018(2) 0.035(3) 0.000 0.000 0.008(2) C9 0.018(2) 0.014(2) 0.036(3) 0.000 0.000 0.0062(19) S1 0.0308(5) 0.0308(5) 0.0222(7) 0.000 0.000 0.0154(2) O1 0.0490(19) 0.0359(16) 0.0412(16) -0.0044(14) -0.0065(15) 0.0246(15) C10 0.059(3) 0.059(3) 0.030(4) 0.000 0.000 0.0296(17) F1 0.087(3) 0.113(3) 0.0385(17) -0.0012(18) -0.0232(17) 0.057(3) _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 Tl N1 2.728(5) . y Tl N11 2.796(3) . y Tl N11 2.796(3) 3 ? Tl N11 2.796(3) 2 ? Tl Tl 4.3755(4) 10_556 y N1 C1 1.486(4) 3 ? N1 C1 1.486(4) 2 ? N1 C1 1.486(4) . ? C1 C2 1.511(5) . ? C2 N11 1.473(5) . ? N11 C3 1.474(5) . ? C3 C4 1.508(5) . ? C4 C9 1.394(4) . ? C4 C5 1.398(6) . ? C5 C6 1.398(5) . ? C6 C5 1.398(5) 10_556 ? C9 C4 1.394(4) 10_556 ? S1 O1 1.445(3) . ? S1 O1 1.445(3) 2_545 ? S1 O1 1.445(3) 3_655 ? S1 C10 1.826(8) . ? C10 F1 1.336(5) . ? C10 F1 1.336(5) 3_655 ? C10 F1 1.336(5) 2_545 ? 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 Tl N11 67.11(6) . . y N1 Tl N11 67.11(6) . 3 ? N11 Tl N11 105.85(7) . 3 y N1 Tl N11 67.11(6) . 2 ? N11 Tl N11 105.85(7) . 2 ? N11 Tl N11 105.85(7) 3 2 ? N1 Tl Tl 180.0 . 10_556 ? N11 Tl Tl 112.89(6) . 10_556 ? N11 Tl Tl 112.89(6) 3 10_556 ? N11 Tl Tl 112.89(6) 2 10_556 ? C1 N1 C1 109.2(2) 3 2 ? C1 N1 C1 109.2(2) 3 . ? C1 N1 C1 109.2(2) 2 . ? C1 N1 Tl 109.7(2) 3 . ? C1 N1 Tl 109.7(2) 2 . ? C1 N1 Tl 109.7(2) . . ? N1 C1 C2 112.9(3) . . ? N11 C2 C1 111.2(3) . . ? C2 N11 C3 109.4(3) . . ? C2 N11 Tl 105.2(2) . . ? C3 N11 Tl 113.9(2) . . ? N11 C3 C4 115.7(3) . . ? C9 C4 C5 118.5(4) . . ? C9 C4 C3 121.2(4) . .. ? C5 C4 C3 120.2(4) . . ? C4 C5 C6 120.4(4) . . ? C5 C6 C5 119.9(5) . 10_556 ? C4 C9 C4 122.2(5) . 10_556 ? O1 S1 O1 114.68(11) . 2_545 ? O1 S1 O1 114.68(11) . 3_655 ? O1 S1 O1 114.68(11) 2_545 3_655 ? O1 S1 C10 103.56(14) . . ? O1 S1 C10 103.56(14) 2_545 . ? O1 S1 C10 103.56(14) 3_655 . ? F1 C10 F1 107.7(4) . 3_655 ? F1 C10 F1 107.7(4) . 2_545 ? F1 C10 F1 107.7(4) 3_655 2_545 ? F1 C10 S1 111.2(4) . . ? F1 C10 S1 111.2(4) 3_655 . ? F1 C10 S1 111.2(4) 2_545 . ? 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 N11 C3 C3 N11 0.0 . . 10_556 10_556 ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N11 H11 O1 0.88(4) 2.52(5) 3.304(5) 149(4) . _diffrn_measured_fraction_theta_max 0.946 _diffrn_reflns_theta_full 29.33 _diffrn_measured_fraction_theta_full 0.946 _refine_diff_density_max 1.575 _refine_diff_density_min -2.041 _refine_diff_density_rms 0.111