# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Prof S Brooker' _publ_contact_author_email SBROOKER@CHEMISTRY.OTAGO.AC.NZ _publ_section_title ; Monomeric, dimeric and 1D chain polymeric copper(II) complexes of a pyrrole-containing tridentate Schiff-base ligand and its 4-brominated analogue ; loop_ _publ_author_name 'S. Brooker' 'Rongqing Li.' 'Boujemaa Moubaraki' 'Keith Murray' # Attachment 'CUL1BR_REV.CIF' data_cul1br _database_code_depnum_ccdc_archive 'CCDC 678456' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H11 Br2 Cu N3' _chemical_formula_weight 420.60 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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 8.9080(8) _cell_length_b 6.6637(6) _cell_length_c 11.1476(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.7890(10) _cell_angle_gamma 90.00 _cell_volume 661.66(10) _cell_formula_units_Z 2 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 3265 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.94 _exptl_crystal_description plate _exptl_crystal_colour green _exptl_crystal_size_max 0.43 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.111 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 406 _exptl_absorpt_coefficient_mu 7.673 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.364 _exptl_absorpt_correction_T_max 0.563 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART Apex' _diffrn_measurement_method 'CCD area detector' _diffrn_detector_area_resol_mean 8.333 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3276 _diffrn_reflns_av_R_equivalents 0.0250 _diffrn_reflns_av_sigmaI/netI 0.0206 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 1.83 _diffrn_reflns_theta_max 27.94 _reflns_number_total 2641 _reflns_number_gt 2532 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART-NT 5.6 (Bruker AXS Inc., 2000)' _computing_cell_refinement 'SMART-NT 5.6 (Bruker AXS Inc., 2000)' _computing_data_reduction 'SAINT+ 6.0 (Bruker AXS Inc., 2000)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. All non-H ANIS. All H calc and ride on attached atom. Given this contains a strong absorber, a face-indexing absorption correction would probably have been a good idea, but the standard multi-scan method was applied. ; _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^)+(0.1348P)^2^+0.6501P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.09(2) _refine_ls_number_reflns 2641 _refine_ls_number_parameters 163 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0599 _refine_ls_R_factor_gt 0.0585 _refine_ls_wR_factor_ref 0.1558 _refine_ls_wR_factor_gt 0.1544 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _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 0.37627(9) 0.28270(13) 0.05519(7) 0.0261(2) Uani 1 1 d . . . Br1 Br 0.59978(7) 0.34873(12) -0.06721(7) 0.0304(2) Uani 1 1 d . . . N1 N 0.2450(6) 0.2780(12) -0.0880(6) 0.0303(13) Uani 1 1 d . . . C2 C 0.0958(7) 0.3174(13) -0.0618(6) 0.0300(17) Uani 1 1 d . . . C3 C 0.0097(8) 0.3228(12) -0.1658(7) 0.0324(16) Uani 1 1 d . . . H3 H -0.0947 0.3503 -0.1733 0.039 Uiso 1 1 calc R . . C4 C 0.1086(9) 0.2793(13) -0.2565(7) 0.0313(15) Uani 1 1 d . . . Br2 Br 0.06430(11) 0.27293(17) -0.42204(8) 0.0461(3) Uani 1 1 d . . . C5 C 0.2538(9) 0.2550(13) -0.2071(7) 0.0317(15) Uani 1 1 d . . . H5 H 0.3424 0.2272 -0.2506 0.038 Uiso 1 1 calc R . . C6 C 0.0664(8) 0.3335(13) 0.0637(7) 0.0307(15) Uani 1 1 d . . . H6 H -0.0319 0.3574 0.0925 0.037 Uiso 1 1 calc R . . N2 N 0.1783(7) 0.3142(10) 0.1349(5) 0.0296(13) Uani 1 1 d . . . C8 C 0.1584(8) 0.3356(15) 0.2679(7) 0.0328(16) Uani 1 1 d . . . H8A H 0.1705 0.2037 0.3078 0.039 Uiso 1 1 calc R . . H8B H 0.0570 0.3877 0.2852 0.039 Uiso 1 1 calc R . . C9 C 0.2786(9) 0.4824(12) 0.3138(8) 0.0316(16) Uani 1 1 d . . . H9A H 0.2760 0.6039 0.2627 0.038 Uiso 1 1 calc R . . H9B H 0.2528 0.5240 0.3963 0.038 Uiso 1 1 calc R . . C10 C 0.4364(8) 0.3999(10) 0.3154(7) 0.0278(15) Uani 1 1 d . . . C11 C 0.5249(11) 0.4181(14) 0.4178(8) 0.0382(19) Uani 1 1 d . . . H11 H 0.4841 0.4824 0.4861 0.046 Uiso 1 1 calc R . . C12 C 0.6688(11) 0.3472(16) 0.4247(9) 0.0429(19) Uani 1 1 d . . . H12 H 0.7295 0.3652 0.4946 0.051 Uiso 1 1 calc R . . C13 C 0.7221(9) 0.2471(14) 0.3238(7) 0.0360(18) Uani 1 1 d . . . H13 H 0.8203 0.1914 0.3238 0.043 Uiso 1 1 calc R . . C14 C 0.6289(9) 0.2306(11) 0.2238(8) 0.0308(15) Uani 1 1 d . . . H14 H 0.6656 0.1601 0.1562 0.037 Uiso 1 1 calc R . . N3 N 0.4902(7) 0.3078(10) 0.2164(6) 0.0302(14) 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 0.0185(4) 0.0287(5) 0.0314(5) -0.0021(4) 0.0035(3) 0.0016(3) Br1 0.0213(3) 0.0290(4) 0.0412(4) -0.0022(3) 0.0079(2) -0.0003(3) N1 0.016(3) 0.031(3) 0.044(4) -0.004(3) 0.004(2) 0.000(3) C2 0.019(3) 0.031(4) 0.040(4) -0.005(3) 0.005(3) 0.003(3) C3 0.021(3) 0.035(4) 0.042(4) -0.005(3) -0.002(3) 0.000(3) C4 0.034(4) 0.027(3) 0.033(4) 0.001(3) 0.002(3) -0.006(3) Br2 0.0462(5) 0.0561(6) 0.0360(5) 0.0024(4) -0.0042(3) -0.0060(4) C5 0.029(3) 0.032(4) 0.034(4) 0.000(3) 0.001(3) -0.001(3) C6 0.023(3) 0.030(4) 0.039(4) -0.003(3) 0.007(3) -0.004(3) N2 0.032(3) 0.030(4) 0.027(3) -0.001(2) 0.006(2) -0.002(3) C8 0.025(3) 0.042(4) 0.032(4) -0.009(3) 0.011(3) -0.005(4) C9 0.033(4) 0.029(4) 0.033(4) -0.004(3) 0.004(3) -0.001(3) C10 0.028(4) 0.020(3) 0.035(4) -0.002(3) 0.001(3) 0.000(3) C11 0.043(5) 0.031(4) 0.041(5) 0.004(3) 0.002(4) -0.003(4) C12 0.047(5) 0.032(4) 0.049(5) 0.013(4) -0.007(4) 0.003(5) C13 0.029(4) 0.033(4) 0.045(5) 0.003(3) -0.001(3) -0.001(3) C14 0.028(4) 0.024(3) 0.041(4) 0.000(3) 0.002(3) 0.006(3) N3 0.024(3) 0.027(3) 0.040(3) -0.002(3) 0.003(2) 0.000(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 N1 1.966(7) . y Cu1 N2 1.996(6) . y Cu1 N3 2.058(7) . y Cu1 Br1 2.4687(10) . y Cu1 Br1 2.9027(13) 2_645 y Cu1 Br1 3.7801(13) 2_655 y Br1 Cu1 2.9027(13) 2_655 ? Br1 Cu1 3.7801(13) 2_645 ? N1 C5 1.340(10) . ? N1 C2 1.389(8) . ? C2 C3 1.382(10) . ? C2 C6 1.431(10) . ? C3 C4 1.381(10) . ? C4 C5 1.408(11) . ? C4 Br2 1.882(8) . ? C6 N2 1.272(10) . ? N2 C8 1.503(9) . ? C8 C9 1.533(11) . ? C9 C10 1.509(11) . ? C10 N3 1.356(10) . ? C10 C11 1.384(12) . ? C11 C12 1.367(14) . ? C12 C13 1.396(13) . ? C13 C14 1.385(11) . ? C14 N3 1.340(10) . ? 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 N1 Cu1 N2 81.0(3) . . y N1 Cu1 N3 172.2(3) . . y N2 Cu1 N3 91.8(3) . . y N1 Cu1 Br1 91.68(18) . . y N2 Cu1 Br1 162.0(2) . . y N3 Cu1 Br1 94.38(18) . . y N1 Cu1 Br1 93.7(2) . 2_645 y N2 Cu1 Br1 98.57(19) . 2_645 y N3 Cu1 Br1 90.33(18) . 2_645 y Br1 Cu1 Br1 98.27(3) . 2_645 y N1 Cu1 Br1 94.4(2) . 2_655 y N2 Cu1 Br1 85.93(19) . 2_655 y N3 Cu1 Br1 82.01(18) . 2_655 y Br1 Cu1 Br1 78.24(3) . 2_655 y Br1 Cu1 Br1 171.25(4) 2_645 2_655 y Cu1 Br1 Cu1 102.20(4) . 2_655 y Cu1 Br1 Cu1 81.26(3) . 2_645 y Cu1 Br1 Cu1 171.25(4) 2_655 2_645 y C5 N1 C2 107.4(6) . . ? C5 N1 Cu1 139.8(5) . . ? C2 N1 Cu1 112.7(5) . . ? C3 C2 N1 110.5(6) . . ? C3 C2 C6 135.3(7) . . ? N1 C2 C6 114.1(6) . . ? C4 C3 C2 104.8(6) . . ? C3 C4 C5 109.3(7) . . ? C3 C4 Br2 126.5(6) . . ? C5 C4 Br2 124.0(6) . . ? N1 C5 C4 107.9(7) . . ? N2 C6 C2 116.7(6) . . ? C6 N2 C8 120.3(6) . . ? C6 N2 Cu1 115.0(5) . . ? C8 N2 Cu1 124.5(5) . . ? N2 C8 C9 107.4(6) . . ? C10 C9 C8 114.6(7) . . ? N3 C10 C11 120.5(7) . . ? N3 C10 C9 119.7(7) . . ? C11 C10 C9 119.8(7) . . ? C12 C11 C10 122.6(9) . . ? C11 C12 C13 116.7(9) . . ? C14 C13 C12 118.6(8) . . ? N3 C14 C13 124.2(8) . . ? C14 N3 C10 117.3(7) . . ? C14 N3 Cu1 117.8(5) . . ? C10 N3 Cu1 124.9(5) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N1 Cu1 Br1 Cu1 95.3(2) . . . 2_655 ? N2 Cu1 Br1 Cu1 29.9(6) . . . 2_655 ? N3 Cu1 Br1 Cu1 -79.80(18) . . . 2_655 ? Br1 Cu1 Br1 Cu1 -170.77(5) 2_645 . . 2_655 ? Br1 Cu1 Br1 Cu1 1.085(6) 2_655 . . 2_655 ? N1 Cu1 Br1 Cu1 -92.9(2) . . . 2_645 ? N2 Cu1 Br1 Cu1 -158.3(6) . . . 2_645 ? N3 Cu1 Br1 Cu1 92.03(18) . . . 2_645 ? Br1 Cu1 Br1 Cu1 1.062(6) 2_645 . . 2_645 ? Br1 Cu1 Br1 Cu1 172.92(4) 2_655 . . 2_645 ? N2 Cu1 N1 C5 -177.1(10) . . . . ? N3 Cu1 N1 C5 160.3(17) . . . . ? Br1 Cu1 N1 C5 19.4(10) . . . . ? Br1 Cu1 N1 C5 -79.0(10) 2_645 . . . ? Br1 Cu1 N1 C5 97.7(10) 2_655 . . . ? N2 Cu1 N1 C2 5.9(6) . . . . ? N3 Cu1 N1 C2 -17(3) . . . . ? Br1 Cu1 N1 C2 -157.6(6) . . . . ? Br1 Cu1 N1 C2 104.0(6) 2_645 . . . ? Br1 Cu1 N1 C2 -79.2(6) 2_655 . . . ? C5 N1 C2 C3 -1.1(10) . . . . ? Cu1 N1 C2 C3 176.9(6) . . . . ? C5 N1 C2 C6 176.3(8) . . . . ? Cu1 N1 C2 C6 -5.7(10) . . . . ? N1 C2 C3 C4 1.9(10) . . . . ? C6 C2 C3 C4 -174.7(10) . . . . ? C2 C3 C4 C5 -2.0(10) . . . . ? C2 C3 C4 Br2 -177.4(6) . . . . ? C2 N1 C5 C4 -0.2(10) . . . . ? Cu1 N1 C5 C4 -177.3(7) . . . . ? C3 C4 C5 N1 1.4(11) . . . . ? Br2 C4 C5 N1 176.9(6) . . . . ? C3 C2 C6 N2 177.8(10) . . . . ? N1 C2 C6 N2 1.3(12) . . . . ? C2 C6 N2 C8 178.0(7) . . . . ? C2 C6 N2 Cu1 3.8(10) . . . . ? N1 Cu1 N2 C6 -5.5(6) . . . . ? N3 Cu1 N2 C6 171.5(6) . . . . ? Br1 Cu1 N2 C6 61.5(10) . . . . ? Br1 Cu1 N2 C6 -97.9(6) 2_645 . . . ? Br1 Cu1 N2 C6 89.7(6) 2_655 . . . ? N1 Cu1 N2 C8 -179.4(7) . . . . ? N3 Cu1 N2 C8 -2.4(7) . . . . ? Br1 Cu1 N2 C8 -112.5(7) . . . . ? Br1 Cu1 N2 C8 88.2(6) 2_645 . . . ? Br1 Cu1 N2 C8 -84.3(6) 2_655 . . . ? C6 N2 C8 C9 -130.1(8) . . . . ? Cu1 N2 C8 C9 43.6(9) . . . . ? N2 C8 C9 C10 -71.9(9) . . . . ? C8 C9 C10 N3 49.4(10) . . . . ? C8 C9 C10 C11 -130.4(8) . . . . ? N3 C10 C11 C12 0.5(14) . . . . ? C9 C10 C11 C12 -179.7(8) . . . . ? C10 C11 C12 C13 -2.4(15) . . . . ? C11 C12 C13 C14 1.6(13) . . . . ? C12 C13 C14 N3 1.1(13) . . . . ? C13 C14 N3 C10 -3.0(12) . . . . ? C13 C14 N3 Cu1 175.9(6) . . . . ? C11 C10 N3 C14 2.2(11) . . . . ? C9 C10 N3 C14 -177.6(7) . . . . ? C11 C10 N3 Cu1 -176.6(6) . . . . ? C9 C10 N3 Cu1 3.6(9) . . . . ? N1 Cu1 N3 C14 180.0(19) . . . . ? N2 Cu1 N3 C14 157.6(6) . . . . ? Br1 Cu1 N3 C14 -39.3(6) . . . . ? Br1 Cu1 N3 C14 59.0(6) 2_645 . . . ? Br1 Cu1 N3 C14 -116.7(6) 2_655 . . . ? N1 Cu1 N3 C10 -1(3) . . . . ? N2 Cu1 N3 C10 -23.5(6) . . . . ? Br1 Cu1 N3 C10 139.5(6) . . . . ? Br1 Cu1 N3 C10 -122.1(6) 2_645 . . . ? Br1 Cu1 N3 C10 62.1(6) 2_655 . . . ? _diffrn_measured_fraction_theta_max 0.918 _diffrn_reflns_theta_full 27.94 _diffrn_measured_fraction_theta_full 0.918 _refine_diff_density_max 1.165 _refine_diff_density_min -1.466 _refine_diff_density_rms 0.232 # Attachment 'CUL1CLR_REV.CIF' data_cul1clr _database_code_depnum_ccdc_archive 'CCDC 678452' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H24 Cl2 Cu2 N6' _chemical_formula_weight 594.48 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' 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 P2(1)/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 8.653(3) _cell_length_b 8.353(3) _cell_length_c 16.116(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.422(4) _cell_angle_gamma 90.00 _cell_volume 1164.7(6) _cell_formula_units_Z 2 _cell_measurement_temperature 169(2) _cell_measurement_reflns_used 5362 _cell_measurement_theta_min 2.35 _cell_measurement_theta_max 26.41 _exptl_crystal_description Plate _exptl_crystal_colour 'dark blue' _exptl_crystal_size_max 0.59 _exptl_crystal_size_mid 0.57 _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_000 604 _exptl_absorpt_coefficient_mu 2.082 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.70 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 169(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 'Bruker SMART area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3244 _diffrn_reflns_av_R_equivalents 0.0211 _diffrn_reflns_av_sigmaI/netI 0.0229 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -2 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 26.43 _reflns_number_total 1591 _reflns_number_gt 1514 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. No disorder. No solvent. All non-H ANIS. BUT: unfortunately only 1 of the 4 runs of data that were harvested were input into SADABS (resulting in a poor absorption correction) then XPREP so the hkl file we received from the remote data collectors was far from complete (66% to 52 degrees). We failed to note this at the time (2002), and do not have the merged .raw file, so can't reprocess. The student concerned has departed (2004) so a recollection is also not viable. ; _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^)+(0.0243P)^2^+7.5929P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1591 _refine_ls_number_parameters 154 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0649 _refine_ls_R_factor_gt 0.0605 _refine_ls_wR_factor_ref 0.1280 _refine_ls_wR_factor_gt 0.1266 _refine_ls_goodness_of_fit_ref 1.446 _refine_ls_restrained_S_all 1.446 _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 0.70497(10) 0.02488(10) 0.49604(4) 0.0144(3) Uani 1 1 d . . . N1 N 0.7720(7) -0.1184(7) 0.5856(3) 0.0157(14) Uani 1 1 d . . . C2 C 0.8984(8) -0.0626(10) 0.6289(4) 0.0177(18) Uani 1 1 d . . . C3 C 0.9393(9) -0.1720(10) 0.6900(4) 0.024(2) Uani 1 1 d . . . H3 H 1.0220 -0.1625 0.7287 0.029 Uiso 1 1 calc R . . C4 C 0.8355(9) -0.2978(10) 0.6834(4) 0.027(2) Uani 1 1 d . . . H4 H 0.8345 -0.3922 0.7163 0.033 Uiso 1 1 calc R . . C5 C 0.7332(9) -0.2597(9) 0.6195(4) 0.0190(17) Uani 1 1 d . . . H5 H 0.6484 -0.3241 0.6023 0.023 Uiso 1 1 calc R . . C6 C 0.9480(8) 0.0921(10) 0.6047(4) 0.0210(19) Uani 1 1 d . . . H6 H 1.0331 0.1428 0.6314 0.025 Uiso 1 1 calc R . . N2 N 0.8733(7) 0.1616(7) 0.5452(3) 0.0182(14) Uani 1 1 d . . . C8 C 0.9072(9) 0.3249(9) 0.5194(4) 0.0202(18) Uani 1 1 d . . . H8A H 0.9869 0.3241 0.4756 0.024 Uiso 1 1 calc R . . H8B H 0.9476 0.3870 0.5671 0.024 Uiso 1 1 calc R . . C9 C 0.7606(9) 0.4021(9) 0.4864(4) 0.0213(18) Uani 1 1 d . . . H9A H 0.6765 0.3852 0.5268 0.026 Uiso 1 1 calc R . . H9B H 0.7774 0.5189 0.4812 0.026 Uiso 1 1 calc R . . N3 N 0.6864(7) 0.1773(8) 0.3973(3) 0.0182(15) Uani 1 1 d . . . C10 C 0.7120(9) 0.3364(10) 0.4042(4) 0.0197(18) Uani 1 1 d . . . C11 C 0.6961(9) 0.4353(10) 0.3365(4) 0.0225(19) Uani 1 1 d . . . H11 H 0.7133 0.5470 0.3427 0.027 Uiso 1 1 calc R . . C12 C 0.6555(9) 0.3747(11) 0.2597(4) 0.025(2) Uani 1 1 d . . . H12 H 0.6434 0.4432 0.2131 0.030 Uiso 1 1 calc R . . C13 C 0.6330(9) 0.2132(11) 0.2528(4) 0.026(2) Uani 1 1 d . . . H13 H 0.6062 0.1674 0.2007 0.031 Uiso 1 1 calc R . . C14 C 0.6496(9) 0.1170(10) 0.3222(4) 0.0216(18) Uani 1 1 d . . . H14 H 0.6345 0.0048 0.3166 0.026 Uiso 1 1 calc R . . Cl1 Cl 0.5530(2) -0.1719(2) 0.43816(9) 0.0207(5) 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 0.0155(6) 0.0153(6) 0.0124(4) 0.0006(3) -0.0021(2) -0.0030(4) N1 0.015(4) 0.015(4) 0.016(3) 0.002(2) 0.000(2) -0.002(3) C2 0.011(5) 0.027(5) 0.015(3) -0.002(2) 0.001(2) -0.003(4) C3 0.017(5) 0.034(6) 0.022(4) 0.003(3) -0.001(3) 0.004(4) C4 0.029(6) 0.030(6) 0.023(4) 0.010(3) 0.004(3) 0.004(5) C5 0.013(5) 0.021(5) 0.023(3) 0.000(3) 0.004(2) -0.003(4) C6 0.014(5) 0.033(5) 0.016(3) -0.008(3) 0.006(2) -0.009(4) N2 0.018(4) 0.012(4) 0.024(3) 0.002(2) -0.002(2) -0.011(3) C8 0.020(5) 0.019(5) 0.021(3) -0.001(3) -0.004(3) -0.007(4) C9 0.029(5) 0.010(5) 0.025(4) -0.001(3) 0.003(3) -0.010(4) N3 0.007(4) 0.027(5) 0.020(3) 0.003(2) -0.001(2) -0.004(3) C10 0.013(5) 0.022(6) 0.025(4) 0.003(3) -0.001(2) 0.000(4) C11 0.015(5) 0.012(5) 0.040(4) 0.008(3) 0.003(3) 0.000(4) C12 0.017(5) 0.032(6) 0.028(4) 0.016(3) 0.001(3) 0.001(4) C13 0.018(5) 0.042(7) 0.019(3) 0.001(3) -0.003(3) 0.003(4) C14 0.022(5) 0.024(5) 0.019(3) 0.001(3) -0.001(3) 0.001(4) Cl1 0.0223(11) 0.0214(12) 0.0184(8) -0.0021(6) -0.0019(6) -0.0051(9) _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 N1 1.959(6) . Y Cu1 N2 2.009(6) . Y Cu1 N3 2.043(6) . Y Cu1 Cl1 2.298(2) . Y Cu1 Cl1 2.766(2) 3_656 Y N1 C5 1.344(9) . ? N1 C2 1.375(8) . ? C2 C3 1.388(10) . ? C2 C6 1.416(11) . ? C3 C4 1.386(11) . ? C4 C5 1.390(10) . ? C6 N2 1.291(9) . ? N2 C8 1.457(9) . ? C8 C9 1.515(10) . ? C9 C10 1.492(9) . ? N3 C14 1.347(9) . ? N3 C10 1.352(10) . ? C10 C11 1.375(10) . ? C11 C12 1.380(11) . ? C12 C13 1.367(12) . ? C13 C14 1.383(10) . ? Cl1 Cu1 2.766(2) 3_656 ? 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 N1 Cu1 N2 81.2(2) . . Y N1 Cu1 N3 167.3(2) . . Y N2 Cu1 N3 90.3(2) . . Y N1 Cu1 Cl1 91.57(18) . . Y N2 Cu1 Cl1 167.8(2) . . Y N3 Cu1 Cl1 95.04(18) . . Y N1 Cu1 Cl1 102.95(17) . 3_656 Y N2 Cu1 Cl1 100.46(19) . 3_656 Y N3 Cu1 Cl1 87.87(17) . 3_656 Y Cl1 Cu1 Cl1 90.69(7) . 3_656 Y C5 N1 C2 106.9(6) . . ? C5 N1 Cu1 139.7(5) . . ? C2 N1 Cu1 113.4(5) . . ? N1 C2 C3 109.5(7) . . ? N1 C2 C6 114.3(6) . . ? C3 C2 C6 136.0(7) . . ? C4 C3 C2 106.5(6) . . ? C3 C4 C5 107.0(7) . . ? N1 C5 C4 110.1(7) . . ? N2 C6 C2 117.6(7) . . ? C6 N2 C8 122.2(6) . . ? C6 N2 Cu1 113.2(5) . . ? C8 N2 Cu1 124.5(5) . . ? N2 C8 C9 109.2(6) . . ? C10 C9 C8 112.6(6) . . ? C14 N3 C10 118.6(6) . . ? C14 N3 Cu1 118.9(5) . . ? C10 N3 Cu1 122.4(4) . . ? N3 C10 C11 120.6(7) . . ? N3 C10 C9 118.7(6) . . ? C11 C10 C9 120.7(8) . . ? C10 C11 C12 121.0(8) . . ? C13 C12 C11 118.0(7) . . ? C12 C13 C14 119.6(7) . . ? N3 C14 C13 122.1(8) . . ? Cu1 Cl1 Cu1 89.31(7) . 3_656 Y loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N2 Cu1 N1 C5 175.8(8) . . . . ? N3 Cu1 N1 C5 -135.4(11) . . . . ? Cl1 Cu1 N1 C5 -14.1(7) . . . . ? Cl1 Cu1 N1 C5 77.0(7) 3_656 . . . ? N2 Cu1 N1 C2 -4.6(5) . . . . ? N3 Cu1 N1 C2 44.2(13) . . . . ? Cl1 Cu1 N1 C2 165.5(4) . . . . ? Cl1 Cu1 N1 C2 -103.4(4) 3_656 . . . ? C5 N1 C2 C3 0.6(8) . . . . ? Cu1 N1 C2 C3 -179.1(5) . . . . ? C5 N1 C2 C6 -175.7(6) . . . . ? Cu1 N1 C2 C6 4.6(7) . . . . ? N1 C2 C3 C4 0.3(8) . . . . ? C6 C2 C3 C4 175.4(8) . . . . ? C2 C3 C4 C5 -1.0(8) . . . . ? C2 N1 C5 C4 -1.3(8) . . . . ? Cu1 N1 C5 C4 178.3(6) . . . . ? C3 C4 C5 N1 1.4(8) . . . . ? N1 C2 C6 N2 -1.3(9) . . . . ? C3 C2 C6 N2 -176.2(8) . . . . ? C2 C6 N2 C8 175.5(6) . . . . ? C2 C6 N2 Cu1 -2.6(8) . . . . ? N1 Cu1 N2 C6 4.0(5) . . . . ? N3 Cu1 N2 C6 -166.5(5) . . . . ? Cl1 Cu1 N2 C6 -50.3(11) . . . . ? Cl1 Cu1 N2 C6 105.6(5) 3_656 . . . ? N1 Cu1 N2 C8 -174.1(6) . . . . ? N3 Cu1 N2 C8 15.5(6) . . . . ? Cl1 Cu1 N2 C8 131.7(7) . . . . ? Cl1 Cu1 N2 C8 -72.4(5) 3_656 . . . ? C6 N2 C8 C9 -149.6(7) . . . . ? Cu1 N2 C8 C9 28.3(7) . . . . ? N2 C8 C9 C10 -71.7(7) . . . . ? N1 Cu1 N3 C14 98.4(12) . . . . ? N2 Cu1 N3 C14 146.5(5) . . . . ? Cl1 Cu1 N3 C14 -22.5(5) . . . . ? Cl1 Cu1 N3 C14 -113.1(5) 3_656 . . . ? N1 Cu1 N3 C10 -80.5(13) . . . . ? N2 Cu1 N3 C10 -32.4(6) . . . . ? Cl1 Cu1 N3 C10 158.5(6) . . . . ? Cl1 Cu1 N3 C10 68.0(6) 3_656 . . . ? C14 N3 C10 C11 2.0(11) . . . . ? Cu1 N3 C10 C11 -179.0(5) . . . . ? C14 N3 C10 C9 -176.9(6) . . . . ? Cu1 N3 C10 C9 2.0(9) . . . . ? C8 C9 C10 N3 57.3(9) . . . . ? C8 C9 C10 C11 -121.6(8) . . . . ? N3 C10 C11 C12 -0.8(12) . . . . ? C9 C10 C11 C12 178.1(7) . . . . ? C10 C11 C12 C13 -0.6(12) . . . . ? C11 C12 C13 C14 0.8(12) . . . . ? C10 N3 C14 C13 -1.9(11) . . . . ? Cu1 N3 C14 C13 179.1(6) . . . . ? C12 C13 C14 N3 0.5(12) . . . . ? N1 Cu1 Cl1 Cu1 102.98(17) . . . 3_656 ? N2 Cu1 Cl1 Cu1 156.3(8) . . . 3_656 ? N3 Cu1 Cl1 Cu1 -87.92(17) . . . 3_656 ? Cl1 Cu1 Cl1 Cu1 0.0 3_656 . . 3_656 ? _diffrn_measured_fraction_theta_max 0.665 _diffrn_reflns_theta_full 26.43 _diffrn_measured_fraction_theta_full 0.665 _refine_diff_density_max 0.459 _refine_diff_density_min -0.761 _refine_diff_density_rms 0.103