Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name 'Enrique Garcia-Espana' 'Manuel G. Basallote' 'Pilar Diaz' 'Laura Gil' 'Julio Latorre' 'Santiago V. Luis' ; M.A.Manez ; 'Conxa Soriano' 'Begona Verdejo' _publ_contact_author_name 'Prof Enrique Garcia-Espana' _publ_contact_author_address ; Inorganic Chemistry University of Valencia C/ Dr. Moliner 50 Burjassot Valencia 46100 SPAIN ; _publ_contact_author_email ENRIQUE.GARCIA-ES@UV.ES _publ_section_title ; Thermodynamic and Kinetic Studies on the Cu2+ Coordination Chemistry of a Novel Binucleating Pyridinophane Ligand. Crystal Structure of [CuL1](ClO4)2. ; data_py3223 _database_code_CSD 194482 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C17 H32 Cl2 Cu N6 O8' _chemical_formula_weight 582.92 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 12.427(5) _cell_length_b 13.143(5) _cell_length_c 16.662(5) _cell_angle_alpha 90.00 _cell_angle_beta 110.000(5) _cell_angle_gamma 90.00 _cell_volume 2557.3(16) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 1 _cell_measurement_theta_max 25 _exptl_crystal_description primatic _exptl_crystal_colour blue _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.125 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas no _exptl_crystal_density_diffrn 1.511 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1208 _exptl_absorpt_coefficient_mu 1.115 _exptl_absorpt_correction_T_min 0.8614 _exptl_absorpt_correction_T_max 0.8618 _exptl_absorpt_correction_t_ave 0.8616 #_exptl_absorpt_coefficient_mu 0.484 _diffrn_ambient_temperature 293(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 'CAD4 Enraf Nonius' _diffrn_measurement_method omega-2theta _diffrn_detector_area_resol_mean ? _diffrn_standards_number 25 _diffrn_standards_interval_count 200 _diffrn_standards_interval_time 3600 _diffrn_standards_decay_% ? _diffrn_reflns_number 4630 _diffrn_reflns_av_R_equivalents 0.1798 _diffrn_reflns_av_sigmaI/netI 0.0527 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max 25.05 _reflns_number_total 4415 _reflns_number_gt 3079 _reflns_threshold_expression >2sigma(I) _computing_structure_solution 'Shelx-86 (Sheldrick, 1985)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ortep-3 _computing_publication_material ? _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^)+(0.2537P)^2^+12.8616P] 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 4415 _refine_ls_number_parameters 347 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1205 _refine_ls_R_factor_gt 0.0883 _refine_ls_wR_factor_ref 0.2715 _refine_ls_wR_factor_gt 0.2259 _refine_ls_goodness_of_fit_ref 0.749 _refine_ls_restrained_S_all 0.749 _refine_ls_shift/su_max 0.080 _refine_ls_shift/su_mean 0.007 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 Cu1 Cu 0.20468(7) 0.23982(6) 0.93791(5) 0.0421(3) Uani 1 1 d . . . Cl1 Cl 0.37792(18) -0.00653(16) 0.22113(12) 0.0620(6) Uani 1 1 d . . . O10 O 0.4140(8) 0.0646(8) 0.1727(5) 0.124(3) Uani 1 1 d . . . O11 O 0.2594(7) -0.0102(7) 0.1904(6) 0.110(3) Uani 1 1 d . . . O12 O 0.4163(8) 0.0231(8) 0.3082(5) 0.122(3) Uani 1 1 d . . . O13 O 0.4139(12) -0.1047(9) 0.2173(8) 0.164(5) Uani 1 1 d . . . Cl2 Cl 0.60649(16) 0.30973(17) 1.10136(12) 0.0608(6) Uani 1 1 d . . . O20 O 0.7039(12) 0.2627(15) 1.1269(11) 0.245(11) Uani 1 1 d . . . O21 O 0.5188(7) 0.2582(7) 1.1181(6) 0.102(3) Uani 1 1 d . . . O22 O 0.5810(7) 0.3446(8) 1.0174(5) 0.126(3) Uani 1 1 d . . . O23 O 0.6376(15) 0.3900(11) 1.1602(7) 0.207(8) Uani 1 1 d . . . N1 N 0.2653(6) 0.2986(5) 1.0828(4) 0.0526(15) Uani 1 1 d . . . H1C H 0.329(7) 0.271(5) 1.116(5) 0.041(19) Uiso 1 1 d . . . N2 N 0.1585(6) 0.3819(5) 0.8842(4) 0.0479(14) Uani 1 1 d . . . H2C H 0.092(5) 0.396(4) 0.870(4) 0.020(15) Uiso 1 1 d . . . N3 N 0.3409(6) 0.2665(6) 0.9005(5) 0.0641(18) Uani 1 1 d . . . N4 N 0.2833(6) 0.0969(5) 0.9759(4) 0.0636(17) Uani 1 1 d . . . H4C H 0.3162 0.1009 1.0338 0.09(3) Uiso 1 1 calc R . . N5 N 0.0590(5) 0.2283(4) 0.9677(4) 0.0432(12) Uani 1 1 d . . . N6 N 0.0543(6) 0.1467(5) 0.8166(4) 0.0569(16) Uani 1 1 d . . . H6C H 0.084(11) 0.144(10) 0.770(8) 0.13(4) Uiso 1 1 d . . . C20 C 0.0655(7) 0.2487(5) 1.0510(5) 0.0509(17) Uani 1 1 d . . . C21 C -0.0321(10) 0.2623(6) 1.0689(7) 0.073(3) Uani 1 1 d . . . H21 H -0.0273 0.2780 1.1244 0.06(2) Uiso 1 1 calc R . . C22 C -0.1354(9) 0.2535(6) 1.0082(7) 0.072(3) Uani 1 1 d . . . H22 H -0.2016 0.2616 1.0217 0.09(3) Uiso 1 1 calc R . . C23 C -0.1426(7) 0.2318(6) 0.9234(6) 0.066(2) Uani 1 1 d . . . H23 H -0.2135 0.2245 0.8805 0.06(2) Uiso 1 1 calc R . . C24 C -0.0442(6) 0.2218(5) 0.9057(5) 0.0466(16) Uani 1 1 d . . . C1 C 0.1841(8) 0.2523(6) 1.1166(5) 0.063(2) Uani 1 1 d . . . H1A H 0.1822 0.2908 1.1658 0.05(2) Uiso 1 1 calc R . . H1B H 0.2089 0.1837 1.1354 0.044(18) Uiso 1 1 calc R . . C2 C 0.2766(8) 0.4101(6) 1.0948(5) 0.064(2) Uani 1 1 d . . . H2A H 0.3518 0.4305 1.0954 0.06(2) Uiso 1 1 calc R . . H2B H 0.2714 0.4270 1.1500 0.07(3) Uiso 1 1 calc R . . C3 C 0.1869(8) 0.4703(6) 1.0265(5) 0.066(2) Uani 1 1 d . . . H3A H 0.1877 0.5397 1.0465 0.15(5) Uiso 1 1 calc R . . H3B H 0.1123 0.4419 1.0196 0.08(3) Uiso 1 1 calc R . . C4 C 0.2017(8) 0.4729(6) 0.9382(5) 0.065(2) Uani 1 1 d . . . H4A H 0.1623 0.5324 0.9075 0.12(4) Uiso 1 1 calc R . . H4B H 0.2824 0.4808 0.9467 0.11(4) Uiso 1 1 calc R . . C5 C 0.1946(7) 0.3824(6) 0.8074(5) 0.062(2) Uani 1 1 d . . . H5A H 0.1876 0.4504 0.7836 0.07(2) Uiso 1 1 calc R . . H5B H 0.1460 0.3371 0.7640 0.11(4) Uiso 1 1 calc R . . C6 C 0.3166(7) 0.3475(7) 0.8341(6) 0.069(2) Uani 1 1 d . . . H6A H 0.3323 0.3216 0.7847 0.14(5) Uiso 1 1 calc R . . H6B H 0.3670 0.4049 0.8564 0.08(3) Uiso 1 1 calc R . . C7 C 0.3698(8) 0.1648(8) 0.8742(6) 0.075(2) Uani 1 1 d . . . H7A H 0.4416 0.1686 0.8632 0.10(3) Uiso 1 1 calc R . . H7B H 0.3104 0.1432 0.8221 0.14(5) Uiso 1 1 calc R . . C8 C 0.3801(8) 0.0901(8) 0.9438(7) 0.080(3) Uani 1 1 d . . . H8A H 0.3832 0.0218 0.9225 0.14(5) Uiso 1 1 calc R . . H8B H 0.4511 0.1023 0.9906 0.11(4) Uiso 1 1 calc R . . C9 C 0.2157(9) 0.0019(6) 0.9599(5) 0.071(2) Uani 1 1 d . . . H9A H 0.1597 0.0062 0.9885 0.05(2) Uiso 1 1 calc R . . H9B H 0.2665 -0.0544 0.9849 0.07(2) Uiso 1 1 calc R . . C10 C 0.1524(9) -0.0210(6) 0.8640(6) 0.074(2) Uani 1 1 d . . . H101 H 0.2019 -0.0031 0.8320 0.10(4) Uiso 1 1 calc R . . H102 H 0.1372 -0.0935 0.8569 0.07(2) Uiso 1 1 calc R . . C11 C 0.0393(8) 0.0370(7) 0.8271(6) 0.072(2) Uani 1 1 d . . . H111 H -0.0043 0.0082 0.7719 0.13(5) Uiso 1 1 calc R . . H112 H -0.0050 0.0277 0.8645 0.08(3) Uiso 1 1 calc R . . C12 C -0.0451(7) 0.2024(7) 0.8156(5) 0.0581(19) Uani 1 1 d . . . H12A H -0.1133 0.1642 0.7840 0.07(2) Uiso 1 1 calc R . . H12B H -0.0476 0.2668 0.7866 0.07(3) 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 Cu1 0.0503(5) 0.0424(5) 0.0377(5) 0.0054(3) 0.0202(4) 0.0060(3) Cl1 0.0683(12) 0.0627(12) 0.0508(10) 0.0107(8) 0.0152(9) -0.0120(9) O10 0.121(6) 0.154(8) 0.086(5) 0.049(5) 0.020(4) -0.052(6) O11 0.076(5) 0.122(7) 0.121(6) 0.005(5) 0.018(4) -0.021(4) O12 0.126(6) 0.167(9) 0.066(4) -0.013(5) 0.026(4) -0.072(6) O13 0.214(12) 0.118(8) 0.185(11) 0.023(8) 0.100(10) 0.055(8) Cl2 0.0541(11) 0.0848(14) 0.0470(10) 0.0055(9) 0.0220(8) -0.0092(9) O20 0.161(11) 0.41(3) 0.220(15) 0.202(16) 0.142(11) 0.158(14) O21 0.083(5) 0.133(7) 0.103(6) -0.001(5) 0.047(4) -0.033(4) O22 0.119(6) 0.185(10) 0.060(4) 0.040(5) 0.012(4) -0.041(6) O23 0.36(2) 0.181(12) 0.118(8) -0.058(8) 0.126(10) -0.161(13) N1 0.059(4) 0.059(4) 0.034(3) -0.008(3) 0.008(3) 0.008(3) N2 0.050(4) 0.052(3) 0.042(3) 0.005(3) 0.017(3) 0.000(3) N3 0.061(4) 0.074(4) 0.064(4) 0.011(3) 0.031(3) 0.008(3) N4 0.086(5) 0.052(4) 0.046(4) -0.002(3) 0.013(3) 0.012(3) N5 0.049(3) 0.045(3) 0.039(3) -0.001(2) 0.019(2) -0.001(2) N6 0.074(4) 0.061(4) 0.037(3) 0.001(3) 0.022(3) -0.005(3) C20 0.074(5) 0.042(4) 0.046(4) 0.000(3) 0.031(4) -0.004(3) C21 0.109(8) 0.055(5) 0.082(7) -0.002(4) 0.067(6) -0.005(5) C22 0.076(6) 0.056(5) 0.105(8) -0.006(5) 0.059(6) -0.009(4) C23 0.054(5) 0.058(5) 0.083(6) -0.008(4) 0.022(4) -0.009(4) C24 0.049(4) 0.038(3) 0.054(4) 0.000(3) 0.020(3) -0.005(3) C1 0.093(6) 0.068(5) 0.032(4) -0.001(3) 0.025(4) 0.010(4) C2 0.076(6) 0.060(5) 0.050(4) -0.015(4) 0.015(4) -0.003(4) C3 0.091(6) 0.051(4) 0.058(5) -0.009(4) 0.029(4) 0.002(4) C4 0.091(6) 0.043(4) 0.064(5) 0.001(4) 0.030(4) -0.009(4) C5 0.087(6) 0.063(5) 0.041(4) 0.018(4) 0.030(4) -0.005(4) C6 0.066(5) 0.081(6) 0.070(5) 0.008(5) 0.035(4) -0.009(4) C7 0.069(5) 0.084(6) 0.081(6) -0.005(5) 0.039(5) 0.014(5) C8 0.064(6) 0.079(6) 0.092(7) -0.014(5) 0.021(5) 0.027(5) C9 0.115(7) 0.046(4) 0.055(5) 0.011(4) 0.031(5) 0.011(4) C10 0.110(7) 0.047(4) 0.072(6) -0.009(4) 0.038(5) 0.002(5) C11 0.087(6) 0.060(5) 0.069(5) -0.015(4) 0.028(5) -0.010(4) C12 0.052(4) 0.067(5) 0.049(4) -0.002(4) 0.009(3) -0.005(4) _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 Cu1 N3 2.025(7) . ? Cu1 N5 2.041(6) . ? Cu1 N2 2.066(6) . ? Cu1 N4 2.112(6) . ? Cu1 N1 2.398(6) . ? Cl1 O13 1.374(11) . ? Cl1 O11 1.385(8) . ? Cl1 O10 1.404(7) . ? Cl1 O12 1.418(8) . ? Cl2 O20 1.295(11) . ? Cl2 O21 1.390(7) . ? Cl2 O23 1.401(11) . ? Cl2 O22 1.401(7) . ? N1 C1 1.447(11) . ? N1 C2 1.478(10) . ? N2 C4 1.482(10) . ? N2 C5 1.494(9) . ? N3 C7 1.489(12) . ? N3 C6 1.489(11) . ? N4 C8 1.477(11) . ? N4 C9 1.478(11) . ? N5 C24 1.346(9) . ? N5 C20 1.388(9) . ? N6 C12 1.430(10) . ? N6 C11 1.472(11) . ? C20 C21 1.357(12) . ? C20 C1 1.505(12) . ? C21 C22 1.340(15) . ? C22 C23 1.413(14) . ? C23 C24 1.361(11) . ? C24 C12 1.519(11) . ? C2 C3 1.515(12) . ? C3 C4 1.544(11) . ? C5 C6 1.499(12) . ? C7 C8 1.492(14) . ? C9 C10 1.550(12) . ? C10 C11 1.532(13) . ? 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 N3 Cu1 N5 173.1(2) . . ? N3 Cu1 N2 81.2(3) . . ? N5 Cu1 N2 92.0(2) . . ? N3 Cu1 N4 84.1(3) . . ? N5 Cu1 N4 102.6(3) . . ? N2 Cu1 N4 164.9(3) . . ? N3 Cu1 N1 104.3(3) . . ? N5 Cu1 N1 77.2(2) . . ? N2 Cu1 N1 95.2(2) . . ? N4 Cu1 N1 91.7(2) . . ? O13 Cl1 O11 105.7(7) . . ? O13 Cl1 O10 115.2(7) . . ? O11 Cl1 O10 108.6(5) . . ? O13 Cl1 O12 107.7(7) . . ? O11 Cl1 O12 109.3(6) . . ? O10 Cl1 O12 110.1(5) . . ? O20 Cl2 O21 114.2(8) . . ? O20 Cl2 O23 97.2(13) . . ? O21 Cl2 O23 105.9(6) . . ? O20 Cl2 O22 110.6(7) . . ? O21 Cl2 O22 115.8(5) . . ? O23 Cl2 O22 111.5(7) . . ? C1 N1 C2 114.2(6) . . ? C1 N1 Cu1 103.6(4) . . ? C2 N1 Cu1 116.0(5) . . ? C4 N2 C5 111.4(6) . . ? C4 N2 Cu1 118.5(5) . . ? C5 N2 Cu1 104.7(5) . . ? C7 N3 C6 115.5(7) . . ? C7 N3 Cu1 104.3(5) . . ? C6 N3 Cu1 112.0(5) . . ? C8 N4 C9 111.4(7) . . ? C8 N4 Cu1 107.2(5) . . ? C9 N4 Cu1 121.4(6) . . ? C24 N5 C20 119.7(6) . . ? C24 N5 Cu1 120.5(5) . . ? C20 N5 Cu1 118.4(5) . . ? C12 N6 C11 111.0(7) . . ? C21 C20 N5 119.6(8) . . ? C21 C20 C1 124.3(8) . . ? N5 C20 C1 116.1(6) . . ? C22 C21 C20 121.4(9) . . ? C21 C22 C23 119.3(8) . . ? C24 C23 C22 118.9(8) . . ? N5 C24 C23 121.1(7) . . ? N5 C24 C12 117.0(6) . . ? C23 C24 C12 121.9(7) . . ? N1 C1 C20 111.8(6) . . ? N1 C2 C3 113.9(7) . . ? C2 C3 C4 115.5(7) . . ? N2 C4 C3 115.1(7) . . ? N2 C5 C6 108.3(6) . . ? N3 C6 C5 111.5(6) . . ? N3 C7 C8 109.1(8) . . ? N4 C8 C7 112.2(7) . . ? N4 C9 C10 114.1(7) . . ? C11 C10 C9 112.9(7) . . ? N6 C11 C10 113.6(7) . . ? N6 C12 C24 111.0(6) . . ? _diffrn_measured_fraction_theta_max 0.973 _diffrn_reflns_theta_full 25.05 _diffrn_measured_fraction_theta_full 0.973 _refine_diff_density_max 2.125 _refine_diff_density_min -1.414 _refine_diff_density_rms 0.150