Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_CCDC175425 _database_code_CSD 175425 _journal_coden_Cambridge 186 _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name 'Bernauer, K.' 'Cabort, Amel' 'Guicher, Nathalie' 'Suss-Fink, G.' _publ_contact_author_name 'Prof K Bernauer' _publ_contact_author_address ; Institut de Chimie Universite de Neuchatel Case postale 2 Neuchatel CH-2007 SWITZERLAND ; _publ_contact_author_email 'KLAUS.BERNAUER@ICH.UNINE.CH' _publ_section_title ; Carbonate binding to copper(II) in solution: Mixed-ligand complex formation and its application to the isolation and seperation of the three isomers of [Cu(bpp)H2)][CIO4]2 (bpp = bis(pyrrolidin-2-yl-pyridine) ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; bis(pyrrolidin-2-yl)-2,6-pyridine ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H25 Cl2 N3 O10' _chemical_formula_weight 454.26 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' 'Cl' 'Cl' 0.1484 0.1585 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'C 2/m' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z' _cell_length_a 14.313(6) _cell_length_b 11.416(4) _cell_length_c 12.481(5) _cell_angle_alpha 90.00 _cell_angle_beta 91.15(3) _cell_angle_gamma 90.00 _cell_volume 2038.9(14) _cell_formula_units_Z 4 _cell_measurement_temperature 233(2) _cell_measurement_reflns_used 12 _cell_measurement_theta_min 10.00 _cell_measurement_theta_max 11.50 _exptl_crystal_description rod _exptl_crystal_colour colourless _exptl_crystal_size_max 0.76 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.480 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 952 _exptl_absorpt_coefficient_mu 0.374 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 233(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 'STOE AED2 4-circle diffractometer' _diffrn_measurement_method 2\q/\w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 2 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 7 _diffrn_reflns_number 4231 _diffrn_reflns_av_R_equivalents 0.0289 _diffrn_reflns_av_sigmaI/netI 0.0305 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.28 _diffrn_reflns_theta_max 25.50 _reflns_number_total 2001 _reflns_number_gt 1577 _reflns_threshold_expression I>2sigma(I) _computing_data_collection 'STADI4 (Stoe & Cie GmbH, Darmstadt, 1997)' _computing_cell_refinement 'STADI4 (Stoe & Cie GmbH, Darmstadt, 1997)' _computing_data_reduction 'X-RED (Stoe & Cie GmbH, Darmstadt, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON/PLUTON (Spek, 1990)' _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. ; _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^)+(0.0767P)^2^+4.7077P] 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 0.0019(8) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2001 _refine_ls_number_parameters 160 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0744 _refine_ls_R_factor_gt 0.0572 _refine_ls_wR_factor_ref 0.1660 _refine_ls_wR_factor_gt 0.1512 _refine_ls_goodness_of_fit_ref 1.069 _refine_ls_restrained_S_all 1.069 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.0164(2) 0.0000 0.2750(3) 0.0350(8) Uani 1 2 d S . . C2 C -0.0190(2) 0.1006(3) 0.3110(2) 0.0376(7) Uani 1 1 d . . . C3 C -0.0891(2) 0.1040(3) 0.3858(3) 0.0482(8) Uani 1 1 d . . . H3 H -0.1127 0.1759 0.4100 0.058 Uiso 1 1 calc R . . C4 C -0.1232(4) 0.0000 0.4237(4) 0.0553(13) Uani 1 2 d S . . H4 H -0.1699 0.0000 0.4757 0.066 Uiso 1 2 calc SR . . C5 C 0.0215(2) 0.2121(3) 0.2692(3) 0.0458(8) Uani 1 1 d . . . H5 H -0.0299 0.2675 0.2520 0.055 Uiso 1 1 calc R . . C6 C 0.0920(4) 0.2717(4) 0.3461(3) 0.0891(17) Uani 1 1 d . . . H6A H 0.0606 0.3270 0.3934 0.107 Uiso 1 1 calc R . . H6B H 0.1257 0.2137 0.3899 0.107 Uiso 1 1 calc R . . C7 C 0.1562(4) 0.3336(5) 0.2735(4) 0.0921(16) Uani 1 1 d . . . H7A H 0.1284 0.4074 0.2484 0.110 Uiso 1 1 calc R . . H7B H 0.2158 0.3507 0.3103 0.110 Uiso 1 1 calc R . . C8 C 0.1699(3) 0.2528(4) 0.1833(4) 0.0668(11) Uani 1 1 d . . . H8A H 0.2200 0.1966 0.1997 0.080 Uiso 1 1 calc R . . H8B H 0.1853 0.2957 0.1180 0.080 Uiso 1 1 calc R . . N9 N 0.0775(2) 0.1920(3) 0.1710(2) 0.0434(7) Uani 1 1 d . . . H9NA H 0.085(2) 0.124(4) 0.163(3) 0.047(11) Uiso 1 1 d . . . H9NB H 0.046(3) 0.223(4) 0.120(4) 0.072(14) Uiso 1 1 d . . . Cl1 Cl 0.33883(11) 0.0000 0.36916(11) 0.0616(4) Uani 1 2 d S . . O11 O 0.4184(5) 0.0000 0.3043(5) 0.134(3) Uani 1 2 d S . . O12 O 0.3361(4) 0.0983(5) 0.4285(5) 0.167(2) Uani 1 1 d . . . O13 O 0.2563(5) 0.0000 0.3026(5) 0.128(2) Uani 1 2 d S . . Cl2 Cl 0.34865(8) 0.5000 0.04931(8) 0.0411(4) Uani 1 2 d S . . O21 O 0.3222(2) 0.5000 -0.0634(3) 0.0539(9) Uani 1 2 d S . . O22 O 0.2659(3) 0.5000 0.1084(4) 0.0786(13) Uani 1 2 d S . . O23 O 0.4002(2) 0.3969(3) 0.0724(2) 0.0868(11) Uani 1 1 d . . . O1W O 0.3815(3) 0.0000 0.0831(4) 0.0585(11) Uani 1 2 d S . . H1WA H 0.388(6) 0.0000 0.152(8) 0.11(3) Uiso 1 2 d S . . H1WB H 0.337(5) 0.0000 0.069(6) 0.09(3) Uiso 1 2 d S . . O2W O 0.0000 0.3317(3) 0.0000 0.0491(9) Uani 1 2 d S . . H2WA H 0.039(3) 0.369(4) -0.021(3) 0.058(13) Uiso 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 N1 0.0361(18) 0.0360(19) 0.0327(18) 0.000 -0.0023(14) 0.000 C2 0.0383(15) 0.0425(18) 0.0319(14) -0.0028(12) -0.0051(12) 0.0022(13) C3 0.0498(18) 0.055(2) 0.0394(17) -0.0073(15) 0.0028(14) 0.0082(16) C4 0.045(3) 0.077(4) 0.044(3) 0.000 0.011(2) 0.000 C5 0.058(2) 0.0380(17) 0.0413(17) -0.0063(14) 0.0004(14) 0.0011(15) C6 0.152(5) 0.068(3) 0.047(2) -0.011(2) -0.008(3) -0.050(3) C7 0.103(4) 0.078(3) 0.094(4) -0.011(3) -0.016(3) -0.039(3) C8 0.055(2) 0.061(2) 0.084(3) 0.005(2) -0.003(2) -0.014(2) N9 0.0529(17) 0.0332(16) 0.0440(16) 0.0028(13) -0.0007(13) -0.0044(13) Cl1 0.0840(10) 0.0524(8) 0.0486(7) 0.000 0.0076(7) 0.000 O11 0.118(5) 0.198(8) 0.087(4) 0.000 0.028(3) 0.000 O12 0.175(5) 0.142(4) 0.186(5) -0.101(4) 0.028(4) -0.033(4) O13 0.130(5) 0.127(5) 0.125(5) 0.000 -0.052(4) 0.000 Cl2 0.0438(6) 0.0443(6) 0.0353(6) 0.000 0.0029(4) 0.000 O21 0.054(2) 0.068(2) 0.0398(18) 0.000 -0.0058(15) 0.000 O22 0.079(3) 0.081(3) 0.077(3) 0.000 0.041(2) 0.000 O23 0.105(2) 0.090(2) 0.0650(18) -0.0116(16) -0.0250(17) 0.055(2) O1W 0.038(2) 0.073(3) 0.066(3) 0.000 0.0044(19) 0.000 O2W 0.060(2) 0.0387(19) 0.048(2) 0.000 0.0045(18) 0.000 _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 N1 C2 1.337(4) 6 ? N1 C2 1.337(4) . ? C2 C3 1.384(4) . ? C2 C5 1.496(5) . ? C3 C4 1.372(4) . ? C3 H3 0.9400 . ? C4 C3 1.372(4) 6 ? C4 H4 0.9400 . ? C5 N9 1.496(4) . ? C5 C6 1.537(5) . ? C5 H5 0.9900 . ? C6 C7 1.482(7) . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C7 C8 1.473(6) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C8 N9 1.499(5) . ? C8 H8A 0.9800 . ? C8 H8B 0.9800 . ? N9 H9NA 0.79(4) . ? N9 H9NB 0.85(5) . ? Cl1 O12 1.346(4) . ? Cl1 O12 1.346(4) 6 ? Cl1 O11 1.410(6) . ? Cl1 O13 1.431(6) . ? Cl2 O22 1.407(4) . ? Cl2 O23 1.416(3) 6_565 ? Cl2 O23 1.416(3) . ? Cl2 O21 1.449(3) . ? O1W H1WA 0.86(9) . ? O1W H1WB 0.66(8) . ? O2W H2WA 0.74(4) . ? 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 C2 N1 C2 118.4(4) 6 . ? N1 C2 C3 122.4(3) . . ? N1 C2 C5 117.5(3) . . ? C3 C2 C5 120.1(3) . . ? C4 C3 C2 118.4(3) . . ? C4 C3 H3 120.8 . . ? C2 C3 H3 120.8 . . ? C3 C4 C3 119.9(4) . 6 ? C3 C4 H4 120.1 . . ? C3 C4 H4 120.1 6 . ? C2 C5 N9 111.9(3) . . ? C2 C5 C6 114.4(3) . . ? N9 C5 C6 102.9(3) . . ? C2 C5 H5 109.1 . . ? N9 C5 H5 109.1 . . ? C6 C5 H5 109.1 . . ? C7 C6 C5 103.8(3) . . ? C7 C6 H6A 111.0 . . ? C5 C6 H6A 111.0 . . ? C7 C6 H6B 111.0 . . ? C5 C6 H6B 111.0 . . ? H6A C6 H6B 109.0 . . ? C8 C7 C6 105.2(4) . . ? C8 C7 H7A 110.7 . . ? C6 C7 H7A 110.7 . . ? C8 C7 H7B 110.7 . . ? C6 C7 H7B 110.7 . . ? H7A C7 H7B 108.8 . . ? C7 C8 N9 103.7(4) . . ? C7 C8 H8A 111.0 . . ? N9 C8 H8A 111.0 . . ? C7 C8 H8B 111.0 . . ? N9 C8 H8B 111.0 . . ? H8A C8 H8B 109.0 . . ? C5 N9 C8 109.4(3) . . ? C5 N9 H9NA 109(3) . . ? C8 N9 H9NA 110(3) . . ? C5 N9 H9NB 106(3) . . ? C8 N9 H9NB 109(3) . . ? H9NA N9 H9NB 113(4) . . ? O12 Cl1 O12 113.1(6) . 6 ? O12 Cl1 O11 110.4(3) . . ? O12 Cl1 O11 110.4(3) 6 . ? O12 Cl1 O13 106.7(3) . . ? O12 Cl1 O13 106.7(3) 6 . ? O11 Cl1 O13 109.5(4) . . ? O22 Cl2 O23 109.49(19) . 6_565 ? O22 Cl2 O23 109.49(19) . . ? O23 Cl2 O23 112.5(3) 6_565 . ? O22 Cl2 O21 107.6(3) . . ? O23 Cl2 O21 108.83(15) 6_565 . ? O23 Cl2 O21 108.83(15) . . ? H1WA O1W H1WB 110(9) . . ? 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 C2 N1 C2 C3 1.6(6) 6 . . . ? C2 N1 C2 C5 -179.8(2) 6 . . . ? N1 C2 C3 C4 -0.1(5) . . . . ? C5 C2 C3 C4 -178.8(4) . . . . ? C2 C3 C4 C3 -1.3(7) . . . 6 ? N1 C2 C5 N9 15.7(4) . . . . ? C3 C2 C5 N9 -165.6(3) . . . . ? N1 C2 C5 C6 -100.8(4) . . . . ? C3 C2 C5 C6 77.9(4) . . . . ? C2 C5 C6 C7 150.4(4) . . . . ? N9 C5 C6 C7 28.8(5) . . . . ? C5 C6 C7 C8 -39.7(5) . . . . ? C6 C7 C8 N9 34.0(5) . . . . ? C2 C5 N9 C8 -131.6(3) . . . . ? C6 C5 N9 C8 -8.3(4) . . . . ? C7 C8 N9 C5 -15.4(4) . . . . ? 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 N9 H9NA N1 0.79(4) 2.23(4) 2.701(4) 119(3) . N9 H9NA O21 0.79(4) 2.32(4) 2.957(4) 139(3) 7 N9 H9NB O2W 0.85(5) 2.04(5) 2.870(4) 164(4) . O1W H1WA O11 0.86(9) 1.94(9) 2.801(8) 173(8) . O1W H1WB O21 0.66(8) 2.28(8) 2.922(6) 167(9) 7 O1W H1WB O22 0.66(8) 2.64(8) 3.157(7) 138(8) 7 O2W H2WA O1W 0.74(4) 2.05(4) 2.777(4) 166(4) 7 _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.50 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.576 _refine_diff_density_min -0.463 _refine_diff_density_rms 0.064