# Copyright The Royal Society of Chemistry, 1999 # CCDC Number: 186/1461 data_lc112f _audit_creation_method SHELXL-97 _chemical_name_systematic ;[((1,4,8,11-tetraaza-\k^4^N)-cyclotetradecane-2,3- dione-(hydrato-/kO)copper(II))2-\k^4^O-copper(II))] bis perchlorate dihydrate ; _chemical_name_common ;{Cu[exoO~2~cyclam]}~2~Cu(ClO4)~2~2H~2~O ; _chemical_melting_point '>160 (dec.)' _chemical_formula_moiety '2 (Cl O4) C20 H44 Cu3 N8 O6' _chemical_formula_sum 'C20 H44 Cl2 Cu3 N8 O16' _chemical_formula_weight 914.16 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0181 0.0091 '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' 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cu' 'Cu' -1.9646 0.5888 '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 / 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 8.6599(17) _cell_length_b 16.907(4) _cell_length_c 12.784(2) _cell_angle_alpha 90.00 _cell_angle_beta 106.208(19) _cell_angle_gamma 90.00 _cell_volume 1797.4(6) _cell_formula_units_Z 2 _cell_measurement_temperature 220(2) _cell_measurement_reflns_used 56 _cell_measurement_theta_min 60 _cell_measurement_theta_max 66 _exptl_crystal_description lath _exptl_crystal_colour red _exptl_crystal_size_max 0.39 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.689 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 938 _exptl_absorpt_coefficient_mu 4.113 _exptl_absorpt_correction_type 'empirical via \y scans' _exptl_absorpt_correction_T_min 0.653 _exptl_absorpt_correction_T_max 0.926 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54180 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Stoe Stadi-4B' _diffrn_measurement_method \w\q _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 150 _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 3746 _diffrn_reflns_av_R_equivalents 0.0494 _diffrn_reflns_av_sigmaI/netI 0.0366 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 4.45 _diffrn_reflns_theta_max 70.07 _reflns_number_total 3171 _reflns_number_gt 2553 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SIR-92 (A. Guagliardi, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'WINGX PACKAGE (L. J. Farrugia, 1998)' _computing_publication_material 'WINGX PACKAGE (L. J. Farrugia, 1998)' _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 perchlorate anions are slightly disordered an this was best modelled by splitting one oxygen atom over two sites (O7A, 70% and O7B 30%), in addition all the oxygen atoms of the perchlorate were restrained using the SADI commnad in SHELXL97. At the end of the refinement there were some large peaks in the fourier difference map that were modelled as 1 water molecule disordered over 3 sites - however as these made no significant contacts with the main body of the structure or the perchlorate anions they were removed using the solvent treatment algorithm (cal squeeze) in PLATON (A. L. Spek, 1990). This corrected for 75 electrons over the cell equal to two water molecules per trimer unit. The PLATON treatment improved the R factors by around 0.5% but made no significant differences in the geometrical parameters and the e.s.d's. ; _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^)+(0.0987P)^2^+0.9945P] 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 'none refined' _refine_ls_number_reflns 3171 _refine_ls_number_parameters 235 _refine_ls_number_restraints 10 _refine_ls_R_factor_all 0.0659 _refine_ls_R_factor_gt 0.0555 _refine_ls_wR_factor_ref 0.1532 _refine_ls_wR_factor_gt 0.1460 _refine_ls_goodness_of_fit_ref 1.048 _refine_ls_restrained_S_all 1.047 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.001 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 1.0000 0.5000 0.5000 0.0402(3) Uani 1 2 d S . . Cu2 Cu 1.46797(6) 0.34872(4) 0.76150(4) 0.0376(2) Uani 1 1 d . . . O1 O 1.2031(3) 0.45600(17) 0.4935(2) 0.0400(6) Uani 1 1 d . . . O2 O 1.0338(3) 0.44284(18) 0.6355(2) 0.0427(7) Uani 1 1 d . . . O3 O 1.6165(5) 0.4762(2) 0.8326(4) 0.0701(11) Uani 1 1 d . . . HC H 1.564(10) 0.508(5) 0.834(8) 0.105 Uiso 1 1 d . . . N1 N 1.2523(4) 0.3859(2) 0.7585(2) 0.0367(7) Uani 1 1 d . . . N2 N 1.4126(4) 0.3881(2) 0.6117(2) 0.0357(7) Uani 1 1 d . . . N3 N 1.6563(4) 0.2841(3) 0.7488(3) 0.0501(9) Uani 1 1 d . . . HA H 1.639(7) 0.236(4) 0.722(5) 0.075 Uiso 1 1 d . . . N4 N 1.5358(5) 0.3170(2) 0.9191(3) 0.0477(9) Uani 1 1 d . . . HB H 1.595(7) 0.361(3) 0.954(5) 0.072 Uiso 1 1 d . . . C1 C 1.1776(4) 0.4160(2) 0.6659(3) 0.0340(8) Uani 1 1 d . . . C2 C 1.2733(4) 0.4211(2) 0.5834(3) 0.0317(7) Uani 1 1 d . . . C3 C 1.5194(5) 0.3922(3) 0.5414(3) 0.0433(9) Uani 1 1 d . . . H3A H 1.5803 0.4410 0.5559 0.052 Uiso 1 1 calc R . . H3B H 1.4551 0.3931 0.4659 0.052 Uiso 1 1 calc R . . C4 C 1.6344(6) 0.3236(4) 0.5580(4) 0.0624(14) Uani 1 1 d . . . H4A H 1.7015 0.3299 0.5092 0.075 Uiso 1 1 calc R . . H4B H 1.5726 0.2754 0.5371 0.075 Uiso 1 1 calc R . . C5 C 1.7426(5) 0.3134(4) 0.6727(4) 0.0569(13) Uani 1 1 d . . . H5A H 1.8280 0.2766 0.6714 0.068 Uiso 1 1 calc R . . H5B H 1.7917 0.3639 0.6987 0.068 Uiso 1 1 calc R . . C6 C 1.7585(6) 0.2687(3) 0.8583(4) 0.0553(12) Uani 1 1 d . . . H6A H 1.8276 0.3138 0.8844 0.066 Uiso 1 1 calc R . . H6B H 1.8260 0.2230 0.8576 0.066 Uiso 1 1 calc R . . C7 C 1.6537(6) 0.2535(3) 0.9323(4) 0.0540(11) Uani 1 1 d . . . H7A H 1.5991 0.2031 0.9144 0.065 Uiso 1 1 calc R . . H7B H 1.7193 0.2514 1.0074 0.065 Uiso 1 1 calc R . . C8 C 1.4057(5) 0.3024(3) 0.9698(3) 0.0506(11) Uani 1 1 d . . . H8A H 1.4523 0.2922 1.0468 0.061 Uiso 1 1 calc R . . H8B H 1.3471 0.2555 0.9376 0.061 Uiso 1 1 calc R . . C9 C 1.2905(6) 0.3704(3) 0.9565(4) 0.0528(11) Uani 1 1 d . . . H9A H 1.3520 0.4190 0.9724 0.063 Uiso 1 1 calc R . . H9B H 1.2308 0.3650 1.0100 0.063 Uiso 1 1 calc R . . C10 C 1.1711(5) 0.3779(3) 0.8444(3) 0.0476(10) Uani 1 1 d . . . H10A H 1.1026 0.3314 0.8301 0.057 Uiso 1 1 calc R . . H10B H 1.1033 0.4237 0.8433 0.057 Uiso 1 1 calc R . . Cl1 Cl 1.29098(18) 0.63432(8) 0.75475(11) 0.0683(4) Uani 1 1 d D . . O4 O 1.3306(6) 0.5753(3) 0.8382(4) 0.0870(13) Uani 1 1 d D . . O5 O 1.1916(6) 0.6048(3) 0.6552(4) 0.0954(14) Uani 1 1 d D . . O6 O 1.2171(10) 0.6982(3) 0.7917(5) 0.144(3) Uani 1 1 d D . . O7A O 1.4346(15) 0.6674(9) 0.7433(12) 0.130(6) Uani 0.70 1 d PD . . O7B O 1.427(2) 0.651(3) 0.719(3) 0.144(17) Uani 0.30 1 d PD . . 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 0.0243(4) 0.0569(5) 0.0392(4) 0.0126(4) 0.0085(3) 0.0083(3) Cu2 0.0263(4) 0.0556(4) 0.0287(3) 0.0045(2) 0.0037(2) 0.0070(2) O1 0.0270(14) 0.0577(17) 0.0337(13) 0.0103(12) 0.0058(11) 0.0073(12) O2 0.0264(14) 0.0613(18) 0.0422(14) 0.0114(13) 0.0124(11) 0.0060(12) O3 0.060(2) 0.071(3) 0.075(2) -0.013(2) 0.011(2) -0.0086(18) N1 0.0287(16) 0.0511(19) 0.0315(15) 0.0020(13) 0.0103(13) 0.0022(14) N2 0.0247(16) 0.0528(19) 0.0291(14) 0.0005(13) 0.0069(12) 0.0035(14) N3 0.0323(19) 0.069(3) 0.045(2) 0.0076(18) 0.0041(15) 0.0170(17) N4 0.043(2) 0.061(2) 0.0373(17) 0.0085(16) 0.0087(15) 0.0037(17) C1 0.0241(19) 0.043(2) 0.0352(18) -0.0002(15) 0.0087(15) 0.0001(15) C2 0.0267(19) 0.0389(19) 0.0288(16) -0.0006(14) 0.0067(14) -0.0006(15) C3 0.031(2) 0.065(3) 0.0351(19) 0.0044(18) 0.0119(16) 0.0070(18) C4 0.054(3) 0.097(4) 0.039(2) 0.005(2) 0.017(2) 0.025(3) C5 0.032(2) 0.096(4) 0.043(2) 0.006(2) 0.0104(18) 0.023(2) C6 0.040(2) 0.077(3) 0.042(2) 0.006(2) 0.0019(19) 0.015(2) C7 0.051(3) 0.062(3) 0.044(2) 0.010(2) 0.003(2) 0.011(2) C8 0.045(3) 0.072(3) 0.0329(19) 0.007(2) 0.0068(17) -0.003(2) C9 0.052(3) 0.075(3) 0.037(2) 0.001(2) 0.0201(19) 0.002(2) C10 0.035(2) 0.077(3) 0.0342(19) 0.0060(19) 0.0149(17) 0.005(2) Cl1 0.0809(10) 0.0585(7) 0.0552(7) 0.0029(5) 0.0018(6) -0.0082(6) O4 0.103(3) 0.080(3) 0.081(3) 0.030(2) 0.031(3) 0.020(2) O5 0.114(4) 0.087(3) 0.074(3) -0.020(2) 0.007(3) -0.029(3) O6 0.239(8) 0.079(3) 0.090(4) -0.008(3) 0.007(4) 0.066(4) O7A 0.129(10) 0.168(10) 0.073(6) 0.028(6) -0.006(5) -0.096(9) O7B 0.048(12) 0.29(4) 0.091(19) -0.015(19) 0.009(12) 0.022(17) _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 O2 1.933(3) . ? Cu1 O2 1.933(3) 3_766 ? Cu1 O1 1.933(3) . ? Cu1 O1 1.933(3) 3_766 ? Cu2 N2 1.957(3) . ? Cu2 N1 1.961(3) . ? Cu2 N3 2.007(4) . ? Cu2 N4 2.007(4) . ? Cu2 O3 2.545(4) . ? O1 C2 1.284(4) . ? O2 C1 1.280(5) . ? N1 C1 1.285(5) . ? N1 C10 1.466(5) . ? N2 C2 1.287(5) . ? N2 C3 1.460(5) . ? N3 C6 1.456(5) . ? N3 C5 1.468(6) . ? N4 C7 1.459(6) . ? N4 C8 1.469(6) . ? C1 C2 1.515(5) . ? C3 C4 1.505(7) . ? C4 C5 1.513(6) . ? C6 C7 1.505(7) . ? C8 C9 1.500(7) . ? C9 C10 1.520(6) . ? Cl1 O6 1.402(5) . ? Cl1 O7B 1.402(14) . ? Cl1 O7A 1.408(9) . ? Cl1 O5 1.414(4) . ? Cl1 O4 1.431(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 O2 Cu1 O2 180.000(1) . 3_766 ? O2 Cu1 O1 86.24(11) . . ? O2 Cu1 O1 93.76(11) 3_766 . ? O2 Cu1 O1 93.76(11) . 3_766 ? O2 Cu1 O1 86.24(11) 3_766 3_766 ? O1 Cu1 O1 180.000(1) . 3_766 ? N2 Cu2 N1 84.28(13) . . ? N2 Cu2 N3 95.06(14) . . ? N1 Cu2 N3 164.59(17) . . ? N2 Cu2 N4 175.02(16) . . ? N1 Cu2 N4 96.62(15) . . ? N3 Cu2 N4 85.37(16) . . ? N2 Cu2 O3 91.31(15) . . ? N1 Cu2 O3 96.84(14) . . ? N3 Cu2 O3 98.57(16) . . ? N4 Cu2 O3 83.72(16) . . ? C2 O1 Cu1 110.3(2) . . ? C1 O2 Cu1 109.9(2) . . ? C1 N1 C10 120.2(3) . . ? C1 N1 Cu2 112.1(2) . . ? C10 N1 Cu2 127.5(3) . . ? C2 N2 C3 120.8(3) . . ? C2 N2 Cu2 112.2(2) . . ? C3 N2 Cu2 126.5(2) . . ? C6 N3 C5 114.4(4) . . ? C6 N3 Cu2 108.0(3) . . ? C5 N3 Cu2 116.4(3) . . ? C7 N4 C8 115.0(4) . . ? C7 N4 Cu2 108.2(3) . . ? C8 N4 Cu2 116.2(3) . . ? O2 C1 N1 128.1(3) . . ? O2 C1 C2 116.3(3) . . ? N1 C1 C2 115.6(3) . . ? O1 C2 N2 128.6(3) . . ? O1 C2 C1 115.8(3) . . ? N2 C2 C1 115.6(3) . . ? N2 C3 C4 112.6(4) . . ? C3 C4 C5 115.5(4) . . ? N3 C5 C4 112.9(4) . . ? N3 C6 C7 108.9(4) . . ? N4 C7 C6 109.1(4) . . ? N4 C8 C9 112.9(4) . . ? C8 C9 C10 115.2(4) . . ? N1 C10 C9 111.8(3) . . ? O6 Cl1 O7B 117.2(19) . . ? O6 Cl1 O7A 103.2(8) . . ? O7B Cl1 O7A 17(2) . . ? O6 Cl1 O5 110.8(4) . . ? O7B Cl1 O5 97.8(16) . . ? O7A Cl1 O5 112.4(7) . . ? O6 Cl1 O4 108.8(3) . . ? O7B Cl1 O4 109.4(15) . . ? O7A Cl1 O4 108.7(6) . . ? O5 Cl1 O4 112.6(3) . . ? 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 O3 HC O4 0.71(8) 2.34(8) 3.007(6) 160(9) . _diffrn_measured_fraction_theta_max 0.929 _diffrn_reflns_theta_full 70.07 _diffrn_measured_fraction_theta_full 0.929 _refine_diff_density_max 0.794 _refine_diff_density_min -0.761 _refine_diff_density_rms 0.104