Electronic Supplementary Material for CrystEngComm This journalis (c) The Royal Society of Chemistry 2006 data_global _journal_name_full CrystEngComm _journal_coden_Cambridge 1350 _publ_contact_author_name 'Malcolm A. Halcrow' _publ_contact_author_address ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; _publ_contact_author_phone '+44 (0)113 3436506' _publ_contact_author_fax '+44 (0)113 3436565' _publ_contact_author_email m.a.halcrow@leeds.ac.uk _publ_contact_letter ; The following set of data is for seven structures included in manuscript B609424D submitted to the 'CrystEngComm' office. ; #======================================================================= # 2. TITLE AND AUTHOR LIST _publ_section_title ; Novel hydrogen bond network topologies in complexes of the ditopic ligand 5-amino-3-(pyrid-2-yl)-1H-pyrazole ; loop_ _publ_author_name _publ_author_address 'Leigh F. Jones' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; 'Kenneth D. Camm' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; 'Colin A. Kilner' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; 'Malcolm A. Halcrow' ; School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK ; #================================================================= data_c:\datasets\leeds\ljf11b\ljf11b _database_code_depnum_ccdc_archive 'CCDC 613018' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Dichloro-bis[5-amino-3-(pyrid-2-yl)pyrazole]manganese(II) dimethanol solvate (1.2CH~3~OH) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H16 Cl2 Mn N8, 2[C H4 O]' _chemical_formula_sum 'C18 H24 Cl2 Mn N8 O2' _chemical_formula_weight 510.29 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' O O 0.0106 0.0060 '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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 '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' 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 18.9615(3) _cell_length_b 11.9420(3) _cell_length_c 12.8415(2) _cell_angle_alpha 90.00 _cell_angle_beta 125.6748(10) _cell_angle_gamma 90.00 _cell_volume 2362.12(8) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 20264 _cell_measurement_theta_min 2.64 _cell_measurement_theta_max 27.53 _exptl_crystal_description 'Rectangular prism' _exptl_crystal_colour Brown _exptl_crystal_size_max 0.63 _exptl_crystal_size_mid 0.36 _exptl_crystal_size_min 0.36 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.435 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1052 _exptl_absorpt_coefficient_mu 0.816 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.536 _exptl_absorpt_correction_T_max 0.816 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 20264 _diffrn_reflns_av_R_equivalents 0.0898 _diffrn_reflns_av_sigmaI/netI 0.0395 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.64 _diffrn_reflns_theta_max 27.53 _reflns_number_total 2711 _reflns_number_gt 2382 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 asymmetric unit contains half a complex molecule lying on the C~2~ axis [0, y, 0.25], and a molecule of methanol lying on a general position. No disorder was detected during refinement, and all non-H atoms were refined anisotropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The N---H and O---H H atoms were all located in the difference map and refined, with a common U~iso~ thermal parameter of 0.067(5)\%A^2^, and the refined restraints N---H = O---H = 0.85(2)\%A and H14A...H14B = 1.38(2)\%A. The highest residual Fourier peak of +1.0 e./%A^-3^ is 1.4\%A from the methanol atom C15 and 1.5\%A from O16, and may represent a weakly occupied (10% or less) alternative disorder site for the solvent methyl group. ; _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^)+(0.0672P)^2^+2.7099P] 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 2711 _refine_ls_number_parameters 155 _refine_ls_number_restraints 5 _refine_ls_R_factor_all 0.0468 _refine_ls_R_factor_gt 0.0406 _refine_ls_wR_factor_ref 0.1239 _refine_ls_wR_factor_gt 0.1185 _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_restrained_S_all 1.058 _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 Mn1 Mn 0.0000 0.31772(4) 0.2500 0.03020(16) Uani 1 2 d S . . Cl2 Cl 0.07653(3) 0.44972(5) 0.19334(5) 0.03857(17) Uani 1 1 d . . . N3 N 0.08940(12) 0.16779(15) 0.27955(18) 0.0354(4) Uani 1 1 d . . . C4 C 0.08073(16) 0.1043(2) 0.1867(2) 0.0452(6) Uani 1 1 d . . . H4 H 0.0367 0.1228 0.0999 0.054 Uiso 1 1 calc R . . C5 C 0.1335(2) 0.0127(2) 0.2125(3) 0.0544(7) Uani 1 1 d . . . H5 H 0.1248 -0.0316 0.1445 0.065 Uiso 1 1 calc R . . C6 C 0.19874(19) -0.0132(2) 0.3380(3) 0.0533(7) Uani 1 1 d . . . H6 H 0.2363 -0.0748 0.3575 0.064 Uiso 1 1 calc R . . C7 C 0.20899(16) 0.05209(19) 0.4359(2) 0.0424(5) Uani 1 1 d . . . H7 H 0.2535 0.0361 0.5233 0.051 Uiso 1 1 calc R . . C8 C 0.15243(14) 0.14120(17) 0.4025(2) 0.0332(4) Uani 1 1 d . . . C9 C 0.15617(13) 0.21269(17) 0.4984(2) 0.0316(4) Uani 1 1 d . . . N10 N 0.09567(12) 0.29244(15) 0.45528(17) 0.0331(4) Uani 1 1 d . . . N11 N 0.11238(12) 0.34247(16) 0.56318(18) 0.0353(4) Uani 1 1 d D . . H11 H 0.0824(19) 0.400(2) 0.560(3) 0.067(5) Uiso 1 1 d D . . C12 C 0.18132(14) 0.29510(19) 0.6714(2) 0.0355(5) Uani 1 1 d . . . C13 C 0.21151(14) 0.21040(18) 0.6323(2) 0.0345(4) Uani 1 1 d . . . H13 H 0.2593 0.1617 0.6851 0.041 Uiso 1 1 calc R . . N14 N 0.20710(16) 0.3273(2) 0.7899(2) 0.0485(5) Uani 1 1 d D . . C15 C 0.4290(3) 0.2109(4) 1.0862(3) 0.0822(12) Uani 1 1 d . . . H15A H 0.4826 0.2495 1.1124 0.123 Uiso 1 1 calc R . . H15B H 0.4423 0.1332 1.1163 0.123 Uiso 1 1 calc R . . H15C H 0.4028 0.2490 1.1235 0.123 Uiso 1 1 calc R . . O16 O 0.37197(16) 0.2123(2) 0.9551(2) 0.0714(6) Uani 1 1 d D . . H16 H 0.386(2) 0.172(3) 0.907(3) 0.067(5) Uiso 1 1 d D . . H14A H 0.1924(19) 0.3920(18) 0.791(3) 0.067(5) Uiso 1 1 d D . . H14B H 0.2583(14) 0.308(3) 0.850(3) 0.067(5) Uiso 1 1 d 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 Mn1 0.0307(3) 0.0297(2) 0.0275(2) 0.000 0.0155(2) 0.000 Cl2 0.0374(3) 0.0379(3) 0.0370(3) 0.0044(2) 0.0198(2) -0.0036(2) N3 0.0358(9) 0.0341(9) 0.0361(10) -0.0006(7) 0.0209(8) 0.0013(7) C4 0.0474(13) 0.0468(14) 0.0403(12) -0.0039(10) 0.0250(11) 0.0048(10) C5 0.0647(17) 0.0494(14) 0.0518(15) -0.0086(12) 0.0355(14) 0.0093(13) C6 0.0604(16) 0.0420(13) 0.0613(17) -0.0004(12) 0.0376(14) 0.0132(12) C7 0.0473(13) 0.0367(11) 0.0468(13) 0.0064(10) 0.0294(11) 0.0089(10) C8 0.0351(10) 0.0302(10) 0.0386(11) 0.0025(8) 0.0240(9) 0.0007(8) C9 0.0321(10) 0.0290(9) 0.0347(11) 0.0040(8) 0.0202(9) 0.0022(8) N10 0.0345(9) 0.0327(9) 0.0299(9) -0.0003(7) 0.0175(8) 0.0020(7) N11 0.0360(9) 0.0366(9) 0.0300(9) -0.0001(7) 0.0174(8) 0.0055(7) C12 0.0343(11) 0.0367(11) 0.0329(11) 0.0024(8) 0.0181(9) 0.0009(8) C13 0.0326(10) 0.0332(10) 0.0349(11) 0.0045(8) 0.0181(9) 0.0031(8) N14 0.0511(13) 0.0536(13) 0.0317(10) 0.0014(9) 0.0189(10) 0.0131(10) C15 0.071(2) 0.126(3) 0.0485(17) 0.0200(19) 0.0345(17) 0.038(2) O16 0.0667(14) 0.0868(16) 0.0487(12) 0.0023(11) 0.0270(11) 0.0193(12) _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 Mn1 N10 2.1802(18) . ? Mn1 N3 2.3395(18) . ? Mn1 Cl2 2.5203(6) . ? N3 C4 1.339(3) . ? N3 C8 1.349(3) . ? C4 C5 1.386(4) . ? C4 H4 0.9500 . ? C5 C6 1.377(4) . ? C5 H5 0.9500 . ? C6 C7 1.394(4) . ? C6 H6 0.9500 . ? C7 C8 1.389(3) . ? C7 H7 0.9500 . ? C8 C9 1.466(3) . ? C9 N10 1.337(3) . ? C9 C13 1.398(3) . ? N10 N11 1.366(3) . ? N11 C12 1.357(3) . ? N11 H11 0.875(18) . ? C12 N14 1.355(3) . ? C12 C13 1.392(3) . ? C13 H13 0.9500 . ? N14 H14A 0.825(17) . ? N14 H14B 0.844(17) . ? C15 O16 1.371(4) . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? O16 H16 0.934(18) . ? 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 N10 Mn1 N10 164.08(10) 2 . ? N10 Mn1 N3 95.94(7) . 2 ? N10 Mn1 N3 71.62(7) . . ? N3 Mn1 N3 80.13(9) 2 . ? N10 Mn1 Cl2 102.86(5) . . ? N3 Mn1 Cl2 92.34(5) . . ? N10 Mn1 Cl2 87.17(5) . 2 ? N3 Mn1 Cl2 156.44(5) . 2 ? Cl2 Mn1 Cl2 102.56(3) . 2 ? C4 N3 C8 118.24(19) . . ? C4 N3 Mn1 125.98(16) . . ? C8 N3 Mn1 115.70(14) . . ? N3 C4 C5 122.5(2) . . ? N3 C4 H4 118.8 . . ? C5 C4 H4 118.8 . . ? C6 C5 C4 119.2(2) . . ? C6 C5 H5 120.4 . . ? C4 C5 H5 120.4 . . ? C5 C6 C7 119.2(2) . . ? C5 C6 H6 120.4 . . ? C7 C6 H6 120.4 . . ? C8 C7 C6 118.2(2) . . ? C8 C7 H7 120.9 . . ? C6 C7 H7 120.9 . . ? N3 C8 C7 122.7(2) . . ? N3 C8 C9 114.94(18) . . ? C7 C8 C9 122.4(2) . . ? N10 C9 C13 111.74(19) . . ? N10 C9 C8 117.22(18) . . ? C13 C9 C8 130.99(19) . . ? C9 N10 N11 104.84(17) . . ? C9 N10 Mn1 120.46(14) . . ? N11 N10 Mn1 134.69(14) . . ? C12 N11 N10 111.80(18) . . ? C12 N11 H11 126(2) . . ? N10 N11 H11 122(2) . . ? N14 C12 N11 122.2(2) . . ? N14 C12 C13 131.0(2) . . ? N11 C12 C13 106.69(19) . . ? C12 C13 C9 104.93(19) . . ? C12 C13 H13 127.5 . . ? C9 C13 H13 127.5 . . ? C12 N14 H14A 112(2) . . ? C12 N14 H14B 115(2) . . ? H14A N14 H14B 117(3) . . ? O16 C15 H15A 109.5 . . ? O16 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? O16 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C15 O16 H16 118(2) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N11 H11 Cl2 0.875(18) 2.53(2) 3.2771(19) 144(3) 6_566 N14 H14A Cl2 0.825(17) 2.600(19) 3.344(2) 151(3) 6_566 N14 H14B O16 0.844(17) 2.096(18) 2.902(3) 159(3) . O16 H16 Cl2 0.934(18) 2.312(19) 3.240(3) 172(3) 7_556 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.53 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 1.013 _refine_diff_density_min -0.398 _refine_diff_density_rms 0.067 #=END data_c:\datasets\leeds\lfj1a\lfj1a _database_code_depnum_ccdc_archive 'CCDC 613019' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Dichloro-bis[5-amino-3-(pyrid-2-yl)pyrazole]iron(III) chloride tetrakis-methanol solvate (2.4CH~3~OH) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H16 Cl2 Fe N8, Cl, 4[C H4 O]' _chemical_formula_sum 'C20 H32 Cl3 Fe N8 O4' _chemical_formula_weight 610.74 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' Fe Fe 0.3463 0.8444 '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' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.7275(2) _cell_length_b 11.6620(2) _cell_length_c 11.9305(2) _cell_angle_alpha 95.9291(6) _cell_angle_beta 96.0695(6) _cell_angle_gamma 110.0749(10) _cell_volume 1378.35(4) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 31506 _cell_measurement_theta_min 2.36 _cell_measurement_theta_max 27.30 _exptl_crystal_description Plate _exptl_crystal_colour Purple _exptl_crystal_size_max 0.66 _exptl_crystal_size_mid 0.33 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.472 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 634 _exptl_absorpt_coefficient_mu 0.879 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.719 _exptl_absorpt_correction_T_max 0.910 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 31506 _diffrn_reflns_av_R_equivalents 0.0881 _diffrn_reflns_av_sigmaI/netI 0.0547 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.36 _diffrn_reflns_theta_max 27.30 _reflns_number_total 6159 _reflns_number_gt 4977 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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. No disorder was detected during refinement, and all non-H atoms were refined anisotropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The N---H and O---H H atoms were all located in the difference map and refined, with a common U~iso~ thermal parameter of 0.046(2)\%A^2^, and the refined restraints N---H = 0.89(2)\%A, O---H = 0.81(2)\%A and the primary amino H...H = 1.45(2)\%A. ; _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^)+(0.0487P)^2^+0.3402P] 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 6159 _refine_ls_number_parameters 362 _refine_ls_number_restraints 12 _refine_ls_R_factor_all 0.0522 _refine_ls_R_factor_gt 0.0360 _refine_ls_wR_factor_ref 0.0974 _refine_ls_wR_factor_gt 0.0895 _refine_ls_goodness_of_fit_ref 1.022 _refine_ls_restrained_S_all 1.022 _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 Fe1 Fe 0.14195(3) 0.01023(2) 0.30323(2) 0.01978(9) Uani 1 1 d . . . Cl2 Cl 0.23913(4) 0.18422(4) 0.44061(4) 0.02390(12) Uani 1 1 d . . . Cl3 Cl -0.07848(4) -0.01174(4) 0.30596(4) 0.02541(12) Uani 1 1 d . . . N4 N 0.33842(15) -0.01822(14) 0.31115(14) 0.0224(3) Uani 1 1 d . . . C5 C 0.44501(19) 0.04438(18) 0.26381(18) 0.0261(4) Uani 1 1 d . . . H5 H 0.4367 0.1029 0.2166 0.031 Uiso 1 1 calc R . . C6 C 0.5664(2) 0.02668(19) 0.28133(19) 0.0294(5) Uani 1 1 d . . . H6 H 0.6400 0.0722 0.2466 0.035 Uiso 1 1 calc R . . C7 C 0.5789(2) -0.05855(19) 0.35038(19) 0.0294(5) Uani 1 1 d . . . H7 H 0.6617 -0.0711 0.3649 0.035 Uiso 1 1 calc R . . C8 C 0.4689(2) -0.12520(18) 0.39790(19) 0.0271(4) Uani 1 1 d . . . H8 H 0.4746 -0.1853 0.4442 0.032 Uiso 1 1 calc R . . C9 C 0.35057(19) -0.10277(17) 0.37676(17) 0.0231(4) Uani 1 1 d . . . C10 C 0.22987(18) -0.16392(17) 0.42597(17) 0.0220(4) Uani 1 1 d . . . N11 N 0.12722(15) -0.12404(14) 0.40239(14) 0.0219(3) Uani 1 1 d . . . N12 N 0.02764(16) -0.19183(15) 0.45764(15) 0.0233(4) Uani 1 1 d D . . H12 H -0.044(2) -0.174(2) 0.467(2) 0.046(2) Uiso 1 1 d D . . C13 C 0.0682(2) -0.26857(18) 0.51670(18) 0.0266(4) Uani 1 1 d . . . C14 C 0.1986(2) -0.25384(18) 0.49583(18) 0.0275(4) Uani 1 1 d . . . H14 H 0.2536 -0.2966 0.5238 0.033 Uiso 1 1 calc R . . N15 N -0.0100(2) -0.34338(19) 0.57995(19) 0.0382(5) Uani 1 1 d D . . H15A H -0.081(2) -0.333(2) 0.596(2) 0.046(2) Uiso 1 1 d D . . H15B H 0.027(2) -0.384(2) 0.622(2) 0.046(2) Uiso 1 1 d D . . N16 N 0.08675(15) -0.12304(14) 0.14600(14) 0.0223(3) Uani 1 1 d . . . C17 C 0.02508(19) -0.24573(18) 0.13803(19) 0.0263(4) Uani 1 1 d . . . H17 H 0.0008 -0.2800 0.2049 0.032 Uiso 1 1 calc R . . C18 C -0.0044(2) -0.32424(19) 0.03533(19) 0.0294(5) Uani 1 1 d . . . H18 H -0.0482 -0.4107 0.0322 0.035 Uiso 1 1 calc R . . C19 C 0.0308(2) -0.27503(19) -0.0624(2) 0.0312(5) Uani 1 1 d . . . H19 H 0.0128 -0.3274 -0.1332 0.037 Uiso 1 1 calc R . . C20 C 0.09286(19) -0.14773(18) -0.05551(18) 0.0263(4) Uani 1 1 d . . . H20 H 0.1169 -0.1117 -0.1216 0.032 Uiso 1 1 calc R . . C21 C 0.11894(18) -0.07472(17) 0.04948(17) 0.0220(4) Uani 1 1 d . . . C22 C 0.18227(18) 0.06026(17) 0.06860(17) 0.0218(4) Uani 1 1 d . . . N23 N 0.19407(16) 0.11504(14) 0.17591(14) 0.0219(3) Uani 1 1 d . . . N24 N 0.26064(16) 0.23810(15) 0.17524(14) 0.0222(3) Uani 1 1 d D . . H24 H 0.267(3) 0.296(2) 0.234(2) 0.046(2) Uiso 1 1 d D . . C25 C 0.28806(19) 0.25987(18) 0.06978(17) 0.0231(4) Uani 1 1 d . . . C26 C 0.23811(19) 0.14622(18) -0.00164(17) 0.0244(4) Uani 1 1 d . . . H26 H 0.2416 0.1310 -0.0808 0.029 Uiso 1 1 calc R . . N27 N 0.34972(19) 0.37685(16) 0.04883(16) 0.0298(4) Uani 1 1 d D . . H27A H 0.415(2) 0.425(2) 0.1024(18) 0.046(2) Uiso 1 1 d D . . H27B H 0.364(2) 0.388(2) -0.0206(16) 0.046(2) Uiso 1 1 d D . . Cl28 Cl 0.15434(6) -0.48100(5) 0.74131(5) 0.03739(14) Uani 1 1 d . . . C29 C 0.2349(2) 0.5407(2) 0.2548(2) 0.0392(5) Uani 1 1 d . . . H29A H 0.1509 0.5454 0.2765 0.059 Uiso 1 1 calc R . . H29B H 0.2234 0.5172 0.1721 0.059 Uiso 1 1 calc R . . H29C H 0.3069 0.6215 0.2775 0.059 Uiso 1 1 calc R . . O30 O 0.26890(17) 0.45071(15) 0.31077(15) 0.0378(4) Uani 1 1 d D . . H30 H 0.289(3) 0.471(2) 0.3784(18) 0.046(2) Uiso 1 1 d D . . C31 C 0.4469(2) 0.6041(2) 0.5954(2) 0.0382(5) Uani 1 1 d . . . H31A H 0.5087 0.6252 0.5396 0.057 Uiso 1 1 calc R . . H31B H 0.4819 0.5642 0.6530 0.057 Uiso 1 1 calc R . . H31C H 0.4382 0.6794 0.6325 0.057 Uiso 1 1 calc R . . O32 O 0.31953(15) 0.52240(14) 0.53953(14) 0.0346(4) Uani 1 1 d D . . H32 H 0.261(2) 0.513(2) 0.582(2) 0.046(2) Uiso 1 1 d D . . C33 C 0.6273(3) 0.6702(2) 0.2584(2) 0.0420(6) Uani 1 1 d . . . H33A H 0.6139 0.6456 0.3336 0.063 Uiso 1 1 calc R . . H33B H 0.5633 0.7094 0.2348 0.063 Uiso 1 1 calc R . . H33C H 0.7191 0.7288 0.2623 0.063 Uiso 1 1 calc R . . O34 O 0.60649(15) 0.56446(14) 0.17817(13) 0.0317(3) Uani 1 1 d D . . H34 H 0.665(2) 0.539(2) 0.192(2) 0.046(2) Uiso 1 1 d D . . C35 C 0.6134(3) 0.2492(3) -0.0011(3) 0.0650(8) Uani 1 1 d . . . H35A H 0.6075 0.3294 -0.0124 0.097 Uiso 1 1 calc R . . H35B H 0.5339 0.1829 -0.0440 0.097 Uiso 1 1 calc R . . H35C H 0.6943 0.2429 -0.0282 0.097 Uiso 1 1 calc R . . O36 O 0.6200(2) 0.2386(2) 0.1146(2) 0.0702(6) Uani 1 1 d D . . H36 H 0.681(2) 0.300(2) 0.147(2) 0.046(2) Uiso 1 1 d 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 Fe1 0.01916(15) 0.02052(15) 0.02001(16) 0.00445(11) 0.00338(11) 0.00702(11) Cl2 0.0233(2) 0.0236(2) 0.0232(2) 0.00146(19) 0.00334(19) 0.00700(19) Cl3 0.0194(2) 0.0302(3) 0.0268(3) 0.0053(2) 0.00413(19) 0.00871(19) N4 0.0210(8) 0.0217(8) 0.0241(9) 0.0020(7) 0.0034(7) 0.0075(7) C5 0.0249(10) 0.0246(10) 0.0285(11) 0.0056(8) 0.0055(8) 0.0076(8) C6 0.0221(10) 0.0297(11) 0.0349(12) 0.0040(9) 0.0086(9) 0.0063(8) C7 0.0233(10) 0.0324(11) 0.0330(12) 0.0006(9) 0.0037(9) 0.0119(9) C8 0.0261(10) 0.0254(10) 0.0312(11) 0.0034(9) 0.0025(9) 0.0118(8) C9 0.0224(9) 0.0203(9) 0.0257(10) 0.0017(8) 0.0038(8) 0.0070(8) C10 0.0209(9) 0.0209(9) 0.0245(10) 0.0020(8) 0.0041(8) 0.0080(8) N11 0.0193(8) 0.0226(8) 0.0239(9) 0.0054(7) 0.0045(7) 0.0069(6) N12 0.0211(8) 0.0257(9) 0.0272(9) 0.0099(7) 0.0087(7) 0.0102(7) C13 0.0298(10) 0.0231(10) 0.0273(11) 0.0062(8) 0.0062(9) 0.0088(8) C14 0.0273(10) 0.0274(11) 0.0321(12) 0.0085(9) 0.0051(9) 0.0139(9) N15 0.0358(10) 0.0432(12) 0.0487(13) 0.0281(10) 0.0202(10) 0.0205(9) N16 0.0211(8) 0.0215(8) 0.0243(9) 0.0036(7) 0.0025(7) 0.0077(7) C17 0.0250(10) 0.0234(10) 0.0296(11) 0.0049(8) 0.0052(8) 0.0070(8) C18 0.0280(10) 0.0202(10) 0.0379(12) 0.0009(9) 0.0035(9) 0.0072(8) C19 0.0303(11) 0.0281(11) 0.0326(12) -0.0028(9) 0.0027(9) 0.0098(9) C20 0.0251(10) 0.0263(10) 0.0271(11) 0.0027(8) 0.0047(8) 0.0088(8) C21 0.0195(9) 0.0237(10) 0.0234(10) 0.0041(8) 0.0024(8) 0.0085(8) C22 0.0193(9) 0.0230(10) 0.0227(10) 0.0021(8) 0.0022(8) 0.0079(8) N23 0.0232(8) 0.0194(8) 0.0225(9) 0.0041(7) 0.0038(7) 0.0066(6) N24 0.0252(8) 0.0179(8) 0.0218(9) 0.0033(7) 0.0044(7) 0.0050(7) C25 0.0216(9) 0.0255(10) 0.0230(10) 0.0071(8) 0.0030(8) 0.0084(8) C26 0.0255(10) 0.0270(10) 0.0202(10) 0.0043(8) 0.0046(8) 0.0084(8) N27 0.0355(10) 0.0248(9) 0.0252(10) 0.0077(8) 0.0059(8) 0.0043(8) Cl28 0.0366(3) 0.0421(3) 0.0383(3) 0.0116(3) 0.0086(2) 0.0178(2) C29 0.0393(13) 0.0307(12) 0.0441(14) 0.0000(10) 0.0073(11) 0.0095(10) O30 0.0470(10) 0.0367(9) 0.0311(9) -0.0011(7) 0.0031(8) 0.0193(8) C31 0.0300(11) 0.0384(13) 0.0455(14) 0.0122(11) 0.0044(10) 0.0102(10) O32 0.0314(8) 0.0375(9) 0.0340(9) 0.0049(7) 0.0061(7) 0.0109(7) C33 0.0566(15) 0.0304(12) 0.0361(13) -0.0014(10) 0.0020(11) 0.0153(11) O34 0.0359(8) 0.0307(8) 0.0283(8) 0.0024(6) 0.0017(7) 0.0133(7) C35 0.0548(17) 0.092(2) 0.0528(19) 0.0117(17) 0.0082(15) 0.0326(17) O36 0.0764(15) 0.0568(13) 0.0533(14) 0.0141(11) 0.0077(12) -0.0076(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 Fe1 N11 2.0319(16) . ? Fe1 N23 2.0513(16) . ? Fe1 N16 2.1946(16) . ? Fe1 N4 2.2373(15) . ? Fe1 Cl3 2.2935(5) . ? Fe1 Cl2 2.3216(5) . ? N4 C5 1.345(3) . ? N4 C9 1.352(2) . ? C5 C6 1.385(3) . ? C5 H5 0.9500 . ? C6 C7 1.386(3) . ? C6 H6 0.9500 . ? C7 C8 1.386(3) . ? C7 H7 0.9500 . ? C8 C9 1.385(3) . ? C8 H8 0.9500 . ? C9 C10 1.464(3) . ? C10 N11 1.350(2) . ? C10 C14 1.380(3) . ? N11 N12 1.370(2) . ? N12 C13 1.349(3) . ? N12 H12 0.876(18) . ? C13 N15 1.342(3) . ? C13 C14 1.402(3) . ? C14 H14 0.9500 . ? N15 H15A 0.853(18) . ? N15 H15B 0.878(18) . ? N16 C17 1.343(2) . ? N16 C21 1.359(3) . ? C17 C18 1.388(3) . ? C17 H17 0.9500 . ? C18 C19 1.383(3) . ? C18 H18 0.9500 . ? C19 C20 1.392(3) . ? C19 H19 0.9500 . ? C20 C21 1.384(3) . ? C20 H20 0.9500 . ? C21 C22 1.466(3) . ? C22 N23 1.343(3) . ? C22 C26 1.390(3) . ? N23 N24 1.367(2) . ? N24 C25 1.352(3) . ? N24 H24 0.899(19) . ? C25 N27 1.359(3) . ? C25 C26 1.397(3) . ? C26 H26 0.9500 . ? N27 H27A 0.880(18) . ? N27 H27B 0.872(18) . ? C29 O30 1.427(3) . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? O30 H30 0.80(2) . ? C31 O32 1.415(3) . ? C31 H31A 0.9800 . ? C31 H31B 0.9800 . ? C31 H31C 0.9800 . ? O32 H32 0.83(2) . ? C33 O34 1.417(3) . ? C33 H33A 0.9800 . ? C33 H33B 0.9800 . ? C33 H33C 0.9800 . ? O34 H34 0.79(2) . ? C35 O36 1.395(4) . ? C35 H35A 0.9800 . ? C35 H35B 0.9800 . ? C35 H35C 0.9800 . ? O36 H36 0.81(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 N11 Fe1 N23 160.24(6) . . ? N11 Fe1 N16 92.12(6) . . ? N23 Fe1 N16 74.88(6) . . ? N11 Fe1 N4 74.60(6) . . ? N23 Fe1 N4 89.03(6) . . ? N16 Fe1 N4 83.89(6) . . ? N11 Fe1 Cl3 91.71(5) . . ? N23 Fe1 Cl3 103.14(5) . . ? N16 Fe1 Cl3 90.99(4) . . ? N4 Fe1 Cl3 165.13(4) . . ? N11 Fe1 Cl2 99.99(5) . . ? N23 Fe1 Cl2 90.86(5) . . ? N16 Fe1 Cl2 164.57(5) . . ? N4 Fe1 Cl2 90.11(4) . . ? Cl3 Fe1 Cl2 98.103(19) . . ? C5 N4 C9 118.30(16) . . ? C5 N4 Fe1 126.85(13) . . ? C9 N4 Fe1 114.71(12) . . ? N4 C5 C6 122.47(19) . . ? N4 C5 H5 118.8 . . ? C6 C5 H5 118.8 . . ? C5 C6 C7 118.88(19) . . ? C5 C6 H6 120.6 . . ? C7 C6 H6 120.6 . . ? C8 C7 C6 119.12(18) . . ? C8 C7 H7 120.4 . . ? C6 C7 H7 120.4 . . ? C9 C8 C7 118.91(19) . . ? C9 C8 H8 120.5 . . ? C7 C8 H8 120.5 . . ? N4 C9 C8 122.30(18) . . ? N4 C9 C10 113.98(16) . . ? C8 C9 C10 123.69(18) . . ? N11 C10 C14 111.36(17) . . ? N11 C10 C9 115.38(17) . . ? C14 C10 C9 133.23(17) . . ? C10 N11 N12 105.21(15) . . ? C10 N11 Fe1 121.27(13) . . ? N12 N11 Fe1 133.53(12) . . ? C13 N12 N11 111.08(15) . . ? C13 N12 H12 124.5(18) . . ? N11 N12 H12 122.7(18) . . ? N15 C13 N12 122.80(19) . . ? N15 C13 C14 130.12(19) . . ? N12 C13 C14 107.07(17) . . ? C10 C14 C13 105.23(17) . . ? C10 C14 H14 127.4 . . ? C13 C14 H14 127.4 . . ? C13 N15 H15A 120.0(17) . . ? C13 N15 H15B 117.2(16) . . ? H15A N15 H15B 120(2) . . ? C17 N16 C21 118.45(17) . . ? C17 N16 Fe1 125.73(14) . . ? C21 N16 Fe1 115.82(12) . . ? N16 C17 C18 122.22(19) . . ? N16 C17 H17 118.9 . . ? C18 C17 H17 118.9 . . ? C19 C18 C17 119.19(19) . . ? C19 C18 H18 120.4 . . ? C17 C18 H18 120.4 . . ? C18 C19 C20 119.1(2) . . ? C18 C19 H19 120.4 . . ? C20 C19 H19 120.4 . . ? C21 C20 C19 118.7(2) . . ? C21 C20 H20 120.6 . . ? C19 C20 H20 120.6 . . ? N16 C21 C20 122.28(18) . . ? N16 C21 C22 113.33(17) . . ? C20 C21 C22 124.39(18) . . ? N23 C22 C26 111.31(17) . . ? N23 C22 C21 115.50(17) . . ? C26 C22 C21 133.16(19) . . ? C22 N23 N24 105.54(16) . . ? C22 N23 Fe1 120.19(13) . . ? N24 N23 Fe1 133.53(13) . . ? C25 N24 N23 110.90(16) . . ? C25 N24 H24 125.4(17) . . ? N23 N24 H24 122.3(17) . . ? N24 C25 N27 120.76(18) . . ? N24 C25 C26 107.37(17) . . ? N27 C25 C26 131.83(19) . . ? C22 C26 C25 104.87(17) . . ? C22 C26 H26 127.6 . . ? C25 C26 H26 127.6 . . ? C25 N27 H27A 115.4(17) . . ? C25 N27 H27B 118.3(17) . . ? H27A N27 H27B 115(2) . . ? O30 C29 H29A 109.5 . . ? O30 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? O30 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? C29 O30 H30 113(2) . . ? O32 C31 H31A 109.5 . . ? O32 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? O32 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? C31 O32 H32 112.1(19) . . ? O34 C33 H33A 109.5 . . ? O34 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? O34 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? C33 O34 H34 109(2) . . ? O36 C35 H35A 109.5 . . ? O36 C35 H35B 109.5 . . ? H35A C35 H35B 109.5 . . ? O36 C35 H35C 109.5 . . ? H35A C35 H35C 109.5 . . ? H35B C35 H35C 109.5 . . ? C35 O36 H36 106(2) . . ? 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 N12 H12 Cl2 0.876(18) 2.45(2) 3.2493(17) 153(2) 2_556 N15 H15A Cl2 0.853(18) 2.84(2) 3.556(2) 142(2) 2_556 N15 H15A O30 0.853(18) 2.46(2) 3.114(3) 134(2) 2_556 N15 H15B Cl28 0.878(18) 2.480(18) 3.355(2) 174(2) . N24 H24 O30 0.899(19) 1.93(2) 2.786(2) 158(2) . N27 H27A O34 0.880(18) 2.17(2) 3.004(2) 159(2) . N27 H27B O34 0.872(18) 2.042(19) 2.908(2) 172(2) 2_665 O30 H30 O32 0.80(2) 1.91(2) 2.710(2) 173(3) . O32 H32 Cl28 0.83(2) 2.33(2) 3.1322(17) 162(3) 1_565 O34 H34 Cl28 0.79(2) 2.35(2) 3.1368(16) 172(3) 2_656 O36 H36 Cl28 0.81(2) 2.39(2) 3.197(2) 173(3) 2_656 _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 27.30 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.395 _refine_diff_density_min -0.582 _refine_diff_density_rms 0.104 #=END data_c:\datasets\leeds\lfj22b\lfj22b _database_code_depnum_ccdc_archive 'CCDC 613020' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[5-amino-3-(pyrid-2-yl)pyrazole]copper(II) diperchlorate methanol solvate (3.CH~3~OH) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H16 Cu N8, 2[Cl O4], C H4 O' _chemical_formula_sum 'C17 H20 Cl2 Cu N8 O9' _chemical_formula_weight 614.85 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 'P 21/c' 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 7.2901(3) _cell_length_b 28.8637(8) _cell_length_c 11.8758(6) _cell_angle_alpha 90.00 _cell_angle_beta 107.874(2) _cell_angle_gamma 90.00 _cell_volume 2378.28(17) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 23842 _cell_measurement_theta_min 1.41 _cell_measurement_theta_max 27.45 _exptl_crystal_description Block _exptl_crystal_colour Green _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.717 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1252 _exptl_absorpt_coefficient_mu 1.210 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.733 _exptl_absorpt_correction_T_max 0.965 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 23842 _diffrn_reflns_av_R_equivalents 0.1019 _diffrn_reflns_av_sigmaI/netI 0.0590 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -37 _diffrn_reflns_limit_k_max 37 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.41 _diffrn_reflns_theta_max 27.45 _reflns_number_total 5378 _reflns_number_gt 3867 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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. Both perchlorate anions, and the methanol solvent molecule, are disordered. Anion Cl26-O30 was refined over two sites labelled 'A' and 'B', with refined occupancies of 0.78:0.22. Similarly, Anion Cl31-O35 was refined in two orientations 'A' and 'B' with refined occupancies of 0.62:0.38. The refined restraints Cl---O = 1.42(2)\%A and O...O = 2.32(2)\%A were applied to these partial anions. The occupancies of the two, 'A' and 'B' orientations of the methanol molecule C36 and O37 refined to 0.51:0.49, so these were modelled as equally occupied using the restraint C---O = 1.43(2)\%A. All non-H atoms, except for the minor perchlorate anion disorder sites, were refined anisotropically. All C-bound H atoms and the partial methanol hydroxyl H atoms were placed in calculated positions and refined using a riding model. The N---H H atoms were all located in the difference map and refined, with a common U~iso~ thermal parameter of 0.089(7)\%A^2^, and the refined restraints N---H = 0.98(1)\%A and primary amino H...H = 1.60(2)\%A. ; _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^)+(0.0774P)^2^+2.2278P] 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 5378 _refine_ls_number_parameters 417 _refine_ls_number_restraints 50 _refine_ls_R_factor_all 0.0852 _refine_ls_R_factor_gt 0.0583 _refine_ls_wR_factor_ref 0.1682 _refine_ls_wR_factor_gt 0.1531 _refine_ls_goodness_of_fit_ref 1.047 _refine_ls_restrained_S_all 1.050 _refine_ls_shift/su_max 0.001 _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 0.26611(7) 0.623250(16) 0.46941(4) 0.04633(18) Uani 1 1 d . . . N2 N 0.2615(5) 0.56862(12) 0.3630(3) 0.0495(8) Uani 1 1 d . . . C3 C 0.2746(6) 0.56961(16) 0.2531(4) 0.0567(10) Uani 1 1 d . . . H3 H 0.2848 0.5987 0.2182 0.068 Uiso 1 1 calc R C . C4 C 0.2739(7) 0.52951(19) 0.1884(4) 0.0678(13) Uani 1 1 d . . . H4 H 0.2817 0.5311 0.1101 0.081 Uiso 1 1 calc R . . C5 C 0.2616(7) 0.48750(19) 0.2398(5) 0.0704(13) Uani 1 1 d . . . H5 H 0.2581 0.4597 0.1965 0.085 Uiso 1 1 calc R C . C6 C 0.2542(6) 0.48583(16) 0.3535(4) 0.0604(11) Uani 1 1 d . . . H6 H 0.2484 0.4569 0.3906 0.072 Uiso 1 1 calc R . . C7 C 0.2554(5) 0.52721(14) 0.4139(4) 0.0480(9) Uani 1 1 d . . . C8 C 0.2542(5) 0.53008(14) 0.5358(3) 0.0457(9) Uani 1 1 d . C . N9 N 0.2744(5) 0.57277(11) 0.5822(3) 0.0464(7) Uani 1 1 d . C . N10 N 0.2700(5) 0.56826(12) 0.6960(3) 0.0512(8) Uani 1 1 d D . . H10 H 0.253(8) 0.5950(13) 0.742(4) 0.089(7) Uiso 1 1 d D . . C11 C 0.2505(6) 0.52300(16) 0.7207(4) 0.0552(10) Uani 1 1 d . . . C12 C 0.2385(5) 0.49741(15) 0.6183(4) 0.0558(10) Uani 1 1 d . . . H12 H 0.2230 0.4649 0.6077 0.067 Uiso 1 1 calc R C . N13 N 0.2350(6) 0.51013(16) 0.8280(4) 0.0706(11) Uani 1 1 d D . . H13A H 0.322(7) 0.5256(13) 0.897(3) 0.089(7) Uiso 1 1 d D . . H13B H 0.250(7) 0.4766(8) 0.840(4) 0.089(7) Uiso 1 1 d D . . N14 N 0.3612(4) 0.67959(11) 0.5704(3) 0.0448(7) Uani 1 1 d . . . C15 C 0.4732(6) 0.68099(15) 0.6835(3) 0.0502(9) Uani 1 1 d . . . H15 H 0.5023 0.6531 0.7278 0.060 Uiso 1 1 calc R C . C16 C 0.5470(6) 0.72241(15) 0.7367(4) 0.0528(10) Uani 1 1 d . . . H16 H 0.6263 0.7229 0.8168 0.063 Uiso 1 1 calc R . . C17 C 0.5057(6) 0.76269(17) 0.6737(4) 0.0599(11) Uani 1 1 d . . . H17 H 0.5539 0.7913 0.7106 0.072 Uiso 1 1 calc R C . C18 C 0.3948(6) 0.76203(15) 0.5571(4) 0.0541(10) Uani 1 1 d . . . H18 H 0.3686 0.7897 0.5114 0.065 Uiso 1 1 calc R . . C19 C 0.3229(5) 0.72003(13) 0.5085(4) 0.0468(9) Uani 1 1 d . . . C20 C 0.2060(5) 0.71468(13) 0.3857(4) 0.0448(8) Uani 1 1 d . C . N21 N 0.1666(5) 0.67119(11) 0.3500(3) 0.0479(8) Uani 1 1 d . C . N22 N 0.0523(5) 0.67310(12) 0.2343(3) 0.0528(8) Uani 1 1 d D . . H22 H -0.031(7) 0.6467(13) 0.204(4) 0.089(7) Uiso 1 1 d D . . C23 C 0.0197(5) 0.71775(14) 0.1980(3) 0.0490(9) Uani 1 1 d . . . C24 C 0.1193(6) 0.74543(14) 0.2928(4) 0.0514(9) Uani 1 1 d . . . H24 H 0.1271 0.7783 0.2945 0.062 Uiso 1 1 calc R C . N25 N -0.0833(6) 0.72831(15) 0.0842(3) 0.0636(10) Uani 1 1 d D . . H25B H -0.123(6) 0.7597(9) 0.059(4) 0.089(7) Uiso 1 1 d D . . H25A H -0.188(5) 0.7066(13) 0.051(4) 0.089(7) Uiso 1 1 d D . . Cl26A Cl 0.6339(2) 0.60710(5) 1.03163(13) 0.0477(4) Uani 0.78 1 d PD A 1 O27A O 0.4922(9) 0.61970(19) 1.0871(5) 0.1004(18) Uani 0.78 1 d PD A 1 O28A O 0.6582(7) 0.64619(18) 0.9657(5) 0.0862(14) Uani 0.78 1 d PD A 1 O29A O 0.5690(9) 0.56756(16) 0.9630(5) 0.0997(18) Uani 0.78 1 d PD A 1 O30A O 0.8099(11) 0.5969(3) 1.1225(8) 0.117(4) Uani 0.78 1 d PD A 1 Cl26B Cl 0.645(3) 0.6051(7) 1.0270(16) 0.186(8) Uiso 0.22 1 d PD B 2 O27B O 0.491(3) 0.5784(9) 1.044(2) 0.162(11) Uiso 0.22 1 d PD B 2 O28B O 0.610(3) 0.6525(6) 1.040(2) 0.128(8) Uiso 0.22 1 d PD B 2 O29B O 0.642(3) 0.5984(8) 0.9056(15) 0.117(7) Uiso 0.22 1 d PD B 2 O30B O 0.823(3) 0.5914(10) 1.1055(19) 0.063(6) Uiso 0.22 1 d PD B 2 Cl31A Cl -0.2297(9) 0.6421(2) 0.4768(5) 0.0529(16) Uani 0.62 1 d PD C 1 O32A O -0.3318(10) 0.6806(2) 0.4169(6) 0.096(3) Uani 0.62 1 d PD C 1 O33A O -0.1339(9) 0.61590(19) 0.4086(6) 0.0663(15) Uani 0.62 1 d PD C 1 O34A O -0.3492(7) 0.61466(15) 0.5230(6) 0.0581(13) Uani 0.62 1 d PD C 1 O35A O -0.0709(9) 0.6621(3) 0.5735(6) 0.092(2) Uani 0.62 1 d PD C 1 Cl31B Cl -0.2184(14) 0.6456(3) 0.4817(6) 0.0336(16) Uiso 0.38 1 d PD C 2 O32B O -0.244(2) 0.6852(4) 0.4142(13) 0.115(6) Uiso 0.38 1 d PD C 2 O33B O -0.0834(15) 0.6143(4) 0.4673(9) 0.074(4) Uiso 0.38 1 d PD C 2 O34B O -0.3990(16) 0.6216(4) 0.4536(12) 0.107(5) Uiso 0.38 1 d PD C 2 O35B O -0.165(2) 0.6589(5) 0.6034(10) 0.122(5) Uiso 0.38 1 d PD C 2 C36A C 0.010(3) 0.6332(12) 0.871(3) 0.097(10) Uani 0.50 1 d PD D 1 H36A H -0.0161 0.6616 0.9092 0.146 Uiso 0.50 1 calc PR D 1 H36B H 0.0109 0.6066 0.9228 0.146 Uiso 0.50 1 calc PR D 1 H36C H -0.0900 0.6289 0.7954 0.146 Uiso 0.50 1 calc PR D 1 O37A O 0.1952(15) 0.6370(3) 0.8522(8) 0.069(2) Uani 0.50 1 d PD D 1 H37A H 0.2826 0.6311 0.9154 0.083 Uiso 0.50 1 calc PR D 1 C36B C 0.059(3) 0.6266(10) 0.883(2) 0.066(4) Uani 0.50 1 d PD E 2 H36D H 0.1383 0.6398 0.9584 0.099 Uiso 0.50 1 calc PR E 2 H36E H 0.0558 0.5928 0.8903 0.099 Uiso 0.50 1 calc PR E 2 H36F H -0.0721 0.6389 0.8636 0.099 Uiso 0.50 1 calc PR E 2 O37B O 0.1403(14) 0.6385(4) 0.7920(8) 0.067(2) Uani 0.50 1 d PD E 2 H37B H 0.0604 0.6543 0.7400 0.080 Uiso 0.50 1 calc PR E 2 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 0.0521(3) 0.0396(3) 0.0447(3) 0.0055(2) 0.0110(2) -0.0022(2) N2 0.0468(18) 0.0486(19) 0.0498(18) 0.0042(15) 0.0101(15) 0.0030(14) C3 0.057(2) 0.062(3) 0.051(2) 0.006(2) 0.0174(19) 0.010(2) C4 0.058(3) 0.085(4) 0.059(3) -0.011(3) 0.015(2) 0.006(2) C5 0.055(3) 0.076(3) 0.076(3) -0.025(3) 0.015(2) -0.004(2) C6 0.040(2) 0.056(3) 0.080(3) -0.013(2) 0.011(2) -0.0036(18) C7 0.0317(17) 0.047(2) 0.059(2) -0.0016(19) 0.0045(16) -0.0015(16) C8 0.0351(18) 0.044(2) 0.051(2) 0.0069(17) 0.0030(16) -0.0042(15) N9 0.0514(18) 0.0451(18) 0.0407(16) 0.0053(14) 0.0109(14) -0.0040(14) N10 0.0527(19) 0.054(2) 0.0434(17) 0.0088(15) 0.0096(15) -0.0079(16) C11 0.0374(19) 0.063(3) 0.058(2) 0.018(2) 0.0048(17) -0.0064(19) C12 0.039(2) 0.048(2) 0.071(3) 0.009(2) 0.0032(18) -0.0043(17) N13 0.065(2) 0.082(3) 0.064(2) 0.024(2) 0.0188(19) -0.003(2) N14 0.0376(15) 0.0466(18) 0.0499(17) 0.0018(14) 0.0132(13) -0.0004(13) C15 0.047(2) 0.052(2) 0.052(2) 0.0009(18) 0.0158(17) -0.0007(18) C16 0.049(2) 0.061(3) 0.048(2) -0.0043(19) 0.0143(18) -0.0053(19) C17 0.057(2) 0.063(3) 0.062(3) -0.005(2) 0.022(2) -0.005(2) C18 0.052(2) 0.052(2) 0.062(2) -0.002(2) 0.023(2) -0.0044(19) C19 0.0383(18) 0.041(2) 0.066(2) -0.0011(18) 0.0239(17) -0.0030(16) C20 0.0353(18) 0.043(2) 0.059(2) 0.0065(17) 0.0180(16) -0.0018(15) N21 0.0459(17) 0.0471(18) 0.0481(17) 0.0101(15) 0.0105(14) -0.0002(14) N22 0.0480(18) 0.051(2) 0.0513(18) 0.0058(16) 0.0031(15) -0.0018(15) C23 0.042(2) 0.053(2) 0.051(2) 0.0131(18) 0.0136(17) 0.0064(17) C24 0.053(2) 0.043(2) 0.062(2) 0.0066(19) 0.0238(19) 0.0013(18) N25 0.063(2) 0.067(2) 0.055(2) 0.0095(19) 0.0093(17) 0.0078(19) Cl26A 0.0517(7) 0.0436(7) 0.0412(6) -0.0025(5) 0.0045(5) -0.0063(5) O27A 0.126(5) 0.087(4) 0.119(4) 0.017(3) 0.082(4) 0.013(3) O28A 0.087(3) 0.084(3) 0.089(3) 0.036(3) 0.030(3) -0.008(3) O29A 0.121(4) 0.069(3) 0.079(3) -0.036(3) -0.013(3) -0.005(3) O30A 0.099(5) 0.057(4) 0.134(7) 0.003(4) -0.055(4) -0.006(3) Cl31A 0.0397(17) 0.0394(19) 0.080(3) 0.0012(10) 0.0193(12) -0.0016(10) O32A 0.074(4) 0.102(5) 0.122(6) 0.075(4) 0.045(4) 0.045(4) O33A 0.076(4) 0.053(3) 0.086(5) -0.018(3) 0.049(4) -0.007(3) O34A 0.053(3) 0.038(2) 0.098(4) 0.017(3) 0.044(3) -0.001(2) O35A 0.067(4) 0.115(5) 0.080(4) -0.025(4) 0.001(3) -0.032(4) C36A 0.080(15) 0.074(13) 0.16(2) 0.003(11) 0.075(14) 0.014(11) O37A 0.072(6) 0.063(5) 0.071(6) 0.001(5) 0.021(5) 0.012(4) C36B 0.065(10) 0.055(8) 0.094(10) -0.006(7) 0.048(8) 0.004(9) O37B 0.065(6) 0.068(5) 0.066(5) -0.004(5) 0.019(5) 0.011(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 N21 1.954(3) . ? Cu1 N9 1.968(3) . ? Cu1 N14 2.013(3) . ? Cu1 N2 2.015(3) . ? Cu1 O33B 2.553(11) . ? Cu1 O33A 2.789(6) . ? N2 C3 1.337(5) . ? N2 C7 1.346(5) . ? C3 C4 1.388(6) . ? C3 H3 0.9500 . ? C4 C5 1.373(7) . ? C4 H4 0.9500 . ? C5 C6 1.369(7) . ? C5 H5 0.9500 . ? C6 C7 1.392(6) . ? C6 H6 0.9500 . ? C7 C8 1.453(6) . ? C8 N9 1.340(5) . ? C8 C12 1.390(6) . ? N9 N10 1.367(4) . ? N10 C11 1.356(5) . ? N10 H10 0.97(2) . ? C11 N13 1.366(6) . ? C11 C12 1.402(6) . ? C12 H12 0.9500 . ? N13 H13A 0.98(2) . ? N13 H13B 0.98(2) . ? N14 C15 1.341(5) . ? N14 C19 1.362(5) . ? C15 C16 1.382(6) . ? C15 H15 0.9500 . ? C16 C17 1.365(6) . ? C16 H16 0.9500 . ? C17 C18 1.373(6) . ? C17 H17 0.9500 . ? C18 C19 1.375(5) . ? C18 H18 0.9500 . ? C19 C20 1.454(6) . ? C20 N21 1.328(5) . ? C20 C24 1.405(5) . ? N21 N22 1.373(4) . ? N22 C23 1.356(5) . ? N22 H22 0.97(2) . ? C23 N25 1.364(5) . ? C23 C24 1.390(6) . ? C24 H24 0.9500 . ? N25 H25B 0.97(2) . ? N25 H25A 0.97(2) . ? Cl26A O29A 1.398(4) . ? Cl26A O28A 1.415(5) . ? Cl26A O30A 1.431(6) . ? Cl26A O27A 1.432(5) . ? Cl26B O30B 1.400(16) . ? Cl26B O28B 1.408(16) . ? Cl26B O27B 1.426(17) . ? Cl26B O29B 1.447(16) . ? Cl31A O32A 1.403(8) . ? Cl31A O34A 1.408(7) . ? Cl31A O33A 1.437(8) . ? Cl31A O35A 1.475(7) . ? Cl31B O32B 1.374(12) . ? Cl31B O33B 1.385(12) . ? Cl31B O35B 1.429(12) . ? Cl31B O34B 1.434(12) . ? C36A O37A 1.439(17) . ? C36A H36A 0.9800 . ? C36A H36B 0.9800 . ? C36A H36C 0.9800 . ? O37A H37A 0.8400 . ? C36B O37B 1.426(16) . ? C36B H36D 0.9800 . ? C36B H36E 0.9800 . ? C36B H36F 0.9800 . ? O37B H37B 0.8400 . ? 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 N21 Cu1 N9 160.93(14) . . ? N21 Cu1 N14 81.01(14) . . ? N9 Cu1 N14 105.02(13) . . ? N21 Cu1 N2 99.67(14) . . ? N9 Cu1 N2 80.73(14) . . ? N14 Cu1 N2 160.44(13) . . ? N21 Cu1 O33B 85.3(3) . . ? N9 Cu1 O33B 75.7(3) . . ? N14 Cu1 O33B 104.3(3) . . ? N2 Cu1 O33B 95.2(3) . . ? N21 Cu1 O33A 74.94(17) . . ? N9 Cu1 O33A 86.05(17) . . ? N14 Cu1 O33A 110.92(13) . . ? N2 Cu1 O33A 87.91(14) . . ? C3 N2 C7 118.6(4) . . ? C3 N2 Cu1 127.1(3) . . ? C7 N2 Cu1 114.2(3) . . ? N2 C3 C4 122.2(4) . . ? N2 C3 H3 118.9 . . ? C4 C3 H3 118.9 . . ? C5 C4 C3 118.7(5) . . ? C5 C4 H4 120.6 . . ? C3 C4 H4 120.6 . . ? C6 C5 C4 119.8(5) . . ? C6 C5 H5 120.1 . . ? C4 C5 H5 120.1 . . ? C5 C6 C7 118.8(5) . . ? C5 C6 H6 120.6 . . ? C7 C6 H6 120.6 . . ? N2 C7 C6 121.8(4) . . ? N2 C7 C8 114.1(3) . . ? C6 C7 C8 124.1(4) . . ? N9 C8 C12 110.9(4) . . ? N9 C8 C7 115.4(3) . . ? C12 C8 C7 133.7(4) . . ? C8 N9 N10 106.6(3) . . ? C8 N9 Cu1 115.1(2) . . ? N10 N9 Cu1 137.6(3) . . ? C11 N10 N9 110.0(4) . . ? C11 N10 H10 127(3) . . ? N9 N10 H10 122(3) . . ? N10 C11 N13 120.6(5) . . ? N10 C11 C12 107.6(4) . . ? N13 C11 C12 131.7(4) . . ? C8 C12 C11 104.9(4) . . ? C8 C12 H12 127.5 . . ? C11 C12 H12 127.5 . . ? C11 N13 H13A 116(3) . . ? C11 N13 H13B 111(3) . . ? H13A N13 H13B 109(2) . . ? C15 N14 C19 118.4(3) . . ? C15 N14 Cu1 127.8(3) . . ? C19 N14 Cu1 113.2(2) . . ? N14 C15 C16 121.0(4) . . ? N14 C15 H15 119.5 . . ? C16 C15 H15 119.5 . . ? C17 C16 C15 119.8(4) . . ? C17 C16 H16 120.1 . . ? C15 C16 H16 120.1 . . ? C16 C17 C18 120.2(4) . . ? C16 C17 H17 119.9 . . ? C18 C17 H17 119.9 . . ? C17 C18 C19 117.8(4) . . ? C17 C18 H18 121.1 . . ? C19 C18 H18 121.1 . . ? N14 C19 C18 122.7(4) . . ? N14 C19 C20 114.2(3) . . ? C18 C19 C20 123.0(4) . . ? N21 C20 C24 110.2(4) . . ? N21 C20 C19 115.0(3) . . ? C24 C20 C19 134.7(4) . . ? C20 N21 N22 106.7(3) . . ? C20 N21 Cu1 116.2(3) . . ? N22 N21 Cu1 137.0(3) . . ? C23 N22 N21 110.4(3) . . ? C23 N22 H22 127(3) . . ? N21 N22 H22 117(3) . . ? N22 C23 N25 121.1(4) . . ? N22 C23 C24 107.0(3) . . ? N25 C23 C24 131.8(4) . . ? C23 C24 C20 105.7(3) . . ? C23 C24 H24 127.2 . . ? C20 C24 H24 127.2 . . ? C23 N25 H25B 122(3) . . ? C23 N25 H25A 113(3) . . ? H25B N25 H25A 111(2) . . ? O29A Cl26A O28A 114.0(4) . . ? O29A Cl26A O30A 109.6(4) . . ? O28A Cl26A O30A 110.3(5) . . ? O29A Cl26A O27A 108.2(4) . . ? O28A Cl26A O27A 106.4(3) . . ? O30A Cl26A O27A 108.2(5) . . ? O30B Cl26B O28B 111.5(15) . . ? O30B Cl26B O27B 111.0(15) . . ? O28B Cl26B O27B 109.4(15) . . ? O30B Cl26B O29B 110.8(15) . . ? O28B Cl26B O29B 107.0(14) . . ? O27B Cl26B O29B 107.0(15) . . ? O32A Cl31A O34A 110.4(6) . . ? O32A Cl31A O33A 113.9(6) . . ? O34A Cl31A O33A 112.9(5) . . ? O32A Cl31A O35A 104.6(6) . . ? O34A Cl31A O35A 110.4(5) . . ? O33A Cl31A O35A 104.1(6) . . ? Cl31A O33A Cu1 117.7(4) . . ? O32B Cl31B O33B 116.4(9) . . ? O32B Cl31B O35B 108.2(10) . . ? O33B Cl31B O35B 108.5(9) . . ? O32B Cl31B O34B 108.4(9) . . ? O33B Cl31B O34B 107.0(9) . . ? O35B Cl31B O34B 108.1(9) . . ? Cl31B O33B Cu1 132.6(8) . . ? O37B C36B H36D 109.5 . . ? O37B C36B H36E 109.5 . . ? H36D C36B H36E 109.5 . . ? O37B C36B H36F 109.5 . . ? H36D C36B H36F 109.5 . . ? H36E C36B H36F 109.5 . . ? C36B O37B H37B 109.5 . . ? 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 N10 H10 O37A 0.97(2) 1.92(3) 2.881(11) 167(5) . N10 H10 O37B 0.97(2) 1.70(3) 2.640(11) 160(5) . N13 H13A O29A 0.98(2) 2.11(4) 2.975(7) 146(5) . N13 H13A O27B 0.98(2) 2.36(4) 3.32(3) 167(4) . N13 H13B O30A 0.98(2) 2.24(3) 3.179(10) 161(5) 3_667 N13 H13B O30B 0.98(2) 2.18(4) 3.10(3) 155(5) 3_667 N22 H22 O30A 0.97(2) 1.91(3) 2.879(9) 172(5) 1_454 N22 H22 O30B 0.97(2) 2.07(4) 3.02(3) 166(5) 1_454 N25 H25A O28A 0.97(2) 2.15(3) 3.086(7) 161(4) 1_454 N25 H25A O28B 0.97(2) 2.12(4) 3.06(2) 160(4) 1_454 N25 H25B O35A 0.97(2) 2.29(3) 3.167(8) 151(4) 4_575 N25 H25B O35B 0.97(2) 2.45(4) 3.329(16) 151(4) 4_575 O37A H37A O27A 0.84 2.16 3.002(11) 174.4 . O37A H37A O27B 0.84 2.35 3.11(3) 150.9 . O37B H37B O35A 0.84 1.93 2.668(11) 146.2 . O37B H37B O35B 0.84 1.93 2.694(16) 151.2 . _diffrn_measured_fraction_theta_max 0.987 _diffrn_reflns_theta_full 27.45 _diffrn_measured_fraction_theta_full 0.987 _refine_diff_density_max 0.773 _refine_diff_density_min -0.565 _refine_diff_density_rms 0.087 #=END data_c:\datasets\leeds\lfj15c\lfj15c _database_code_depnum_ccdc_archive 'CCDC 613021' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Bis[5-amino-3-(pyrid-2-yl)pyrazole][acetonitrile]copper(II) diperchlorate (4) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C18 H19 Cu N9, 2[Cl O4]' _chemical_formula_sum 'C18 H19 Cl2 Cu N9 O8' _chemical_formula_weight 623.86 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 'C 2/c' 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 20.5384(7) _cell_length_b 8.2388(2) _cell_length_c 14.5781(6) _cell_angle_alpha 90.00 _cell_angle_beta 101.4093(13) _cell_angle_gamma 90.00 _cell_volume 2418.04(14) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 17974 _cell_measurement_theta_min 2.67 _cell_measurement_theta_max 27.50 _exptl_crystal_description Plate _exptl_crystal_colour 'light brown' _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.714 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1268 _exptl_absorpt_coefficient_mu 1.190 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.733 _exptl_absorpt_correction_T_max 0.965 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 17974 _diffrn_reflns_av_R_equivalents 0.0768 _diffrn_reflns_av_sigmaI/netI 0.0482 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.67 _diffrn_reflns_theta_max 27.50 _reflns_number_total 2771 _reflns_number_gt 2122 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 asymmetric unit contains half a complex molecule, with Cu1, N14, C15 and C16 lying on the C~2~ axis [0, y, 0.25], and a perchlorate anion lying on a general position. Slightly high thermal parameters on the ClO~4~ anion suggest some librational motion of this residue. Attempts to build a disorder model for this moiety did not lead to any appreciable improvement in the refinement, however. So, this residue was left as ordered in the final analysis. All non-H atoms were refined anisotropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The N---H H atoms were all located in the difference map and refined, with a common U~iso~ thermal parameter of 0.067(8)\%A^2^, and the refined restraints N---H = 0.86(1)\%A and H13A...H13B = 1.40(2)\%A. ; _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^)+(0.0763P)^2^+2.9672P] 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 2771 _refine_ls_number_parameters 186 _refine_ls_number_restraints 4 _refine_ls_R_factor_all 0.0654 _refine_ls_R_factor_gt 0.0458 _refine_ls_wR_factor_ref 0.1329 _refine_ls_wR_factor_gt 0.1210 _refine_ls_goodness_of_fit_ref 1.028 _refine_ls_restrained_S_all 1.028 _refine_ls_shift/su_max 0.001 _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 0.0000 0.57687(5) 0.2500 0.02537(18) Uani 1 2 d S . . N2 N 0.07303(12) 0.5914(3) 0.36375(17) 0.0280(5) Uani 1 1 d . . . C3 C 0.13683(15) 0.5506(3) 0.3693(2) 0.0330(7) Uani 1 1 d . . . H3 H 0.1496 0.5017 0.3165 0.040 Uiso 1 1 calc R . . C4 C 0.18474(16) 0.5766(4) 0.4486(2) 0.0393(7) Uani 1 1 d . . . H4 H 0.2298 0.5485 0.4497 0.047 Uiso 1 1 calc R . . C5 C 0.16639(17) 0.6442(4) 0.5264(2) 0.0423(8) Uani 1 1 d . . . H5 H 0.1986 0.6627 0.5819 0.051 Uiso 1 1 calc R . . C6 C 0.10069(16) 0.6845(4) 0.5225(2) 0.0384(7) Uani 1 1 d . . . H6 H 0.0870 0.7312 0.5752 0.046 Uiso 1 1 calc R . . C7 C 0.05515(15) 0.6561(3) 0.44081(19) 0.0306(6) Uani 1 1 d . . . C8 C -0.01602(14) 0.6922(3) 0.42786(19) 0.0293(6) Uani 1 1 d . . . N9 N -0.05206(12) 0.6572(3) 0.34385(16) 0.0294(5) Uani 1 1 d . . . N10 N -0.11550(13) 0.7016(3) 0.34820(18) 0.0322(5) Uani 1 1 d D . . H10 H -0.1476(16) 0.706(5) 0.301(2) 0.067(8) Uiso 1 1 d D . . C11 C -0.11869(16) 0.7640(4) 0.4332(2) 0.0344(7) Uani 1 1 d . . . C12 C -0.05454(16) 0.7594(4) 0.4862(2) 0.0371(7) Uani 1 1 d . . . H12 H -0.0402 0.7948 0.5489 0.045 Uiso 1 1 calc R . . N13 N -0.17624(15) 0.8206(4) 0.4526(2) 0.0466(7) Uani 1 1 d D . . H13A H -0.2142(14) 0.796(5) 0.420(2) 0.067(8) Uiso 1 1 d D . . H13B H -0.1771(18) 0.832(5) 0.5108(18) 0.067(8) Uiso 1 1 d D . . N14 N 0.0000 0.3144(4) 0.2500 0.0334(8) Uani 1 2 d S . . C15 C 0.0000 0.1783(5) 0.2500 0.0347(9) Uani 1 2 d S . . C16 C 0.0000 0.0007(6) 0.2500 0.0673(17) Uani 1 2 d S . . H16A H 0.0143 -0.0389 0.3142 0.101 Uiso 0.50 1 calc PR . . H16B H 0.0306 -0.0389 0.2113 0.101 Uiso 0.50 1 calc PR . . H16C H -0.0449 -0.0389 0.2245 0.101 Uiso 0.50 1 calc PR . . Cl17 Cl -0.31025(4) 0.56798(9) 0.28178(5) 0.0350(2) Uani 1 1 d . . . O18 O -0.24652(15) 0.5606(4) 0.2576(3) 0.0826(11) Uani 1 1 d . . . O19 O -0.30922(18) 0.6949(4) 0.3499(2) 0.0769(9) Uani 1 1 d . . . O20 O -0.36039(14) 0.5985(4) 0.2016(2) 0.0613(8) Uani 1 1 d . . . O21 O -0.32417(18) 0.4199(4) 0.3228(2) 0.0802(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 0.0275(3) 0.0254(3) 0.0223(3) 0.000 0.00292(19) 0.000 N2 0.0297(13) 0.0263(12) 0.0272(12) 0.0033(9) 0.0040(10) 0.0004(9) C3 0.0332(16) 0.0310(15) 0.0345(16) 0.0048(11) 0.0057(13) 0.0020(11) C4 0.0275(16) 0.0418(18) 0.0453(19) 0.0071(13) -0.0010(14) 0.0031(12) C5 0.0406(19) 0.0417(18) 0.0379(18) 0.0003(13) -0.0081(14) -0.0020(14) C6 0.0398(18) 0.0406(17) 0.0312(16) -0.0019(12) -0.0014(13) -0.0001(13) C7 0.0326(15) 0.0304(15) 0.0273(15) 0.0009(11) 0.0025(12) -0.0023(12) C8 0.0347(16) 0.0253(14) 0.0275(14) 0.0002(10) 0.0053(12) 0.0004(11) N9 0.0276(12) 0.0348(13) 0.0260(12) -0.0008(9) 0.0058(10) 0.0015(10) N10 0.0279(13) 0.0372(14) 0.0322(13) 0.0003(10) 0.0075(10) 0.0042(10) C11 0.0410(17) 0.0346(16) 0.0295(15) 0.0023(12) 0.0119(13) 0.0044(13) C12 0.0472(19) 0.0383(17) 0.0257(15) -0.0045(12) 0.0068(13) 0.0039(14) N13 0.0424(17) 0.060(2) 0.0394(16) -0.0037(14) 0.0140(13) 0.0107(14) N14 0.037(2) 0.028(2) 0.0331(19) 0.000 0.0025(15) 0.000 C15 0.033(2) 0.031(2) 0.039(2) 0.000 0.0035(19) 0.000 C16 0.063(4) 0.023(3) 0.114(5) 0.000 0.012(4) 0.000 Cl17 0.0339(4) 0.0375(4) 0.0330(4) 0.0002(3) 0.0055(3) 0.0029(3) O18 0.0438(17) 0.126(3) 0.083(2) -0.0317(19) 0.0230(16) -0.0077(16) O19 0.107(3) 0.064(2) 0.0651(19) -0.0190(14) 0.0283(18) -0.0004(17) O20 0.0513(16) 0.082(2) 0.0464(15) 0.0197(14) 0.0002(13) 0.0141(14) O21 0.086(2) 0.062(2) 0.077(2) 0.0294(15) -0.0217(18) -0.0234(15) _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 2.008(2) . ? Cu1 N9 2.008(2) . ? Cu1 N14 2.163(4) . ? N2 C3 1.340(4) . ? N2 C7 1.358(4) . ? C3 C4 1.379(4) . ? C3 H3 0.9500 . ? C4 C5 1.381(5) . ? C4 H4 0.9500 . ? C5 C6 1.380(5) . ? C5 H5 0.9500 . ? C6 C7 1.381(4) . ? C6 H6 0.9500 . ? C7 C8 1.467(4) . ? C8 N9 1.331(4) . ? C8 C12 1.386(4) . ? N9 N10 1.367(3) . ? N10 C11 1.355(4) . ? N10 H10 0.86(2) . ? C11 N13 1.352(4) . ? C11 C12 1.389(4) . ? C12 H12 0.9500 . ? N13 H13A 0.85(2) . ? N13 H13B 0.86(2) . ? N14 C15 1.121(5) . ? C15 C16 1.463(6) . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? Cl17 O21 1.412(3) . ? Cl17 O20 1.419(3) . ? Cl17 O18 1.423(3) . ? Cl17 O19 1.439(3) . ? 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 173.16(13) 2 . ? N2 Cu1 N9 80.16(10) . . ? N2 Cu1 N9 97.56(10) . 2 ? N9 Cu1 N9 141.52(14) . 2 ? N2 Cu1 N14 93.42(6) . . ? N9 Cu1 N14 109.24(7) . . ? C3 N2 C7 118.0(3) . . ? C3 N2 Cu1 126.6(2) . . ? C7 N2 Cu1 115.25(19) . . ? N2 C3 C4 122.6(3) . . ? N2 C3 H3 118.7 . . ? C4 C3 H3 118.7 . . ? C3 C4 C5 119.1(3) . . ? C3 C4 H4 120.5 . . ? C5 C4 H4 120.5 . . ? C6 C5 C4 119.1(3) . . ? C6 C5 H5 120.4 . . ? C4 C5 H5 120.4 . . ? C5 C6 C7 119.0(3) . . ? C5 C6 H6 120.5 . . ? C7 C6 H6 120.5 . . ? N2 C7 C6 122.1(3) . . ? N2 C7 C8 113.5(2) . . ? C6 C7 C8 124.4(3) . . ? N9 C8 C12 111.7(3) . . ? N9 C8 C7 115.7(2) . . ? C12 C8 C7 132.6(3) . . ? C8 N9 N10 105.1(2) . . ? C8 N9 Cu1 115.10(19) . . ? N10 N9 Cu1 139.54(19) . . ? C11 N10 N9 111.3(2) . . ? C11 N10 H10 124(3) . . ? N9 N10 H10 124(3) . . ? N13 C11 N10 121.6(3) . . ? N13 C11 C12 131.7(3) . . ? N10 C11 C12 106.6(3) . . ? C8 C12 C11 105.3(3) . . ? C8 C12 H12 127.4 . . ? C11 C12 H12 127.4 . . ? C11 N13 H13A 123(3) . . ? C11 N13 H13B 116(3) . . ? H13A N13 H13B 112(2) . . ? C15 N14 Cu1 180.000(1) . . ? N14 C15 C16 180.000(1) . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? O21 Cl17 O20 109.09(18) . . ? O21 Cl17 O18 109.9(2) . . ? O20 Cl17 O18 110.9(2) . . ? O21 Cl17 O19 108.2(2) . . ? O20 Cl17 O19 110.4(2) . . ? O18 Cl17 O19 108.3(2) . . ? 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 N10 H10 O18 0.86(2) 2.34(4) 2.988(4) 133(4) . N13 H13A O19 0.85(2) 2.18(3) 3.026(5) 171(4) . N13 H13B O19 0.86(2) 2.12(3) 2.956(4) 166(4) 7_466 _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.899 _refine_diff_density_min -0.545 _refine_diff_density_rms 0.098 # Attachment 'B609424D 5_xH2O revised.cif' data_c:\datasets\leeds\lfj51f\lfj51f _database_code_depnum_ccdc_archive 'CCDC 613022' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Nitrato-bis[5-amino-3-(pyrid-2-yl)pyrazole]copper(II) nitrate hydrate (0.5/0.13) (5.xH~2~O; x = 0.13) ; _chemical_name_common ; Nitrato-bis(5-amino-3-(pyrid-2-yl)pyrazole)copper(ii) nitrate hydrate (0.5/0.13) (5.xH!2$O; x = 0.13) ; _chemical_melting_point ? _chemical_formula_moiety 'C16 H16 Cu N9 O3, N O3, 0.13[H 2 O]' _chemical_formula_sum 'C16 H16.26 Cu N10 O6.13' _chemical_formula_weight 510.27 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 Orthorhombic _symmetry_space_group_name_H-M 'P b c a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' _cell_length_a 14.3848(2) _cell_length_b 16.2140(2) _cell_length_c 34.3029(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8000.64(19) _cell_formula_units_Z 16 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 63428 _cell_measurement_theta_min 2.51 _cell_measurement_theta_max 27.49 _exptl_crystal_description Block _exptl_crystal_colour Turquoise _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.695 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4165 _exptl_absorpt_coefficient_mu 1.154 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.693 _exptl_absorpt_correction_T_max 0.868 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 63428 _diffrn_reflns_av_R_equivalents 0.1130 _diffrn_reflns_av_sigmaI/netI 0.0844 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -44 _diffrn_reflns_limit_l_max 44 _diffrn_reflns_theta_min 2.51 _diffrn_reflns_theta_max 27.49 _reflns_number_total 9162 _reflns_number_gt 4655 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 asymmetric unit contains two complex cations, labelled 'A' and 'B'; two nitrate anions, also labelled 'A' and 'B'; and, one Fourier peak of height +1.6 e.\%A^-3^, not bound to any other atom, that was modelled as a partially occupied water site. The nitrate anion N30A-O33A is disordered, over two sites labelled N30A-O33A and N30C-O33C, with a refined occupancy ratio of 0.26:0.74. The thermal parameters on the partial water molecule O34A implied that this also has an occupancy of <0.5, while inspection of the packing diagram showed that N30C-O33C and O34A cannot be simultaneously occupied (because of a steric clash of 2.16\%A between O31C and O34A). Hence, O34A was given the same occupancy as N30A-O33A, 0.26, in the final least squares cycles. In this interpretation, the anion disorder is governed by whether O34A is present or absent in a particular unit cell. The refined restraints N---O = 1.25(2)\%A and O...O = 2.17(2)\%A were applied to the disordered anion. The hydrogen-bonded distance O28A...O34A at 2.47\%A is considerably shorter than the sum of covalent radii of two O atoms (2.8\%A). That may imply that the coordinated nitrate ion N26A--O29A should also be disordered over two sites, depending on the presence or absence of O34A. No disorder in that residue could be resolved, however. All non-H atoms except the minor anion disorder site N30A-O33A and O34A, were refined anisotropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The N-bound H atoms were all located in the difference map and refined, with a common U~iso~ thermal parameter of 0.060(4)\%A^2^, and the refined restraints N---H = 0.85(1)\%A and primary amino H...H = 1.39(1)\%A. ; _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^)+(0.0821P)^2^+0.0000P] 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 9162 _refine_ls_number_parameters 655 _refine_ls_number_restraints 30 _refine_ls_R_factor_all 0.1364 _refine_ls_R_factor_gt 0.0576 _refine_ls_wR_factor_ref 0.1661 _refine_ls_wR_factor_gt 0.1373 _refine_ls_goodness_of_fit_ref 1.010 _refine_ls_restrained_S_all 1.009 _refine_ls_shift/su_max 0.001 _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 Cu1A Cu 0.75197(4) 0.49650(4) 0.183905(15) 0.05576(19) Uani 1 1 d . . . N2A N 0.7045(3) 0.3813(2) 0.16679(11) 0.0534(9) Uani 1 1 d . A . C3A C 0.6904(3) 0.3526(3) 0.13075(14) 0.0613(12) Uani 1 1 d . . . H3A H 0.7041 0.3872 0.1092 0.074 Uiso 1 1 calc R A . C4A C 0.6567(3) 0.2746(3) 0.12387(15) 0.0678(14) Uani 1 1 d . A . H4A H 0.6466 0.2565 0.0979 0.081 Uiso 1 1 calc R . . C5A C 0.6378(3) 0.2234(3) 0.15431(16) 0.0656(13) Uani 1 1 d . . . H5A H 0.6143 0.1695 0.1498 0.079 Uiso 1 1 calc R A . C6A C 0.6534(3) 0.2512(3) 0.19174(15) 0.0601(13) Uani 1 1 d . A . H6A H 0.6427 0.2162 0.2135 0.072 Uiso 1 1 calc R . . C7A C 0.6847(3) 0.3300(3) 0.19690(14) 0.0523(11) Uani 1 1 d . . . C8A C 0.6952(3) 0.3688(3) 0.23462(14) 0.0553(12) Uani 1 1 d . A . N9A N 0.7203(3) 0.4478(2) 0.23507(10) 0.0570(10) Uani 1 1 d . A . N10A N 0.7247(3) 0.4707(3) 0.27331(12) 0.0606(10) Uani 1 1 d D . . H10A H 0.743(3) 0.5204(12) 0.2752(13) 0.057(4) Uiso 1 1 d D . . C11A C 0.7020(3) 0.4042(4) 0.29613(15) 0.0646(13) Uani 1 1 d . A . C12A C 0.6829(3) 0.3393(3) 0.27210(14) 0.0621(13) Uani 1 1 d . . . H12A H 0.6650 0.2852 0.2796 0.074 Uiso 1 1 calc R A . N13A N 0.6971(3) 0.4118(4) 0.33589(12) 0.0802(14) Uani 1 1 d D . . H13A H 0.724(3) 0.4530(13) 0.3454(11) 0.057(4) Uiso 1 1 d D . . H13B H 0.712(3) 0.3684(12) 0.3475(11) 0.057(4) Uiso 1 1 d D . . N14A N 0.6477(2) 0.5895(2) 0.18155(10) 0.0506(9) Uani 1 1 d . A . C15A C 0.5878(3) 0.6131(3) 0.20922(13) 0.0558(12) Uani 1 1 d . . . H15A H 0.5865 0.5835 0.2331 0.067 Uiso 1 1 calc R A . C16A C 0.5274(3) 0.6788(3) 0.20442(15) 0.0700(14) Uani 1 1 d . A . H16A H 0.4839 0.6922 0.2242 0.084 Uiso 1 1 calc R . . C17A C 0.5311(4) 0.7247(4) 0.17072(14) 0.0746(15) Uani 1 1 d . . . H17A H 0.4933 0.7723 0.1677 0.090 Uiso 1 1 calc R A . C18A C 0.5904(3) 0.7005(3) 0.14152(13) 0.0586(12) Uani 1 1 d . A . H18A H 0.5925 0.7298 0.1176 0.070 Uiso 1 1 calc R . . C19A C 0.6466(3) 0.6331(3) 0.14752(12) 0.0490(11) Uani 1 1 d . . . C20A C 0.7137(3) 0.6019(3) 0.11891(12) 0.0456(10) Uani 1 1 d . A . N21A N 0.7700(2) 0.5413(2) 0.13052(11) 0.0554(9) Uani 1 1 d . A . N22A N 0.8308(3) 0.5288(2) 0.10070(11) 0.0575(10) Uani 1 1 d D . . H22A H 0.872(2) 0.4928(19) 0.1019(12) 0.057(4) Uiso 1 1 d D . . C23A C 0.8135(3) 0.5807(3) 0.07088(12) 0.0479(11) Uani 1 1 d . A . C24A C 0.7379(3) 0.6281(3) 0.08170(12) 0.0472(10) Uani 1 1 d . . . H24A H 0.7085 0.6699 0.0667 0.057 Uiso 1 1 calc R A . N25A N 0.8690(3) 0.5838(2) 0.03885(11) 0.0584(10) Uani 1 1 d D . . H25A H 0.896(3) 0.5389(15) 0.0346(10) 0.057(4) Uiso 1 1 d D . . H25B H 0.844(3) 0.602(2) 0.0187(7) 0.057(4) Uiso 1 1 d D . . N26A N 0.9375(3) 0.5149(4) 0.19837(13) 0.0738(13) Uani 1 1 d . . . O27A O 0.8693(3) 0.5572(3) 0.20740(11) 0.1036(14) Uani 1 1 d . A . O28A O 0.9230(3) 0.4513(3) 0.17973(17) 0.1261(18) Uani 1 1 d . A . O29A O 1.0166(3) 0.5374(3) 0.20692(10) 0.1035(14) Uani 1 1 d . A . N30A N 0.9358(18) 0.3364(12) 0.0309(5) 0.040(6) Uiso 0.26 1 d PD A 1 O31A O 0.9432(12) 0.3257(11) 0.0672(4) 0.082(5) Uiso 0.26 1 d PD A 1 O32A O 0.935(2) 0.4096(12) 0.0183(8) 0.057(8) Uiso 0.26 1 d PD A 1 O33A O 0.9077(16) 0.2786(12) 0.0103(6) 0.077(8) Uiso 0.26 1 d PD A 1 O34A O 1.0066(9) 0.4451(7) 0.1170(3) 0.071(3) Uiso 0.26 1 d P B 1 N30C N 0.9313(5) 0.3646(4) 0.03601(19) 0.0512(19) Uani 0.74 1 d PD C 2 O31C O 0.9215(4) 0.3701(3) 0.07178(14) 0.0736(15) Uani 0.74 1 d PD C 2 O32C O 0.9486(8) 0.4264(4) 0.0152(2) 0.057(2) Uani 0.74 1 d PD C 2 O33C O 0.9301(5) 0.2939(3) 0.01936(19) 0.0645(16) Uani 0.74 1 d PD C 2 Cu1B Cu 0.56645(3) 0.62585(3) -0.081490(14) 0.04469(17) Uani 1 1 d . . . N2B N 0.4518(2) 0.62397(19) -0.04426(9) 0.0403(8) Uani 1 1 d . . . C3B C 0.4033(3) 0.6879(2) -0.03024(11) 0.0454(10) Uani 1 1 d . A . H3B H 0.4247 0.7424 -0.0351 0.054 Uiso 1 1 calc R . . C4B C 0.3230(3) 0.6767(3) -0.00894(12) 0.0489(11) Uani 1 1 d . . . H4B H 0.2890 0.7230 0.0003 0.059 Uiso 1 1 calc R A . C5B C 0.2931(3) 0.5990(3) -0.00129(12) 0.0531(11) Uani 1 1 d . A . H5B H 0.2379 0.5906 0.0134 0.064 Uiso 1 1 calc R . . C6B C 0.3427(3) 0.5326(3) -0.01472(12) 0.0499(11) Uani 1 1 d . . . H6B H 0.3230 0.4779 -0.0092 0.060 Uiso 1 1 calc R A . C7B C 0.4217(3) 0.5469(2) -0.03648(11) 0.0402(9) Uani 1 1 d . A . C8B C 0.4805(3) 0.4819(2) -0.05271(11) 0.0402(9) Uani 1 1 d . . . N9B N 0.5482(2) 0.50721(19) -0.07633(9) 0.0458(9) Uani 1 1 d . A . N10B N 0.5951(3) 0.4374(2) -0.08706(10) 0.0534(9) Uani 1 1 d D . . H10B H 0.6460(17) 0.439(3) -0.0994(11) 0.057(4) Uiso 1 1 d D . . C11B C 0.5540(3) 0.3700(2) -0.07093(12) 0.0494(11) Uani 1 1 d D A . C12B C 0.4821(3) 0.3966(2) -0.04846(11) 0.0452(10) Uani 1 1 d . A . H12B H 0.4415 0.3638 -0.0331 0.054 Uiso 1 1 calc R . . N13B N 0.5908(3) 0.2939(2) -0.07755(11) 0.0642(11) Uani 1 1 d D . . H13C H 0.625(2) 0.2841(11) -0.0969(8) 0.057(4) Uiso 1 1 d D . . H13D H 0.568(2) 0.2506(6) -0.0685(10) 0.057(4) Uiso 1 1 d D . . N14B N 0.5591(2) 0.6339(2) -0.14337(9) 0.0422(8) Uani 1 1 d . . . C15B C 0.5474(3) 0.5728(3) -0.16907(12) 0.0470(10) Uani 1 1 d . A . H15B H 0.5352 0.5189 -0.1596 0.056 Uiso 1 1 calc R . . C16B C 0.5524(3) 0.5848(3) -0.20896(13) 0.0548(11) Uani 1 1 d . . . H16B H 0.5415 0.5406 -0.2266 0.066 Uiso 1 1 calc R A . C17B C 0.5738(3) 0.6631(3) -0.22239(12) 0.0556(12) Uani 1 1 d . A . H17B H 0.5803 0.6731 -0.2495 0.067 Uiso 1 1 calc R . . C18B C 0.5856(3) 0.7269(3) -0.19580(13) 0.0523(11) Uani 1 1 d . . . H18B H 0.5997 0.7811 -0.2044 0.063 Uiso 1 1 calc R A . C19B C 0.5763(3) 0.7097(2) -0.15663(12) 0.0430(10) Uani 1 1 d . A . C20B C 0.5836(3) 0.7725(2) -0.12556(12) 0.0434(10) Uani 1 1 d . . . N21B N 0.5782(2) 0.7444(2) -0.08925(10) 0.0456(9) Uani 1 1 d . A . N22B N 0.5835(3) 0.8126(2) -0.06577(10) 0.0509(9) Uani 1 1 d D . . H22B H 0.593(3) 0.803(3) -0.0419(5) 0.057(4) Uiso 1 1 d D . . C23B C 0.5912(3) 0.8816(3) -0.08750(14) 0.0536(12) Uani 1 1 d . A . C24B C 0.5910(3) 0.8583(3) -0.12634(13) 0.0505(11) Uani 1 1 d . A . H24B H 0.5951 0.8931 -0.1486 0.061 Uiso 1 1 calc R . . N25B N 0.6033(4) 0.9563(3) -0.06969(14) 0.0783(13) Uani 1 1 d D . . H25C H 0.589(3) 0.968(3) -0.0466(5) 0.057(4) Uiso 1 1 d D . . H25D H 0.567(2) 0.981(3) -0.0852(7) 0.057(4) Uiso 1 1 d D . . N26B N 0.7500(3) 0.62846(19) -0.05268(11) 0.0446(8) Uani 1 1 d . A . O27B O 0.7188(2) 0.60882(19) -0.08546(8) 0.0653(9) Uani 1 1 d . . . O28B O 0.6946(2) 0.64876(18) -0.02672(9) 0.0614(8) Uani 1 1 d . . . O29B O 0.8348(2) 0.62704(18) -0.04603(10) 0.0676(9) Uani 1 1 d . . . N30B N 0.7108(3) 0.3625(3) -0.17077(13) 0.0630(11) Uani 1 1 d . . . O31B O 0.7050(3) 0.4303(2) -0.15251(10) 0.0745(10) Uani 1 1 d . A . O32B O 0.6926(2) 0.2967(2) -0.15377(10) 0.0699(9) Uani 1 1 d . A . O33B O 0.7359(2) 0.3634(2) -0.20530(10) 0.0761(10) Uani 1 1 d . A . 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 Cu1A 0.0560(4) 0.0603(4) 0.0509(4) 0.0139(3) 0.0048(3) 0.0073(3) N2A 0.058(2) 0.053(2) 0.049(2) 0.0070(19) -0.0037(19) 0.0100(19) C3A 0.067(3) 0.059(3) 0.058(3) 0.005(2) -0.001(2) 0.014(3) C4A 0.078(4) 0.057(3) 0.068(3) -0.009(3) -0.015(3) 0.016(3) C5A 0.060(3) 0.053(3) 0.083(4) 0.001(3) -0.004(3) 0.008(2) C6A 0.049(3) 0.057(3) 0.074(4) 0.010(3) 0.009(2) -0.004(2) C7A 0.040(2) 0.058(3) 0.059(3) 0.009(2) 0.004(2) 0.004(2) C8A 0.043(2) 0.065(3) 0.058(3) 0.017(3) 0.000(2) 0.000(2) N9A 0.058(2) 0.068(3) 0.046(2) 0.011(2) 0.0046(18) 0.002(2) N10A 0.060(2) 0.069(3) 0.053(3) 0.011(2) 0.000(2) 0.005(2) C11A 0.052(3) 0.087(4) 0.055(3) 0.025(3) -0.006(2) 0.004(3) C12A 0.054(3) 0.069(3) 0.063(3) 0.019(3) -0.002(2) -0.004(3) N13A 0.076(3) 0.113(4) 0.052(3) 0.021(3) -0.004(2) -0.006(3) N14A 0.051(2) 0.055(2) 0.046(2) -0.0008(18) 0.0047(18) 0.0003(18) C15A 0.057(3) 0.068(3) 0.042(3) -0.007(2) 0.001(2) -0.007(2) C16A 0.048(3) 0.098(4) 0.064(3) -0.015(3) -0.001(3) 0.010(3) C17A 0.067(3) 0.101(4) 0.056(3) -0.011(3) -0.011(3) 0.031(3) C18A 0.055(3) 0.070(3) 0.051(3) -0.007(2) -0.009(2) 0.022(2) C19A 0.042(2) 0.062(3) 0.044(2) -0.003(2) -0.002(2) 0.002(2) C20A 0.044(2) 0.046(3) 0.048(3) 0.001(2) 0.000(2) 0.004(2) N21A 0.058(2) 0.052(2) 0.056(2) 0.0096(19) 0.0115(19) 0.0151(19) N22A 0.059(2) 0.052(2) 0.062(2) 0.011(2) 0.019(2) 0.0182(19) C23A 0.053(3) 0.044(3) 0.047(3) -0.005(2) 0.006(2) -0.006(2) C24A 0.050(3) 0.045(3) 0.046(3) 0.000(2) -0.003(2) 0.000(2) N25A 0.066(3) 0.057(3) 0.053(2) -0.006(2) 0.010(2) -0.003(2) N26A 0.064(3) 0.096(4) 0.062(3) 0.034(3) -0.001(3) 0.017(3) O27A 0.119(3) 0.101(3) 0.091(3) 0.034(2) 0.032(3) 0.025(3) O28A 0.127(4) 0.089(4) 0.163(5) 0.002(3) -0.051(3) -0.002(3) O29A 0.068(3) 0.175(4) 0.068(2) 0.021(3) -0.013(2) -0.031(3) N30C 0.065(4) 0.030(4) 0.059(5) 0.000(3) -0.006(3) 0.014(4) O31C 0.121(5) 0.048(3) 0.052(3) 0.002(2) 0.008(3) 0.017(3) O32C 0.072(5) 0.037(3) 0.061(4) 0.001(3) 0.005(3) -0.008(3) O33C 0.098(5) 0.027(3) 0.069(4) -0.005(3) -0.013(4) 0.007(3) Cu1B 0.0561(3) 0.0346(3) 0.0433(3) 0.0009(2) 0.0045(2) -0.0011(2) N2B 0.0502(19) 0.0341(19) 0.0366(18) 0.0014(15) -0.0024(15) -0.0006(16) C3B 0.053(3) 0.036(2) 0.047(2) -0.0003(19) 0.000(2) 0.001(2) C4B 0.048(2) 0.049(3) 0.050(3) -0.007(2) -0.002(2) 0.005(2) C5B 0.048(3) 0.061(3) 0.050(3) -0.005(2) 0.002(2) -0.005(2) C6B 0.053(3) 0.048(3) 0.049(3) 0.001(2) -0.005(2) -0.007(2) C7B 0.048(2) 0.035(2) 0.037(2) 0.0028(18) -0.0051(19) -0.0020(19) C8B 0.049(2) 0.035(2) 0.037(2) 0.0014(17) -0.004(2) -0.0020(19) N9B 0.059(2) 0.0315(19) 0.047(2) -0.0002(16) 0.0057(17) 0.0051(16) N10B 0.063(2) 0.047(2) 0.050(2) -0.0023(18) 0.0080(19) 0.007(2) C11B 0.076(3) 0.030(2) 0.043(2) 0.0005(18) -0.015(2) 0.001(2) C12B 0.059(3) 0.037(2) 0.040(2) 0.0054(18) -0.006(2) -0.001(2) N13B 0.102(4) 0.035(2) 0.055(3) -0.0041(18) -0.005(2) 0.014(2) N14B 0.0456(19) 0.039(2) 0.0415(19) -0.0004(16) 0.0007(15) 0.0026(16) C15B 0.053(3) 0.042(2) 0.047(3) -0.001(2) 0.000(2) 0.006(2) C16B 0.055(3) 0.061(3) 0.048(3) -0.011(2) -0.004(2) -0.001(2) C17B 0.061(3) 0.067(3) 0.038(2) 0.006(2) 0.002(2) 0.009(2) C18B 0.056(3) 0.053(3) 0.048(3) 0.011(2) 0.005(2) -0.004(2) C19B 0.044(2) 0.040(2) 0.045(2) 0.007(2) 0.0014(19) 0.004(2) C20B 0.042(2) 0.037(2) 0.051(3) 0.002(2) 0.001(2) -0.0008(18) N21B 0.057(2) 0.0318(19) 0.047(2) -0.0036(16) 0.0034(16) -0.0059(16) N22B 0.064(2) 0.042(2) 0.047(2) -0.0048(19) 0.004(2) -0.0123(18) C23B 0.054(3) 0.038(3) 0.069(3) -0.005(2) 0.011(2) -0.007(2) C24B 0.054(3) 0.040(3) 0.058(3) 0.008(2) 0.010(2) -0.004(2) N25B 0.106(4) 0.051(3) 0.078(3) -0.013(2) 0.018(3) -0.016(3) N26B 0.056(2) 0.0291(19) 0.049(2) 0.0059(16) -0.001(2) -0.0026(17) O27B 0.092(2) 0.063(2) 0.0412(19) -0.0063(15) -0.0128(17) 0.0051(18) O28B 0.074(2) 0.052(2) 0.0582(19) 0.0062(15) 0.0249(17) 0.0060(17) O29B 0.054(2) 0.053(2) 0.096(3) -0.0026(17) -0.0096(18) -0.0021(16) N30B 0.056(2) 0.076(3) 0.057(3) -0.006(3) -0.003(2) 0.013(2) O31B 0.096(3) 0.061(2) 0.066(2) -0.0113(18) 0.0129(19) 0.023(2) O32B 0.073(2) 0.072(3) 0.064(2) -0.0094(19) 0.0037(17) -0.002(2) O33B 0.093(3) 0.081(3) 0.055(2) -0.0133(18) 0.0109(19) 0.0055(19) _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 Cu1A N9A 1.977(4) . ? Cu1A N21A 1.987(4) . ? Cu1A N2A 2.074(4) . ? Cu1A O27A 2.114(5) . ? Cu1A N14A 2.128(4) . ? Cu1A O28A 2.571(5) . ? N2A C3A 1.336(5) . ? N2A C7A 1.356(5) . ? C3A C4A 1.374(6) . ? C3A H3A 0.9500 . ? C4A C5A 1.362(7) . ? C4A H4A 0.9500 . ? C5A C6A 1.379(6) . ? C5A H5A 0.9500 . ? C6A C7A 1.367(6) . ? C6A H6A 0.9500 . ? C7A C8A 1.446(6) . ? C8A N9A 1.332(5) . ? C8A C12A 1.383(6) . ? N9A N10A 1.365(5) . ? N10A C11A 1.372(6) . ? N10A H10A 0.850(14) . ? C11A C12A 1.364(7) . ? C11A N13A 1.371(6) . ? C12A H12A 0.9500 . ? N13A H13A 0.837(14) . ? N13A H13B 0.837(14) . ? N14A C15A 1.338(5) . ? N14A C19A 1.365(5) . ? C15A C16A 1.384(6) . ? C15A H15A 0.9500 . ? C16A C17A 1.375(7) . ? C16A H16A 0.9500 . ? C17A C18A 1.373(6) . ? C17A H17A 0.9500 . ? C18A C19A 1.375(6) . ? C18A H18A 0.9500 . ? C19A C20A 1.467(6) . ? C20A N21A 1.334(5) . ? C20A C24A 1.390(5) . ? N21A N22A 1.360(5) . ? N22A C23A 1.348(5) . ? N22A H22A 0.837(14) . ? C23A N25A 1.359(5) . ? C23A C24A 1.382(6) . ? C24A H24A 0.9500 . ? N25A H25A 0.841(14) . ? N25A H25B 0.835(14) . ? N26A O29A 1.230(5) . ? N26A O28A 1.232(6) . ? N26A O27A 1.236(5) . ? N30A O33A 1.242(16) . ? N30A O31A 1.262(16) . ? N30A O32A 1.262(17) . ? N30C O31C 1.238(7) . ? N30C O32C 1.254(8) . ? N30C O33C 1.281(8) . ? Cu1B N21B 1.948(3) . ? Cu1B N9B 1.949(3) . ? Cu1B N2B 2.086(3) . ? Cu1B N14B 2.129(3) . ? Cu1B O27B 2.213(3) . ? Cu1B O28B 2.658(3) . ? N2B C3B 1.340(5) . ? N2B C7B 1.349(5) . ? C3B C4B 1.378(6) . ? C3B H3B 0.9500 . ? C4B C5B 1.358(6) . ? C4B H4B 0.9500 . ? C5B C6B 1.371(6) . ? C5B H5B 0.9500 . ? C6B C7B 1.380(5) . ? C6B H6B 0.9500 . ? C7B C8B 1.461(5) . ? C8B N9B 1.331(5) . ? C8B C12B 1.391(5) . ? N9B N10B 1.368(5) . ? N10B C11B 1.360(5) . ? N10B H10B 0.846(14) . ? C11B C12B 1.360(6) . ? C11B N13B 1.362(5) . ? C12B H12B 0.9500 . ? N13B H13C 0.841(11) . ? N13B H13D 0.836(11) . ? N14B C19B 1.334(5) . ? N14B C15B 1.337(5) . ? C15B C16B 1.384(6) . ? C15B H15B 0.9500 . ? C16B C17B 1.386(6) . ? C16B H16B 0.9500 . ? C17B C18B 1.389(6) . ? C17B H17B 0.9500 . ? C18B C19B 1.378(6) . ? C18B H18B 0.9500 . ? C19B C20B 1.477(6) . ? C20B N21B 1.328(5) . ? C20B C24B 1.396(5) . ? N21B N22B 1.371(5) . ? N22B C23B 1.348(5) . ? N22B H22B 0.842(14) . ? C23B N25B 1.368(6) . ? C23B C24B 1.385(6) . ? C24B H24B 0.9500 . ? N25B H25C 0.840(14) . ? N25B H25D 0.844(14) . ? N26B O28B 1.240(4) . ? N26B O29B 1.241(4) . ? N26B O27B 1.252(4) . ? N30B O33B 1.238(5) . ? N30B O32B 1.244(5) . ? N30B O31B 1.268(5) . ? 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 N9A Cu1A N21A 173.67(15) . . ? N9A Cu1A N2A 79.40(16) . . ? N21A Cu1A N2A 96.42(15) . . ? N9A Cu1A O27A 91.81(15) . . ? N21A Cu1A O27A 94.38(15) . . ? N2A Cu1A O27A 142.25(16) . . ? N9A Cu1A N14A 98.85(14) . . ? N21A Cu1A N14A 78.34(14) . . ? N2A Cu1A N14A 113.28(13) . . ? O27A Cu1A N14A 104.30(15) . . ? N9A Cu1A O28A 98.99(16) . . ? N21A Cu1A O28A 85.86(16) . . ? N2A Cu1A O28A 92.46(15) . . ? O27A Cu1A O28A 52.41(16) . . ? N14A Cu1A O28A 150.95(15) . . ? C3A N2A C7A 117.3(4) . . ? C3A N2A Cu1A 128.7(3) . . ? C7A N2A Cu1A 113.9(3) . . ? N2A C3A C4A 122.2(5) . . ? N2A C3A H3A 118.9 . . ? C4A C3A H3A 118.9 . . ? C5A C4A C3A 120.0(5) . . ? C5A C4A H4A 120.0 . . ? C3A C4A H4A 120.0 . . ? C4A C5A C6A 118.8(5) . . ? C4A C5A H5A 120.6 . . ? C6A C5A H5A 120.6 . . ? C7A C6A C5A 118.7(5) . . ? C7A C6A H6A 120.7 . . ? C5A C6A H6A 120.7 . . ? N2A C7A C6A 122.9(4) . . ? N2A C7A C8A 113.2(4) . . ? C6A C7A C8A 123.8(4) . . ? N9A C8A C12A 110.9(5) . . ? N9A C8A C7A 117.2(4) . . ? C12A C8A C7A 132.0(5) . . ? C8A N9A N10A 106.6(4) . . ? C8A N9A Cu1A 115.9(3) . . ? N10A N9A Cu1A 137.2(3) . . ? N9A N10A C11A 108.9(4) . . ? N9A N10A H10A 110(3) . . ? C11A N10A H10A 141(3) . . ? C12A C11A N13A 131.3(5) . . ? C12A C11A N10A 108.0(4) . . ? N13A C11A N10A 120.6(5) . . ? C11A C12A C8A 105.7(5) . . ? C11A C12A H12A 127.2 . . ? C8A C12A H12A 127.2 . . ? C11A N13A H13A 116(3) . . ? C11A N13A H13B 113(3) . . ? H13A N13A H13B 111.6(18) . . ? C15A N14A C19A 116.8(4) . . ? C15A N14A Cu1A 129.0(3) . . ? C19A N14A Cu1A 114.1(3) . . ? N14A C15A C16A 122.7(4) . . ? N14A C15A H15A 118.7 . . ? C16A C15A H15A 118.7 . . ? C17A C16A C15A 119.5(5) . . ? C17A C16A H16A 120.3 . . ? C15A C16A H16A 120.3 . . ? C18A C17A C16A 118.9(5) . . ? C18A C17A H17A 120.6 . . ? C16A C17A H17A 120.6 . . ? C17A C18A C19A 118.9(4) . . ? C17A C18A H18A 120.6 . . ? C19A C18A H18A 120.6 . . ? N14A C19A C18A 123.2(4) . . ? N14A C19A C20A 112.7(4) . . ? C18A C19A C20A 124.1(4) . . ? N21A C20A C24A 110.3(4) . . ? N21A C20A C19A 117.0(4) . . ? C24A C20A C19A 132.4(4) . . ? C20A N21A N22A 106.0(3) . . ? C20A N21A Cu1A 117.7(3) . . ? N22A N21A Cu1A 136.2(3) . . ? C23A N22A N21A 111.0(3) . . ? C23A N22A H22A 127(3) . . ? N21A N22A H22A 122(3) . . ? N22A C23A N25A 121.9(4) . . ? N22A C23A C24A 106.8(4) . . ? N25A C23A C24A 131.2(4) . . ? C23A C24A C20A 105.9(4) . . ? C23A C24A H24A 127.0 . . ? C20A C24A H24A 127.0 . . ? C23A N25A H25A 113(3) . . ? C23A N25A H25B 115(3) . . ? H25A N25A H25B 111.6(18) . . ? O29A N26A O28A 121.9(5) . . ? O29A N26A O27A 120.6(6) . . ? O28A N26A O27A 117.4(6) . . ? N26A O27A Cu1A 106.2(4) . . ? N26A O28A Cu1A 83.9(4) . . ? O33A N30A O31A 119.0(17) . . ? O33A N30A O32A 120.7(18) . . ? O31A N30A O32A 117.9(17) . . ? O31C N30C O32C 122.0(7) . . ? O31C N30C O33C 120.3(6) . . ? O32C N30C O33C 117.6(6) . . ? N21B Cu1B N9B 176.21(15) . . ? N21B Cu1B N2B 99.61(13) . . ? N9B Cu1B N2B 79.85(13) . . ? N21B Cu1B N14B 78.91(13) . . ? N9B Cu1B N14B 98.29(13) . . ? N2B Cu1B N14B 124.89(12) . . ? N21B Cu1B O27B 91.63(13) . . ? N9B Cu1B O27B 90.90(13) . . ? N2B Cu1B O27B 144.96(11) . . ? N14B Cu1B O27B 89.74(11) . . ? N21B Cu1B O28B 84.17(12) . . ? N9B Cu1B O28B 99.62(12) . . ? N2B Cu1B O28B 96.75(11) . . ? N14B Cu1B O28B 136.93(11) . . ? O27B Cu1B O28B 51.26(10) . . ? C3B N2B C7B 118.6(3) . . ? C3B N2B Cu1B 128.3(3) . . ? C7B N2B Cu1B 112.8(3) . . ? N2B C3B C4B 121.6(4) . . ? N2B C3B H3B 119.2 . . ? C4B C3B H3B 119.2 . . ? C5B C4B C3B 119.4(4) . . ? C5B C4B H4B 120.3 . . ? C3B C4B H4B 120.3 . . ? C4B C5B C6B 120.0(4) . . ? C4B C5B H5B 120.0 . . ? C6B C5B H5B 120.0 . . ? C5B C6B C7B 118.6(4) . . ? C5B C6B H6B 120.7 . . ? C7B C6B H6B 120.7 . . ? N2B C7B C6B 121.8(4) . . ? N2B C7B C8B 114.0(3) . . ? C6B C7B C8B 124.2(4) . . ? N9B C8B C12B 111.0(4) . . ? N9B C8B C7B 115.7(3) . . ? C12B C8B C7B 133.3(4) . . ? C8B N9B N10B 105.6(3) . . ? C8B N9B Cu1B 117.2(3) . . ? N10B N9B Cu1B 136.5(3) . . ? C11B N10B N9B 109.9(4) . . ? C11B N10B H10B 127(3) . . ? N9B N10B H10B 123(3) . . ? C12B C11B N10B 107.8(4) . . ? C12B C11B N13B 132.7(4) . . ? N10B C11B N13B 119.4(4) . . ? C11B C12B C8B 105.6(4) . . ? C11B C12B H12B 127.2 . . ? C8B C12B H12B 127.2 . . ? C11B N13B H13C 122.1(13) . . ? C11B N13B H13D 123.2(13) . . ? H13C N13B H13D 111.3(15) . . ? C19B N14B C15B 118.8(3) . . ? C19B N14B Cu1B 112.8(3) . . ? C15B N14B Cu1B 128.2(3) . . ? N14B C15B C16B 122.8(4) . . ? N14B C15B H15B 118.6 . . ? C16B C15B H15B 118.6 . . ? C15B C16B C17B 118.0(4) . . ? C15B C16B H16B 121.0 . . ? C17B C16B H16B 121.0 . . ? C16B C17B C18B 119.4(4) . . ? C16B C17B H17B 120.3 . . ? C18B C17B H17B 120.3 . . ? C19B C18B C17B 118.6(4) . . ? C19B C18B H18B 120.7 . . ? C17B C18B H18B 120.7 . . ? N14B C19B C18B 122.4(4) . . ? N14B C19B C20B 113.7(3) . . ? C18B C19B C20B 123.9(4) . . ? N21B C20B C24B 111.4(4) . . ? N21B C20B C19B 115.8(3) . . ? C24B C20B C19B 132.7(4) . . ? C20B N21B N22B 105.7(3) . . ? C20B N21B Cu1B 118.1(3) . . ? N22B N21B Cu1B 136.1(3) . . ? C23B N22B N21B 110.4(3) . . ? C23B N22B H22B 133(3) . . ? N21B N22B H22B 115(3) . . ? N22B C23B N25B 119.9(4) . . ? N22B C23B C24B 107.8(4) . . ? N25B C23B C24B 132.1(4) . . ? C23B C24B C20B 104.7(4) . . ? C23B C24B H24B 127.7 . . ? C20B C24B H24B 127.7 . . ? C23B N25B H25C 125(3) . . ? C23B N25B H25D 93(3) . . ? H25C N25B H25D 109.8(17) . . ? O28B N26B O29B 120.3(4) . . ? O28B N26B O27B 118.8(4) . . ? O29B N26B O27B 120.9(4) . . ? N26B O27B Cu1B 105.5(3) . . ? N26B O28B Cu1B 84.3(2) . . ? O33B N30B O32B 121.3(4) . . ? O33B N30B O31B 118.8(5) . . ? O32B N30B O31B 119.9(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 N10A H10A O33B 0.850(14) 2.02(2) 2.845(6) 163(4) 2_665 N13A H13A O31B 0.837(14) 2.153(19) 2.949(7) 159(4) 2_665 N13A H13A O27B 0.837(14) 2.70(3) 2.976(5) 101(3) 2_665 N13A H13B O27B 0.837(14) 2.53(3) 2.976(5) 114(3) 2_665 N13A H13B O32B 0.837(14) 2.69(2) 3.400(7) 143(3) 8_566 N22A H22A O34A 0.837(14) 2.14(3) 2.924(12) 155(4) . N22A H22A O31C 0.837(14) 2.35(3) 3.051(6) 142(4) . N25A H25A O32A 0.841(14) 2.24(3) 3.06(3) 166(4) . N25A H25A O32C 0.841(14) 2.082(19) 2.912(9) 169(3) . N25A H25B O29B 0.835(14) 2.26(2) 3.035(5) 154(3) . N10B H10B O31B 0.846(14) 2.02(3) 2.748(5) 144(4) . N13B H13C O32B 0.841(11) 2.190(17) 2.997(5) 161(2) . N13B H13D O29B 0.836(11) 2.56(2) 3.105(5) 124(3) 7_755 N13B H13D O31A 0.836(11) 2.18(3) 2.897(18) 144(4) 3_455 N22B H22B O33A 0.842(14) 1.84(3) 2.67(2) 171(4) 7_765 N22B H22B O33C 0.842(14) 2.13(2) 2.942(7) 161(4) 7_765 N25B H25C O32A 0.840(14) 2.44(3) 3.16(3) 144(4) 7_765 N25B H25C O32C 0.840(14) 2.29(2) 3.046(9) 151(4) 7_765 N25B H25D O34A 0.844(14) 1.84(2) 2.670(13) 166(5) 3_465 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.653 _refine_diff_density_min -0.545 _refine_diff_density_rms 0.094 #=END data_c:\datasets\leeds\lfj43a\lfj43a _database_code_depnum_ccdc_archive 'CCDC 613023' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Nitrato-bis[5-amino-3-(pyrid-2-yl)pyrazole]zinc(II) nitrate hydrate (0.5/0.29) (5.xH~2~O; x = 0.29) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H16 N9 O3 Zn, N O3, 0.29[H 2 O]' _chemical_formula_sum 'C16 H16.58 N10 O6.29 Zn' _chemical_formula_weight 514.98 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P b c a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z' 'x, -y-1/2, z-1/2' _cell_length_a 14.1680(1) _cell_length_b 16.4064(2) _cell_length_c 35.0658(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8150.90(15) _cell_formula_units_Z 16 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 53964 _cell_measurement_theta_min 2.55 _cell_measurement_theta_max 27.49 _exptl_crystal_description block _exptl_crystal_colour 'light brown' _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.679 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4206 _exptl_absorpt_coefficient_mu 1.267 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.482 _exptl_absorpt_correction_T_max 0.727 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD area detector diffractometer' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 53964 _diffrn_reflns_av_R_equivalents 0.1001 _diffrn_reflns_av_sigmaI/netI 0.0530 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -44 _diffrn_reflns_limit_l_max 45 _diffrn_reflns_theta_min 2.55 _diffrn_reflns_theta_max 27.49 _reflns_number_total 9285 _reflns_number_gt 7001 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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 asymmetric unit contains two complex cations, labelled 'A' and 'B'; two nitrate anions, also labelled 'A' and 'B'; and, one Fourier peak not bound to any other atom, that was modelled as a partially occupied water site. The nitrate anion N30A-O33A is disordered, over two sites labelled N30A-O33A and N30C-O33C, with a refined occupancy ratio of 0.58:0.42. The thermal parameters on the partial water molecule O34A implied that this also has an occupancy of ca. 0.5, while inspection of the packing diagram showed that N30C-O33C and O34A cannot be simultaneously occupied (because of a steric clash of 2.16\%A between O31C and O34A). Hence, O34A was given the same occupancy as N30A-O33A, 0.58, in the final least squares cycles. In this interpretation, the anion disorder is governed by whether O34A is present or absent in a particular unit cell. The refined restraints N---O = 1.25(2)\%A and O...O = 2.17(2)\%A were applied to the disordered anion. All non-H atoms except the minor anion disorder site N30C-O33C were refined aniostropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The N-bound H atoms were all located in the difference map and refined, with a common U~iso~ thermal parameter of 0.083(4)\%A^2^, and the refined restraints N---H = 0.95(1)\%A and primary amino H...H = 1.55(1)\%A. ; _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^)+(0.0593P)^2^+5.8008P] 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 9284 _refine_ls_number_parameters 660 _refine_ls_number_restraints 30 _refine_ls_R_factor_all 0.0713 _refine_ls_R_factor_gt 0.0476 _refine_ls_wR_factor_ref 0.1340 _refine_ls_wR_factor_gt 0.1224 _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_restrained_S_all 1.054 _refine_ls_shift/su_max 0.001 _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 Zn1A Zn 0.75915(3) 0.49369(2) 0.185804(11) 0.05070(12) Uani 1 1 d . . . N2A N 0.71081(19) 0.37909(16) 0.16800(8) 0.0514(6) Uani 1 1 d . A . C3A C 0.6996(3) 0.3532(2) 0.13206(10) 0.0611(9) Uani 1 1 d . . . H3A H 0.7162 0.3888 0.1118 0.073 Uiso 1 1 calc R A . C4A C 0.6653(3) 0.2777(2) 0.12348(11) 0.0698(10) Uani 1 1 d . A . H4A H 0.6561 0.2618 0.0977 0.084 Uiso 1 1 calc R . . C5A C 0.6441(3) 0.2250(2) 0.15259(12) 0.0656(9) Uani 1 1 d . . . H5A H 0.6211 0.1718 0.1471 0.079 Uiso 1 1 calc R A . C6A C 0.6562(2) 0.2495(2) 0.18946(11) 0.0576(8) Uani 1 1 d . A . H6A H 0.6424 0.2136 0.2100 0.069 Uiso 1 1 calc R . . C7A C 0.6888(2) 0.32737(19) 0.19645(9) 0.0483(7) Uani 1 1 d . . . C8A C 0.6971(2) 0.36147(19) 0.23454(9) 0.0475(7) Uani 1 1 d . A . N9A N 0.71991(18) 0.44046(16) 0.23747(7) 0.0497(6) Uani 1 1 d . A . N10A N 0.72043(19) 0.45622(18) 0.27555(8) 0.0523(6) Uani 1 1 d D . . H10A H 0.741(3) 0.5060(13) 0.2823(11) 0.068(3) Uiso 1 1 d D . . C11A C 0.6981(2) 0.3890(2) 0.29570(9) 0.0559(8) Uani 1 1 d . A . C12A C 0.6830(2) 0.3263(2) 0.27025(10) 0.0550(8) Uani 1 1 d . . . H12A H 0.6667 0.2715 0.2758 0.066 Uiso 1 1 calc R A . N13A N 0.6885(2) 0.3904(2) 0.33481(9) 0.0719(9) Uani 1 1 d D . . H13A H 0.717(2) 0.4338(12) 0.3446(10) 0.068(3) Uiso 1 1 d D . . H13B H 0.711(2) 0.3442(11) 0.3443(10) 0.068(3) Uiso 1 1 d D . . N14A N 0.65200(17) 0.58127(15) 0.18083(7) 0.0467(6) Uani 1 1 d . A . C15A C 0.5913(2) 0.6025(2) 0.20844(9) 0.0540(7) Uani 1 1 d . . . H15A H 0.5933 0.5738 0.2320 0.065 Uiso 1 1 calc R A . C16A C 0.5262(2) 0.6641(3) 0.20412(10) 0.0657(9) Uani 1 1 d . A . H16A H 0.4827 0.6764 0.2239 0.079 Uiso 1 1 calc R . . C17A C 0.5252(3) 0.7079(3) 0.17032(10) 0.0696(10) Uani 1 1 d . . . H17A H 0.4823 0.7519 0.1670 0.084 Uiso 1 1 calc R A . C18A C 0.5871(2) 0.6869(2) 0.14147(10) 0.0572(8) Uani 1 1 d . A . H18A H 0.5874 0.7159 0.1180 0.069 Uiso 1 1 calc R . . C19A C 0.6488(2) 0.62258(19) 0.14757(8) 0.0460(7) Uani 1 1 d . . . C20A C 0.7186(2) 0.59618(18) 0.11898(8) 0.0442(6) Uani 1 1 d . A . N21A N 0.78002(19) 0.53959(17) 0.13035(8) 0.0566(7) Uani 1 1 d . A . N22A N 0.8406(2) 0.52996(17) 0.10022(9) 0.0575(7) Uani 1 1 d D . . H22A H 0.8881(19) 0.4939(18) 0.0999(11) 0.068(3) Uiso 1 1 d D . . C23A C 0.8180(2) 0.57991(19) 0.07101(9) 0.0490(7) Uani 1 1 d . A . C24A C 0.7384(2) 0.62339(18) 0.08225(8) 0.0451(7) Uani 1 1 d . . . H24A H 0.7049 0.6631 0.0679 0.054 Uiso 1 1 calc R A . N25A N 0.8726(2) 0.58534(19) 0.03935(8) 0.0582(7) Uani 1 1 d D . . H25A H 0.902(2) 0.5402(14) 0.0322(9) 0.068(3) Uiso 1 1 d D . . H25B H 0.843(2) 0.6080(18) 0.0196(7) 0.068(3) Uiso 1 1 d D . . N26A N 0.9389(2) 0.5131(2) 0.20219(8) 0.0609(8) Uani 1 1 d . . . O27A O 0.87401(18) 0.56296(16) 0.20988(7) 0.0674(6) Uani 1 1 d . A . O28A O 0.91517(19) 0.44663(19) 0.18808(9) 0.0751(7) Uani 1 1 d . A . O29A O 1.02149(19) 0.5311(2) 0.20858(8) 0.0861(9) Uani 1 1 d . A . N30A N 0.9282(5) 0.3366(6) 0.03344(18) 0.0552(16) Uani 0.58 1 d PD A 1 O31A O 0.9404(4) 0.3176(3) 0.06752(12) 0.0689(12) Uani 0.58 1 d PD A 1 O32A O 0.9379(7) 0.4081(5) 0.0222(2) 0.0603(18) Uani 0.58 1 d PD A 1 O33A O 0.9055(5) 0.2809(4) 0.01112(19) 0.0746(19) Uani 0.58 1 d PD A 1 O34A O 1.0060(3) 0.4362(2) 0.11467(10) 0.0541(9) Uani 0.58 1 d P B 1 N30C N 0.9328(12) 0.3634(8) 0.0367(4) 0.067(4) Uiso 0.42 1 d PD . 2 O31C O 0.9283(5) 0.3679(5) 0.0723(2) 0.0758(19) Uiso 0.42 1 d PD C 2 O32C O 0.9441(12) 0.4251(8) 0.0158(4) 0.066(4) Uiso 0.42 1 d PD D 2 O33C O 0.9296(9) 0.2955(7) 0.0194(4) 0.081(4) Uiso 0.42 1 d PD E 2 Zn1B Zn 0.58046(3) 0.62958(2) -0.081317(10) 0.04546(11) Uani 1 1 d . . . N2B N 0.45815(17) 0.62142(14) -0.04640(7) 0.0439(5) Uani 1 1 d . . . C3B C 0.4067(2) 0.68358(19) -0.03233(8) 0.0474(7) Uani 1 1 d . A . H3B H 0.4273 0.7378 -0.0370 0.057 Uiso 1 1 calc R . . C4B C 0.3257(2) 0.6719(2) -0.01151(9) 0.0524(7) Uani 1 1 d . . . H4B H 0.2905 0.7171 -0.0024 0.063 Uiso 1 1 calc R A . C5B C 0.2966(2) 0.5934(2) -0.00418(9) 0.0544(8) Uani 1 1 d . A . H5B H 0.2410 0.5838 0.0102 0.065 Uiso 1 1 calc R . . C6B C 0.3489(2) 0.52867(19) -0.01789(8) 0.0486(7) Uani 1 1 d . . . H6B H 0.3302 0.4742 -0.0128 0.058 Uiso 1 1 calc R A . C7B C 0.4293(2) 0.54460(17) -0.03929(8) 0.0421(6) Uani 1 1 d . A . C8B C 0.4907(2) 0.48085(17) -0.05519(8) 0.0430(6) Uani 1 1 d . . . N9B N 0.56016(19) 0.50536(15) -0.07810(7) 0.0478(6) Uani 1 1 d . A . N10B N 0.6071(2) 0.43601(16) -0.08795(7) 0.0517(6) Uani 1 1 d D . . H10B H 0.652(2) 0.437(2) -0.1060(8) 0.068(3) Uiso 1 1 d D . . C11B C 0.5671(2) 0.36954(18) -0.07226(9) 0.0506(7) Uani 1 1 d D A . C12B C 0.4915(2) 0.39648(18) -0.05048(8) 0.0478(7) Uani 1 1 d . A . H12B H 0.4495 0.3644 -0.0356 0.057 Uiso 1 1 calc R . . N13B N 0.6041(3) 0.29437(17) -0.07785(8) 0.0654(8) Uani 1 1 d D . . H13C H 0.638(2) 0.2842(10) -0.0985(7) 0.068(3) Uiso 1 1 d D . . H13D H 0.574(2) 0.2510(6) -0.0692(9) 0.068(3) Uiso 1 1 d D . . N14B N 0.56282(17) 0.64418(14) -0.14143(7) 0.0436(5) Uani 1 1 d . . . C15B C 0.5506(2) 0.58446(18) -0.16715(9) 0.0493(7) Uani 1 1 d . A . H15B H 0.5394 0.5305 -0.1584 0.059 Uiso 1 1 calc R . . C16B C 0.5538(2) 0.5987(2) -0.20585(9) 0.0555(8) Uani 1 1 d . . . H16B H 0.5439 0.5555 -0.2235 0.067 Uiso 1 1 calc R A . C17B C 0.5714(2) 0.6764(2) -0.21846(10) 0.0607(9) Uani 1 1 d . A . H17B H 0.5756 0.6873 -0.2450 0.073 Uiso 1 1 calc R . . C18B C 0.5831(2) 0.7390(2) -0.19221(10) 0.0545(8) Uani 1 1 d . . . H18B H 0.5947 0.7932 -0.2005 0.065 Uiso 1 1 calc R A . C19B C 0.5774(2) 0.72082(19) -0.15380(9) 0.0464(7) Uani 1 1 d . A . C20B C 0.5853(2) 0.78157(18) -0.12321(10) 0.0479(7) Uani 1 1 d . . . N21B N 0.58612(19) 0.75342(16) -0.08759(8) 0.0524(6) Uani 1 1 d . A . N22B N 0.5934(2) 0.81978(18) -0.06444(9) 0.0636(8) Uani 1 1 d D . . H22B H 0.600(3) 0.816(2) -0.0391(4) 0.068(3) Uiso 1 1 d D . . C23B C 0.5963(3) 0.8879(2) -0.08471(12) 0.0680(11) Uani 1 1 d . A . C24B C 0.5907(2) 0.8667(2) -0.12299(12) 0.0614(9) Uani 1 1 d . A . H24B H 0.5906 0.9023 -0.1444 0.074 Uiso 1 1 calc R . . N25B N 0.6101(3) 0.9624(2) -0.06615(12) 0.0832(11) Uani 1 1 d D . . H25C H 0.583(2) 0.969(2) -0.0434(5) 0.068(3) Uiso 1 1 d D . . H25D H 0.570(2) 0.983(2) -0.0844(6) 0.068(3) Uiso 1 1 d D . . N26B N 0.75610(18) 0.63003(14) -0.05297(7) 0.0454(6) Uani 1 1 d . A . O27B O 0.73721(17) 0.61891(15) -0.08763(6) 0.0592(6) Uani 1 1 d . . . O28B O 0.68756(16) 0.64062(13) -0.03064(6) 0.0544(5) Uani 1 1 d . . . O29B O 0.83783(16) 0.63173(14) -0.04121(7) 0.0593(6) Uani 1 1 d . . . N30B N 0.7175(2) 0.37686(18) -0.17196(8) 0.0561(7) Uani 1 1 d . . . O31B O 0.71544(18) 0.44391(14) -0.15397(7) 0.0623(6) Uani 1 1 d . A . O32B O 0.69618(18) 0.31233(15) -0.15520(7) 0.0630(6) Uani 1 1 d . A . O33B O 0.7404(2) 0.37663(16) -0.20592(7) 0.0708(7) Uani 1 1 d . A . 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 Zn1A 0.0475(2) 0.0536(2) 0.0510(2) 0.01293(16) 0.00536(16) 0.00320(15) N2A 0.0477(14) 0.0584(15) 0.0481(15) 0.0062(12) 0.0009(12) 0.0102(11) C3A 0.067(2) 0.063(2) 0.053(2) 0.0013(16) -0.0002(16) 0.0203(17) C4A 0.081(3) 0.066(2) 0.063(2) -0.0142(19) -0.0147(19) 0.0271(19) C5A 0.059(2) 0.061(2) 0.077(3) -0.0109(19) -0.0034(18) 0.0071(16) C6A 0.0451(17) 0.0570(19) 0.071(2) 0.0027(16) 0.0048(15) 0.0038(14) C7A 0.0346(14) 0.0571(17) 0.0533(18) 0.0063(14) 0.0021(12) 0.0046(12) C8A 0.0381(14) 0.0552(17) 0.0491(17) 0.0098(14) -0.0011(12) 0.0003(12) N9A 0.0470(14) 0.0586(15) 0.0434(14) 0.0083(12) 0.0014(11) 0.0012(11) N10A 0.0505(15) 0.0630(16) 0.0434(14) 0.0058(12) -0.0006(12) 0.0038(13) C11A 0.0432(16) 0.078(2) 0.0460(18) 0.0177(16) 0.0007(14) 0.0020(15) C12A 0.0455(17) 0.0638(19) 0.056(2) 0.0171(16) -0.0008(14) -0.0046(14) N13A 0.071(2) 0.096(2) 0.0496(18) 0.0164(17) -0.0067(15) -0.0019(18) N14A 0.0433(13) 0.0542(14) 0.0426(14) 0.0006(11) 0.0037(10) 0.0007(11) C15A 0.0433(16) 0.073(2) 0.0461(17) -0.0020(15) 0.0050(13) -0.0018(15) C16A 0.0500(19) 0.094(3) 0.053(2) -0.0119(19) 0.0063(15) 0.0127(18) C17A 0.058(2) 0.092(3) 0.059(2) -0.010(2) -0.0078(17) 0.0294(19) C18A 0.0518(18) 0.072(2) 0.0478(18) -0.0032(15) -0.0085(14) 0.0166(16) C19A 0.0377(14) 0.0579(17) 0.0423(16) -0.0027(13) -0.0030(12) 0.0024(12) C20A 0.0419(14) 0.0476(15) 0.0431(16) 0.0012(12) 0.0004(12) 0.0048(12) N21A 0.0527(15) 0.0583(16) 0.0588(17) 0.0153(13) 0.0191(13) 0.0117(12) N22A 0.0537(16) 0.0540(15) 0.0649(18) 0.0105(13) 0.0197(14) 0.0111(12) C23A 0.0499(17) 0.0508(16) 0.0463(17) -0.0045(13) 0.0055(13) -0.0071(13) C24A 0.0450(16) 0.0494(16) 0.0407(16) -0.0029(12) -0.0038(12) -0.0026(12) N25A 0.0584(17) 0.0699(18) 0.0462(15) -0.0064(13) 0.0108(13) -0.0071(14) N26A 0.0483(16) 0.087(2) 0.0470(16) 0.0193(15) 0.0001(13) 0.0085(15) O27A 0.0601(15) 0.0736(16) 0.0684(16) 0.0154(13) 0.0038(12) 0.0047(12) O28A 0.0636(16) 0.0767(18) 0.085(2) 0.0059(15) 0.0038(13) 0.0057(14) O29A 0.0500(15) 0.143(3) 0.0655(17) 0.0041(17) -0.0132(13) 0.0010(16) N30A 0.046(3) 0.072(6) 0.048(4) -0.003(4) -0.012(2) 0.007(4) O31A 0.088(3) 0.069(3) 0.050(3) 0.001(2) -0.012(2) -0.012(2) O32A 0.067(4) 0.064(4) 0.050(4) 0.004(3) -0.003(3) 0.007(3) O33A 0.090(4) 0.056(3) 0.078(4) -0.014(3) -0.030(3) 0.020(3) O34A 0.058(2) 0.054(2) 0.051(2) 0.0013(17) 0.0066(18) 0.0051(17) Zn1B 0.0495(2) 0.04557(19) 0.0413(2) 0.00166(14) 0.00350(14) -0.00348(14) N2B 0.0475(13) 0.0464(13) 0.0379(13) -0.0015(10) -0.0006(10) -0.0013(10) C3B 0.0501(16) 0.0488(16) 0.0434(16) -0.0018(13) -0.0010(13) 0.0007(13) C4B 0.0515(17) 0.0609(19) 0.0448(17) -0.0055(14) -0.0004(14) 0.0061(14) C5B 0.0428(16) 0.075(2) 0.0452(17) -0.0021(15) 0.0012(13) -0.0074(15) C6B 0.0502(17) 0.0560(17) 0.0395(16) 0.0011(13) -0.0042(13) -0.0133(13) C7B 0.0458(15) 0.0475(15) 0.0331(14) 0.0015(12) -0.0055(12) -0.0046(12) C8B 0.0489(16) 0.0447(14) 0.0353(14) 0.0027(11) -0.0056(12) -0.0039(12) N9B 0.0559(15) 0.0436(13) 0.0440(14) 0.0000(10) 0.0031(12) 0.0020(11) N10B 0.0636(17) 0.0468(14) 0.0447(15) -0.0003(11) 0.0022(12) 0.0084(12) C11B 0.070(2) 0.0444(16) 0.0379(15) 0.0014(12) -0.0114(14) 0.0022(14) C12B 0.0581(18) 0.0437(15) 0.0415(16) 0.0033(12) -0.0106(14) -0.0039(13) N13B 0.098(2) 0.0464(15) 0.0520(17) 0.0012(13) -0.0039(16) 0.0130(15) N14B 0.0445(13) 0.0438(13) 0.0426(13) 0.0007(10) 0.0021(10) 0.0026(10) C15B 0.0504(17) 0.0469(16) 0.0507(18) -0.0031(14) -0.0013(14) 0.0038(13) C16B 0.0519(18) 0.068(2) 0.0462(18) -0.0092(15) -0.0013(14) 0.0035(15) C17B 0.0498(18) 0.089(3) 0.0436(18) 0.0103(17) 0.0031(14) 0.0065(17) C18B 0.0492(17) 0.0610(19) 0.0534(19) 0.0132(15) 0.0064(14) 0.0029(14) C19B 0.0402(15) 0.0503(16) 0.0486(17) 0.0060(13) 0.0058(12) 0.0031(12) C20B 0.0410(15) 0.0410(14) 0.062(2) -0.0001(14) 0.0091(13) -0.0025(12) N21B 0.0587(16) 0.0473(14) 0.0511(16) -0.0078(11) 0.0084(12) -0.0124(12) N22B 0.0695(19) 0.0573(17) 0.0641(19) -0.0184(15) 0.0181(16) -0.0213(14) C23B 0.061(2) 0.0537(19) 0.089(3) -0.0209(19) 0.0307(19) -0.0142(16) C24B 0.0509(18) 0.0471(17) 0.086(3) 0.0061(17) 0.0200(17) -0.0046(14) N25B 0.089(3) 0.065(2) 0.096(3) -0.022(2) 0.025(2) -0.0181(18) N26B 0.0533(15) 0.0408(12) 0.0422(14) 0.0005(10) 0.0033(11) -0.0021(10) O27B 0.0666(15) 0.0709(15) 0.0402(12) -0.0063(10) -0.0021(10) 0.0084(11) O28B 0.0548(13) 0.0583(12) 0.0501(13) 0.0052(10) 0.0120(10) -0.0004(10) O29B 0.0525(14) 0.0620(14) 0.0633(14) 0.0012(11) -0.0057(11) -0.0018(10) N30B 0.0473(15) 0.0640(18) 0.0570(18) -0.0076(14) -0.0006(13) 0.0099(12) O31B 0.0675(15) 0.0584(13) 0.0609(14) -0.0084(11) 0.0068(12) 0.0112(11) O32B 0.0606(14) 0.0641(14) 0.0642(15) -0.0067(12) 0.0049(12) -0.0003(11) O33B 0.0879(19) 0.0710(16) 0.0534(15) -0.0094(12) 0.0118(13) 0.0058(13) _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 Zn1A N9A 2.087(2) . ? Zn1A N2A 2.096(3) . ? Zn1A N14A 2.097(3) . ? Zn1A N21A 2.106(3) . ? Zn1A O27A 2.157(3) . ? Zn1A O28A 2.343(3) . ? N2A C3A 1.339(4) . ? N2A C7A 1.346(4) . ? C3A C4A 1.365(5) . ? C3A H3A 0.9500 . ? C4A C5A 1.371(6) . ? C4A H4A 0.9500 . ? C5A C6A 1.365(5) . ? C5A H5A 0.9500 . ? C6A C7A 1.381(5) . ? C6A H6A 0.9500 . ? C7A C8A 1.453(5) . ? C8A N9A 1.339(4) . ? C8A C12A 1.393(4) . ? N9A N10A 1.360(4) . ? N10A C11A 1.347(4) . ? N10A H10A 0.898(14) . ? C11A C12A 1.378(5) . ? C11A N13A 1.378(5) . ? C12A H12A 0.9500 . ? N13A H13A 0.890(14) . ? N13A H13B 0.885(13) . ? N14A C15A 1.340(4) . ? N14A C19A 1.350(4) . ? C15A C16A 1.378(5) . ? C15A H15A 0.9500 . ? C16A C17A 1.386(5) . ? C16A H16A 0.9500 . ? C17A C18A 1.382(5) . ? C17A H17A 0.9500 . ? C18A C19A 1.388(4) . ? C18A H18A 0.9500 . ? C19A C20A 1.473(4) . ? C20A N21A 1.333(4) . ? C20A C24A 1.392(4) . ? N21A N22A 1.371(4) . ? N22A C23A 1.350(4) . ? N22A H22A 0.896(14) . ? C23A N25A 1.357(4) . ? C23A C24A 1.391(4) . ? C24A H24A 0.9500 . ? N25A H25A 0.886(13) . ? N25A H25B 0.894(13) . ? N26A O29A 1.227(4) . ? N26A O28A 1.244(4) . ? N26A O27A 1.260(4) . ? N30A O33A 1.245(10) . ? N30A O32A 1.245(10) . ? N30A O31A 1.247(7) . ? N30C O31C 1.249(12) . ? N30C O32C 1.260(13) . ? N30C O33C 1.272(13) . ? Zn1B N21B 2.045(3) . ? Zn1B N9B 2.061(2) . ? Zn1B N2B 2.126(2) . ? Zn1B N14B 2.136(2) . ? Zn1B O27B 2.239(2) . ? Zn1B O28B 2.344(2) . ? N2B C3B 1.347(4) . ? N2B C7B 1.348(4) . ? C3B C4B 1.373(4) . ? C3B H3B 0.9500 . ? C4B C5B 1.377(5) . ? C4B H4B 0.9500 . ? C5B C6B 1.381(5) . ? C5B H5B 0.9500 . ? C6B C7B 1.389(4) . ? C6B H6B 0.9500 . ? C7B C8B 1.470(4) . ? C8B N9B 1.332(4) . ? C8B C12B 1.394(4) . ? N9B N10B 1.363(4) . ? N10B C11B 1.347(4) . ? N10B H10B 0.892(14) . ? C11B N13B 1.354(4) . ? C11B C12B 1.388(5) . ? C12B H12B 0.9500 . ? N13B H13C 0.882(11) . ? N13B H13D 0.884(11) . ? N14B C15B 1.343(4) . ? N14B C19B 1.346(4) . ? C15B C16B 1.378(5) . ? C15B H15B 0.9500 . ? C16B C17B 1.372(5) . ? C16B H16B 0.9500 . ? C17B C18B 1.389(5) . ? C17B H17B 0.9500 . ? C18B C19B 1.382(4) . ? C18B H18B 0.9500 . ? C19B C20B 1.469(4) . ? C20B N21B 1.332(4) . ? C20B C24B 1.399(4) . ? N21B N22B 1.362(4) . ? N22B C23B 1.325(5) . ? N22B H22B 0.896(14) . ? C23B C24B 1.389(6) . ? C23B N25B 1.398(5) . ? C24B H24B 0.9500 . ? N25B H25C 0.890(13) . ? N25B H25D 0.917(13) . ? N26B O29B 1.229(3) . ? N26B O27B 1.258(3) . ? N26B O28B 1.259(3) . ? N30B O33B 1.235(4) . ? N30B O32B 1.248(4) . ? N30B O31B 1.268(3) . ? 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 N9A Zn1A N2A 78.23(10) . . ? N9A Zn1A N14A 99.56(10) . . ? N2A Zn1A N14A 110.68(10) . . ? N9A Zn1A N21A 171.37(11) . . ? N2A Zn1A N21A 95.26(11) . . ? N14A Zn1A N21A 77.28(10) . . ? N9A Zn1A O27A 94.68(10) . . ? N2A Zn1A O27A 146.68(10) . . ? N14A Zn1A O27A 102.57(10) . . ? N21A Zn1A O27A 93.85(11) . . ? N9A Zn1A O28A 94.81(10) . . ? N2A Zn1A O28A 91.31(11) . . ? N14A Zn1A O28A 155.71(10) . . ? N21A Zn1A O28A 90.96(10) . . ? O27A Zn1A O28A 56.53(10) . . ? C3A N2A C7A 118.1(3) . . ? C3A N2A Zn1A 127.1(2) . . ? C7A N2A Zn1A 114.9(2) . . ? N2A C3A C4A 122.5(3) . . ? N2A C3A H3A 118.8 . . ? C4A C3A H3A 118.8 . . ? C3A C4A C5A 119.1(4) . . ? C3A C4A H4A 120.4 . . ? C5A C4A H4A 120.4 . . ? C6A C5A C4A 119.5(4) . . ? C6A C5A H5A 120.3 . . ? C4A C5A H5A 120.3 . . ? C5A C6A C7A 118.9(3) . . ? C5A C6A H6A 120.6 . . ? C7A C6A H6A 120.6 . . ? N2A C7A C6A 122.0(3) . . ? N2A C7A C8A 114.8(3) . . ? C6A C7A C8A 123.1(3) . . ? N9A C8A C12A 111.5(3) . . ? N9A C8A C7A 117.5(3) . . ? C12A C8A C7A 131.0(3) . . ? C8A N9A N10A 105.1(2) . . ? C8A N9A Zn1A 113.7(2) . . ? N10A N9A Zn1A 140.5(2) . . ? C11A N10A N9A 111.0(3) . . ? C11A N10A H10A 133(3) . . ? N9A N10A H10A 116(3) . . ? N10A C11A C12A 107.9(3) . . ? N10A C11A N13A 122.1(3) . . ? C12A C11A N13A 129.9(3) . . ? C11A C12A C8A 104.6(3) . . ? C11A C12A H12A 127.7 . . ? C8A C12A H12A 127.7 . . ? C11A N13A H13A 111(2) . . ? C11A N13A H13B 109(2) . . ? H13A N13A H13B 112.2(16) . . ? C15A N14A C19A 118.2(3) . . ? C15A N14A Zn1A 125.6(2) . . ? C19A N14A Zn1A 116.12(19) . . ? N14A C15A C16A 122.7(3) . . ? N14A C15A H15A 118.6 . . ? C16A C15A H15A 118.6 . . ? C15A C16A C17A 118.8(3) . . ? C15A C16A H16A 120.6 . . ? C17A C16A H16A 120.6 . . ? C18A C17A C16A 119.3(3) . . ? C18A C17A H17A 120.3 . . ? C16A C17A H17A 120.3 . . ? C17A C18A C19A 118.5(3) . . ? C17A C18A H18A 120.8 . . ? C19A C18A H18A 120.8 . . ? N14A C19A C18A 122.4(3) . . ? N14A C19A C20A 114.7(3) . . ? C18A C19A C20A 122.8(3) . . ? N21A C20A C24A 111.6(3) . . ? N21A C20A C19A 116.1(3) . . ? C24A C20A C19A 132.1(3) . . ? C20A N21A N22A 105.0(2) . . ? C20A N21A Zn1A 115.7(2) . . ? N22A N21A Zn1A 139.3(2) . . ? C23A N22A N21A 111.5(3) . . ? C23A N22A H22A 125(3) . . ? N21A N22A H22A 124(3) . . ? N22A C23A N25A 121.7(3) . . ? N22A C23A C24A 106.8(3) . . ? N25A C23A C24A 131.4(3) . . ? C23A C24A C20A 105.1(3) . . ? C23A C24A H24A 127.4 . . ? C20A C24A H24A 127.4 . . ? C23A N25A H25A 116(2) . . ? C23A N25A H25B 113(2) . . ? H25A N25A H25B 110.6(16) . . ? O29A N26A O28A 122.8(3) . . ? O29A N26A O27A 120.0(4) . . ? O28A N26A O27A 117.2(3) . . ? N26A O27A Zn1A 97.2(2) . . ? N26A O28A Zn1A 88.8(2) . . ? O33A N30A O32A 121.4(6) . . ? O33A N30A O31A 117.0(8) . . ? O32A N30A O31A 121.6(8) . . ? O31C N30C O32C 122.6(13) . . ? O31C N30C O33C 121.9(13) . . ? O32C N30C O33C 115.4(13) . . ? N21B Zn1B N9B 173.49(11) . . ? N21B Zn1B N2B 99.00(10) . . ? N9B Zn1B N2B 78.03(10) . . ? N21B Zn1B N14B 77.70(10) . . ? N9B Zn1B N14B 98.54(10) . . ? N2B Zn1B N14B 118.68(9) . . ? N21B Zn1B O27B 91.61(10) . . ? N9B Zn1B O27B 93.82(10) . . ? N2B Zn1B O27B 149.39(9) . . ? N14B Zn1B O27B 91.56(8) . . ? N21B Zn1B O28B 88.82(10) . . ? N9B Zn1B O28B 97.20(9) . . ? N2B Zn1B O28B 95.51(8) . . ? N14B Zn1B O28B 144.61(8) . . ? O27B Zn1B O28B 55.86(8) . . ? C3B N2B C7B 118.4(3) . . ? C3B N2B Zn1B 127.2(2) . . ? C7B N2B Zn1B 114.35(19) . . ? N2B C3B C4B 122.8(3) . . ? N2B C3B H3B 118.6 . . ? C4B C3B H3B 118.6 . . ? C3B C4B C5B 118.7(3) . . ? C3B C4B H4B 120.7 . . ? C5B C4B H4B 120.7 . . ? C4B C5B C6B 119.6(3) . . ? C4B C5B H5B 120.2 . . ? C6B C5B H5B 120.2 . . ? C5B C6B C7B 118.9(3) . . ? C5B C6B H6B 120.6 . . ? C7B C6B H6B 120.6 . . ? N2B C7B C6B 121.6(3) . . ? N2B C7B C8B 114.6(3) . . ? C6B C7B C8B 123.8(3) . . ? N9B C8B C12B 111.4(3) . . ? N9B C8B C7B 116.8(2) . . ? C12B C8B C7B 131.8(3) . . ? C8B N9B N10B 105.2(2) . . ? C8B N9B Zn1B 115.7(2) . . ? N10B N9B Zn1B 138.0(2) . . ? C11B N10B N9B 111.5(3) . . ? C11B N10B H10B 126(2) . . ? N9B N10B H10B 121(2) . . ? N10B C11B N13B 121.0(3) . . ? N10B C11B C12B 107.0(3) . . ? N13B C11B C12B 131.9(3) . . ? C11B C12B C8B 104.9(3) . . ? C11B C12B H12B 127.5 . . ? C8B C12B H12B 127.5 . . ? C11B N13B H13C 120.0(12) . . ? C11B N13B H13D 119.7(12) . . ? H13C N13B H13D 113.0(14) . . ? C15B N14B C19B 119.0(3) . . ? C15B N14B Zn1B 126.6(2) . . ? C19B N14B Zn1B 113.9(2) . . ? N14B C15B C16B 122.2(3) . . ? N14B C15B H15B 118.9 . . ? C16B C15B H15B 118.9 . . ? C17B C16B C15B 118.8(3) . . ? C17B C16B H16B 120.6 . . ? C15B C16B H16B 120.6 . . ? C16B C17B C18B 119.7(3) . . ? C16B C17B H17B 120.2 . . ? C18B C17B H17B 120.2 . . ? C19B C18B C17B 118.7(3) . . ? C19B C18B H18B 120.7 . . ? C17B C18B H18B 120.7 . . ? N14B C19B C18B 121.6(3) . . ? N14B C19B C20B 114.2(3) . . ? C18B C19B C20B 124.1(3) . . ? N21B C20B C24B 109.9(3) . . ? N21B C20B C19B 116.8(3) . . ? C24B C20B C19B 133.3(3) . . ? C20B N21B N22B 106.4(3) . . ? C20B N21B Zn1B 116.4(2) . . ? N22B N21B Zn1B 137.1(2) . . ? C23B N22B N21B 110.9(3) . . ? C23B N22B H22B 126(2) . . ? N21B N22B H22B 123(3) . . ? N22B C23B C24B 107.8(3) . . ? N22B C23B N25B 119.5(4) . . ? C24B C23B N25B 132.6(4) . . ? C23B C24B C20B 105.0(3) . . ? C23B C24B H24B 127.5 . . ? C20B C24B H24B 127.5 . . ? C23B N25B H25C 118(3) . . ? C23B N25B H25D 85(3) . . ? H25C N25B H25D 108.8(16) . . ? O29B N26B O27B 121.8(3) . . ? O29B N26B O28B 121.0(3) . . ? O27B N26B O28B 117.2(3) . . ? N26B O27B Zn1B 95.97(17) . . ? N26B O28B Zn1B 90.99(17) . . ? O33B N30B O32B 121.0(3) . . ? O33B N30B O31B 119.2(3) . . ? O32B N30B O31B 119.8(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 N10A H10A O33B 0.898(14) 1.987(16) 2.872(4) 168(4) 2_665 N13A H13A O31B 0.890(14) 2.222(17) 3.065(5) 158(3) 2_665 N13A H13A O27B 0.890(14) 2.61(3) 2.920(4) 101(2) 2_665 N13A H13B O27B 0.885(13) 2.57(3) 2.920(4) 104(2) 2_665 N13A H13B O32B 0.885(13) 2.576(19) 3.346(5) 146(3) 8_566 N22A H22A O34A 0.896(14) 1.989(19) 2.848(5) 160(4) . N22A H22A O31C 0.896(14) 2.35(3) 3.094(8) 140(3) . N25A H25A O32A 0.886(13) 2.253(19) 3.110(8) 163(3) . N25A H25A O32C 0.886(13) 2.06(2) 2.936(14) 169(4) . N25A H25B O29B 0.894(13) 2.17(2) 2.967(4) 148(3) . N10B H10B O31B 0.892(14) 1.914(18) 2.780(4) 163(4) . N13B H13C O32B 0.882(11) 2.203(17) 3.024(4) 154.8(17) . N13B H13D O31A 0.884(11) 2.20(2) 2.980(6) 147(3) 3_455 N13B H13D O29B 0.884(11) 2.52(2) 3.074(4) 121(2) 7_755 N22B H22B O33A 0.896(14) 1.856(19) 2.725(7) 163(4) 7_765 N22B H22B O33C 0.896(14) 2.12(2) 2.983(13) 161(3) 7_765 N25B H25C O32A 0.890(13) 2.53(2) 3.294(9) 145(3) 7_765 N25B H25C O32C 0.890(13) 2.23(2) 3.037(14) 150(3) 7_765 N25B H25D O34A 0.917(13) 1.93(2) 2.800(6) 158(4) 3_465 _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.622 _refine_diff_density_min -0.596 _refine_diff_density_rms 0.096 #=END data_c:\datasets\leeds\kc2004~1\kc2004 _database_code_depnum_ccdc_archive 'CCDC 613024' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Tetrakis(5-amino-3-{pyrid-2-yl}pyrazolido)dicopper(II) hydrate (0.5/0.25) (7.xH~2~O; x = 0.25) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C32 H28 Cu2 N16, 0.25[H2 O]' _chemical_formula_sum 'C32 H28.50 Cu2 N16 O0.25' _chemical_formula_weight 768.29 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' Cu Cu 0.3201 1.2651 '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 'P 21/c' 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 12.3753(7) _cell_length_b 17.1300(13) _cell_length_c 16.3243(12) _cell_angle_alpha 90.00 _cell_angle_beta 110.892(4) _cell_angle_gamma 90.00 _cell_volume 3233.1(4) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 19808 _cell_measurement_theta_min 3.72 _cell_measurement_theta_max 27.70 _exptl_crystal_description 'Square prism' _exptl_crystal_colour 'Dark green' _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.578 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1570 _exptl_absorpt_coefficient_mu 1.369 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.717 _exptl_absorpt_correction_T_max 0.811 _exptl_absorpt_process_details ; Using multiple and symmetry-related data measurements via the program SORTAV See R.H. Blessing, Acta Cryst (1995), A51, 33-38 ; _exptl_special_details ; Detector set at 30mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings ; _diffrn_ambient_temperature 150(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 'Nonius KappaCCD diffractometer' _diffrn_measurement_method '/w and /f scans' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 19808 _diffrn_reflns_av_R_equivalents 0.0887 _diffrn_reflns_av_sigmaI/netI 0.0806 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.72 _diffrn_reflns_theta_max 27.70 _reflns_number_total 6706 _reflns_number_gt 5132 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Nonius, 1999)' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (McArdle, 1995)' _computing_publication_material 'local program' _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-H atoms were refined anisotropically. All C-bound H atoms were placed in calculated positions and refined using a riding model. The eight N-bound H atoms were located in the difference map and refined with a common U~iso~ subject to the refined restraints N---H = 0.88(2)\%A and H...H = 1.44(2)\%A. Two weak Fourier peaks of 1.5-1.7 e.\%A^-3^ were located lying on or near the crystallographic inversion centre [0.5, 0.5, 0.5] and not interacting with any other atom in the structure. These were modelled as partially occupied water molecules, giving a total formula water content of 0.25. Although not included in the model, the H atoms from this putative partial water molecule were included in the density calculation. Given the O51A...O51B distance of 1.10\%A, and the linearity of the O51B...O51A...O51B^i^ fragment (symm. code (i) 1-x, -y, -z), an alternative assignment for this region of the model might be a 0.125-occupied molecule of CO~2~. ; _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^)+(0.0760P)^2^+8.9318P] 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 0.0139(19) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 6706 _refine_ls_number_parameters 483 _refine_ls_number_restraints 12 _refine_ls_R_factor_all 0.0897 _refine_ls_R_factor_gt 0.0678 _refine_ls_wR_factor_ref 0.1947 _refine_ls_wR_factor_gt 0.1699 _refine_ls_goodness_of_fit_ref 1.021 _refine_ls_restrained_S_all 1.020 _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 0.69465(5) 0.21161(3) 0.12683(4) 0.0414(2) Uani 1 1 d . . . Cu2 Cu 0.99730(5) 0.22492(3) 0.27621(4) 0.0414(2) Uani 1 1 d . . . N3 N 0.6240(4) 0.1908(2) -0.0097(3) 0.0420(9) Uani 1 1 d . . . C4 C 0.5132(5) 0.1995(3) -0.0642(4) 0.0477(11) Uani 1 1 d . . . H4 H 0.4574 0.2177 -0.0411 0.057 Uiso 1 1 calc R . . C5 C 0.4789(5) 0.1830(4) -0.1522(4) 0.0546(13) Uani 1 1 d . . . H5 H 0.4009 0.1907 -0.1896 0.066 Uiso 1 1 calc R . . C6 C 0.5600(5) 0.1549(3) -0.1852(4) 0.0548(13) Uani 1 1 d . . . H6 H 0.5378 0.1420 -0.2456 0.066 Uiso 1 1 calc R . . C7 C 0.6731(5) 0.1459(3) -0.1301(3) 0.0495(12) Uani 1 1 d . . . H7 H 0.7297 0.1274 -0.1523 0.059 Uiso 1 1 calc R . . C8 C 0.7035(4) 0.1639(3) -0.0424(3) 0.0418(10) Uani 1 1 d . . . C9 C 0.8200(4) 0.1607(3) 0.0215(3) 0.0409(10) Uani 1 1 d . . . N10 N 0.8331(3) 0.1820(2) 0.1037(3) 0.0417(9) Uani 1 1 d . . . N11 N 0.9479(4) 0.1805(2) 0.1544(3) 0.0426(9) Uani 1 1 d . . . C12 C 1.0057(4) 0.1575(3) 0.1016(3) 0.0409(10) Uani 1 1 d . . . C13 C 0.9276(5) 0.1445(3) 0.0169(3) 0.0461(11) Uani 1 1 d . . . H13 H 0.9444 0.1281 -0.0330 0.055 Uiso 1 1 calc R . . N14 N 1.1250(4) 0.1539(3) 0.1328(3) 0.0506(11) Uani 1 1 d D . . H14A H 1.163(5) 0.145(4) 0.1880(19) 0.069(7) Uiso 1 1 d D . . H14B H 1.154(5) 0.130(3) 0.099(3) 0.069(7) Uiso 1 1 d D . . N15 N 1.0917(4) 0.3217(2) 0.3495(3) 0.0433(9) Uani 1 1 d . . . C16 C 1.1962(5) 0.3202(3) 0.4111(4) 0.0493(12) Uani 1 1 d . . . H16 H 1.2384 0.2726 0.4213 0.059 Uiso 1 1 calc R . . C17 C 1.2475(5) 0.3854(3) 0.4619(4) 0.0513(12) Uani 1 1 d . . . H17 H 1.3226 0.3829 0.5057 0.062 Uiso 1 1 calc R . . C18 C 1.1835(5) 0.4537(3) 0.4452(4) 0.0524(13) Uani 1 1 d . . . H18 H 1.2151 0.4993 0.4781 0.063 Uiso 1 1 calc R . . C19 C 1.0746(5) 0.4564(3) 0.3815(4) 0.0468(11) Uani 1 1 d . . . H19 H 1.0311 0.5034 0.3702 0.056 Uiso 1 1 calc R . . C20 C 1.0292(4) 0.3887(3) 0.3337(3) 0.0427(11) Uani 1 1 d . . . C21 C 0.9145(4) 0.3814(3) 0.2683(3) 0.0399(10) Uani 1 1 d . . . N22 N 0.8795(4) 0.3082(2) 0.2408(3) 0.0427(9) Uani 1 1 d . . . N23 N 0.7690(4) 0.3115(2) 0.1827(3) 0.0427(9) Uani 1 1 d . . . C24 C 0.7348(4) 0.3866(3) 0.1725(3) 0.0443(11) Uani 1 1 d . . . C25 C 0.8249(4) 0.4341(3) 0.2273(3) 0.0438(11) Uani 1 1 d . . . H25 H 0.8248 0.4891 0.2347 0.053 Uiso 1 1 calc R . . N26 N 0.6269(4) 0.4074(2) 0.1149(3) 0.0480(10) Uani 1 1 d D . . H26A H 0.574(4) 0.373(2) 0.116(5) 0.069(7) Uiso 1 1 d D . . H26B H 0.601(5) 0.4548(18) 0.118(4) 0.069(7) Uiso 1 1 d D . . N27 N 0.6956(3) 0.1086(2) 0.2015(3) 0.0430(9) Uani 1 1 d . . . C28 C 0.7759(5) 0.0524(3) 0.2288(3) 0.0466(11) Uani 1 1 d . . . H28 H 0.8459 0.0584 0.2179 0.056 Uiso 1 1 calc R . . C29 C 0.7614(5) -0.0138(3) 0.2719(4) 0.0494(12) Uani 1 1 d . . . H29 H 0.8190 -0.0533 0.2885 0.059 Uiso 1 1 calc R . . C30 C 0.6615(5) -0.0212(3) 0.2902(4) 0.0545(13) Uani 1 1 d . . . H30 H 0.6502 -0.0655 0.3212 0.065 Uiso 1 1 calc R . . C31 C 0.5780(5) 0.0361(3) 0.2633(4) 0.0494(12) Uani 1 1 d . . . H31 H 0.5083 0.0313 0.2749 0.059 Uiso 1 1 calc R . . C32 C 0.5970(4) 0.1010(3) 0.2190(3) 0.0423(10) Uani 1 1 d . . . C33 C 0.5144(4) 0.1644(3) 0.1844(3) 0.0408(10) Uani 1 1 d . . . N34 N 0.5462(4) 0.2215(2) 0.1409(3) 0.0416(9) Uani 1 1 d . . . N35 N 0.4576(4) 0.2749(2) 0.1105(3) 0.0430(9) Uani 1 1 d . . . C36 C 0.3741(4) 0.2492(3) 0.1379(3) 0.0401(10) Uani 1 1 d . . . C37 C 0.4047(4) 0.1795(3) 0.1847(3) 0.0435(11) Uani 1 1 d . . . H37 H 0.3608 0.1496 0.2107 0.052 Uiso 1 1 calc R . . N38 N 0.2737(4) 0.2939(3) 0.1215(3) 0.0480(10) Uani 1 1 d D . . H38A H 0.258(5) 0.316(3) 0.070(3) 0.069(7) Uiso 1 1 d D . . H38B H 0.214(4) 0.266(3) 0.121(4) 0.069(7) Uiso 1 1 d D . . N39 N 0.9419(3) 0.1706(2) 0.3774(3) 0.0406(9) Uani 1 1 d . . . C40 C 0.8462(5) 0.1811(3) 0.3954(4) 0.0477(12) Uani 1 1 d . . . H40 H 0.7855 0.2114 0.3560 0.057 Uiso 1 1 calc R . . C41 C 0.8307(5) 0.1498(3) 0.4692(4) 0.0534(13) Uani 1 1 d . . . H41 H 0.7604 0.1574 0.4791 0.064 Uiso 1 1 calc R . . C42 C 0.9204(5) 0.1072(3) 0.5278(4) 0.0555(14) Uani 1 1 d . . . H42 H 0.9137 0.0866 0.5798 0.067 Uiso 1 1 calc R . . C43 C 1.0201(5) 0.0954(3) 0.5090(4) 0.0510(12) Uani 1 1 d . . . H43 H 1.0823 0.0658 0.5479 0.061 Uiso 1 1 calc R . . C44 C 1.0286(5) 0.1267(3) 0.4334(3) 0.0438(11) Uani 1 1 d . . . C45 C 1.1305(4) 0.1186(3) 0.4087(3) 0.0426(11) Uani 1 1 d . . . N46 N 1.1264(4) 0.1535(2) 0.3340(3) 0.0423(9) Uani 1 1 d . . . N47 N 1.2327(4) 0.1475(2) 0.3252(3) 0.0456(9) Uani 1 1 d . . . C48 C 1.2993(4) 0.1070(3) 0.3949(3) 0.0441(11) Uani 1 1 d . . . C49 C 1.2390(4) 0.0869(3) 0.4498(3) 0.0443(11) Uani 1 1 d . . . H49 H 1.2664 0.0581 0.5030 0.053 Uiso 1 1 calc R . . N50 N 1.4148(4) 0.0889(3) 0.4035(3) 0.0509(10) Uani 1 1 d D . . H50A H 1.439(5) 0.120(3) 0.369(3) 0.069(7) Uiso 1 1 d D . . H50B H 1.448(5) 0.107(3) 0.458(2) 0.069(7) Uiso 1 1 d D . . O51A O 0.5000 0.5000 0.5000 0.073(7) Uiso 0.25 2 d SP A 1 O51B O 0.457(2) 0.5003(14) 0.5484(17) 0.041(5) Uiso 0.13 1 d P B 2 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 0.0404(4) 0.0434(3) 0.0451(4) -0.0005(2) 0.0209(3) 0.0017(2) Cu2 0.0424(4) 0.0404(3) 0.0437(4) -0.0009(2) 0.0182(3) 0.0037(2) N3 0.045(2) 0.043(2) 0.040(2) -0.0022(17) 0.0169(19) -0.0047(17) C4 0.045(3) 0.053(3) 0.046(3) 0.006(2) 0.017(2) -0.002(2) C5 0.047(3) 0.070(3) 0.046(3) 0.000(3) 0.015(2) -0.006(3) C6 0.056(3) 0.064(3) 0.046(3) 0.000(3) 0.020(3) -0.007(3) C7 0.052(3) 0.056(3) 0.044(3) -0.004(2) 0.022(2) -0.005(2) C8 0.047(3) 0.043(2) 0.039(2) 0.000(2) 0.019(2) -0.002(2) C9 0.043(3) 0.041(2) 0.043(3) 0.003(2) 0.021(2) 0.0012(19) N10 0.039(2) 0.044(2) 0.044(2) -0.0012(17) 0.0165(18) -0.0022(16) N11 0.041(2) 0.046(2) 0.044(2) -0.0036(18) 0.0194(19) -0.0015(17) C12 0.042(3) 0.040(2) 0.046(3) 0.000(2) 0.022(2) 0.0007(18) C13 0.051(3) 0.045(2) 0.051(3) 0.001(2) 0.030(3) 0.002(2) N14 0.046(3) 0.060(3) 0.054(3) 0.002(2) 0.027(2) 0.0044(19) N15 0.047(2) 0.039(2) 0.046(2) 0.0005(17) 0.019(2) -0.0008(17) C16 0.047(3) 0.042(2) 0.058(3) 0.000(2) 0.018(3) -0.002(2) C17 0.052(3) 0.049(3) 0.052(3) 0.000(2) 0.016(3) -0.003(2) C18 0.057(3) 0.046(3) 0.059(3) -0.003(2) 0.028(3) -0.007(2) C19 0.052(3) 0.039(2) 0.054(3) 0.002(2) 0.025(3) -0.002(2) C20 0.049(3) 0.041(2) 0.046(3) 0.005(2) 0.027(2) 0.000(2) C21 0.046(3) 0.039(2) 0.040(2) -0.0012(19) 0.023(2) -0.0018(19) N22 0.042(2) 0.0383(19) 0.050(2) -0.0045(18) 0.020(2) -0.0030(16) N23 0.043(2) 0.042(2) 0.049(2) 0.0018(18) 0.023(2) 0.0047(16) C24 0.052(3) 0.040(2) 0.050(3) 0.005(2) 0.028(2) 0.003(2) C25 0.048(3) 0.035(2) 0.053(3) 0.003(2) 0.025(2) 0.0016(19) N26 0.048(3) 0.040(2) 0.056(3) 0.009(2) 0.020(2) 0.0038(18) N27 0.042(2) 0.044(2) 0.045(2) 0.0004(17) 0.0176(19) 0.0042(17) C28 0.045(3) 0.046(3) 0.049(3) -0.001(2) 0.016(2) 0.006(2) C29 0.056(3) 0.043(2) 0.048(3) 0.005(2) 0.018(2) 0.012(2) C30 0.065(4) 0.046(3) 0.052(3) 0.009(2) 0.021(3) 0.003(2) C31 0.052(3) 0.047(3) 0.053(3) 0.004(2) 0.023(3) -0.001(2) C32 0.042(3) 0.044(2) 0.044(3) 0.000(2) 0.020(2) 0.0031(19) C33 0.041(3) 0.041(2) 0.043(3) 0.000(2) 0.018(2) 0.0023(19) N34 0.043(2) 0.0391(19) 0.047(2) 0.0013(17) 0.0212(19) 0.0015(16) N35 0.039(2) 0.043(2) 0.049(2) 0.0041(17) 0.0171(19) 0.0037(16) C36 0.036(2) 0.042(2) 0.041(2) -0.002(2) 0.013(2) -0.0010(18) C37 0.039(3) 0.048(3) 0.046(3) 0.001(2) 0.018(2) -0.001(2) N38 0.042(2) 0.048(2) 0.057(3) 0.003(2) 0.022(2) 0.0023(18) N39 0.044(2) 0.0378(19) 0.042(2) -0.0017(16) 0.0183(18) 0.0013(16) C40 0.053(3) 0.045(3) 0.049(3) -0.007(2) 0.023(2) 0.001(2) C41 0.061(3) 0.052(3) 0.060(3) -0.006(3) 0.038(3) -0.002(2) C42 0.070(4) 0.051(3) 0.058(3) 0.002(2) 0.037(3) -0.001(3) C43 0.059(3) 0.048(3) 0.049(3) 0.003(2) 0.023(3) -0.001(2) C44 0.054(3) 0.038(2) 0.043(3) -0.003(2) 0.021(2) -0.003(2) C45 0.047(3) 0.037(2) 0.047(3) -0.003(2) 0.021(2) -0.0002(19) N46 0.042(2) 0.045(2) 0.042(2) -0.0010(17) 0.0170(18) 0.0020(16) N47 0.046(2) 0.045(2) 0.050(2) -0.0008(18) 0.022(2) 0.0040(17) C48 0.042(3) 0.042(2) 0.047(3) -0.005(2) 0.015(2) 0.003(2) C49 0.048(3) 0.042(2) 0.041(3) 0.000(2) 0.014(2) 0.002(2) N50 0.046(3) 0.050(2) 0.058(3) -0.003(2) 0.021(2) 0.0050(19) _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 N34 1.938(4) . ? Cu1 N10 1.948(4) . ? Cu1 N23 2.002(4) . ? Cu1 N3 2.113(4) . ? Cu1 N27 2.141(4) . ? Cu1 Cu2 3.6759(9) . ? Cu2 N46 1.965(4) . ? Cu2 N22 1.973(4) . ? Cu2 N11 2.010(4) . ? Cu2 N15 2.133(4) . ? Cu2 N39 2.208(4) . ? N3 C4 1.351(7) . ? N3 C8 1.357(6) . ? C4 C5 1.374(8) . ? C4 H4 0.9500 . ? C5 C6 1.384(8) . ? C5 H5 0.9500 . ? C6 C7 1.376(8) . ? C6 H6 0.9500 . ? C7 C8 1.379(7) . ? C7 H7 0.9500 . ? C8 C9 1.448(7) . ? C9 N10 1.344(6) . ? C9 C13 1.390(7) . ? N10 N11 1.366(6) . ? N11 C12 1.359(6) . ? C12 N14 1.381(7) . ? C12 C13 1.394(7) . ? C13 H13 0.9500 . ? N14 H14A 0.87(3) . ? N14 H14B 0.87(3) . ? N15 C16 1.326(7) . ? N15 C20 1.357(6) . ? C16 C17 1.401(7) . ? C16 H16 0.9500 . ? C17 C18 1.383(7) . ? C17 H17 0.9500 . ? C18 C19 1.379(8) . ? C18 H18 0.9500 . ? C19 C20 1.398(7) . ? C19 H19 0.9500 . ? C20 C21 1.446(7) . ? C21 N22 1.351(6) . ? C21 C25 1.400(7) . ? N22 N23 1.360(6) . ? N23 C24 1.345(6) . ? C24 N26 1.378(7) . ? C24 C25 1.413(7) . ? C25 H25 0.9500 . ? N26 H26A 0.88(3) . ? N26 H26B 0.88(3) . ? N27 C28 1.341(6) . ? N27 C32 1.355(6) . ? C28 C29 1.379(7) . ? C28 H28 0.9500 . ? C29 C30 1.378(8) . ? C29 H29 0.9500 . ? C30 C31 1.378(7) . ? C30 H30 0.9500 . ? C31 C32 1.392(7) . ? C31 H31 0.9500 . ? C32 C33 1.459(7) . ? C33 N34 1.347(6) . ? C33 C37 1.384(7) . ? N34 N35 1.377(5) . ? N35 C36 1.339(6) . ? C36 C37 1.395(7) . ? C36 N38 1.402(6) . ? C37 H37 0.9500 . ? N38 H38A 0.88(3) . ? N38 H38B 0.88(3) . ? N39 C40 1.330(6) . ? N39 C44 1.361(6) . ? C40 C41 1.393(7) . ? C40 H40 0.9500 . ? C41 C42 1.386(8) . ? C41 H41 0.9500 . ? C42 C43 1.390(7) . ? C42 H42 0.9500 . ? C43 C44 1.383(7) . ? C43 H43 0.9500 . ? C44 C45 1.462(7) . ? C45 N46 1.343(6) . ? C45 C49 1.381(7) . ? N46 N47 1.377(6) . ? N47 C48 1.336(7) . ? C48 C49 1.398(7) . ? C48 N50 1.420(6) . ? C49 H49 0.9500 . ? N50 H50A 0.90(3) . ? N50 H50B 0.89(3) . ? 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 N34 Cu1 N10 169.05(16) . . ? N34 Cu1 N23 99.90(16) . . ? N10 Cu1 N23 91.02(16) . . ? N34 Cu1 N3 94.96(17) . . ? N10 Cu1 N3 79.27(17) . . ? N23 Cu1 N3 125.07(16) . . ? N34 Cu1 N27 79.50(15) . . ? N10 Cu1 N27 93.96(16) . . ? N23 Cu1 N27 122.44(17) . . ? N3 Cu1 N27 112.16(16) . . ? N46 Cu2 N22 168.43(17) . . ? N46 Cu2 N11 98.47(17) . . ? N22 Cu2 N11 92.96(17) . . ? N46 Cu2 N15 91.46(16) . . ? N22 Cu2 N15 78.59(17) . . ? N11 Cu2 N15 139.63(16) . . ? N46 Cu2 N39 78.16(15) . . ? N22 Cu2 N39 97.47(15) . . ? N11 Cu2 N39 120.95(15) . . ? N15 Cu2 N39 99.36(15) . . ? C4 N3 C8 119.1(4) . . ? C4 N3 Cu1 128.1(3) . . ? C8 N3 Cu1 112.8(3) . . ? N3 C4 C5 121.9(5) . . ? N3 C4 H4 119.1 . . ? C5 C4 H4 119.1 . . ? C4 C5 C6 118.9(5) . . ? C4 C5 H5 120.6 . . ? C6 C5 H5 120.6 . . ? C7 C6 C5 119.6(5) . . ? C7 C6 H6 120.2 . . ? C5 C6 H6 120.2 . . ? C6 C7 C8 119.4(5) . . ? C6 C7 H7 120.3 . . ? C8 C7 H7 120.3 . . ? N3 C8 C7 121.1(5) . . ? N3 C8 C9 113.8(4) . . ? C7 C8 C9 125.0(4) . . ? N10 C9 C13 109.4(5) . . ? N10 C9 C8 116.4(4) . . ? C13 C9 C8 134.1(5) . . ? C9 N10 N11 109.1(4) . . ? C9 N10 Cu1 117.6(3) . . ? N11 N10 Cu1 133.2(3) . . ? C12 N11 N10 106.9(4) . . ? C12 N11 Cu2 133.9(3) . . ? N10 N11 Cu2 118.4(3) . . ? N11 C12 N14 121.0(5) . . ? N11 C12 C13 109.9(4) . . ? N14 C12 C13 129.0(4) . . ? C9 C13 C12 104.6(4) . . ? C9 C13 H13 127.7 . . ? C12 C13 H13 127.7 . . ? C12 N14 H14A 120(4) . . ? C12 N14 H14B 115(4) . . ? H14A N14 H14B 113(3) . . ? C16 N15 C20 119.8(4) . . ? C16 N15 Cu2 127.0(3) . . ? C20 N15 Cu2 112.9(3) . . ? N15 C16 C17 123.2(5) . . ? N15 C16 H16 118.4 . . ? C17 C16 H16 118.4 . . ? C18 C17 C16 116.8(5) . . ? C18 C17 H17 121.6 . . ? C16 C17 H17 121.6 . . ? C19 C18 C17 120.9(5) . . ? C19 C18 H18 119.6 . . ? C17 C18 H18 119.6 . . ? C18 C19 C20 118.9(5) . . ? C18 C19 H19 120.5 . . ? C20 C19 H19 120.5 . . ? N15 C20 C19 120.4(5) . . ? N15 C20 C21 114.2(4) . . ? C19 C20 C21 125.3(4) . . ? N22 C21 C25 109.6(4) . . ? N22 C21 C20 116.1(4) . . ? C25 C21 C20 134.3(4) . . ? C21 N22 N23 108.4(4) . . ? C21 N22 Cu2 117.3(3) . . ? N23 N22 Cu2 133.6(3) . . ? C24 N23 N22 108.7(4) . . ? C24 N23 Cu1 133.4(4) . . ? N22 N23 Cu1 117.8(3) . . ? N23 C24 N26 121.2(5) . . ? N23 C24 C25 109.3(5) . . ? N26 C24 C25 129.5(4) . . ? C21 C25 C24 104.0(4) . . ? C21 C25 H25 128.0 . . ? C24 C25 H25 128.0 . . ? C24 N26 H26A 111(4) . . ? C24 N26 H26B 119(4) . . ? H26A N26 H26B 109(3) . . ? C28 N27 C32 118.5(4) . . ? C28 N27 Cu1 129.3(3) . . ? C32 N27 Cu1 112.1(3) . . ? N27 C28 C29 122.9(5) . . ? N27 C28 H28 118.5 . . ? C29 C28 H28 118.5 . . ? C30 C29 C28 118.5(5) . . ? C30 C29 H29 120.7 . . ? C28 C29 H29 120.7 . . ? C31 C30 C29 119.6(5) . . ? C31 C30 H30 120.2 . . ? C29 C30 H30 120.2 . . ? C30 C31 C32 119.2(5) . . ? C30 C31 H31 120.4 . . ? C32 C31 H31 120.4 . . ? N27 C32 C31 121.2(4) . . ? N27 C32 C33 113.9(4) . . ? C31 C32 C33 124.8(4) . . ? N34 C33 C37 109.7(4) . . ? N34 C33 C32 116.7(4) . . ? C37 C33 C32 133.6(4) . . ? C33 N34 N35 109.1(4) . . ? C33 N34 Cu1 117.8(3) . . ? N35 N34 Cu1 133.0(3) . . ? C36 N35 N34 105.8(4) . . ? N35 C36 C37 111.9(4) . . ? N35 C36 N38 119.6(4) . . ? C37 C36 N38 128.4(4) . . ? C33 C37 C36 103.5(4) . . ? C33 C37 H37 128.3 . . ? C36 C37 H37 128.3 . . ? C36 N38 H38A 107(4) . . ? C36 N38 H38B 113(4) . . ? H38A N38 H38B 109(3) . . ? C40 N39 C44 118.5(4) . . ? C40 N39 Cu2 130.3(3) . . ? C44 N39 Cu2 110.8(3) . . ? N39 C40 C41 123.1(5) . . ? N39 C40 H40 118.4 . . ? C41 C40 H40 118.4 . . ? C42 C41 C40 118.5(5) . . ? C42 C41 H41 120.8 . . ? C40 C41 H41 120.8 . . ? C41 C42 C43 118.7(5) . . ? C41 C42 H42 120.7 . . ? C43 C42 H42 120.7 . . ? C44 C43 C42 119.7(5) . . ? C44 C43 H43 120.1 . . ? C42 C43 H43 120.1 . . ? N39 C44 C43 121.5(5) . . ? N39 C44 C45 114.7(4) . . ? C43 C44 C45 123.8(5) . . ? N46 C45 C49 109.4(4) . . ? N46 C45 C44 116.9(4) . . ? C49 C45 C44 133.5(5) . . ? C45 N46 N47 109.4(4) . . ? C45 N46 Cu2 118.3(3) . . ? N47 N46 Cu2 129.8(3) . . ? C48 N47 N46 105.8(4) . . ? N47 C48 C49 111.4(4) . . ? N47 C48 N50 119.4(5) . . ? C49 C48 N50 129.1(5) . . ? C45 C49 C48 103.9(4) . . ? C45 C49 H49 128.1 . . ? C48 C49 H49 128.1 . . ? C48 N50 H50A 111(4) . . ? C48 N50 H50B 97(4) . . ? H50A N50 H50B 106(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 N14 H14A N47 0.87(3) 2.09(3) 2.944(7) 167(5) . N26 H26A N35 0.88(3) 2.20(3) 3.073(6) 171(5) . N26 H26B N50 0.88(3) 2.32(3) 3.148(6) 157(5) 2_755 N38 H38B N14 0.88(3) 2.26(4) 3.069(6) 154(6) 1_455 _diffrn_measured_fraction_theta_max 0.885 _diffrn_reflns_theta_full 27.70 _diffrn_measured_fraction_theta_full 0.885 _refine_diff_density_max 0.781 _refine_diff_density_min -0.923 _refine_diff_density_rms 0.102