# Electronic Supplementary Material (ESI) for CrystEngComm # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full CrystEngComm _journal_coden_Cambridge 1350 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Daniel J. Price' _publ_contact_author_address ; WestCHEM, School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK. ; _publ_contact_author_email Daniel.Price@glasgow.ac.uk _publ_contact_author_fax 0141-3304888 _publ_contact_author_phone 0141-3308794 _publ_section_title ; Recurrent H-bond graph motifs between metal tris-ethylenediamine cations and uncoordinated oxalate anions: Fitting a three pin plug into a two pin socket ; # Attachment '- en1234_x.cif' #TrackingRef '- en1234_x.cif' #============================================================================== _audit_creation_method 'form.cif (version 2.0)' loop_ _publ_author_name D.Price M.Hursthouse T.Keene #============================================================================== #============================================================================== data_en1_x _database_code_depnum_ccdc_archive 'CCDC 829507' #TrackingRef '- en1234_x.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Trans-diaqua-bis(ethylenediamine-N, N')-copper(II) oxalate ; _chemical_name_common "Trans-diaqua-bis(ethylenediamine-N, N')-copper(ii) oxalate" _chemical_melting_point N/A _chemical_formula_moiety 'C4 H20 Cu N4 O2, C2 O4' _chemical_formula_sum 'C6 H20 Cu N4 O6' _chemical_formula_weight 307.80 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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.4347(6) _cell_length_b 6.9170(7) _cell_length_c 7.7596(6) _cell_angle_alpha 90.268(4) _cell_angle_beta 107.581(4) _cell_angle_gamma 108.201(3) _cell_volume 310.89(5) _cell_formula_units_Z 1 _cell_measurement_temperature 167(2) _cell_measurement_reflns_used 2037 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour purple _exptl_crystal_size_max 0.06 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.644 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 161 _exptl_absorpt_coefficient_mu 1.780 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.49073 _exptl_absorpt_correction_T_max 0.80041 _exptl_absorpt_process_details 'SORTAV (Blessing, 1997)' _exptl_special_details ; PLEASE NOTE cell_measurement_fields are not relavent to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. ; _diffrn_ambient_temperature 167(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Nonius FR591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD Area Detector' _diffrn_measurement_method '\f and \w scans to fill Ewald Sphere' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3144 _diffrn_reflns_av_R_equivalents 0.0811 _diffrn_reflns_av_sigmaI/netI 0.0710 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.12 _diffrn_reflns_theta_max 27.58 _reflns_number_total 1407 _reflns_number_gt 1318 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'DENZO (Otwinowski and Minor, 1997)' _computing_cell_refinement 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_data_reduction 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_structure_solution ;SIR 92 (Altomore, Cascarno, Giacovazzo and Gualardi, 1993) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_structure_refinement ;SHELXS-97 (Sheldrick, 1997a) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_molecular_graphics 'Diamond (Brandenburg, 1999)' _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. All non hydrogen atoms were refined anisotropically. All N-H and C-H hydrogen atoms were fixed in calculated positions and refined in riding mode. Water hydrogen atoms were found and distances and angles were restrained to literature values. All H atoms had their thermal parameters constrained to 1.2 times that of the equivalent isotropic thermal parameter of the parent atom. ; _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^)+(0.0172P)^2^+0.4051P] 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 1407 _refine_ls_number_parameters 85 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0460 _refine_ls_R_factor_gt 0.0414 _refine_ls_wR_factor_ref 0.0982 _refine_ls_wR_factor_gt 0.0951 _refine_ls_goodness_of_fit_ref 1.081 _refine_ls_restrained_S_all 1.080 _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_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu1 Cu 0.5000 0.0000 0.0000 0.01746(16) Uani 1 2 d S . . O1W O 0.7361(4) 0.0164(3) -0.2217(3) 0.0246(5) Uani 1 1 d D . . H1W H 0.683(6) -0.098(3) -0.293(3) 0.030 Uiso 1 1 d D . . H2W H 0.690(6) 0.106(3) -0.290(3) 0.030 Uiso 1 1 d D . . N1 N 0.7697(4) -0.0101(4) 0.2150(3) 0.0198(5) Uani 1 1 d . . . H1A H 0.7194 -0.1020 0.2875 0.024 Uiso 1 1 calc R . . H1B H 0.8714 -0.0471 0.1759 0.024 Uiso 1 1 calc R . . N2 N 0.6420(4) 0.3037(3) 0.0558(3) 0.0188(5) Uani 1 1 d . . . H2A H 0.6414 0.3623 -0.0476 0.023 Uiso 1 1 calc R . . H2B H 0.5606 0.3531 0.1098 0.023 Uiso 1 1 calc R . . C1 C 0.8806(5) 0.1973(5) 0.3160(4) 0.0231(6) Uani 1 1 d . . . H1C H 1.0373 0.2138 0.3910 0.028 Uiso 1 1 calc R . . H1D H 0.7952 0.2175 0.3943 0.028 Uiso 1 1 calc R . . C2 C 0.8823(5) 0.3515(5) 0.1786(4) 0.0247(6) Uani 1 1 d . . . H2C H 0.9383 0.4892 0.2398 0.030 Uiso 1 1 calc R . . H2D H 0.9826 0.3423 0.1096 0.030 Uiso 1 1 calc R . . O1 O 0.4177(4) 0.4652(3) 0.2629(3) 0.0248(5) Uani 1 1 d . . . O2 O 0.5011(4) 0.7459(3) 0.4465(3) 0.0273(5) Uani 1 1 d . . . C3 C 0.4764(5) 0.5602(4) 0.4157(4) 0.0169(6) 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 Cu1 0.0172(3) 0.0166(3) 0.0174(3) 0.00219(18) 0.00352(19) 0.00587(19) O1W 0.0278(12) 0.0221(10) 0.0238(11) -0.0024(8) 0.0071(9) 0.0092(9) N1 0.0174(12) 0.0232(12) 0.0205(12) 0.0064(9) 0.0063(10) 0.0088(10) N2 0.0195(13) 0.0182(11) 0.0188(12) 0.0007(9) 0.0062(10) 0.0062(10) C1 0.0165(14) 0.0289(15) 0.0193(14) -0.0015(12) 0.0015(11) 0.0051(12) C2 0.0191(15) 0.0239(15) 0.0263(16) 0.0007(12) 0.0039(12) 0.0038(12) O1 0.0305(12) 0.0294(11) 0.0164(10) -0.0006(8) 0.0067(9) 0.0133(10) O2 0.0382(14) 0.0171(10) 0.0250(11) 0.0035(8) 0.0084(10) 0.0087(10) C3 0.0146(13) 0.0184(13) 0.0185(14) 0.0022(11) 0.0072(11) 0.0048(11) _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 N2 1.997(2) 2_655 ? Cu1 N2 1.997(2) . ? Cu1 N1 2.031(2) 2_655 ? Cu1 N1 2.031(2) . ? O1W H1W 0.875(10) . ? O1W H2W 0.878(10) . ? N1 C1 1.481(4) . ? N1 H1A 0.9000 . ? N1 H1B 0.9000 . ? N2 C2 1.482(4) . ? N2 H2A 0.9000 . ? N2 H2B 0.9000 . ? C1 C2 1.511(4) . ? C1 H1C 0.9700 . ? C1 H1D 0.9700 . ? C2 H2C 0.9700 . ? C2 H2D 0.9700 . ? O1 C3 1.244(3) . ? O2 C3 1.256(3) . ? C3 C3 1.557(5) 2_666 ? 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 N2 Cu1 N2 180.0 2_655 . ? N2 Cu1 N1 85.21(10) 2_655 2_655 ? N2 Cu1 N1 94.79(10) . 2_655 ? N2 Cu1 N1 94.79(10) 2_655 . ? N2 Cu1 N1 85.21(10) . . ? N1 Cu1 N1 180.0 2_655 . ? H1W O1W H2W 105.7(15) . . ? C1 N1 Cu1 107.45(17) . . ? C1 N1 H1A 110.2 . . ? Cu1 N1 H1A 110.2 . . ? C1 N1 H1B 110.2 . . ? Cu1 N1 H1B 110.2 . . ? H1A N1 H1B 108.5 . . ? C2 N2 Cu1 108.42(17) . . ? C2 N2 H2A 110.0 . . ? Cu1 N2 H2A 110.0 . . ? C2 N2 H2B 110.0 . . ? Cu1 N2 H2B 110.0 . . ? H2A N2 H2B 108.4 . . ? N1 C1 C2 108.0(2) . . ? N1 C1 H1C 110.1 . . ? C2 C1 H1C 110.1 . . ? N1 C1 H1D 110.1 . . ? C2 C1 H1D 110.1 . . ? H1C C1 H1D 108.4 . . ? N2 C2 C1 107.4(2) . . ? N2 C2 H2C 110.2 . . ? C1 C2 H2C 110.2 . . ? N2 C2 H2D 110.2 . . ? C1 C2 H2D 110.2 . . ? H2C C2 H2D 108.5 . . ? O1 C3 O2 125.7(3) . . ? O1 C3 C3 117.6(3) . 2_666 ? O2 C3 C3 116.8(3) . 2_666 ? 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 O1W H1W O1 0.875(10) 2.45(2) 3.149(3) 138(3) 2_655 O1W H1W O2 0.875(10) 2.092(19) 2.872(3) 148(2) 1_544 O1W H2W O2 0.878(10) 1.986(15) 2.839(3) 164(3) 2_665 N1 H1A O2 0.90 2.18 3.024(3) 156.6 1_545 N1 H1B O1W 0.90 2.38 3.179(3) 147.7 2_755 N2 H2A O1 0.90 2.07 2.944(3) 163.9 2_665 N2 H2B O1 0.90 1.99 2.881(3) 171.6 . _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 27.58 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 0.531 _refine_diff_density_min -0.562 _refine_diff_density_rms 0.098 ############################################################## data_en2_x _database_code_depnum_ccdc_archive 'CCDC 829508' #TrackingRef '- en1234_x.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; tris(ethylenediamine-N,N')-copper(II) oxalate ; _chemical_name_common "tris(ethylenediamine-N,N')-copper(ii) oxalate" _chemical_melting_point N/A _chemical_formula_moiety 'C6 H24 Cu N6, C2 O4' _chemical_formula_sum 'C8 H24 Cu N6 O4' _chemical_formula_weight 331.87 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' 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 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 9.8795(9) _cell_length_b 9.6336(9) _cell_length_c 14.4612(15) _cell_angle_alpha 90.00 _cell_angle_beta 91.718(5) _cell_angle_gamma 90.00 _cell_volume 1375.7(2) _cell_formula_units_Z 4 _cell_measurement_temperature 167(2) _cell_measurement_reflns_used 18008 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour blue _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.602 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 700 _exptl_absorpt_coefficient_mu 1.609 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.84768 _exptl_absorpt_correction_T_max 0.93216 _exptl_absorpt_process_details 'SORTAV (Blessing, 1997)' _exptl_special_details ; PLEASE NOTE cell_measurement_fields are not relavent to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. ; _diffrn_ambient_temperature 167(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Nonius FR591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD Area Detector' _diffrn_measurement_method '\f and \w scans to fill Ewald Sphere' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12548 _diffrn_reflns_av_R_equivalents 0.1087 _diffrn_reflns_av_sigmaI/netI 0.1053 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.95 _diffrn_reflns_theta_max 27.51 _reflns_number_total 3153 _reflns_number_gt 2020 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'DENZO (Otwinowski and Minor, 1997)' _computing_cell_refinement 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_data_reduction 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_structure_solution ;SIR 92 (Altomore, Cascarno, Giacovazzo and Gualardi, 1993) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_structure_refinement ;SHELXS-97 (Sheldrick, 1997a) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_molecular_graphics 'Diamond (Brandenburg, 1999)' _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. All atoms except hydrogen atoms were refined anisotropically. All hydrogen atoms were fixed in calculated positions and refined in riding mode, with their thermal parameters fixed at 1.2 timed the equivalent isotropic thermal parameter of the parent atom. ; _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^)+(0.0555P)^2^+1.1952P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3153 _refine_ls_number_parameters 172 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1153 _refine_ls_R_factor_gt 0.0628 _refine_ls_wR_factor_ref 0.1430 _refine_ls_wR_factor_gt 0.1265 _refine_ls_goodness_of_fit_ref 1.038 _refine_ls_restrained_S_all 1.038 _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_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu1 Cu 0.75015(5) 0.02922(6) 0.33073(4) 0.0235(2) Uani 1 1 d . . . O4 O 0.6380(3) -0.1271(4) 0.7124(3) 0.0409(10) Uani 1 1 d . . . O2 O 0.6398(3) 0.1080(3) 0.6046(2) 0.0333(8) Uani 1 1 d . . . O1 O 0.8531(3) 0.1377(3) 0.6544(3) 0.0334(8) Uani 1 1 d . . . O3 O 0.8580(3) -0.1434(4) 0.6876(3) 0.0462(11) Uani 1 1 d . . . N5 N 0.6380(4) 0.0833(4) 0.1823(3) 0.0297(10) Uani 1 1 d . . . H5A H 0.5494 0.0617 0.1821 0.036 Uiso 1 1 calc R . . H5B H 0.6478 0.1733 0.1672 0.036 Uiso 1 1 calc R . . N4 N 0.8895(4) -0.1048(4) 0.4515(3) 0.0338(10) Uani 1 1 d . . . H4A H 0.9782 -0.1058 0.4389 0.041 Uiso 1 1 calc R . . H4B H 0.8784 -0.0718 0.5090 0.041 Uiso 1 1 calc R . . N6 N 0.8849(4) -0.0545(4) 0.2413(3) 0.0245(9) Uani 1 1 d . . . H6A H 0.9698 -0.0346 0.2612 0.029 Uiso 1 1 calc R . . H6B H 0.8756 -0.1474 0.2405 0.029 Uiso 1 1 calc R . . N2 N 0.6121(4) 0.1380(4) 0.4027(3) 0.0266(9) Uani 1 1 d . . . H2A H 0.5279 0.1199 0.3805 0.032 Uiso 1 1 calc R . . H2B H 0.6169 0.1138 0.4629 0.032 Uiso 1 1 calc R . . N1 N 0.8581(4) 0.2094(4) 0.3369(3) 0.0262(9) Uani 1 1 d . . . H1A H 0.9442 0.1917 0.3553 0.031 Uiso 1 1 calc R . . H1B H 0.8589 0.2491 0.2806 0.031 Uiso 1 1 calc R . . N3 N 0.6384(4) -0.1466(4) 0.3441(3) 0.0269(9) Uani 1 1 d . . . H3A H 0.5502 -0.1236 0.3452 0.032 Uiso 1 1 calc R . . H3B H 0.6502 -0.2010 0.2944 0.032 Uiso 1 1 calc R . . C2 C 0.6430(5) 0.2867(5) 0.3924(4) 0.0329(12) Uani 1 1 d . . . H2C H 0.5982 0.3401 0.4394 0.039 Uiso 1 1 calc R . . H2D H 0.6115 0.3194 0.3321 0.039 Uiso 1 1 calc R . . C6 C 0.8626(5) 0.0003(5) 0.1470(3) 0.0279(11) Uani 1 1 d . . . H6C H 0.9140 -0.0537 0.1036 0.033 Uiso 1 1 calc R . . H6D H 0.8931 0.0959 0.1442 0.033 Uiso 1 1 calc R . . C4 C 0.8266(5) -0.2410(5) 0.4381(4) 0.0352(13) Uani 1 1 d . . . H4C H 0.8490 -0.3001 0.4907 0.042 Uiso 1 1 calc R . . H4D H 0.8612 -0.2844 0.3831 0.042 Uiso 1 1 calc R . . C1 C 0.7951(5) 0.3037(5) 0.4029(4) 0.0336(12) Uani 1 1 d . . . H1C H 0.8205 0.3989 0.3901 0.040 Uiso 1 1 calc R . . H1D H 0.8252 0.2811 0.4656 0.040 Uiso 1 1 calc R . . C5 C 0.7131(5) -0.0077(5) 0.1213(3) 0.0285(11) Uani 1 1 d . . . H5C H 0.6981 0.0208 0.0575 0.034 Uiso 1 1 calc R . . H5D H 0.6816 -0.1025 0.1274 0.034 Uiso 1 1 calc R . . C3 C 0.6745(5) -0.2254(5) 0.4279(4) 0.0367(13) Uani 1 1 d . . . H3D H 0.6326 -0.3164 0.4247 0.044 Uiso 1 1 calc R . . H3C H 0.6406 -0.1777 0.4816 0.044 Uiso 1 1 calc R . . C7 C 0.7470(5) 0.0676(5) 0.6442(3) 0.0240(11) Uani 1 1 d . . . C8 C 0.7486(5) -0.0820(5) 0.6851(3) 0.0274(11) 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 Cu1 0.0208(3) 0.0207(3) 0.0294(3) -0.0022(3) 0.0036(2) -0.0005(3) O4 0.0214(18) 0.039(2) 0.062(3) 0.0198(19) 0.0038(18) -0.0017(16) O2 0.0291(19) 0.033(2) 0.038(2) 0.0045(16) 0.0001(16) 0.0037(16) O1 0.0279(19) 0.0224(17) 0.050(2) -0.0022(16) 0.0028(17) -0.0042(15) O3 0.025(2) 0.032(2) 0.082(3) 0.018(2) 0.015(2) 0.0086(16) N5 0.022(2) 0.026(2) 0.041(3) -0.0001(19) 0.0003(19) -0.0004(17) N4 0.026(2) 0.046(3) 0.029(2) -0.004(2) 0.0004(19) 0.000(2) N6 0.023(2) 0.020(2) 0.031(2) -0.0006(17) 0.0051(17) -0.0012(16) N2 0.022(2) 0.026(2) 0.033(2) -0.0054(18) 0.0000(18) -0.0009(17) N1 0.025(2) 0.023(2) 0.030(2) -0.0023(18) 0.0011(18) -0.0005(17) N3 0.022(2) 0.023(2) 0.036(2) -0.0030(18) 0.0024(18) -0.0019(17) C2 0.032(3) 0.029(3) 0.037(3) -0.006(2) 0.005(2) 0.001(2) C6 0.032(3) 0.028(3) 0.025(3) -0.005(2) 0.005(2) 0.002(2) C4 0.036(3) 0.031(3) 0.039(3) 0.013(2) -0.007(2) -0.001(2) C1 0.032(3) 0.023(3) 0.045(3) -0.011(2) 0.001(2) -0.004(2) C5 0.033(3) 0.025(3) 0.027(3) -0.002(2) -0.003(2) 0.002(2) C3 0.033(3) 0.038(3) 0.038(3) 0.005(3) 0.001(2) -0.010(2) C7 0.026(3) 0.022(2) 0.024(3) -0.0036(19) 0.007(2) 0.002(2) C8 0.022(2) 0.029(2) 0.031(3) 0.001(2) -0.004(2) 0.001(2) _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 N2 2.032(4) . ? Cu1 N3 2.034(3) . ? Cu1 N1 2.038(4) . ? Cu1 N6 2.048(3) . ? Cu1 N5 2.442(4) . ? Cu1 N4 2.544(4) . ? O4 C8 1.250(5) . ? O2 C7 1.251(6) . ? O1 C7 1.251(5) . ? O3 C8 1.232(5) . ? N5 C5 1.462(6) . ? N5 H5A 0.9000 . ? N5 H5B 0.9000 . ? N4 C4 1.462(6) . ? N4 H4A 0.9000 . ? N4 H4B 0.9000 . ? N6 C6 1.473(6) . ? N6 H6A 0.9000 . ? N6 H6B 0.9000 . ? N2 C2 1.473(6) . ? N2 H2A 0.9000 . ? N2 H2B 0.9000 . ? N1 C1 1.469(6) . ? N1 H1A 0.9000 . ? N1 H1B 0.9000 . ? N3 C3 1.465(6) . ? N3 H3A 0.9000 . ? N3 H3B 0.9000 . ? C2 C1 1.515(7) . ? C2 H2C 0.9700 . ? C2 H2D 0.9700 . ? C6 C5 1.514(7) . ? C6 H6C 0.9700 . ? C6 H6D 0.9700 . ? C4 C3 1.514(7) . ? C4 H4C 0.9700 . ? C4 H4D 0.9700 . ? C1 H1C 0.9700 . ? C1 H1D 0.9700 . ? C5 H5C 0.9700 . ? C5 H5D 0.9700 . ? C3 H3D 0.9700 . ? C3 H3C 0.9700 . ? C7 C8 1.558(7) . ? 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 N2 Cu1 N3 90.35(15) . . ? N2 Cu1 N1 84.07(14) . . ? N3 Cu1 N1 171.83(16) . . ? N2 Cu1 N6 170.17(15) . . ? N3 Cu1 N6 95.58(15) . . ? N1 Cu1 N6 90.79(14) . . ? N2 Cu1 N5 92.66(15) . . ? N3 Cu1 N5 91.62(15) . . ? N1 Cu1 N5 94.59(15) . . ? N6 Cu1 N5 79.38(14) . . ? N2 Cu1 N4 105.54(15) . . ? N3 Cu1 N4 78.24(14) . . ? N1 Cu1 N4 97.48(15) . . ? N6 Cu1 N4 83.40(14) . . ? N5 Cu1 N4 159.06(13) . . ? C5 N5 Cu1 100.2(3) . . ? C5 N5 H5A 111.7 . . ? Cu1 N5 H5A 111.7 . . ? C5 N5 H5B 111.7 . . ? Cu1 N5 H5B 111.7 . . ? H5A N5 H5B 109.5 . . ? C4 N4 Cu1 98.3(3) . . ? C4 N4 H4A 112.1 . . ? Cu1 N4 H4A 112.1 . . ? C4 N4 H4B 112.1 . . ? Cu1 N4 H4B 112.1 . . ? H4A N4 H4B 109.7 . . ? C6 N6 Cu1 111.2(3) . . ? C6 N6 H6A 109.4 . . ? Cu1 N6 H6A 109.4 . . ? C6 N6 H6B 109.4 . . ? Cu1 N6 H6B 109.4 . . ? H6A N6 H6B 108.0 . . ? C2 N2 Cu1 107.8(3) . . ? C2 N2 H2A 110.2 . . ? Cu1 N2 H2A 110.2 . . ? C2 N2 H2B 110.2 . . ? Cu1 N2 H2B 110.2 . . ? H2A N2 H2B 108.5 . . ? C1 N1 Cu1 108.9(3) . . ? C1 N1 H1A 109.9 . . ? Cu1 N1 H1A 109.9 . . ? C1 N1 H1B 109.9 . . ? Cu1 N1 H1B 109.9 . . ? H1A N1 H1B 108.3 . . ? C3 N3 Cu1 113.0(3) . . ? C3 N3 H3A 109.0 . . ? Cu1 N3 H3A 109.0 . . ? C3 N3 H3B 109.0 . . ? Cu1 N3 H3B 109.0 . . ? H3A N3 H3B 107.8 . . ? N2 C2 C1 107.7(4) . . ? N2 C2 H2C 110.2 . . ? C1 C2 H2C 110.2 . . ? N2 C2 H2D 110.2 . . ? C1 C2 H2D 110.2 . . ? H2C C2 H2D 108.5 . . ? N6 C6 C5 109.1(4) . . ? N6 C6 H6C 109.9 . . ? C5 C6 H6C 109.9 . . ? N6 C6 H6D 109.9 . . ? C5 C6 H6D 109.9 . . ? H6C C6 H6D 108.3 . . ? N4 C4 C3 109.9(4) . . ? N4 C4 H4C 109.7 . . ? C3 C4 H4C 109.7 . . ? N4 C4 H4D 109.7 . . ? C3 C4 H4D 109.7 . . ? H4C C4 H4D 108.2 . . ? N1 C1 C2 107.9(4) . . ? N1 C1 H1C 110.1 . . ? C2 C1 H1C 110.1 . . ? N1 C1 H1D 110.1 . . ? C2 C1 H1D 110.1 . . ? H1C C1 H1D 108.4 . . ? N5 C5 C6 109.3(4) . . ? N5 C5 H5C 109.8 . . ? C6 C5 H5C 109.8 . . ? N5 C5 H5D 109.8 . . ? C6 C5 H5D 109.8 . . ? H5C C5 H5D 108.3 . . ? N3 C3 C4 110.4(4) . . ? N3 C3 H3D 109.6 . . ? C4 C3 H3D 109.6 . . ? N3 C3 H3C 109.6 . . ? C4 C3 H3C 109.6 . . ? H3D C3 H3C 108.1 . . ? O1 C7 O2 125.5(4) . . ? O1 C7 C8 117.1(4) . . ? O2 C7 C8 117.4(4) . . ? O3 C8 O4 126.7(5) . . ? O3 C8 C7 117.0(4) . . ? O4 C8 C7 116.3(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 N1 H1A O3 0.90 2.12 2.907(5) 145.7 3_756 N1 H1B O1 0.90 2.13 3.022(5) 173.9 4_565 N2 H2A O4 0.90 2.09 2.939(5) 157.3 3_656 N2 H2B O2 0.90 2.06 2.938(5) 166.2 . N3 H3A O2 0.90 2.04 2.892(5) 157.9 3_656 N3 H3B O4 0.90 2.04 2.895(5) 158.6 4 N4 H4A O1 0.90 2.20 3.024(5) 152.4 3_756 N5 H5A O4 0.90 2.51 3.191(5) 132.3 3_656 N5 H5B O2 0.90 2.29 3.179(5) 168.0 4_565 N6 H6A O1 0.90 2.33 3.063(5) 139.2 3_756 N6 H6A O3 0.90 2.51 3.314(5) 148.9 3_756 N6 H6B O3 0.90 2.16 3.022(5) 159.9 4 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.621 _refine_diff_density_min -0.431 _refine_diff_density_rms 0.112 #################################################################### data_en3 _database_code_depnum_ccdc_archive 'CCDC 829509' #TrackingRef '- en1234_x.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; di-[tris-(ethylenediamine-N,N')-cobalt(III)] tris- oxalate. 3.61 H2O ; _chemical_name_common ;di-(tris-(ethylenediamine-N,N')-cobalt(iii)) tris-oxalate. 3.61 H2O ; _chemical_melting_point N/A _chemical_formula_moiety ; C6 H24 Co N6, 1.5(C2 O4), 1.805(H2 O) ; _chemical_formula_sum 'C9 H27.61 Co N6 O7.805' _chemical_formula_weight 403.78 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.4525(19) _cell_length_b 8.971(2) _cell_length_c 13.349(4) _cell_angle_alpha 71.49(2) _cell_angle_beta 89.61(2) _cell_angle_gamma 82.827(18) _cell_volume 839.2(4) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 9989 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.598 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 426 _exptl_absorpt_coefficient_mu 1.073 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.72843 _exptl_absorpt_correction_T_max 1.24686 _exptl_absorpt_process_details 'SORTAV (Blessing, 1997)' _exptl_special_details ; PLEASE NOTE cell_measurement_fields are not relavent to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Nonius FR591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD Area Detector' _diffrn_measurement_method '\f and \w scans to fill Ewald Sphere' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10682 _diffrn_reflns_av_R_equivalents 0.1896 _diffrn_reflns_av_sigmaI/netI 0.1302 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.14 _diffrn_reflns_theta_max 27.56 _reflns_number_total 3799 _reflns_number_gt 3207 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'DENZO (Otwinowski and Minor, 1997)' _computing_cell_refinement 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_data_reduction 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_structure_solution ;SIR 92 (Altomore, Cascarno, Giacovazzo and Gualardi, 1993) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_structure_refinement ;SHELXS-97 (Sheldrick, 1997a) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_molecular_graphics 'Diamond (Brandenburg, 1999)' _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. All non-hydrogen atoms, with the exception of the water of crystallisation, were refined with anisotropic displacement parameters. All hydrogen atoms were fixed in calculated positions and refined in riding mode, with isotropic thermal paremters fixed at 1.2 times that of the parent atom. Aqua hydrogens could not be found from difference maps and were not included in the model. The water of crystallisation is greatly disordered. There are two pairs of sites which are so close to each other, that their occupancies must be mutually exclusive. We could have O1W not O3W (and viceaversa), and O2W not O4W (and viceaversa). After much consideration of the structural possibilities that this presents, we decided that the best model was to refine the occupancy of each of these sites freely, but to apply a single isotropic thermal parameter for all water molecules. This give a non-stiochoimetric hydrate. ; _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^)+(0.0819P)^2^+2.4783P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3799 _refine_ls_number_parameters 216 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0896 _refine_ls_R_factor_gt 0.0789 _refine_ls_wR_factor_ref 0.2147 _refine_ls_wR_factor_gt 0.2028 _refine_ls_goodness_of_fit_ref 1.071 _refine_ls_restrained_S_all 1.071 _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_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Co1 Co 0.92194(7) 0.12810(7) 0.22435(4) 0.0172(2) Uani 1 1 d . . . O1 O 0.5910(5) 0.5234(5) 0.1750(3) 0.0341(8) Uani 1 1 d . . . O3 O 0.8060(5) 0.6416(4) 0.0106(2) 0.0274(7) Uani 1 1 d . . . O2 O 0.6473(6) 0.7148(5) 0.2390(3) 0.0434(10) Uani 1 1 d . . . O4 O 0.7881(6) 0.8675(4) 0.0499(3) 0.0331(8) Uani 1 1 d . . . O5 O 0.2716(5) -0.0275(6) 0.4946(3) 0.0450(12) Uani 1 1 d . . . C7 C 0.6548(7) 0.6489(6) 0.1697(3) 0.0265(10) Uani 1 1 d . . . C8 C 0.7588(6) 0.7258(6) 0.0676(3) 0.0221(9) Uani 1 1 d . . . C9 C 0.4154(7) 0.0206(10) 0.4601(4) 0.0482(18) Uani 1 1 d . . . N3 N 1.1360(5) 0.2353(5) 0.2260(3) 0.0256(9) Uani 1 1 d . . . H3A H 1.2237 0.1674 0.2722 0.031 Uiso 1 1 calc R . . H3B H 1.1828 0.2657 0.1596 0.031 Uiso 1 1 calc R . . N6 N 0.6936(5) 0.0444(5) 0.2152(3) 0.0249(8) Uani 1 1 d . . . H6A H 0.7168 -0.0516 0.2034 0.030 Uiso 1 1 calc R . . H6B H 0.6350 0.0290 0.2779 0.030 Uiso 1 1 calc R . . N5 N 0.8403(5) 0.2925(5) 0.0907(3) 0.0223(8) Uani 1 1 d . . . H5A H 0.7957 0.3848 0.1034 0.027 Uiso 1 1 calc R . . H5B H 0.9364 0.3124 0.0468 0.027 Uiso 1 1 calc R . . N2 N 0.9979(6) -0.0514(5) 0.3540(3) 0.0240(8) Uani 1 1 d . . . H2A H 1.0828 -0.0234 0.3921 0.029 Uiso 1 1 calc R . . H2B H 0.8997 -0.0750 0.3955 0.029 Uiso 1 1 calc R . . N1 N 1.0511(6) -0.0075(5) 0.1492(3) 0.0253(8) Uani 1 1 d . . . H1A H 0.9695 -0.0531 0.1206 0.030 Uiso 1 1 calc R . . H1B H 1.1145 0.0524 0.0951 0.030 Uiso 1 1 calc R . . N4 N 0.8109(6) 0.2528(5) 0.3106(3) 0.0265(9) Uani 1 1 d . . . H4A H 0.7232 0.3301 0.2710 0.032 Uiso 1 1 calc R . . H4B H 0.7569 0.1882 0.3673 0.032 Uiso 1 1 calc R . . C5 C 0.6972(6) 0.2386(6) 0.0388(3) 0.0242(9) Uani 1 1 d . . . H5C H 0.7510 0.1625 0.0036 0.029 Uiso 1 1 calc R . . H5D H 0.6270 0.3298 -0.0147 0.029 Uiso 1 1 calc R . . C4 C 0.9510(8) 0.3272(7) 0.3489(4) 0.0344(12) Uani 1 1 d . . . H4C H 1.0166 0.2505 0.4122 0.041 Uiso 1 1 calc R . . H4D H 0.8946 0.4201 0.3677 0.041 Uiso 1 1 calc R . . C6 C 0.5764(6) 0.1594(7) 0.1268(3) 0.0282(10) Uani 1 1 d . . . H6C H 0.5050 0.2402 0.1521 0.034 Uiso 1 1 calc R . . H6D H 0.4913 0.1031 0.1001 0.034 Uiso 1 1 calc R . . O6 O 0.4433(5) 0.1028(8) 0.3657(3) 0.0657(18) Uani 1 1 d . . . C1 C 1.1777(8) -0.1331(7) 0.2254(4) 0.0346(12) Uani 1 1 d . . . H1C H 1.2865 -0.0890 0.2397 0.041 Uiso 1 1 calc R . . H1D H 1.2164 -0.2204 0.1965 0.041 Uiso 1 1 calc R . . C2 C 1.0759(9) -0.1929(6) 0.3256(4) 0.0367(13) Uani 1 1 d . . . H2C H 0.9785 -0.2518 0.3139 0.044 Uiso 1 1 calc R . . H2D H 1.1589 -0.2647 0.3831 0.044 Uiso 1 1 calc R . . C3 C 1.0801(8) 0.3780(6) 0.2599(4) 0.0340(12) Uani 1 1 d . . . H3C H 1.0194 0.4663 0.2003 0.041 Uiso 1 1 calc R . . H3D H 1.1869 0.4136 0.2848 0.041 Uiso 1 1 calc R . . O1W O 0.3272(14) 0.2423(12) 0.5623(7) 0.0525(19) Uiso 0.526(14) 1 d P . . O2W O 0.4511(12) 0.4478(13) 0.3962(7) 0.0525(19) Uiso 0.596(18) 1 d P . . O3W O 0.227(3) 0.313(2) 0.5566(14) 0.0525(19) Uiso 0.266(12) 1 d P . . O4W O 0.4374(18) 0.5181(19) 0.4064(9) 0.0525(19) Uiso 0.416(16) 1 d P . . 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 Co1 0.0123(3) 0.0279(4) 0.0100(3) -0.0047(2) 0.0024(2) -0.0009(2) O1 0.0213(18) 0.038(2) 0.0316(17) 0.0040(15) 0.0033(14) -0.0038(16) O3 0.0295(19) 0.0314(18) 0.0217(14) -0.0101(13) 0.0068(13) -0.0017(15) O2 0.060(3) 0.052(2) 0.0212(16) -0.0158(16) 0.0147(17) -0.005(2) O4 0.044(2) 0.0341(19) 0.0251(16) -0.0107(14) 0.0087(15) -0.0163(17) O5 0.0160(17) 0.091(3) 0.0155(15) -0.0012(17) 0.0009(13) -0.0019(19) C7 0.020(2) 0.036(3) 0.0170(19) -0.0001(18) 0.0018(17) 0.000(2) C8 0.015(2) 0.035(2) 0.0150(17) -0.0054(17) 0.0020(15) -0.0028(18) C9 0.016(2) 0.106(5) 0.0101(19) -0.004(2) 0.0038(18) -0.003(3) N3 0.0175(19) 0.041(2) 0.0155(15) -0.0035(15) 0.0004(14) -0.0067(17) N6 0.0171(19) 0.043(2) 0.0138(15) -0.0066(15) 0.0035(14) -0.0063(17) N5 0.0187(19) 0.030(2) 0.0165(15) -0.0055(14) 0.0050(14) -0.0027(16) N2 0.023(2) 0.031(2) 0.0141(15) -0.0038(14) 0.0024(14) 0.0009(16) N1 0.027(2) 0.030(2) 0.0167(16) -0.0065(15) 0.0010(15) -0.0002(17) N4 0.028(2) 0.032(2) 0.0154(16) -0.0072(15) 0.0033(15) 0.0080(17) C5 0.020(2) 0.036(3) 0.0146(17) -0.0073(17) -0.0006(16) -0.0019(19) C4 0.047(3) 0.037(3) 0.021(2) -0.015(2) -0.002(2) 0.000(2) C6 0.013(2) 0.047(3) 0.023(2) -0.009(2) -0.0022(17) -0.005(2) O6 0.0133(18) 0.148(5) 0.0108(15) 0.008(2) 0.0024(13) -0.003(2) C1 0.035(3) 0.041(3) 0.020(2) -0.006(2) 0.000(2) 0.013(2) C2 0.051(4) 0.032(3) 0.019(2) -0.0015(19) 0.005(2) 0.009(2) C3 0.046(3) 0.033(3) 0.024(2) -0.0083(19) -0.005(2) -0.010(2) _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 Co1 N4 1.959(4) . ? Co1 N5 1.962(4) . ? Co1 N6 1.963(4) . ? Co1 N3 1.966(4) . ? Co1 N1 1.970(4) . ? Co1 N2 1.981(4) . ? O1 C7 1.257(7) . ? O3 C8 1.253(6) . ? O2 C7 1.244(6) . ? O4 C8 1.264(6) . ? O5 C9 1.236(7) . ? C7 C8 1.567(6) . ? C9 O6 1.273(6) . ? C9 C9 1.585(10) 2_656 ? N3 C3 1.501(7) . ? N3 H3A 0.9200 . ? N3 H3B 0.9200 . ? N6 C6 1.496(6) . ? N6 H6A 0.9200 . ? N6 H6B 0.9200 . ? N5 C5 1.484(6) . ? N5 H5A 0.9200 . ? N5 H5B 0.9200 . ? N2 C2 1.487(6) . ? N2 H2A 0.9200 . ? N2 H2B 0.9200 . ? N1 C1 1.488(6) . ? N1 H1A 0.9200 . ? N1 H1B 0.9200 . ? N4 C4 1.481(7) . ? N4 H4A 0.9200 . ? N4 H4B 0.9200 . ? C5 C6 1.519(6) . ? C5 H5C 0.9900 . ? C5 H5D 0.9900 . ? C4 C3 1.514(8) . ? C4 H4C 0.9900 . ? C4 H4D 0.9900 . ? C6 H6C 0.9900 . ? C6 H6D 0.9900 . ? C1 C2 1.512(7) . ? C1 H1C 0.9900 . ? C1 H1D 0.9900 . ? C2 H2C 0.9900 . ? C2 H2D 0.9900 . ? C3 H3C 0.9900 . ? C3 H3D 0.9900 . ? O1W O3W 0.899(19) . ? O2W O4W 0.682(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 N4 Co1 N5 93.42(16) . . ? N4 Co1 N6 90.94(18) . . ? N5 Co1 N6 85.85(17) . . ? N4 Co1 N3 85.89(18) . . ? N5 Co1 N3 88.88(17) . . ? N6 Co1 N3 173.68(17) . . ? N4 Co1 N1 174.36(15) . . ? N5 Co1 N1 91.59(16) . . ? N6 Co1 N1 92.02(18) . . ? N3 Co1 N1 91.60(18) . . ? N4 Co1 N2 90.16(16) . . ? N5 Co1 N2 175.07(16) . . ? N6 Co1 N2 90.70(17) . . ? N3 Co1 N2 94.78(17) . . ? N1 Co1 N2 85.01(15) . . ? O2 C7 O1 126.1(5) . . ? O2 C7 C8 117.2(5) . . ? O1 C7 C8 116.7(4) . . ? O3 C8 O4 125.6(4) . . ? O3 C8 C7 117.3(4) . . ? O4 C8 C7 117.2(4) . . ? O5 C9 O6 126.7(5) . . ? O5 C9 C9 118.2(5) . 2_656 ? O6 C9 C9 115.1(6) . 2_656 ? C3 N3 Co1 108.5(3) . . ? C3 N3 H3A 110.0 . . ? Co1 N3 H3A 110.0 . . ? C3 N3 H3B 110.0 . . ? Co1 N3 H3B 110.0 . . ? H3A N3 H3B 108.4 . . ? C6 N6 Co1 109.4(3) . . ? C6 N6 H6A 109.8 . . ? Co1 N6 H6A 109.8 . . ? C6 N6 H6B 109.8 . . ? Co1 N6 H6B 109.8 . . ? H6A N6 H6B 108.2 . . ? C5 N5 Co1 109.6(3) . . ? C5 N5 H5A 109.7 . . ? Co1 N5 H5A 109.7 . . ? C5 N5 H5B 109.7 . . ? Co1 N5 H5B 109.7 . . ? H5A N5 H5B 108.2 . . ? C2 N2 Co1 110.1(3) . . ? C2 N2 H2A 109.6 . . ? Co1 N2 H2A 109.6 . . ? C2 N2 H2B 109.6 . . ? Co1 N2 H2B 109.6 . . ? H2A N2 H2B 108.2 . . ? C1 N1 Co1 108.8(3) . . ? C1 N1 H1A 109.9 . . ? Co1 N1 H1A 109.9 . . ? C1 N1 H1B 109.9 . . ? Co1 N1 H1B 109.9 . . ? H1A N1 H1B 108.3 . . ? C4 N4 Co1 109.7(3) . . ? C4 N4 H4A 109.7 . . ? Co1 N4 H4A 109.7 . . ? C4 N4 H4B 109.7 . . ? Co1 N4 H4B 109.7 . . ? H4A N4 H4B 108.2 . . ? N5 C5 C6 105.7(3) . . ? N5 C5 H5C 110.6 . . ? C6 C5 H5C 110.6 . . ? N5 C5 H5D 110.6 . . ? C6 C5 H5D 110.6 . . ? H5C C5 H5D 108.7 . . ? N4 C4 C3 107.1(4) . . ? N4 C4 H4C 110.3 . . ? C3 C4 H4C 110.3 . . ? N4 C4 H4D 110.3 . . ? C3 C4 H4D 110.3 . . ? H4C C4 H4D 108.5 . . ? N6 C6 C5 108.5(4) . . ? N6 C6 H6C 110.0 . . ? C5 C6 H6C 110.0 . . ? N6 C6 H6D 110.0 . . ? C5 C6 H6D 110.0 . . ? H6C C6 H6D 108.4 . . ? N1 C1 C2 106.6(4) . . ? N1 C1 H1C 110.4 . . ? C2 C1 H1C 110.4 . . ? N1 C1 H1D 110.4 . . ? C2 C1 H1D 110.4 . . ? H1C C1 H1D 108.6 . . ? N2 C2 C1 106.9(4) . . ? N2 C2 H2C 110.3 . . ? C1 C2 H2C 110.3 . . ? N2 C2 H2D 110.3 . . ? C1 C2 H2D 110.3 . . ? H2C C2 H2D 108.6 . . ? N3 C3 C4 106.2(4) . . ? N3 C3 H3C 110.5 . . ? C4 C3 H3C 110.5 . . ? N3 C3 H3D 110.5 . . ? C4 C3 H3D 110.5 . . ? H3C C3 H3D 108.7 . . ? 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 N1 H1A O4 0.92 1.98 2.895(6) 175.0 1_545 N1 H1B O4 0.92 2.01 2.880(5) 158.3 2_765 N2 H2A O5 0.92 1.96 2.854(6) 164.0 1_655 N2 H2B O5 0.92 2.27 3.019(5) 138.0 2_656 N2 H2B O1W 0.92 2.35 3.136(11) 143.6 2_656 N2 H2B O3W 0.92 2.34 2.99(2) 127.0 2_656 N3 H3B O3 0.92 2.16 3.044(5) 160.1 2_765 N3 H3A O6 0.92 1.98 2.848(5) 157.5 1_655 N4 H4A O1 0.92 1.95 2.848(5) 165.1 . N4 H4B O5 0.92 1.98 2.860(6) 160.4 2_656 N4 H4B O6 0.92 2.55 3.182(7) 126.2 . N5 H5A O1 0.92 2.25 3.083(6) 150.9 . N5 H5A O3 0.92 2.25 2.949(5) 131.9 . N5 H5B O3 0.92 2.10 2.992(5) 162.5 2_765 N6 H6A O2 0.92 2.13 2.936(6) 146.3 1_545 N6 H6A O4 0.92 2.42 3.132(5) 134.6 1_545 N6 H6B O6 0.92 2.02 2.856(6) 150.2 . N6 H6B O1W 0.92 2.66 3.272(10) 124.3 2_656 _diffrn_measured_fraction_theta_max 0.980 _diffrn_reflns_theta_full 27.56 _diffrn_measured_fraction_theta_full 0.980 _refine_diff_density_max 1.725 _refine_diff_density_min -1.215 _refine_diff_density_rms 0.151 ############################################################## data_en4_x _database_code_depnum_ccdc_archive 'CCDC 829510' #TrackingRef '- en1234_x.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; di-[tris-(ethylenediamine-N,N')-cobalt(III)] tris- oxalate. 3.5 H2O ; _chemical_name_common ;di-(tris-(ethylenediamine-N,N')-cobalt(iii)) tris-oxalate. 3.5 H2O ; _chemical_melting_point N/A _chemical_formula_moiety '2(C6 H24 Co N6), 3(C2 O4), 7(H2 O)' _chemical_formula_sum 'C18 H62 Co2 N12 O19' _chemical_formula_weight 868.66 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' Co Co 0.3494 0.9721 '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/c' _symmetry_space_group_name_Hall '-C 2yc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 28.964(2) _cell_length_b 10.3615(5) _cell_length_c 12.7579(8) _cell_angle_alpha 90.00 _cell_angle_beta 114.446(2) _cell_angle_gamma 90.00 _cell_volume 3485.6(4) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 6385 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.655 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1840 _exptl_absorpt_coefficient_mu 1.046 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.72583 _exptl_absorpt_correction_T_max 1.46882 _exptl_absorpt_process_details 'SORTAV (Blessing, 1997)' _exptl_special_details ; PLEASE NOTE cell_measurement_fields are not relavent to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Nonius FR591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD Area Detector' _diffrn_measurement_method '\f and \w scans to fill Ewald Sphere' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12762 _diffrn_reflns_av_R_equivalents 0.1440 _diffrn_reflns_av_sigmaI/netI 0.1148 _diffrn_reflns_limit_h_min -37 _diffrn_reflns_limit_h_max 37 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.94 _diffrn_reflns_theta_max 27.49 _reflns_number_total 3970 _reflns_number_gt 2516 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'DENZO (Otwinowski and Minor, 1997)' _computing_cell_refinement 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_data_reduction 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_structure_solution ;SIR 92 (Altomore, Cascarno, Giacovazzo and Gualardi, 1993) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_structure_refinement ;SHELXS-97 (Sheldrick, 1997a) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_molecular_graphics 'Diamond 3.2e (Brandenburg, 2010)' _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. All non-hydrogen atoms were refined anisotropically. The confromational disorder in one of the ligand molecules, was also subject to some constraints. The occupancy of the two conformers was set to sum to 100%. The anisotropic displacement parameters of like atoms was set to be equal, and similar N-C and C-C bond lengths were restrained to be equal. H atoms on the amine (N-H) and alkyl (C-H) groups were fixed in calculated geometries and refined in riding mode. Water of crystallisation at sites O4Wa and O4Wb, have occopancies that are correlated with the conformational disorder in the ligand. The anisotropic thermal parameters of these two site were set to be equal. Hydrogen atoms on water molecules O1W, O2W, O3W and O4Wa were not modelled. H atoms on the ethylenediamine molecule were place in calculated geometries and refined in riding mode. All H atoms had isotropic thermal parmeters constrained to 1.2 times that of the parent atom. ; _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^)+(0.0651P)^2^+6.4301P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3970 _refine_ls_number_parameters 241 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.1132 _refine_ls_R_factor_gt 0.0641 _refine_ls_wR_factor_ref 0.1759 _refine_ls_wR_factor_gt 0.1532 _refine_ls_goodness_of_fit_ref 1.052 _refine_ls_restrained_S_all 1.051 _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_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Co1 Co 0.13019(2) 0.15520(6) 0.11749(5) 0.01569(19) Uani 1 1 d . A . O4 O 0.33147(13) 0.1340(3) 0.5743(3) 0.0341(9) Uani 1 1 d . . . O3 O 0.27859(13) 0.1498(3) 0.3860(3) 0.0340(8) Uani 1 1 d . . . O1 O 0.20288(12) 0.0514(3) 0.4330(3) 0.0290(8) Uani 1 1 d . . . O2 O 0.25717(12) 0.0128(4) 0.6124(3) 0.0337(9) Uani 1 1 d . . . C4 C 0.15718(18) -0.1037(5) 0.1810(4) 0.0259(10) Uani 1 1 d . . . H4A H 0.1426 -0.1168 0.2363 0.031 Uiso 1 1 calc R . . H4B H 0.1822 -0.1707 0.1920 0.031 Uiso 1 1 calc R . . N3 N 0.18131(14) 0.2893(4) 0.1886(3) 0.0232(8) Uani 1 1 d . . . H3A H 0.1660 0.3655 0.1864 0.028 Uiso 1 1 calc R . . H3B H 0.2003 0.2693 0.2627 0.028 Uiso 1 1 calc R . . C7 C 0.24556(17) 0.0573(4) 0.5134(4) 0.0205(10) Uani 1 1 d . . . N5 N 0.08489(13) 0.0090(4) 0.0459(3) 0.0201(8) Uani 1 1 d . . . H5A H 0.0633 -0.0026 0.0794 0.024 Uiso 1 1 calc R . . H5B H 0.0666 0.0245 -0.0296 0.024 Uiso 1 1 calc R . . C5 C 0.18033(17) 0.2817(5) -0.0014(4) 0.0253(11) Uani 1 1 d . . . H5C H 0.1581 0.3556 -0.0305 0.030 Uiso 1 1 calc R . . H5D H 0.2007 0.2733 -0.0451 0.030 Uiso 1 1 calc R . . N6 N 0.18110(14) 0.0253(3) 0.1968(3) 0.0199(8) Uani 1 1 d . . . H6A H 0.2049 0.0251 0.1687 0.024 Uiso 1 1 calc R . . H6B H 0.1963 0.0442 0.2724 0.024 Uiso 1 1 calc R . . C3 C 0.11675(18) -0.1081(5) 0.0611(4) 0.0259(11) Uani 1 1 d . . . H3C H 0.1318 -0.1084 0.0058 0.031 Uiso 1 1 calc R . . H3D H 0.0964 -0.1854 0.0499 0.031 Uiso 1 1 calc R . . N4 N 0.15035(13) 0.1641(3) -0.0126(3) 0.0200(8) Uani 1 1 d . . . H4C H 0.1689 0.0942 -0.0122 0.024 Uiso 1 1 calc R . . H4D H 0.1226 0.1654 -0.0797 0.024 Uiso 1 1 calc R . . C6 C 0.21412(17) 0.2996(5) 0.1251(4) 0.0235(10) Uani 1 1 d . . . H6C H 0.2402 0.2336 0.1511 0.028 Uiso 1 1 calc R . . H6D H 0.2304 0.3835 0.1381 0.028 Uiso 1 1 calc R . . C8 C 0.28959(19) 0.1220(4) 0.4897(4) 0.0247(11) Uani 1 1 d . . . O5 O 0.01234(13) -0.1204(4) 0.1292(3) 0.0364(9) Uani 1 1 d . . . O6 O 0.06399(13) -0.0495(4) 0.3058(3) 0.0364(9) Uani 1 1 d . . . C9 C 0.02164(16) -0.0853(5) 0.2311(4) 0.0232(10) Uani 1 1 d . . . N1 N 0.07515(14) 0.2803(4) 0.0391(3) 0.0250(9) Uani 1 1 d D . . H1B H 0.0866 0.3444 0.0086 0.030 Uiso 0.780(6) 1 calc PR A 1 H1A H 0.0494 0.2408 -0.0184 0.030 Uiso 0.780(6) 1 calc PR A 1 H1C H 0.0879 0.3603 0.0435 0.030 Uiso 0.220(6) 1 calc PR A 2 H1D H 0.0582 0.2592 -0.0356 0.030 Uiso 0.220(6) 1 calc PR A 2 C1A C 0.0570(3) 0.3345(6) 0.1236(6) 0.0299(16) Uani 0.780(6) 1 d PD A 1 H1E H 0.0788 0.4046 0.1664 0.036 Uiso 0.780(6) 1 calc PR A 1 H1F H 0.0227 0.3674 0.0839 0.036 Uiso 0.780(6) 1 calc PR A 1 C2A C 0.0581(2) 0.2285(7) 0.2026(6) 0.0308(17) Uani 0.780(6) 1 d PD A 1 H2E H 0.0320 0.1655 0.1624 0.037 Uiso 0.780(6) 1 calc PR A 1 H2F H 0.0522 0.2623 0.2669 0.037 Uiso 0.780(6) 1 calc PR A 1 C1B C 0.0407(7) 0.275(3) 0.0994(16) 0.0299(16) Uani 0.220(6) 1 d PD A 2 H1G H 0.0170 0.3462 0.0768 0.036 Uiso 0.220(6) 1 calc PR A 2 H1H H 0.0217 0.1943 0.0824 0.036 Uiso 0.220(6) 1 calc PR A 2 C2B C 0.0753(8) 0.2825(18) 0.2236(18) 0.0308(17) Uani 0.220(6) 1 d PD A 2 H2G H 0.0563 0.2790 0.2709 0.037 Uiso 0.220(6) 1 calc PR A 2 H2H H 0.0948 0.3618 0.2402 0.037 Uiso 0.220(6) 1 calc PR A 2 N2 N 0.10959(14) 0.1665(4) 0.2453(3) 0.0231(8) Uani 1 1 d D . . H2B H 0.1084 0.0871 0.2726 0.028 Uiso 0.780(6) 1 calc PR A 1 H2A H 0.1322 0.2139 0.3027 0.028 Uiso 0.780(6) 1 calc PR A 1 H2C H 0.0930 0.0944 0.2489 0.028 Uiso 0.220(6) 1 calc PR A 2 H2D H 0.1370 0.1756 0.3124 0.028 Uiso 0.220(6) 1 calc PR A 2 O1W O 0.15831(12) 0.5635(3) 0.2154(3) 0.0306(8) Uani 1 1 d . . . O2W O 0.08288(15) 0.4542(4) 0.4543(4) 0.0527(11) Uani 1 1 d . . . O3W O 0.0000 0.5186(7) 0.2500 0.0591(17) Uani 1 2 d S . . O4WA O 0.0776(2) 0.6637(5) 0.2449(6) 0.0505(15) Uani 0.780(6) 1 d P . . O4WB O 0.0614(8) 0.6317(18) 0.152(2) 0.0505(15) Uani 0.220(6) 1 d P . . 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 Co1 0.0155(3) 0.0148(3) 0.0161(3) -0.0013(3) 0.0059(2) -0.0012(2) O4 0.0223(18) 0.037(2) 0.039(2) -0.0008(17) 0.0085(17) -0.0060(15) O3 0.040(2) 0.037(2) 0.0292(19) 0.0048(17) 0.0188(17) -0.0067(17) O1 0.0204(18) 0.039(2) 0.0254(18) 0.0004(15) 0.0070(15) -0.0016(15) O2 0.0220(18) 0.050(2) 0.0276(18) 0.0145(17) 0.0089(15) 0.0016(16) C4 0.026(3) 0.017(2) 0.035(3) 0.002(2) 0.013(2) -0.001(2) N3 0.023(2) 0.019(2) 0.027(2) -0.0039(17) 0.0103(18) -0.0047(17) C7 0.019(2) 0.023(3) 0.019(2) -0.0021(19) 0.007(2) 0.0047(18) N5 0.0176(19) 0.021(2) 0.020(2) 0.0008(16) 0.0061(17) 0.0011(15) C5 0.025(3) 0.022(3) 0.030(3) 0.004(2) 0.012(2) -0.004(2) N6 0.022(2) 0.019(2) 0.0192(19) 0.0023(16) 0.0087(17) 0.0032(16) C3 0.026(3) 0.018(2) 0.035(3) -0.004(2) 0.014(2) -0.0020(19) N4 0.0196(19) 0.019(2) 0.0197(18) 0.0008(16) 0.0067(16) -0.0006(16) C6 0.019(2) 0.025(3) 0.029(3) -0.001(2) 0.012(2) -0.0043(19) C8 0.031(3) 0.015(2) 0.032(3) -0.003(2) 0.017(2) -0.0030(19) O5 0.027(2) 0.058(3) 0.0266(19) -0.0008(18) 0.0135(17) -0.0012(17) O6 0.0233(19) 0.054(2) 0.0253(18) 0.0068(17) 0.0036(16) -0.0138(17) C9 0.015(2) 0.029(3) 0.020(2) 0.001(2) 0.002(2) -0.0076(19) N1 0.023(2) 0.027(2) 0.025(2) -0.0005(18) 0.0104(18) 0.0027(17) C1A 0.026(4) 0.027(4) 0.037(4) 0.002(3) 0.013(3) 0.010(3) C2A 0.031(4) 0.030(4) 0.039(4) 0.005(3) 0.022(4) 0.011(3) C1B 0.026(4) 0.027(4) 0.037(4) 0.002(3) 0.013(3) 0.010(3) C2B 0.031(4) 0.030(4) 0.039(4) 0.005(3) 0.022(4) 0.011(3) N2 0.021(2) 0.022(2) 0.026(2) -0.0018(17) 0.0093(17) 0.0013(16) O1W 0.0273(19) 0.028(2) 0.034(2) -0.0019(16) 0.0102(17) 0.0070(15) O2W 0.046(3) 0.044(3) 0.068(3) -0.014(2) 0.023(2) 0.000(2) O3W 0.040(4) 0.078(5) 0.057(4) 0.000 0.017(3) 0.000 O4WA 0.048(3) 0.043(3) 0.074(4) 0.010(3) 0.040(3) 0.007(2) O4WB 0.048(3) 0.043(3) 0.074(4) 0.010(3) 0.040(3) 0.007(2) _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 Co1 N6 1.943(4) . ? Co1 N2 1.957(4) . ? Co1 N3 1.958(4) . ? Co1 N5 1.964(4) . ? Co1 N1 1.975(4) . ? Co1 N4 1.977(3) . ? O4 C8 1.252(6) . ? O3 C8 1.259(6) . ? O1 C7 1.239(5) . ? O2 C7 1.252(5) . ? C4 N6 1.481(6) . ? C4 C3 1.494(7) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? N3 C6 1.485(5) . ? N3 H3A 0.9000 . ? N3 H3B 0.9000 . ? C7 C8 1.577(6) . ? N5 C3 1.488(6) . ? N5 H5A 0.9000 . ? N5 H5B 0.9000 . ? C5 N4 1.469(5) . ? C5 C6 1.513(6) . ? C5 H5C 0.9700 . ? C5 H5D 0.9700 . ? N6 H6A 0.9000 . ? N6 H6B 0.9000 . ? C3 H3C 0.9700 . ? C3 H3D 0.9700 . ? N4 H4C 0.9000 . ? N4 H4D 0.9000 . ? C6 H6C 0.9700 . ? C6 H6D 0.9700 . ? O5 C9 1.267(5) . ? O6 C9 1.258(5) . ? C9 C9 1.518(8) 2 ? N1 C1A 1.491(6) . ? N1 C1B 1.492(10) . ? N1 H1B 0.9000 . ? N1 H1A 0.9000 . ? N1 H1C 0.9000 . ? N1 H1D 0.9000 . ? C1A C2A 1.482(8) . ? C1A H1E 0.9700 . ? C1A H1F 0.9700 . ? C2A N2 1.502(6) . ? C2A H2E 0.9700 . ? C2A H2F 0.9700 . ? C1B C2B 1.485(12) . ? C1B H1G 0.9700 . ? C1B H1H 0.9700 . ? C2B N2 1.510(10) . ? C2B H2G 0.9700 . ? C2B H2H 0.9700 . ? N2 H2B 0.9000 . ? N2 H2A 0.9000 . ? N2 H2C 0.9000 . ? N2 H2D 0.9000 . ? O4WA O4WB 1.13(2) . ? 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 N6 Co1 N2 92.00(15) . . ? N6 Co1 N3 89.13(16) . . ? N2 Co1 N3 90.26(15) . . ? N6 Co1 N5 85.71(16) . . ? N2 Co1 N5 93.36(15) . . ? N3 Co1 N5 173.80(15) . . ? N6 Co1 N1 176.18(15) . . ? N2 Co1 N1 85.52(15) . . ? N3 Co1 N1 93.78(17) . . ? N5 Co1 N1 91.52(16) . . ? N6 Co1 N4 92.60(15) . . ? N2 Co1 N4 173.87(16) . . ? N3 Co1 N4 85.77(15) . . ? N5 Co1 N4 91.02(14) . . ? N1 Co1 N4 90.08(15) . . ? N6 C4 C3 106.9(4) . . ? N6 C4 H4A 110.3 . . ? C3 C4 H4A 110.3 . . ? N6 C4 H4B 110.3 . . ? C3 C4 H4B 110.3 . . ? H4A C4 H4B 108.6 . . ? C6 N3 Co1 109.3(3) . . ? C6 N3 H3A 109.8 . . ? Co1 N3 H3A 109.8 . . ? C6 N3 H3B 109.8 . . ? Co1 N3 H3B 109.8 . . ? H3A N3 H3B 108.3 . . ? O1 C7 O2 125.2(4) . . ? O1 C7 C8 118.1(4) . . ? O2 C7 C8 116.7(4) . . ? C3 N5 Co1 108.0(3) . . ? C3 N5 H5A 110.1 . . ? Co1 N5 H5A 110.1 . . ? C3 N5 H5B 110.1 . . ? Co1 N5 H5B 110.1 . . ? H5A N5 H5B 108.4 . . ? N4 C5 C6 107.5(4) . . ? N4 C5 H5C 110.2 . . ? C6 C5 H5C 110.2 . . ? N4 C5 H5D 110.2 . . ? C6 C5 H5D 110.2 . . ? H5C C5 H5D 108.5 . . ? C4 N6 Co1 110.1(3) . . ? C4 N6 H6A 109.6 . . ? Co1 N6 H6A 109.6 . . ? C4 N6 H6B 109.6 . . ? Co1 N6 H6B 109.6 . . ? H6A N6 H6B 108.2 . . ? N5 C3 C4 106.9(4) . . ? N5 C3 H3C 110.3 . . ? C4 C3 H3C 110.3 . . ? N5 C3 H3D 110.3 . . ? C4 C3 H3D 110.3 . . ? H3C C3 H3D 108.6 . . ? C5 N4 Co1 109.0(3) . . ? C5 N4 H4C 109.9 . . ? Co1 N4 H4C 109.9 . . ? C5 N4 H4D 109.9 . . ? Co1 N4 H4D 109.9 . . ? H4C N4 H4D 108.3 . . ? N3 C6 C5 107.2(3) . . ? N3 C6 H6C 110.3 . . ? C5 C6 H6C 110.3 . . ? N3 C6 H6D 110.3 . . ? C5 C6 H6D 110.3 . . ? H6C C6 H6D 108.5 . . ? O4 C8 O3 128.0(4) . . ? O4 C8 C7 116.7(4) . . ? O3 C8 C7 115.2(4) . . ? O6 C9 O5 126.1(4) . . ? O6 C9 C9 115.7(5) . 2 ? O5 C9 C9 118.3(5) . 2 ? C1A N1 C1B 29.6(9) . . ? C1A N1 Co1 109.5(3) . . ? C1B N1 Co1 106.5(10) . . ? C1A N1 H1B 109.8 . . ? C1B N1 H1B 134.2 . . ? Co1 N1 H1B 109.8 . . ? C1A N1 H1A 109.8 . . ? C1B N1 H1A 84.0 . . ? Co1 N1 H1A 109.8 . . ? H1B N1 H1A 108.2 . . ? C1A N1 H1C 82.3 . . ? C1B N1 H1C 110.4 . . ? Co1 N1 H1C 110.4 . . ? H1B N1 H1C 29.7 . . ? H1A N1 H1C 130.5 . . ? C1A N1 H1D 131.0 . . ? C1B N1 H1D 110.4 . . ? Co1 N1 H1D 110.4 . . ? H1B N1 H1D 81.8 . . ? H1A N1 H1D 28.5 . . ? H1C N1 H1D 108.6 . . ? C2A C1A N1 107.3(5) . . ? C2A C1A H1E 110.3 . . ? N1 C1A H1E 110.3 . . ? C2A C1A H1F 110.3 . . ? N1 C1A H1F 110.3 . . ? H1E C1A H1F 108.5 . . ? C1A C2A N2 107.6(5) . . ? C1A C2A H2E 110.2 . . ? N2 C2A H2E 110.2 . . ? C1A C2A H2F 110.2 . . ? N2 C2A H2F 110.2 . . ? H2E C2A H2F 108.5 . . ? C2B C1B N1 104.3(15) . . ? C2B C1B H1G 110.9 . . ? N1 C1B H1G 110.9 . . ? C2B C1B H1H 110.9 . . ? N1 C1B H1H 110.9 . . ? H1G C1B H1H 108.9 . . ? C1B C2B N2 104.7(15) . . ? C1B C2B H2G 110.8 . . ? N2 C2B H2G 110.8 . . ? C1B C2B H2H 110.8 . . ? N2 C2B H2H 110.8 . . ? H2G C2B H2H 108.9 . . ? C2A N2 C2B 27.8(9) . . ? C2A N2 Co1 108.8(3) . . ? C2B N2 Co1 107.4(10) . . ? C2A N2 H2B 109.9 . . ? C2B N2 H2B 132.2 . . ? Co1 N2 H2B 109.9 . . ? C2A N2 H2A 109.9 . . ? C2B N2 H2A 85.3 . . ? Co1 N2 H2A 109.9 . . ? H2B N2 H2A 108.3 . . ? C2A N2 H2C 84.4 . . ? C2B N2 H2C 110.2 . . ? Co1 N2 H2C 110.2 . . ? H2B N2 H2C 27.7 . . ? H2A N2 H2C 129.5 . . ? C2A N2 H2D 130.7 . . ? C2B N2 H2D 110.2 . . ? Co1 N2 H2D 110.2 . . ? H2B N2 H2D 83.5 . . ? H2A N2 H2D 27.1 . . ? H2C N2 H2D 108.5 . . ? 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 N1 H1A O5 0.90 2.16 3.045(5) 168.4 5 N1 H1B O2W 0.90 2.19 2.999(5) 149.6 6_565 N2 H2A O4 0.90 2.17 3.039(5) 163.5 7_556 N2 H2C O6 0.90 1.99 2.863(5) 162.9 . N3 H3A O1W 0.90 2.11 2.970(5) 158.8 . N3 H3B O3 0.90 2.49 3.240(5) 141.2 . N4 H4C O1 0.90 2.08 2.942(5) 161.5 6 N4 H4D O6 0.90 2.10 2.870(5) 143.2 6 N5 H5B O5 0.90 2.33 3.007(5) 132.0 5 N5 H5B O6 0.90 2.09 2.896(5) 149.2 6 N6 H6B O1 0.90 1.98 2.824(5) 155.8 . N6 H6B O3 0.90 2.47 3.134(5) 130.5 . N6 H6A O2 0.90 1.96 2.852(5) 168.5 6 _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.758 _refine_diff_density_min -0.724 _refine_diff_density_rms 0.136