# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/1781 data_global #======================================================================= # 1. SUBMISSION DETAILS #---------------------- _publ_contact_author_name 'Leonard F. Lindoy' _publ_contact_author_address ; School of Chemistry, University of Sydney, Sydney NSW 2006, Australia. ; _publ_contact_author_email 'l.lindoy@chem.usyd.edu.au' _publ_contact_author_fax '61-2-9351-3329' _publ_contact_author_phone '61-2-9351-4400' _publ_contact_letter ; ? ; _publ_requested_journal ' Dalton Communications ' _publ_section_title ; Fine-tuning of supramolecular motifs: perturbation of the structure of an extended hydrogen-bonded biuret array by interaction with an intercalated copper complex and methanol molecules ; loop_ _publ_author_name _publ_author_address 'Michael M. Bishop' ; Sydney Grammar School, College Street, Darlinghurst, NSW, 2010, Australia ; 'Leonard F. Lindoy' ; School of Chemistry, University of Sydney, Sydney NSW 2006, Australia. ; 'Srihari Mahadevb ' ; Sydney Grammar School, College Street, Darlinghurst, NSW, 2010, Australia ; 'Peter Turner' ; School of Chemistry, University of Sydney, Sydney NSW 2006, Australia. ; _publ_section_experimental ; A blue prismatic crystal was attached to a thin glass fibre and mounted on a Bruker SMART 1000 CCD diffractometer employing graphite monochromated MoKa generated from a sealed tube. Cell constants were obtained from a least squares refinement against 6703 reflections located between 4.46 and 52.06 deg. two theta. Data were collected at 297(2) Kelvin with \w scans to 55.98 deg. 2\q. The intensities of 399 reflections recollected at the end of the experiment did not change significantly during the data collection. An empirical correction determined with SADABS was applied to the data and the data integration and reduction were undertaken with SAINT and XPREP. The reflection statistics were not unamiguously centric or acentric, however the systematic absences indicated the non-centrosymmetric space group P212121(#19). Systematic absence exceptions: b-- c-- n-- 21-- -c- -a- -n- -21- --a --b --n --21 N 1109 1086 1085 14 787 775 774 25 628 630 634 34 N I>3s 505 540 733 1 293 395 338 0 178 313 277 0 15.0 68.1 77.1 0.7 12.7 61.1 55.4 0.6 5.0 99.0 97.0 0.4 6.8 12.2 15.6 1.4 5.8 13.1 11.0 0.4 3.2 12.1 11.3 0.5 The structure was accordingly solved in the space group P212121(#19) by direct methods with SIR97, and extended and refined with SHELXL-97 using the teXsan interface. A subsequent examination of the structure with PLATON revealed the presence of an approximate centre of symmetry at 0.252 0.249 0.246, with atoms O(1) O(3) N(19) C(1) C(5) C(17) C(18) C(19) and C(20) deviating by more than 0.4 Ang. from inversion symmetry. The N(19) C(17) C(18) C(19) and C(20) solvate atom deviation from inversion symmetry was more than 0.6 Ang. A structure could be obtained in the centrosymmetric space group Pbca, however the refinement was poor with double figure residuals following anisotropic refinement of the non-hydrogen atoms. Accordingly the non-centrosymmetric model was adopted. There was no significant refinement variable correlation in P212121, however the presence of the pseudo symmetry resulted in the Flack (SHELXL BASF) parameter refining to 0.423(8). That is, the structure appears to be non-centrosymmetric and the crystal is close to being an equimolecular inversion twin. Anisotropic thermal parameters were refined for the 56 non-hydrogen atoms in the asymmetric unit of the structure model and a riding atom model was used for the 49 hydrogen atoms. In addition to a complex cation, the asymmetric unit contains two bromide counterions, four biuret molecules, two methanol molecules and an acetonitrile molecule. The population of the acetonitrile molecule refined to 0.8. ; _publ_section_references ; 1. Sheldrick, G.M.; SADABS. Empirical absorption correction program for area detector data. University of G"ttingen, Germany, 1996. 2. Bruker (1995). SMART, SAINT and XPREP. Area detector control and data integration and reduction software. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. 3. Altomare, A., Cascarano, M., Giacovazzo, C., Guagliardi, A. J. Appl. Cryst.,(1993), 26, 343. 4. Sheldrick, G.M.; SHELXL97. Program for crystal structure refinement. University of G"ttingen, Germany, 1997. 5. Molecular Structure Corporation (1997-1998). teXsan for Windows: Single Crystal Structure Analysis Software, MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. 6. PLATON/PLUTON - (a) A. L. Spek, Acta Crystallogr., Sect A 1990, 46, C34. (b) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands, A. L. Spek, 1998. 7. (a) Flack, H.D. Acta Crystallogr., Sect A 1983, 39, 876-881. (b) Bernardinelli, G.; Flack, H. D. Acta Crystallogr., Sect A 1985, 41, 500-511. 8. (a) Johnson,C.K.; ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Oak Ridge, Tennessee (1976). (b)Hall, S.R., du Boulay, D.J. & Olthof-Hazekamp, R. (1999) Eds. Xtal3.6 System . University of Western Australia. ; #======================================================================= # Data block for single structure (one for each study in the paper) #======================================================================= data_lfl1 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19.60 H48.40 Br2 Cu N18.80 O14' _chemical_formula_weight 994.93 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' 'Br' 'Br' -0.2901 2.4595 '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 orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21 ' _symmetry_Int_Tables_number 19 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 17.1111(7) _cell_length_b 18.1222(7) _cell_length_c 13.4364(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4166.5(3) _cell_formula_units_Z 4 _cell_measurement_temperature 297(2) _cell_measurement_reflns_used 6703 _cell_measurement_theta_min 2.23 _cell_measurement_theta_max 26.03 _exptl_crystal_description prism _exptl_crystal_colour blue _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.586 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2034 _exptl_absorpt_coefficient_mu 2.521 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.4983 _exptl_absorpt_correction_T_max 0.7402 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 297(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 399 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 44202 _diffrn_reflns_av_R_equivalents 0.036 _diffrn_reflns_av_sigmaI/netI 0.0274 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.64 _diffrn_reflns_theta_max 27.99 _reflns_number_total 9808 _reflns_number_gt 8080 _reflns_threshold_expression >2sigma(I) _computing_data_collection SMART _computing_cell_refinement SAINT _computing_data_reduction 'SAINT and XPREP' _computing_structure_solution 'SIR97 (Altomare, et. al. 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'teXsan for Windows (MSC, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0481P)^2^+2.4052P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.423(8) _refine_ls_number_reflns 9803 _refine_ls_number_parameters 514 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0531 _refine_ls_R_factor_gt 0.0378 _refine_ls_wR_factor_ref 0.0986 _refine_ls_wR_factor_gt 0.0910 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.027 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.93207(2) 0.36968(2) 0.07350(3) 0.04766(11) Uani 1 1 d . . . Br2 Br 0.57178(2) 0.12887(2) 0.41821(3) 0.05030(11) Uani 1 1 d . . . Cu1 Cu 0.76228(2) 0.24845(3) 0.25694(4) 0.03795(10) Uani 1 1 d . . . O1 O 0.78355(17) 0.47590(14) 0.3108(2) 0.0546(7) Uani 1 1 d . . . O2 O 0.55738(16) 0.36617(16) 0.3227(2) 0.0546(7) Uani 1 1 d . . . O3 O 0.75159(17) 0.01867(15) 0.2142(3) 0.0569(8) Uani 1 1 d . . . O4 O 0.97010(16) 0.13759(16) 0.1813(2) 0.0532(7) Uani 1 1 d . . . O5 O 0.71958(14) 0.26454(13) 0.0439(2) 0.0461(7) Uani 1 1 d . . . O6 O 0.83634(15) 0.08047(15) -0.0582(2) 0.0510(7) Uani 1 1 d . . . O7 O 0.78377(14) 0.23642(13) 0.4612(2) 0.0422(6) Uani 1 1 d . . . O8 O 0.66666(15) 0.41301(15) 0.5859(2) 0.0523(7) Uani 1 1 d . . . O9 O 0.86341(15) -0.01996(15) 0.4568(3) 0.0496(7) Uani 1 1 d . . . O10 O 0.98314(13) 0.17724(14) 0.4330(2) 0.0416(6) Uani 1 1 d . . . O11 O 0.63855(14) 0.52153(14) 0.0681(3) 0.0492(7) Uani 1 1 d . . . O12 O 0.52037(14) 0.32372(15) 0.0625(2) 0.0470(7) Uani 1 1 d . . . O13 O 0.8948(2) 0.4637(2) -0.1305(3) 0.0725(10) Uani 1 1 d . . . H13O H 0.8955 0.4424 -0.0767 0.109 Uiso 1 1 calc R . . O14 O 0.5772(3) 0.03988(19) 0.6396(3) 0.0792(10) Uani 1 1 d . . . H14O H 0.6081 0.0401 0.5929 0.119 Uiso 1 1 calc R . . N1 N 0.79531(18) 0.35181(15) 0.2673(2) 0.0425(7) Uani 1 1 d . . . H1N H 0.8428 0.3607 0.2502 0.051 Uiso 1 1 calc R . . N2 N 0.67806(19) 0.40581(18) 0.3146(3) 0.0458(8) Uani 1 1 d . . . H2N H 0.6569 0.4463 0.3345 0.055 Uiso 1 1 calc R . . N3 N 0.65435(18) 0.28078(18) 0.2820(2) 0.0428(7) Uani 1 1 d . . . H3N H 0.6190 0.2473 0.2769 0.051 Uiso 1 1 calc R . . N4 N 0.73192(18) 0.14394(15) 0.2484(2) 0.0428(7) Uani 1 1 d . . . H4N H 0.6844 0.1339 0.2642 0.051 Uiso 1 1 calc R . . N5 N 0.8521(2) 0.09284(18) 0.1996(3) 0.0473(8) Uani 1 1 d . . . H5N H 0.8747 0.0528 0.1806 0.057 Uiso 1 1 calc R . . N6 N 0.87006(18) 0.21829(17) 0.2272(3) 0.0440(8) Uani 1 1 d . . . H6N H 0.9043 0.2530 0.2298 0.053 Uiso 1 1 calc R . . N7 N 0.61147(18) 0.19394(18) 0.0252(3) 0.0501(9) Uani 1 1 d . . . H7NA H 0.5811 0.2282 0.0468 0.060 Uiso 1 1 calc R . . H7NB H 0.5923 0.1521 0.0074 0.060 Uiso 1 1 calc R . . N8 N 0.73128(18) 0.14625(16) -0.0138(2) 0.0397(7) Uani 1 1 d . . . H8N H 0.7048 0.1067 -0.0245 0.048 Uiso 1 1 calc R . . N9 N 0.85513(18) 0.20039(18) -0.0203(3) 0.0424(8) Uani 1 1 d . . . H9NA H 0.9047 0.1975 -0.0305 0.051 Uiso 1 1 calc R . . H9NB H 0.8346 0.2416 -0.0022 0.051 Uiso 1 1 calc R . . N10 N 0.89146(18) 0.30479(18) 0.4907(3) 0.0486(9) Uani 1 1 d . . . H10NA H 0.9217 0.2717 0.4658 0.058 Uiso 1 1 calc R . . H10NB H 0.9109 0.3451 0.5137 0.058 Uiso 1 1 calc R . . N11 N 0.77232(17) 0.35052(16) 0.5333(3) 0.0397(7) Uani 1 1 d . . . H11N H 0.7985 0.3893 0.5489 0.048 Uiso 1 1 calc R . . N12 N 0.64872(18) 0.29547(18) 0.5347(3) 0.0434(8) Uani 1 1 d . . . H12NA H 0.5994 0.2968 0.5471 0.052 Uiso 1 1 calc R . . H12NB H 0.6695 0.2560 0.5111 0.052 Uiso 1 1 calc R . . N13 N 0.75652(17) 0.05346(19) 0.4702(3) 0.0504(9) Uani 1 1 d . . . H13NA H 0.7254 0.0163 0.4744 0.060 Uiso 1 1 calc R . . H13NB H 0.7382 0.0976 0.4723 0.060 Uiso 1 1 calc R . . N14 N 0.87654(16) 0.10601(16) 0.4536(3) 0.0385(7) Uani 1 1 d . . . H14N H 0.8506 0.1464 0.4597 0.046 Uiso 1 1 calc R . . N15 N 0.99956(16) 0.05335(18) 0.4290(3) 0.0485(9) Uani 1 1 d . . . H15NA H 1.0490 0.0568 0.4186 0.058 Uiso 1 1 calc R . . H15NB H 0.9779 0.0106 0.4334 0.058 Uiso 1 1 calc R . . N16 N 0.74691(16) 0.45120(18) 0.0602(3) 0.0475(8) Uani 1 1 d . . . H16NA H 0.7773 0.4890 0.0614 0.057 Uiso 1 1 calc R . . H16NB H 0.7664 0.4075 0.0570 0.057 Uiso 1 1 calc R . . N17 N 0.62732(16) 0.39594(16) 0.0622(3) 0.0408(8) Uani 1 1 d . . . H17N H 0.6541 0.3559 0.0594 0.049 Uiso 1 1 calc R . . N18 N 0.50235(16) 0.44607(18) 0.0707(3) 0.0477(9) Uani 1 1 d . . . H18NA H 0.4524 0.4415 0.0728 0.048 Uiso 1 1 calc R . . H18NB H 0.5233 0.4892 0.0723 0.048 Uiso 1 1 calc R . . N19 N 0.7919(5) 0.2058(4) 0.7165(6) 0.115(3) Uani 0.80 1 d P . . C1 C 0.8664(3) 0.4870(3) 0.3033(4) 0.0621(12) Uani 1 1 d . . . H1A H 0.8928 0.4540 0.3479 0.093 Uiso 1 1 calc R . . H1B H 0.8787 0.5371 0.3207 0.093 Uiso 1 1 calc R . . H1C H 0.8830 0.4775 0.2363 0.093 Uiso 1 1 calc R . . C2 C 0.7560(2) 0.4075(2) 0.2958(3) 0.0390(8) Uani 1 1 d . . . C3 C 0.6298(2) 0.3459(2) 0.3051(3) 0.0413(9) Uani 1 1 d . . . C4 C 0.4959(2) 0.3125(3) 0.3130(4) 0.0609(13) Uani 1 1 d . . . H4A H 0.4956 0.2933 0.2464 0.091 Uiso 1 1 calc R . . H4B H 0.4465 0.3355 0.3269 0.091 Uiso 1 1 calc R . . H4C H 0.5045 0.2729 0.3592 0.091 Uiso 1 1 calc R . . C5 C 0.6703(3) 0.0019(2) 0.2218(4) 0.0603(12) Uani 1 1 d . . . H5A H 0.6527 0.0117 0.2883 0.091 Uiso 1 1 calc R . . H5B H 0.6621 -0.0493 0.2064 0.091 Uiso 1 1 calc R . . H5C H 0.6415 0.0319 0.1758 0.091 Uiso 1 1 calc R . . C6 C 0.7743(2) 0.08906(19) 0.2223(3) 0.0401(8) Uani 1 1 d . . . C7 C 0.8965(2) 0.1547(2) 0.2046(3) 0.0403(8) Uani 1 1 d . . . C8 C 1.0289(3) 0.1945(3) 0.1881(4) 0.0626(13) Uani 1 1 d . . . H8A H 1.0113 0.2377 0.1536 0.094 Uiso 1 1 calc R . . H8B H 1.0766 0.1772 0.1584 0.094 Uiso 1 1 calc R . . H8C H 1.0380 0.2063 0.2568 0.094 Uiso 1 1 calc R . . C9 C 0.6887(2) 0.2058(2) 0.0194(3) 0.0363(8) Uani 1 1 d . . . C10 C 0.81015(19) 0.1410(2) -0.0324(3) 0.0352(8) Uani 1 1 d . . . C11 C 0.8151(2) 0.29372(19) 0.4935(3) 0.0349(8) Uani 1 1 d . . . C12 C 0.6924(2) 0.3541(2) 0.5519(3) 0.0377(8) Uani 1 1 d . . . C13 C 0.83297(19) 0.0426(2) 0.4604(3) 0.0373(8) Uani 1 1 d . . . C14 C 0.95619(19) 0.1146(2) 0.4384(3) 0.0349(8) Uani 1 1 d . . . C15 C 0.6694(2) 0.46036(19) 0.0634(3) 0.0363(8) Uani 1 1 d . . . C16 C 0.5464(2) 0.38757(19) 0.0651(3) 0.0369(8) Uani 1 1 d . . . C17 C 0.9629(4) 0.4472(5) -0.1833(5) 0.123(3) Uani 1 1 d . . . H17A H 0.9663 0.4782 -0.2410 0.185 Uiso 1 1 calc R . . H17B H 0.9618 0.3964 -0.2036 0.185 Uiso 1 1 calc R . . H17C H 1.0075 0.4555 -0.1414 0.185 Uiso 1 1 calc R . . C18 C 0.5918(5) 0.1007(4) 0.7010(5) 0.117(3) Uani 1 1 d . . . H18C H 0.5970 0.0844 0.7687 0.176 Uiso 1 1 calc R . . H18D H 0.5491 0.1349 0.6962 0.176 Uiso 1 1 calc R . . H18E H 0.6392 0.1245 0.6803 0.176 Uiso 1 1 calc R . . C19 C 0.7830(6) 0.2602(4) 0.7525(6) 0.097(3) Uani 0.80 1 d P . . C20 C 0.7712(6) 0.3274(5) 0.7986(6) 0.117(3) Uani 0.80 1 d P . . H20A H 0.7826 0.3229 0.8683 0.175 Uiso 0.80 1 calc PR . . H20B H 0.7178 0.3423 0.7902 0.175 Uiso 0.80 1 calc PR . . H20C H 0.8050 0.3637 0.7694 0.175 Uiso 0.80 1 calc PR . . 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 Br1 0.04012(19) 0.0376(2) 0.0653(3) 0.00569(19) 0.00739(18) 0.00123(16) Br2 0.0415(2) 0.0399(2) 0.0695(3) 0.0026(2) 0.00633(19) -0.00059(17) Cu1 0.0374(2) 0.02866(18) 0.0478(2) 0.00104(19) 0.00577(19) 0.00199(18) O1 0.0599(18) 0.0300(13) 0.074(2) -0.0094(13) 0.0081(15) 0.0006(12) O2 0.0398(15) 0.0495(16) 0.0745(19) 0.0002(15) 0.0060(13) 0.0079(13) O3 0.0597(19) 0.0312(14) 0.080(2) -0.0100(14) 0.0054(14) -0.0020(12) O4 0.0412(14) 0.0452(16) 0.0732(19) -0.0024(15) 0.0093(13) 0.0086(13) O5 0.0292(13) 0.0304(15) 0.0785(19) -0.0113(13) -0.0017(12) -0.0009(10) O6 0.0318(13) 0.0368(15) 0.084(2) -0.0182(14) 0.0076(13) -0.0008(11) O7 0.0318(13) 0.0298(15) 0.0649(17) -0.0090(12) -0.0025(11) 0.0020(10) O8 0.0344(13) 0.0410(15) 0.081(2) -0.0202(15) 0.0045(14) -0.0005(11) O9 0.0328(13) 0.0291(13) 0.087(2) 0.0080(14) 0.0018(13) 0.0006(11) O10 0.0280(12) 0.0258(13) 0.0710(19) -0.0038(13) -0.0009(12) -0.0017(10) O11 0.0308(13) 0.0275(13) 0.089(2) 0.0063(14) 0.0027(13) 0.0005(10) O12 0.0321(13) 0.0337(15) 0.075(2) -0.0021(14) -0.0015(13) 0.0023(11) O13 0.071(2) 0.072(2) 0.074(2) 0.0236(19) 0.0058(18) 0.0299(18) O14 0.101(3) 0.052(2) 0.085(3) 0.0084(19) 0.002(2) 0.019(2) N1 0.0400(15) 0.0334(16) 0.0542(19) 0.0031(14) 0.0113(14) 0.0030(12) N2 0.0471(18) 0.0340(17) 0.056(2) -0.0042(15) 0.0050(16) 0.0064(14) N3 0.0362(16) 0.0367(16) 0.055(2) 0.0002(14) 0.0054(14) 0.0025(13) N4 0.0400(14) 0.0344(16) 0.0540(18) -0.0018(15) 0.0044(16) -0.0040(12) N5 0.0516(19) 0.0349(17) 0.055(2) -0.0013(15) 0.0093(16) 0.0071(15) N6 0.0391(16) 0.0327(16) 0.060(2) -0.0012(15) 0.0043(14) -0.0011(12) N7 0.0277(16) 0.0313(17) 0.091(3) -0.0114(17) -0.0016(16) -0.0004(13) N8 0.0283(14) 0.0264(15) 0.064(2) -0.0084(13) 0.0022(14) -0.0018(12) N9 0.0325(16) 0.0326(17) 0.062(2) -0.0101(15) 0.0031(15) 0.0008(13) N10 0.0240(15) 0.0398(19) 0.082(3) -0.0145(17) -0.0013(15) 0.0005(13) N11 0.0279(14) 0.0301(16) 0.0612(19) -0.0067(14) 0.0020(14) -0.0048(12) N12 0.0264(15) 0.0346(18) 0.069(2) -0.0062(16) 0.0028(15) -0.0023(12) N13 0.0285(16) 0.0329(17) 0.090(3) 0.0097(17) 0.0036(15) 0.0005(12) N14 0.0275(14) 0.0248(15) 0.063(2) 0.0006(14) 0.0024(13) 0.0022(11) N15 0.0268(15) 0.0307(18) 0.088(3) -0.0004(18) 0.0013(16) 0.0031(12) N16 0.0278(16) 0.0333(17) 0.082(2) 0.0064(17) 0.0036(14) 0.0001(11) N17 0.0309(15) 0.0257(15) 0.066(2) 0.0001(15) -0.0002(14) 0.0019(11) N18 0.0264(15) 0.0288(17) 0.088(3) -0.0046(18) -0.0024(16) -0.0003(12) N19 0.131(7) 0.099(5) 0.116(6) 0.018(5) -0.023(5) 0.004(5) C1 0.056(3) 0.048(2) 0.083(3) -0.008(2) 0.007(2) -0.017(2) C2 0.044(2) 0.0323(18) 0.0408(19) 0.0012(15) 0.0049(15) -0.0030(15) C3 0.0397(19) 0.045(2) 0.039(2) 0.0051(17) 0.0058(15) 0.0085(16) C4 0.039(2) 0.073(3) 0.070(3) 0.009(3) 0.010(2) 0.007(2) C5 0.063(3) 0.045(2) 0.072(3) -0.002(2) 0.007(2) -0.016(2) C6 0.050(2) 0.0307(17) 0.0401(19) 0.0002(15) -0.0010(16) -0.0035(16) C7 0.0412(19) 0.0365(19) 0.043(2) 0.0013(16) 0.0036(16) 0.0042(16) C8 0.041(2) 0.053(3) 0.093(4) 0.008(3) 0.011(2) 0.008(2) C9 0.0291(18) 0.034(2) 0.046(2) -0.0003(16) -0.0012(15) 0.0011(14) C10 0.0276(16) 0.0299(18) 0.048(2) -0.0040(15) 0.0009(14) 0.0003(13) C11 0.0287(17) 0.0298(19) 0.046(2) -0.0010(15) -0.0050(14) 0.0038(14) C12 0.0305(17) 0.035(2) 0.048(2) 0.0008(16) -0.0020(14) 0.0037(14) C13 0.0265(17) 0.0350(19) 0.050(2) 0.0019(16) 0.0005(14) 0.0013(14) C14 0.0247(15) 0.034(2) 0.046(2) -0.0021(16) -0.0010(14) -0.0009(13) C15 0.0303(16) 0.0309(18) 0.048(2) 0.0068(16) -0.0011(14) -0.0010(13) C16 0.0337(17) 0.0295(19) 0.048(2) 0.0001(16) -0.0022(15) 0.0000(13) C17 0.120(6) 0.139(7) 0.111(5) 0.048(5) 0.048(5) 0.064(5) C18 0.172(8) 0.089(5) 0.091(5) -0.008(4) 0.002(5) 0.030(5) C19 0.142(7) 0.072(5) 0.079(5) 0.029(4) -0.044(5) -0.018(5) C20 0.164(9) 0.109(7) 0.078(5) 0.020(5) -0.009(6) 0.017(7) _geom_special_details ; All standard uncertainties (sus) are estimated using the full covariance matrix. The cell sus are taken into account individually in the estimation of sus in distances, angles and torsion angles; correlations between sus in cell parameters are only used when they are defined by crystal symmetry. ; 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 1.962(3) . ? Cu1 N6 1.965(3) . ? Cu1 N3 1.966(3) . ? Cu1 N4 1.967(3) . ? O1 C2 1.342(4) . ? O1 C1 1.435(5) . ? O2 C3 1.314(4) . ? O2 C4 1.439(5) . ? O3 C6 1.338(4) . ? O3 C5 1.427(5) . ? O4 C7 1.334(4) . ? O4 C8 1.443(5) . ? O5 C9 1.233(4) . ? O6 C10 1.234(4) . ? O7 C11 1.246(4) . ? O8 C12 1.242(4) . ? O9 C13 1.248(4) . ? O10 C14 1.228(4) . ? O11 C15 1.229(4) . ? O12 C16 1.241(4) . ? O13 C17 1.397(6) . ? O14 C18 1.399(7) . ? N1 C2 1.272(5) . ? N2 C2 1.357(5) . ? N2 C3 1.370(5) . ? N3 C3 1.290(5) . ? N4 C6 1.280(5) . ? N5 C7 1.356(5) . ? N5 C6 1.367(5) . ? N6 C7 1.275(5) . ? N7 C9 1.342(5) . ? N8 C10 1.376(4) . ? N8 C9 1.376(5) . ? N9 C10 1.334(5) . ? N10 C11 1.323(5) . ? N11 C11 1.371(4) . ? N11 C12 1.391(4) . ? N12 C12 1.320(5) . ? N13 C13 1.329(4) . ? N14 C13 1.373(5) . ? N14 C14 1.387(4) . ? N15 C14 1.341(5) . ? N16 C15 1.338(4) . ? N17 C15 1.372(4) . ? N17 C16 1.393(4) . ? N18 C16 1.303(5) . ? N19 C19 1.109(10) . ? C19 C20 1.380(11) . ? 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 N6 90.54(13) . . ? N1 Cu1 N3 88.51(13) . . ? N6 Cu1 N3 177.83(15) . . ? N1 Cu1 N4 178.38(13) . . ? N6 Cu1 N4 88.19(13) . . ? N3 Cu1 N4 92.80(13) . . ? C2 O1 C1 117.8(3) . . ? C3 O2 C4 119.0(3) . . ? C6 O3 C5 118.8(3) . . ? C7 O4 C8 118.5(3) . . ? C2 N1 Cu1 128.8(3) . . ? C2 N2 C3 126.3(3) . . ? C3 N3 Cu1 128.3(3) . . ? C6 N4 Cu1 127.9(3) . . ? C7 N5 C6 125.1(3) . . ? C7 N6 Cu1 129.3(3) . . ? C10 N8 C9 129.2(3) . . ? C11 N11 C12 129.0(3) . . ? C13 N14 C14 129.6(3) . . ? C15 N17 C16 127.9(3) . . ? N1 C2 O1 126.3(3) . . ? N1 C2 N2 123.9(3) . . ? O1 C2 N2 109.8(3) . . ? N3 C3 O2 127.3(4) . . ? N3 C3 N2 123.4(3) . . ? O2 C3 N2 109.3(3) . . ? N4 C6 O3 126.7(4) . . ? N4 C6 N5 125.0(3) . . ? O3 C6 N5 108.2(3) . . ? N6 C7 O4 127.0(4) . . ? N6 C7 N5 124.1(3) . . ? O4 C7 N5 108.9(3) . . ? O5 C9 N7 123.0(3) . . ? O5 C9 N8 122.5(3) . . ? N7 C9 N8 114.5(3) . . ? O6 C10 N9 122.8(3) . . ? O6 C10 N8 118.0(3) . . ? N9 C10 N8 119.2(3) . . ? O7 C11 N10 122.7(3) . . ? O7 C11 N11 122.2(3) . . ? N10 C11 N11 115.1(3) . . ? O8 C12 N12 123.7(3) . . ? O8 C12 N11 117.1(3) . . ? N12 C12 N11 119.2(3) . . ? O9 C13 N13 123.3(3) . . ? O9 C13 N14 122.1(3) . . ? N13 C13 N14 114.6(3) . . ? O10 C14 N15 123.5(3) . . ? O10 C14 N14 118.8(3) . . ? N15 C14 N14 117.7(3) . . ? O11 C15 N16 122.6(3) . . ? O11 C15 N17 122.9(3) . . ? N16 C15 N17 114.5(3) . . ? O12 C16 N18 123.5(3) . . ? O12 C16 N17 117.3(3) . . ? N18 C16 N17 119.2(3) . . ? N19 C19 C20 179.1(11) . . ? 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 N6 Cu1 N1 C2 -172.4(4) . . . . ? N3 Cu1 N1 C2 9.5(4) . . . . ? N4 Cu1 N1 C2 -134(5) . . . . ? N1 Cu1 N3 C3 -6.2(4) . . . . ? N6 Cu1 N3 C3 -70(4) . . . . ? N4 Cu1 N3 C3 172.9(4) . . . . ? N1 Cu1 N4 C6 -44(5) . . . . ? N6 Cu1 N4 C6 -6.0(4) . . . . ? N3 Cu1 N4 C6 172.1(4) . . . . ? N1 Cu1 N6 C7 -175.7(4) . . . . ? N3 Cu1 N6 C7 -112(4) . . . . ? N4 Cu1 N6 C7 5.3(4) . . . . ? Cu1 N1 C2 O1 172.9(3) . . . . ? Cu1 N1 C2 N2 -7.8(6) . . . . ? C1 O1 C2 N1 -6.2(6) . . . . ? C1 O1 C2 N2 174.5(4) . . . . ? C3 N2 C2 N1 -1.0(6) . . . . ? C3 N2 C2 O1 178.4(4) . . . . ? Cu1 N3 C3 O2 -179.1(3) . . . . ? Cu1 N3 C3 N2 1.1(6) . . . . ? C4 O2 C3 N3 -2.3(6) . . . . ? C4 O2 C3 N2 177.6(4) . . . . ? C2 N2 C3 N3 4.4(6) . . . . ? C2 N2 C3 O2 -175.4(4) . . . . ? Cu1 N4 C6 O3 -177.8(3) . . . . ? Cu1 N4 C6 N5 3.6(6) . . . . ? C5 O3 C6 N4 9.1(6) . . . . ? C5 O3 C6 N5 -172.0(4) . . . . ? C7 N5 C6 N4 2.4(6) . . . . ? C7 N5 C6 O3 -176.5(4) . . . . ? Cu1 N6 C7 O4 177.2(3) . . . . ? Cu1 N6 C7 N5 -2.0(6) . . . . ? C8 O4 C7 N6 4.7(7) . . . . ? C8 O4 C7 N5 -176.0(4) . . . . ? C6 N5 C7 N6 -3.2(7) . . . . ? C6 N5 C7 O4 177.5(3) . . . . ? C10 N8 C9 O5 -4.8(7) . . . . ? C10 N8 C9 N7 176.8(4) . . . . ? C9 N8 C10 O6 177.1(4) . . . . ? C9 N8 C10 N9 -1.8(6) . . . . ? C12 N11 C11 O7 5.1(6) . . . . ? C12 N11 C11 N10 -175.8(4) . . . . ? C11 N11 C12 O8 -177.8(4) . . . . ? C11 N11 C12 N12 3.4(6) . . . . ? C14 N14 C13 O9 2.9(7) . . . . ? C14 N14 C13 N13 -176.7(4) . . . . ? C13 N14 C14 O10 178.7(4) . . . . ? C13 N14 C14 N15 -0.4(6) . . . . ? C16 N17 C15 O11 0.5(7) . . . . ? C16 N17 C15 N16 179.8(4) . . . . ? C15 N17 C16 O12 179.5(4) . . . . ? C15 N17 C16 N18 -0.8(7) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O13 H13O Br1 0.82 2.49 3.291(3) 165.4 . O14 H14O Br2 0.82 2.91 3.385(4) 118.8 . N1 H1N Br1 0.86 2.83 3.516(3) 138.2 . N2 H2N O13 0.86 1.91 2.772(4) 175.5 2_665 N3 H3N Br2 0.86 2.98 3.595(3) 130.5 . N4 H4N Br2 0.86 2.83 3.576(3) 146.2 . N5 H5N O14 0.86 1.95 2.810(5) 178.0 2_654 N6 H6N Br1 0.86 3.02 3.594(3) 126.2 . N7 H7NA O12 0.86 2.03 2.866(4) 163.7 . N7 H7NB O9 0.86 2.60 3.312(4) 140.7 2_654 N7 H7NB Br1 0.86 2.98 3.537(3) 124.7 4_455 N8 H8N O9 0.86 1.97 2.832(4) 175.2 2_654 N9 H9NA O12 0.86 2.06 2.917(4) 172.2 4 N9 H9NB O5 0.86 2.11 2.734(4) 129.5 . N9 H9NB Br1 0.86 3.03 3.568(3) 122.3 . N10 H10N O10 0.86 2.06 2.899(4) 166.3 . N10 H10N Br2 0.86 2.94 3.530(3) 127.6 4_556 N11 H11N O11 0.86 1.96 2.814(4) 173.3 2_665 N12 H12N O10 0.86 2.06 2.909(4) 167.8 4_456 N12 H12N O7 0.86 2.10 2.731(4) 130.1 . N12 H12N Br2 0.86 3.11 3.646(3) 122.8 . N13 H13N O6 0.86 2.09 2.926(4) 162.6 2_655 N13 H13N O7 0.86 2.64 3.350(4) 141.1 . N13 H13N Br2 0.86 2.99 3.514(3) 121.0 . N14 H14N O7 0.86 1.99 2.849(4) 173.8 . N15 H15N O8 0.86 2.09 2.930(4) 166.6 4_556 N15 H15N O9 0.86 2.06 2.708(4) 131.4 . N15 H15N Br1 0.86 2.98 3.528(3) 123.1 3_745 N16 H16N O8 0.86 2.04 2.892(4) 168.0 2_664 N16 H16N Br1 0.86 2.93 3.500(3) 126.0 . N17 H17N O5 0.86 2.01 2.868(4) 176.2 . N18 H18N O6 0.86 2.03 2.886(4) 170.5 4_455 N18 H18N O11 0.86 2.06 2.702(4) 131.0 . N18 H18N Br2 0.86 3.01 3.551(3) 122.7 3_655 _diffrn_measured_fraction_theta_max 0.985 _diffrn_reflns_theta_full 27.99 _diffrn_measured_fraction_theta_full 0.984 _refine_diff_density_max 0.922 _refine_diff_density_min -0.304 _refine_diff_density_rms 0.071