# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # ####################################################################### data_ks-95s _database_code_depnum_ccdc_archive 'CCDC 896588' #TrackingRef 'KS_Cu4grids.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '(C76 H86 Cu4 N28 O10), 4(B F4), (C H4 O) ' _chemical_formula_sum 'C77 H90 B4 Cu4 F16 N28 O11' _chemical_formula_weight 2185.17 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' B B 0.0013 0.0007 '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' F F 0.0171 0.0103 '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 tetragonal _symmetry_space_group_name_H-M 'I 41/a' _symmetry_space_group_name_Hall '-I 4ad' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 24.9162(16) _cell_length_b 24.9162(16) _cell_length_c 14.2676(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8857.6(10) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 26635 _cell_measurement_theta_min 1.63 _cell_measurement_theta_max 27.61 _exptl_crystal_description block _exptl_crystal_colour 'dark brown' _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.639 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4464 _exptl_absorpt_coefficient_mu 1.058 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.618 _exptl_absorpt_correction_T_max 0.715 _exptl_absorpt_process_details ; XPREP in SHELXTL 6.14 (BrukerAXS Inc., 2003) ; _exptl_special_details ; ? ; _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 'Stoe IPDS II' _diffrn_measurement_method 'area detector' _diffrn_detector_area_resol_mean 6.667 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 66863 _diffrn_reflns_av_R_equivalents 0.0687 _diffrn_reflns_av_sigmaI/netI 0.0310 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.63 _diffrn_reflns_theta_max 27.61 _reflns_number_total 5111 _reflns_number_gt 3906 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'WinXpose 1.6.8 (Stoe & Cie GmbH, 2004)' _computing_cell_refinement 'X-Area 1.38 (Stoe & Cie GmbH, 2006)' _computing_data_reduction 'X-Area 1.38 (Stoe & Cie GmbH, 2006)' _computing_structure_solution 'SHELXTL 6.14 (BrukerAXS Inc., 2003)' _computing_structure_refinement 'SHELXTL 6.14 (BrukerAXS Inc., 2003)' _computing_molecular_graphics 'Diamond 2.1 (Crystal Impact, 1998)' _computing_publication_material 'SHELXTL 6.14 (BrukerAXS Inc., 2003)' _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 carbon atom C(15) of the five-membered ring in the ligand is two-fold disordered, resulting in a further disorder of the methyl groups on C(15A) and C(15B), and also those on the neighbouring C(14). Geometrical similarity restraints were applied to the affected bond lengths. Difference maps indicated that a partial occupancy oxygen atom O(3B) was bonded to N(7), disordered against a hydrogen atom H(7A). The relative occupancy factors were refined, with both H(7A) and O(3B) assigned an isotropic temperature factor fixed at 1.2 x the equivalent isotropic factor for N(7), and H(7A) was placed in its calculated position. The s.o.f. for O(3B) refined to values close to 0.5, and was fixed at this value in the final refinements, with O(3B) assigned an anisotropic temperature factor and N(7)-O(3B) unrestrained. One (BF4)- anion could be refined on the four-fold special position at (1/2, 1/4, 3/8). The other three were apparently disordered against a lattice MeOH over four equivalent sites per Cu4 unit, and were further disordered. They were therefore handled using the SQUEEZE option in PLATON (see below). ; # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.250 0.000 0.024 257 108 '3(BF4)^-^ + MeOH' 2 0.250 0.500 -0.054 256 108 ' ' 3 0.750 0.500 -0.015 257 108 ' ' 4 0.750 1.000 -0.031 257 108 ' ' _platon_squeeze_details ; Spek, A.L. (2003), J.Appl.Cryst. 36, 7-13 ; _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^)+(0.0983P)^2^+5.0626P] 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 5111 _refine_ls_number_parameters 287 _refine_ls_number_restraints 19 _refine_ls_R_factor_all 0.0876 _refine_ls_R_factor_gt 0.0622 _refine_ls_wR_factor_ref 0.1690 _refine_ls_wR_factor_gt 0.1548 _refine_ls_goodness_of_fit_ref 1.088 _refine_ls_restrained_S_all 1.092 _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 0.448668(18) 0.352042(17) 0.35036(3) 0.04359(16) Uani 1 1 d . . . N1 N 0.36285(14) 0.38384(15) 0.3540(2) 0.0588(8) Uani 1 1 d . . . C1 C 0.3337(2) 0.40405(19) 0.2831(3) 0.0678(12) Uani 1 1 d . . . H1A H 0.3482 0.4026 0.2215 0.081 Uiso 1 1 calc R . . C2 C 0.2842(2) 0.4266(2) 0.2956(4) 0.0745(13) Uani 1 1 d . . . H2A H 0.2648 0.4413 0.2443 0.089 Uiso 1 1 calc R . . C3 C 0.2631(2) 0.4272(2) 0.3851(4) 0.0780(14) Uani 1 1 d . . . H3A H 0.2285 0.4421 0.3959 0.094 Uiso 1 1 calc R . . C4 C 0.29236(17) 0.40618(19) 0.4593(4) 0.0661(11) Uani 1 1 d . . . H4A H 0.2783 0.4065 0.5212 0.079 Uiso 1 1 calc R . . C5 C 0.34279(16) 0.38467(15) 0.4406(3) 0.0525(9) Uani 1 1 d . . . C6 C 0.37774(15) 0.36263(15) 0.5150(3) 0.0490(8) Uani 1 1 d . . . N2 N 0.42836(12) 0.34820(11) 0.48802(19) 0.0417(6) Uani 1 1 d . . . C7 C 0.36228(18) 0.35683(17) 0.6084(3) 0.0598(10) Uani 1 1 d . . . H7B H 0.3273 0.3674 0.6276 0.072 Uiso 1 1 calc R . . C8 C 0.39747(19) 0.33593(18) 0.6727(3) 0.0605(10) Uani 1 1 d . . . H8A H 0.3866 0.3310 0.7360 0.073 Uiso 1 1 calc R . . C9 C 0.44890(17) 0.32199(17) 0.6453(3) 0.0530(9) Uani 1 1 d . . . H9A H 0.4739 0.3079 0.6892 0.064 Uiso 1 1 calc R . . C10 C 0.46309(15) 0.32914(14) 0.5515(2) 0.0443(7) Uani 1 1 d . . . C11 C 0.51760(14) 0.31667(13) 0.5160(2) 0.0409(7) Uani 1 1 d . . . O1 O 0.52601(9) 0.32059(10) 0.42726(15) 0.0424(5) Uani 1 1 d . . . N3 N 0.55333(12) 0.30361(12) 0.5797(2) 0.0447(6) Uani 1 1 d . . . N4 N 0.60245(12) 0.29328(12) 0.5361(2) 0.0456(7) Uani 1 1 d . . . C12 C 0.64245(16) 0.28740(16) 0.5929(3) 0.0507(8) Uani 1 1 d . . . N5 N 0.63789(16) 0.28917(16) 0.6867(2) 0.0661(10) Uani 1 1 d . . . H51 H 0.6063 0.2946 0.7127 0.079 Uiso 1 1 calc R . . H52 H 0.6665 0.2849 0.7221 0.079 Uiso 1 1 calc R . . C13 C 0.69640(16) 0.28029(18) 0.5530(3) 0.0554(9) Uani 1 1 d . B . N6 N 0.70755(14) 0.27515(19) 0.4634(3) 0.0687(11) Uani 1 1 d . B . O2 O 0.67417(12) 0.27023(17) 0.3911(2) 0.0741(9) Uani 1 1 d . . . N7 N 0.74237(15) 0.2781(2) 0.6038(3) 0.0763(12) Uani 1 1 d . . . H7A H 0.7450 0.2866 0.6634 0.092 Uiso 0.50 1 calc PR A 1 O3B O 0.7444(3) 0.2835(4) 0.7008(4) 0.084(2) Uani 0.50 1 d P B 2 C14 C 0.76601(17) 0.27183(19) 0.4454(3) 0.0655(11) Uani 1 1 d D . . C15A C 0.7892(4) 0.2586(4) 0.5425(7) 0.066(3) Uani 0.50 1 d PD B 1 C16A C 0.7761(5) 0.3271(4) 0.4041(9) 0.086(3) Uiso 0.50 1 d PD B 1 H16A H 0.7588 0.3295 0.3425 0.130 Uiso 0.50 1 calc PR B 1 H16B H 0.8148 0.3328 0.3972 0.130 Uiso 0.50 1 calc PR B 1 H16C H 0.7611 0.3545 0.4458 0.130 Uiso 0.50 1 calc PR B 1 C17A C 0.7799(4) 0.2293(4) 0.3703(8) 0.078(3) Uiso 0.50 1 d PD B 1 H17A H 0.7640 0.2398 0.3102 0.117 Uiso 0.50 1 calc PR B 1 H17B H 0.7655 0.1943 0.3894 0.117 Uiso 0.50 1 calc PR B 1 H17C H 0.8189 0.2267 0.3636 0.117 Uiso 0.50 1 calc PR B 1 C18A C 0.8407(4) 0.2887(4) 0.5634(8) 0.078(3) Uiso 0.50 1 d PD B 1 H18A H 0.8537 0.2788 0.6259 0.117 Uiso 0.50 1 calc PR B 1 H18B H 0.8338 0.3275 0.5614 0.117 Uiso 0.50 1 calc PR B 1 H18C H 0.8679 0.2794 0.5165 0.117 Uiso 0.50 1 calc PR B 1 C19A C 0.7957(4) 0.1989(4) 0.5619(9) 0.082(3) Uiso 0.50 1 d PD B 1 H19A H 0.8107 0.1938 0.6247 0.123 Uiso 0.50 1 calc PR B 1 H19B H 0.8200 0.1832 0.5153 0.123 Uiso 0.50 1 calc PR B 1 H19C H 0.7606 0.1812 0.5581 0.123 Uiso 0.50 1 calc PR B 1 C15B C 0.7884(4) 0.2894(4) 0.5450(8) 0.066(3) Uani 0.50 1 d PD B 2 C16B C 0.7715(4) 0.2128(3) 0.4311(8) 0.072(2) Uiso 0.50 1 d PD B 2 H16D H 0.7571 0.1938 0.4858 0.108 Uiso 0.50 1 calc PR B 2 H16E H 0.8095 0.2037 0.4233 0.108 Uiso 0.50 1 calc PR B 2 H16F H 0.7515 0.2021 0.3750 0.108 Uiso 0.50 1 calc PR B 2 C17B C 0.7861(5) 0.3053(4) 0.3691(8) 0.083(3) Uiso 0.50 1 d PD B 2 H17D H 0.7809 0.3432 0.3849 0.124 Uiso 0.50 1 calc PR B 2 H17E H 0.7664 0.2969 0.3114 0.124 Uiso 0.50 1 calc PR B 2 H17F H 0.8244 0.2982 0.3596 0.124 Uiso 0.50 1 calc PR B 2 C18B C 0.7992(6) 0.3501(4) 0.5542(10) 0.103(4) Uiso 0.50 1 d PD B 2 H18D H 0.7676 0.3701 0.5330 0.155 Uiso 0.50 1 calc PR B 2 H18E H 0.8302 0.3599 0.5156 0.155 Uiso 0.50 1 calc PR B 2 H18F H 0.8066 0.3589 0.6199 0.155 Uiso 0.50 1 calc PR B 2 C19B C 0.8379(4) 0.2588(4) 0.5782(8) 0.075(3) Uiso 0.50 1 d PD B 2 H19D H 0.8315 0.2201 0.5723 0.113 Uiso 0.50 1 calc PR B 2 H19E H 0.8452 0.2676 0.6439 0.113 Uiso 0.50 1 calc PR B 2 H19F H 0.8689 0.2689 0.5397 0.113 Uiso 0.50 1 calc PR B 2 B1 B 0.5000 0.2500 0.8750 0.0477(18) Uani 1 4 d S . . F1 F 0.54020(11) 0.27083(11) 0.81911(19) 0.0713(7) 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 0.0555(3) 0.0452(2) 0.0300(2) 0.00094(16) 0.00308(17) 0.00154(18) N1 0.064(2) 0.066(2) 0.0458(18) -0.0017(15) -0.0003(15) 0.0136(16) C1 0.074(3) 0.074(3) 0.056(2) -0.001(2) -0.012(2) 0.014(2) C2 0.067(3) 0.082(3) 0.075(3) 0.000(3) -0.012(2) 0.010(2) C3 0.061(3) 0.084(3) 0.089(4) -0.015(3) -0.010(3) 0.015(2) C4 0.056(2) 0.075(3) 0.067(3) -0.017(2) 0.006(2) 0.002(2) C5 0.056(2) 0.0486(19) 0.053(2) -0.0071(16) 0.0043(17) 0.0004(16) C6 0.053(2) 0.0515(19) 0.0421(19) -0.0073(15) 0.0110(15) -0.0029(15) N2 0.0492(15) 0.0434(14) 0.0325(13) -0.0027(11) 0.0059(11) -0.0032(12) C7 0.064(2) 0.065(2) 0.050(2) -0.0059(19) 0.0194(19) 0.0018(19) C8 0.074(3) 0.069(3) 0.0384(19) -0.0019(17) 0.0173(18) -0.007(2) C9 0.066(2) 0.060(2) 0.0329(17) 0.0002(15) 0.0070(16) -0.0061(18) C10 0.059(2) 0.0426(17) 0.0315(16) -0.0024(13) 0.0039(14) -0.0028(15) C11 0.0544(19) 0.0391(16) 0.0291(15) 0.0018(12) -0.0008(13) -0.0048(14) O1 0.0493(13) 0.0509(13) 0.0270(10) -0.0002(9) 0.0009(9) -0.0003(10) N3 0.0487(16) 0.0533(16) 0.0320(14) 0.0007(12) 0.0015(12) -0.0040(13) N4 0.0493(15) 0.0536(16) 0.0338(14) 0.0003(12) -0.0026(12) -0.0048(13) C12 0.056(2) 0.060(2) 0.0359(17) 0.0054(15) -0.0072(15) -0.0109(17) N5 0.067(2) 0.096(3) 0.0348(16) 0.0031(17) -0.0096(15) -0.0116(19) C13 0.052(2) 0.071(2) 0.043(2) 0.0052(18) -0.0077(16) -0.0053(18) N6 0.0476(18) 0.117(3) 0.0421(18) 0.0141(19) -0.0084(14) -0.0008(18) O2 0.0508(16) 0.133(3) 0.0381(15) -0.0008(16) -0.0055(12) 0.0131(17) N7 0.055(2) 0.127(4) 0.047(2) -0.012(2) -0.0127(16) 0.002(2) O3B 0.063(4) 0.155(7) 0.033(3) 0.012(3) -0.014(3) -0.030(4) C14 0.046(2) 0.090(3) 0.060(3) 0.011(2) -0.0013(18) -0.003(2) C15A 0.042(4) 0.093(8) 0.062(6) -0.001(6) -0.006(4) -0.001(6) C15B 0.045(4) 0.075(7) 0.078(7) 0.005(6) -0.011(4) 0.001(5) B1 0.058(3) 0.058(3) 0.027(3) 0.000 0.000 0.000 F1 0.0723(16) 0.0851(17) 0.0565(14) 0.0107(13) 0.0211(12) -0.0045(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 Cu1 N4 1.958(3) 16_656 ? Cu1 O2 1.961(3) 16_656 ? Cu1 O1 1.994(2) 16_656 ? Cu1 N2 2.031(3) . ? Cu1 N1 2.281(3) . ? Cu1 O1 2.352(2) . ? N1 C5 1.333(5) . ? N1 C1 1.343(5) . ? C1 C2 1.368(7) . ? C1 H1A 0.9500 . ? C2 C3 1.380(8) . ? C2 H2A 0.9500 . ? C3 C4 1.389(7) . ? C3 H3A 0.9500 . ? C4 C5 1.392(6) . ? C4 H4A 0.9500 . ? C5 C6 1.479(6) . ? C6 N2 1.367(5) . ? C6 C7 1.395(5) . ? N2 C10 1.339(5) . ? C7 C8 1.372(7) . ? C7 H7B 0.9500 . ? C8 C9 1.384(6) . ? C8 H8A 0.9500 . ? C9 C10 1.396(5) . ? C9 H9A 0.9500 . ? C10 C11 1.483(5) . ? C11 O1 1.286(4) . ? C11 N3 1.314(4) . ? O1 Cu1 1.994(2) 11_666 ? N3 N4 1.397(4) . ? N4 C12 1.293(5) . ? N4 Cu1 1.958(3) 11_666 ? C12 N5 1.343(5) . ? C12 C13 1.471(6) . ? N5 H51 0.8800 . ? N5 H52 0.8800 . ? C13 N6 1.314(5) . ? C13 N7 1.356(5) . ? N6 O2 1.331(4) . ? N6 C14 1.481(5) . ? O2 Cu1 1.961(3) 11_666 ? N7 O3B 1.392(7) . ? N7 C15B 1.449(12) . ? N7 C15A 1.536(12) . ? N7 H7A 0.8800 . ? C14 C17B 1.460(10) . ? C14 C16B 1.491(9) . ? C14 C16A 1.518(10) . ? C14 C15A 1.536(10) . ? C14 C17A 1.548(9) . ? C14 C15B 1.588(11) . ? C15A C18A 1.518(10) . ? C15A C19A 1.521(11) . ? C16A H16A 0.9800 . ? C16A H16B 0.9800 . ? C16A H16C 0.9800 . ? C17A H17A 0.9800 . ? C17A H17B 0.9800 . ? C17A H17C 0.9800 . ? C18A H18A 0.9800 . ? C18A H18B 0.9800 . ? C18A H18C 0.9800 . ? C19A H19A 0.9800 . ? C19A H19B 0.9800 . ? C19A H19C 0.9800 . ? C15B C19B 1.527(10) . ? C15B C18B 1.540(11) . ? C16B H16D 0.9800 . ? C16B H16E 0.9800 . ? C16B H16F 0.9800 . ? C17B H17D 0.9800 . ? C17B H17E 0.9800 . ? C17B H17F 0.9800 . ? C18B H18D 0.9800 . ? C18B H18E 0.9800 . ? C18B H18F 0.9800 . ? C19B H19D 0.9800 . ? C19B H19E 0.9800 . ? C19B H19F 0.9800 . ? B1 F1 1.381(2) 11_667 ? B1 F1 1.381(2) . ? B1 F1 1.381(2) 16_657 ? B1 F1 1.381(2) 6_554 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N4 Cu1 O2 90.93(12) 16_656 16_656 ? N4 Cu1 O1 80.39(11) 16_656 16_656 ? O2 Cu1 O1 168.03(13) 16_656 16_656 ? N4 Cu1 N2 171.11(12) 16_656 . ? O2 Cu1 N2 94.70(12) 16_656 . ? O1 Cu1 N2 94.95(10) 16_656 . ? N4 Cu1 N1 96.71(12) 16_656 . ? O2 Cu1 N1 92.91(15) 16_656 . ? O1 Cu1 N1 96.26(12) 16_656 . ? N2 Cu1 N1 76.16(12) . . ? N4 Cu1 O1 112.45(10) 16_656 . ? O2 Cu1 O1 87.29(13) 16_656 . ? O1 Cu1 O1 88.43(12) 16_656 . ? N2 Cu1 O1 74.76(10) . . ? N1 Cu1 O1 150.83(10) . . ? C5 N1 C1 119.3(4) . . ? C5 N1 Cu1 112.2(3) . . ? C1 N1 Cu1 128.3(3) . . ? N1 C1 C2 122.9(5) . . ? N1 C1 H1A 118.5 . . ? C2 C1 H1A 118.5 . . ? C1 C2 C3 117.9(5) . . ? C1 C2 H2A 121.0 . . ? C3 C2 H2A 121.0 . . ? C2 C3 C4 120.1(5) . . ? C2 C3 H3A 120.0 . . ? C4 C3 H3A 120.0 . . ? C3 C4 C5 118.3(4) . . ? C3 C4 H4A 120.9 . . ? C5 C4 H4A 120.9 . . ? N1 C5 C4 121.5(4) . . ? N1 C5 C6 116.0(3) . . ? C4 C5 C6 122.5(4) . . ? N2 C6 C7 119.8(4) . . ? N2 C6 C5 116.0(3) . . ? C7 C6 C5 124.2(4) . . ? C10 N2 C6 119.9(3) . . ? C10 N2 Cu1 120.6(2) . . ? C6 N2 Cu1 119.3(2) . . ? C8 C7 C6 120.1(4) . . ? C8 C7 H7B 119.9 . . ? C6 C7 H7B 119.9 . . ? C7 C8 C9 119.9(4) . . ? C7 C8 H8A 120.1 . . ? C9 C8 H8A 120.1 . . ? C8 C9 C10 118.2(4) . . ? C8 C9 H9A 120.9 . . ? C10 C9 H9A 120.9 . . ? N2 C10 C9 122.0(3) . . ? N2 C10 C11 115.8(3) . . ? C9 C10 C11 122.2(3) . . ? O1 C11 N3 126.1(3) . . ? O1 C11 C10 118.0(3) . . ? N3 C11 C10 115.8(3) . . ? C11 O1 Cu1 109.3(2) . 11_666 ? C11 O1 Cu1 110.5(2) . . ? Cu1 O1 Cu1 140.05(11) 11_666 . ? C11 N3 N4 109.3(3) . . ? C12 N4 N3 114.6(3) . . ? C12 N4 Cu1 129.7(3) . 11_666 ? N3 N4 Cu1 114.8(2) . 11_666 ? N4 C12 N5 123.7(4) . . ? N4 C12 C13 118.4(3) . . ? N5 C12 C13 117.8(4) . . ? C12 N5 H51 120.0 . . ? C12 N5 H52 120.0 . . ? H51 N5 H52 120.0 . . ? N6 C13 N7 109.7(4) . . ? N6 C13 C12 125.6(4) . . ? N7 C13 C12 124.7(4) . . ? C13 N6 O2 129.1(4) . . ? C13 N6 C14 112.5(3) . . ? O2 N6 C14 118.4(3) . . ? N6 O2 Cu1 119.2(3) . 11_666 ? C13 N7 O3B 123.9(5) . . ? C13 N7 C15B 110.6(5) . . ? O3B N7 C15B 121.9(5) . . ? C13 N7 C15A 110.5(5) . . ? O3B N7 C15A 124.7(5) . . ? C13 N7 H7A 124.8 . . ? C15B N7 H7A 117.0 . . ? C15A N7 H7A 124.8 . . ? C17B C14 N6 115.7(6) . . ? C17B C14 C16B 115.4(7) . . ? N6 C14 C16B 99.7(5) . . ? N6 C14 C16A 100.3(6) . . ? N6 C14 C15A 103.0(5) . . ? C16A C14 C15A 118.9(7) . . ? N6 C14 C17A 112.2(5) . . ? C16A C14 C17A 108.4(7) . . ? C15A C14 C17A 113.2(7) . . ? C17B C14 C15B 112.9(7) . . ? N6 C14 C15B 100.1(5) . . ? C16B C14 C15B 111.3(6) . . ? C18A C15A C19A 110.9(8) . . ? C18A C15A C14 112.9(8) . . ? C19A C15A C14 114.5(8) . . ? C18A C15A N7 111.9(8) . . ? C19A C15A N7 106.7(8) . . ? C14 C15A N7 99.2(6) . . ? C14 C16A H16A 109.5 . . ? C14 C16A H16B 109.5 . . ? H16A C16A H16B 109.5 . . ? C14 C16A H16C 109.5 . . ? H16A C16A H16C 109.5 . . ? H16B C16A H16C 109.5 . . ? C14 C17A H17A 109.5 . . ? C14 C17A H17B 109.5 . . ? H17A C17A H17B 109.5 . . ? C14 C17A H17C 109.5 . . ? H17A C17A H17C 109.5 . . ? H17B C17A H17C 109.5 . . ? C15A C18A H18A 109.5 . . ? C15A C18A H18B 109.5 . . ? H18A C18A H18B 109.5 . . ? C15A C18A H18C 109.5 . . ? H18A C18A H18C 109.5 . . ? H18B C18A H18C 109.5 . . ? C15A C19A H19A 109.5 . . ? C15A C19A H19B 109.5 . . ? H19A C19A H19B 109.5 . . ? C15A C19A H19C 109.5 . . ? H19A C19A H19C 109.5 . . ? H19B C19A H19C 109.5 . . ? N7 C15B C19B 111.3(8) . . ? N7 C15B C18B 106.3(9) . . ? C19B C15B C18B 108.9(8) . . ? N7 C15B C14 100.7(6) . . ? C19B C15B C14 115.0(8) . . ? C18B C15B C14 114.1(9) . . ? C14 C16B H16D 109.5 . . ? C14 C16B H16E 109.5 . . ? H16D C16B H16E 109.5 . . ? C14 C16B H16F 109.5 . . ? H16D C16B H16F 109.5 . . ? H16E C16B H16F 109.5 . . ? C14 C17B H17D 109.5 . . ? C14 C17B H17E 109.5 . . ? H17D C17B H17E 109.5 . . ? C14 C17B H17F 109.5 . . ? H17D C17B H17F 109.5 . . ? H17E C17B H17F 109.5 . . ? C15B C18B H18D 109.5 . . ? C15B C18B H18E 109.5 . . ? H18D C18B H18E 109.5 . . ? C15B C18B H18F 109.5 . . ? H18D C18B H18F 109.5 . . ? H18E C18B H18F 109.5 . . ? C15B C19B H19D 109.5 . . ? C15B C19B H19E 109.5 . . ? H19D C19B H19E 109.5 . . ? C15B C19B H19F 109.5 . . ? H19D C19B H19F 109.5 . . ? H19E C19B H19F 109.5 . . ? F1 B1 F1 109.47(12) 11_667 . ? F1 B1 F1 109.5(2) 11_667 16_657 ? F1 B1 F1 109.46(12) . 16_657 ? F1 B1 F1 109.46(12) 11_667 6_554 ? F1 B1 F1 109.5(2) . 6_554 ? F1 B1 F1 109.46(12) 16_657 6_554 ? 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 N5 H51 F1 0.88 2.32 3.115(5) 150.7 . N5 H52 O3B 0.88 1.97 2.666(8) 135.4 . _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.25 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.641 _refine_diff_density_min -0.796 _refine_diff_density_rms 0.082 data_ks-90s _database_code_depnum_ccdc_archive 'CCDC 896589' #TrackingRef 'KS_Cu4grids.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C76 H87.5 B4 Cu4 F16 N28 O8.5, 4(B F4), (C H4 O)' _chemical_formula_sum 'C77 H91.5 B4 Cu4 F16 N28 O9.5' _chemical_formula_weight 2162.68 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' B B 0.0013 0.0007 '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' F F 0.0171 0.0103 '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 tetragonal _symmetry_space_group_name_H-M 'I 41/a' _symmetry_space_group_name_Hall '-I 4ad' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2' 'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4' _cell_length_a 24.891(4) _cell_length_b 24.891(4) _cell_length_c 14.388(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8915(3) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 7655 _cell_measurement_theta_min 1.63 _cell_measurement_theta_max 26.14 _exptl_crystal_description block _exptl_crystal_colour brown _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.599 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4390 _exptl_absorpt_coefficient_mu 1.047 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.521 _exptl_absorpt_correction_T_max 0.622 _exptl_absorpt_process_details ; XPREP in SHELXTL 6.14 (BrukerAXS Inc., 2003) ; _exptl_special_details ; ? ; _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 'Stoe IPDS II' _diffrn_measurement_method 'area detector' _diffrn_detector_area_resol_mean 6.667 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 18620 _diffrn_reflns_av_R_equivalents 0.0570 _diffrn_reflns_av_sigmaI/netI 0.0622 _diffrn_reflns_limit_h_min -30 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min -30 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.31 _diffrn_reflns_theta_max 26.40 _reflns_number_total 4485 _reflns_number_gt 2888 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'WinXpose 1.6.8 (Stoe & Cie GmbH, 2004)' _computing_cell_refinement 'X-Area 1.38 (Stoe & Cie GmbH, 2006)' _computing_data_reduction 'X-Area 1.38 (Stoe & Cie GmbH, 2006)' _computing_structure_solution 'SHELXTL 6.14 (BrukerAXS Inc., 2003)' _computing_structure_refinement 'SHELXTL 6.14 (BrukerAXS Inc., 2003)' _computing_molecular_graphics 'Diamond 2.1 (Crystal Impact, 1998)' _computing_publication_material 'SHELXTL 6.14 (BrukerAXS Inc., 2003)' _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 carbon atom C(15) of the five-membered ring in the ligand is two-fold disordered, resulting in a further disorder of the methyl groups on C(15A) and C(15B), and also those on the neighbouring C(14). Geometrical similarity restraints were applied to the affected bond lengths. Difference maps indicated that a partial occupancy oxygen atom O(3B) was bonded to N(7), disordered against a hydrogen atom H(7A). The relative occupancy factors were refined, with both H(7A) and O(3B) assigned an isotropic temperature factor fixed at 1.2 x the equivalent isotropic factor for N(7); N(7)-O(3B) was restrained to 1.35 Ang, while H(7A) was placed in its calculated position. The sof for O(3B) refined to values between 0.11 and 0.15, and was fixed at 0.125 in the final refinements. One (BF4)- anion could be refined on the four-fold special position at (1/2, 1/4, 3/8). The other three were apparently disordered against a lattice MeOH over four equivalent sites per Cu4 unit, and were further disordered. They were therefore handled using the SQUEEZE option in PLATON (see below). ; # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.250 0.000 0.004 249 112 '3(BF4)^-^ + MeOH' 2 0.250 0.500 -0.030 249 112 '3(BF4)^-^ + MeOH' 3 0.750 0.500 -0.008 249 112 '3(BF4)^-^ + MeOH' 4 0.750 1.000 -0.019 249 112 '3(BF4)^-^ + MeOH' _platon_squeeze_details ; Spek, A.L. (2003), J.Appl.Cryst. 36, 7-13 ; _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^)+(0.0964P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4485 _refine_ls_number_parameters 271 _refine_ls_number_restraints 21 _refine_ls_R_factor_all 0.0941 _refine_ls_R_factor_gt 0.0604 _refine_ls_wR_factor_ref 0.1612 _refine_ls_wR_factor_gt 0.1491 _refine_ls_goodness_of_fit_ref 0.993 _refine_ls_restrained_S_all 1.001 _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 0.60240(2) 0.29963(2) 0.89918(3) 0.03875(18) Uani 1 1 d . . . N1 N 0.63443(17) 0.38574(18) 0.8956(3) 0.0538(10) Uani 1 1 d . . . C1 C 0.6554(2) 0.4147(2) 0.9663(4) 0.0635(14) Uani 1 1 d . . . H1A H 0.6543 0.4004 1.0260 0.076 Uiso 1 1 calc R . . C2 C 0.6782(3) 0.4642(2) 0.9531(5) 0.0765(17) Uani 1 1 d . . . H2A H 0.6934 0.4829 1.0026 0.092 Uiso 1 1 calc R . . C3 C 0.6781(3) 0.4857(2) 0.8652(5) 0.0760(17) Uani 1 1 d . . . H3A H 0.6924 0.5197 0.8547 0.091 Uiso 1 1 calc R . . C4 C 0.6565(2) 0.4563(2) 0.7918(4) 0.0629(14) Uani 1 1 d . . . H4A H 0.6565 0.4702 0.7318 0.075 Uiso 1 1 calc R . . C5 C 0.63535(19) 0.4066(2) 0.8094(3) 0.0493(11) Uani 1 1 d . . . C6 C 0.61269(19) 0.3713(2) 0.7361(3) 0.0474(11) Uani 1 1 d . . . N2 N 0.59823(14) 0.32055(15) 0.7624(2) 0.0394(8) Uani 1 1 d . . . C7 C 0.6069(2) 0.3872(2) 0.6441(3) 0.0578(13) Uani 1 1 d . . . H7B H 0.6171 0.4216 0.6260 0.069 Uiso 1 1 calc R . . C8 C 0.5860(2) 0.3520(3) 0.5798(3) 0.0632(15) Uani 1 1 d . . . H8A H 0.5815 0.3629 0.5185 0.076 Uiso 1 1 calc R . . C9 C 0.5716(2) 0.3001(2) 0.6062(3) 0.0513(12) Uani 1 1 d . . . H9A H 0.5578 0.2758 0.5634 0.062 Uiso 1 1 calc R . . C10 C 0.57874(17) 0.28597(19) 0.6995(3) 0.0399(10) Uani 1 1 d . . . C11 C 0.56609(17) 0.23155(18) 0.7341(2) 0.0387(9) Uani 1 1 d . . . O1 O 0.56932(12) 0.22315(12) 0.82294(16) 0.0382(6) Uani 1 1 d . . . N3 N 0.55301(15) 0.19543(16) 0.6714(2) 0.0421(8) Uani 1 1 d . . . N4 N 0.54272(15) 0.14671(16) 0.7152(2) 0.0428(8) Uani 1 1 d . . . C12 C 0.5372(2) 0.1059(2) 0.6598(3) 0.0509(12) Uani 1 1 d . . . N5 N 0.5389(2) 0.1099(2) 0.5671(3) 0.0673(13) Uani 1 1 d . . . H5A H 0.5439 0.1406 0.5413 0.081 Uiso 1 1 calc R . . H5B H 0.5351 0.0816 0.5334 0.081 Uiso 1 1 calc R . . C13 C 0.5304(2) 0.0528(2) 0.7019(3) 0.0547(12) Uani 1 1 d . B . N6 N 0.5232(2) 0.04249(17) 0.7900(3) 0.0634(12) Uani 1 1 d . B . O2 O 0.51728(18) 0.07613(14) 0.8607(2) 0.0660(10) Uani 1 1 d . . . N7 N 0.5326(2) 0.0061(2) 0.6511(3) 0.0724(14) Uani 1 1 d D . . H7A H 0.5436 0.0029 0.5947 0.087 Uiso 0.88 1 calc PR A 1 O3B O 0.5241(16) 0.0014(16) 0.5554(13) 0.087 Uiso 0.13 1 d PD B 2 C14 C 0.5207(2) -0.0161(2) 0.8092(4) 0.0680(16) Uani 1 1 d D . . C15A C 0.5113(4) -0.0402(4) 0.7145(6) 0.069(3) Uiso 0.56 1 d PD B 1 C16A C 0.5745(4) -0.0266(6) 0.8529(8) 0.082(3) Uiso 0.56 1 d PD B 1 H16A H 0.5759 -0.0099 0.9130 0.123 Uiso 0.56 1 calc PR B 1 H16B H 0.6023 -0.0120 0.8141 0.123 Uiso 0.56 1 calc PR B 1 H16C H 0.5797 -0.0647 0.8595 0.123 Uiso 0.56 1 calc PR B 1 C17A C 0.4772(4) -0.0298(5) 0.8812(8) 0.083(3) Uiso 0.56 1 d PD B 1 H17A H 0.4859 -0.0132 0.9395 0.124 Uiso 0.56 1 calc PR B 1 H17B H 0.4754 -0.0681 0.8892 0.124 Uiso 0.56 1 calc PR B 1 H17C H 0.4430 -0.0167 0.8599 0.124 Uiso 0.56 1 calc PR B 1 C18A C 0.5410(5) -0.0937(5) 0.7001(9) 0.088(4) Uiso 0.56 1 d PD B 1 H18A H 0.5341 -0.1068 0.6385 0.132 Uiso 0.56 1 calc PR B 1 H18B H 0.5284 -0.1195 0.7447 0.132 Uiso 0.56 1 calc PR B 1 H18C H 0.5789 -0.0883 0.7081 0.132 Uiso 0.56 1 calc PR B 1 C19A C 0.4516(5) -0.0487(6) 0.6913(9) 0.090(4) Uiso 0.56 1 d PD B 1 H19A H 0.4483 -0.0638 0.6302 0.135 Uiso 0.56 1 calc PR B 1 H19B H 0.4331 -0.0149 0.6936 0.135 Uiso 0.56 1 calc PR B 1 H19C H 0.4360 -0.0729 0.7358 0.135 Uiso 0.56 1 calc PR B 1 C15B C 0.5427(5) -0.0398(5) 0.7139(7) 0.071(4) Uiso 0.44 1 d PD B 2 C16B C 0.4619(4) -0.0228(6) 0.8125(10) 0.075(4) Uiso 0.44 1 d PD B 2 H16D H 0.4463 -0.0088 0.7564 0.113 Uiso 0.44 1 calc PR B 2 H16E H 0.4477 -0.0037 0.8650 0.113 Uiso 0.44 1 calc PR B 2 H16F H 0.4533 -0.0603 0.8181 0.113 Uiso 0.44 1 calc PR B 2 C17B C 0.5498(6) -0.0355(7) 0.8899(9) 0.081(4) Uiso 0.44 1 d PD B 2 H17D H 0.5876 -0.0295 0.8813 0.121 Uiso 0.44 1 calc PR B 2 H17E H 0.5432 -0.0732 0.8977 0.121 Uiso 0.44 1 calc PR B 2 H17F H 0.5378 -0.0166 0.9443 0.121 Uiso 0.44 1 calc PR B 2 C18B C 0.6038(6) -0.0508(8) 0.7112(13) 0.112(6) Uiso 0.44 1 d PD B 2 H18D H 0.6226 -0.0213 0.7393 0.167 Uiso 0.44 1 calc PR B 2 H18E H 0.6152 -0.0548 0.6479 0.167 Uiso 0.44 1 calc PR B 2 H18F H 0.6115 -0.0832 0.7449 0.167 Uiso 0.44 1 calc PR B 2 C19B C 0.5144(6) -0.0888(6) 0.6704(10) 0.078(4) Uiso 0.44 1 d PD B 2 H19D H 0.4762 -0.0834 0.6717 0.116 Uiso 0.44 1 calc PR B 2 H19E H 0.5232 -0.1205 0.7052 0.116 Uiso 0.44 1 calc PR B 2 H19F H 0.5260 -0.0931 0.6072 0.116 Uiso 0.44 1 calc PR B 2 B1 B 0.5000 0.2500 0.3750 0.047(3) Uani 1 4 d S . . F1 F 0.45867(14) 0.23208(14) 0.3191(2) 0.0708(9) 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 0.0367(3) 0.0457(3) 0.0339(2) 0.0042(2) -0.00264(19) -0.0018(2) N1 0.051(3) 0.054(3) 0.056(2) 0.0030(19) -0.0004(18) -0.007(2) C1 0.068(4) 0.055(3) 0.067(3) -0.007(2) 0.003(3) -0.011(3) C2 0.086(5) 0.051(4) 0.092(4) -0.013(3) 0.005(3) -0.012(3) C3 0.082(5) 0.043(3) 0.102(4) -0.003(3) 0.020(4) -0.009(3) C4 0.064(4) 0.048(3) 0.076(3) 0.012(3) 0.021(3) 0.000(3) C5 0.039(3) 0.046(3) 0.063(3) 0.009(2) 0.009(2) 0.001(2) C6 0.040(3) 0.050(3) 0.052(2) 0.014(2) 0.0042(18) 0.003(2) N2 0.0322(19) 0.046(2) 0.0402(17) 0.0096(15) 0.0039(14) 0.0043(16) C7 0.053(3) 0.061(3) 0.059(3) 0.025(2) 0.003(2) 0.004(3) C8 0.061(3) 0.080(4) 0.048(2) 0.030(3) 0.000(2) 0.004(3) C9 0.046(3) 0.070(3) 0.037(2) 0.010(2) -0.0047(18) 0.007(2) C10 0.034(2) 0.052(3) 0.0342(19) 0.0076(17) 0.0009(16) 0.001(2) C11 0.030(2) 0.053(3) 0.0335(18) -0.0002(17) -0.0004(15) 0.0056(19) O1 0.0429(17) 0.0431(17) 0.0287(12) 0.0002(11) -0.0015(11) 0.0015(14) N3 0.042(2) 0.049(2) 0.0353(16) 0.0002(14) -0.0013(14) 0.0056(18) N4 0.042(2) 0.047(2) 0.0388(17) -0.0070(15) 0.0013(14) 0.0046(18) C12 0.053(3) 0.055(3) 0.045(2) -0.016(2) -0.0060(19) 0.014(2) N5 0.091(4) 0.073(3) 0.0379(19) -0.0188(19) -0.005(2) 0.014(3) C13 0.060(3) 0.050(3) 0.054(3) -0.017(2) -0.008(2) 0.009(2) N6 0.095(4) 0.040(2) 0.056(2) -0.0150(18) -0.016(2) 0.000(2) O2 0.105(3) 0.043(2) 0.0504(17) -0.0100(15) 0.0032(18) -0.012(2) N7 0.087(4) 0.055(3) 0.075(3) -0.025(2) 0.006(2) 0.001(3) C14 0.085(4) 0.038(3) 0.081(4) -0.006(2) -0.015(3) 0.001(3) B1 0.057(4) 0.057(4) 0.029(4) 0.000 0.000 0.000 F1 0.070(2) 0.086(2) 0.0564(15) -0.0097(15) -0.0185(14) -0.0036(18) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 O2 1.958(4) 16_657 ? Cu1 N4 1.959(3) 16_657 ? Cu1 O1 1.984(3) 16_657 ? Cu1 N2 2.038(3) . ? Cu1 N1 2.288(4) . ? Cu1 O1 2.346(3) . ? N1 C5 1.344(6) . ? N1 C1 1.351(7) . ? C1 C2 1.371(8) . ? C1 H1A 0.9300 . ? C2 C3 1.374(9) . ? C2 H2A 0.9300 . ? C3 C4 1.392(9) . ? C3 H3A 0.9300 . ? C4 C5 1.369(7) . ? C4 H4A 0.9300 . ? C5 C6 1.484(7) . ? C6 N2 1.366(6) . ? C6 C7 1.390(6) . ? N2 C10 1.340(6) . ? C7 C8 1.376(8) . ? C7 H7B 0.9300 . ? C8 C9 1.393(8) . ? C8 H8A 0.9300 . ? C9 C10 1.399(5) . ? C9 H9A 0.9300 . ? C10 C11 1.477(6) . ? C11 O1 1.297(4) . ? C11 N3 1.315(5) . ? O1 Cu1 1.984(3) 11_667 ? N3 N4 1.390(5) . ? N4 C12 1.298(6) . ? N4 Cu1 1.959(3) 11_667 ? C12 N5 1.338(6) . ? C12 C13 1.464(8) . ? N5 H5A 0.8600 . ? N5 H5B 0.8600 . ? C13 N6 1.306(6) . ? C13 N7 1.376(6) . ? N6 O2 1.325(5) . ? N6 C14 1.485(7) . ? O2 Cu1 1.958(4) 11_667 ? N7 O3B 1.398(18) . ? N7 C15B 1.477(12) . ? N7 C15A 1.560(11) . ? N7 H7A 0.8600 . ? C14 C17B 1.451(11) . ? C14 C16B 1.476(11) . ? C14 C16A 1.502(10) . ? C14 C15A 1.508(11) . ? C14 C17A 1.538(10) . ? C14 C15B 1.590(12) . ? C15A C19A 1.538(12) . ? C15A C18A 1.539(12) . ? C16A H16A 0.9600 . ? C16A H16B 0.9600 . ? C16A H16C 0.9600 . ? C17A H17A 0.9600 . ? C17A H17B 0.9600 . ? C17A H17C 0.9600 . ? C18A H18A 0.9600 . ? C18A H18B 0.9600 . ? C18A H18C 0.9600 . ? C19A H19A 0.9600 . ? C19A H19B 0.9600 . ? C19A H19C 0.9600 . ? C15B C19B 1.542(13) . ? C15B C18B 1.545(14) . ? C16B H16D 0.9600 . ? C16B H16E 0.9600 . ? C16B H16F 0.9600 . ? C17B H17D 0.9600 . ? C17B H17E 0.9600 . ? C17B H17F 0.9600 . ? C18B H18D 0.9600 . ? C18B H18E 0.9600 . ? C18B H18F 0.9600 . ? C19B H19D 0.9600 . ? C19B H19E 0.9600 . ? C19B H19F 0.9600 . ? B1 F1 1.380(3) 6_554 ? B1 F1 1.380(3) 16_656 ? B1 F1 1.380(3) 11_666 ? B1 F1 1.380(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 O2 Cu1 N4 91.48(15) 16_657 16_657 ? O2 Cu1 O1 167.77(15) 16_657 16_657 ? N4 Cu1 O1 80.28(14) 16_657 16_657 ? O2 Cu1 N2 94.66(14) 16_657 . ? N4 Cu1 N2 169.95(16) 16_657 . ? O1 Cu1 N2 94.81(12) 16_657 . ? O2 Cu1 N1 93.85(17) 16_657 . ? N4 Cu1 N1 95.77(15) 16_657 . ? O1 Cu1 N1 95.94(14) 16_657 . ? N2 Cu1 N1 75.92(14) . . ? O2 Cu1 O1 87.21(14) 16_657 . ? N4 Cu1 O1 113.48(13) 16_657 . ? O1 Cu1 O1 87.84(15) 16_657 . ? N2 Cu1 O1 74.82(12) . . ? N1 Cu1 O1 150.70(12) . . ? C5 N1 C1 118.8(5) . . ? C5 N1 Cu1 112.9(3) . . ? C1 N1 Cu1 128.1(4) . . ? N1 C1 C2 122.4(6) . . ? N1 C1 H1A 118.8 . . ? C2 C1 H1A 118.8 . . ? C1 C2 C3 118.4(6) . . ? C1 C2 H2A 120.8 . . ? C3 C2 H2A 120.8 . . ? C2 C3 C4 119.7(6) . . ? C2 C3 H3A 120.1 . . ? C4 C3 H3A 120.1 . . ? C5 C4 C3 118.8(5) . . ? C5 C4 H4A 120.6 . . ? C3 C4 H4A 120.6 . . ? N1 C5 C4 121.8(5) . . ? N1 C5 C6 114.8(4) . . ? C4 C5 C6 123.4(5) . . ? N2 C6 C7 120.0(5) . . ? N2 C6 C5 116.8(4) . . ? C7 C6 C5 123.2(5) . . ? C10 N2 C6 120.1(4) . . ? C10 N2 Cu1 120.4(3) . . ? C6 N2 Cu1 119.3(3) . . ? C8 C7 C6 119.9(5) . . ? C8 C7 H7B 120.1 . . ? C6 C7 H7B 120.1 . . ? C7 C8 C9 120.2(4) . . ? C7 C8 H8A 119.9 . . ? C9 C8 H8A 119.9 . . ? C8 C9 C10 117.6(5) . . ? C8 C9 H9A 121.2 . . ? C10 C9 H9A 121.2 . . ? N2 C10 C9 122.1(4) . . ? N2 C10 C11 116.0(3) . . ? C9 C10 C11 121.8(4) . . ? O1 C11 N3 125.5(4) . . ? O1 C11 C10 117.8(4) . . ? N3 C11 C10 116.7(3) . . ? C11 O1 Cu1 109.7(3) . 11_667 ? C11 O1 Cu1 110.6(3) . . ? Cu1 O1 Cu1 139.56(12) 11_667 . ? C11 N3 N4 109.4(3) . . ? C12 N4 N3 115.0(4) . . ? C12 N4 Cu1 129.1(3) . 11_667 ? N3 N4 Cu1 115.2(3) . 11_667 ? N4 C12 N5 123.5(5) . . ? N4 C12 C13 117.7(4) . . ? N5 C12 C13 118.8(4) . . ? C12 N5 H5A 120.0 . . ? C12 N5 H5B 120.0 . . ? H5A N5 H5B 120.0 . . ? N6 C13 N7 110.7(5) . . ? N6 C13 C12 126.5(4) . . ? N7 C13 C12 122.7(4) . . ? C13 N6 O2 129.4(4) . . ? C13 N6 C14 112.3(4) . . ? O2 N6 C14 118.2(4) . . ? N6 O2 Cu1 118.2(3) . 11_667 ? C13 N7 O3B 126.0(17) . . ? C13 N7 C15B 109.6(6) . . ? O3B N7 C15B 124.3(17) . . ? C13 N7 C15A 107.5(5) . . ? O3B N7 C15A 117.6(17) . . ? C13 N7 H7A 126.2 . . ? C15B N7 H7A 116.8 . . ? C15A N7 H7A 126.2 . . ? C17B C14 C16B 115.6(9) . . ? C17B C14 N6 117.0(8) . . ? C16B C14 N6 99.1(7) . . ? N6 C14 C16A 102.2(7) . . ? N6 C14 C15A 103.2(5) . . ? C16A C14 C15A 116.6(7) . . ? N6 C14 C17A 111.9(7) . . ? C16A C14 C17A 107.9(7) . . ? C15A C14 C17A 114.3(7) . . ? C17B C14 C15B 113.3(9) . . ? C16B C14 C15B 109.1(8) . . ? N6 C14 C15B 100.9(6) . . ? C14 C15A C19A 113.7(8) . . ? C14 C15A C18A 113.0(8) . . ? C19A C15A C18A 108.4(9) . . ? C14 C15A N7 100.5(6) . . ? C19A C15A N7 107.7(8) . . ? C18A C15A N7 113.4(8) . . ? C14 C16A H16A 109.5 . . ? C14 C16A H16B 109.5 . . ? H16A C16A H16B 109.5 . . ? C14 C16A H16C 109.5 . . ? H16A C16A H16C 109.5 . . ? H16B C16A H16C 109.5 . . ? C14 C17A H17A 109.5 . . ? C14 C17A H17B 109.5 . . ? H17A C17A H17B 109.5 . . ? C14 C17A H17C 109.5 . . ? H17A C17A H17C 109.5 . . ? H17B C17A H17C 109.5 . . ? C15A C18A H18A 109.5 . . ? C15A C18A H18B 109.5 . . ? H18A C18A H18B 109.5 . . ? C15A C18A H18C 109.5 . . ? H18A C18A H18C 109.5 . . ? H18B C18A H18C 109.5 . . ? C15A C19A H19A 109.5 . . ? C15A C19A H19B 109.5 . . ? H19A C19A H19B 109.5 . . ? C15A C19A H19C 109.5 . . ? H19A C19A H19C 109.5 . . ? H19B C19A H19C 109.5 . . ? N7 C15B C19B 106.6(10) . . ? N7 C15B C18B 106.9(11) . . ? C19B C15B C18B 107.5(10) . . ? N7 C15B C14 100.5(7) . . ? C19B C15B C14 119.1(10) . . ? C18B C15B C14 115.2(10) . . ? C14 C16B H16D 109.5 . . ? C14 C16B H16E 109.5 . . ? H16D C16B H16E 109.5 . . ? C14 C16B H16F 109.5 . . ? H16D C16B H16F 109.5 . . ? H16E C16B H16F 109.5 . . ? C14 C17B H17D 109.5 . . ? C14 C17B H17E 109.5 . . ? H17D C17B H17E 109.5 . . ? C14 C17B H17F 109.5 . . ? H17D C17B H17F 109.5 . . ? H17E C17B H17F 109.5 . . ? C15B C18B H18D 109.5 . . ? C15B C18B H18E 109.5 . . ? H18D C18B H18E 109.5 . . ? C15B C18B H18F 109.5 . . ? H18D C18B H18F 109.5 . . ? H18E C18B H18F 109.5 . . ? C15B C19B H19D 109.5 . . ? C15B C19B H19E 109.5 . . ? H19D C19B H19E 109.5 . . ? C15B C19B H19F 109.5 . . ? H19D C19B H19F 109.5 . . ? H19E C19B H19F 109.5 . . ? F1 B1 F1 109.84(14) 6_554 16_656 ? F1 B1 F1 109.84(14) 6_554 11_666 ? F1 B1 F1 108.7(3) 16_656 11_666 ? F1 B1 F1 108.7(3) 6_554 . ? F1 B1 F1 109.85(14) 16_656 . ? F1 B1 F1 109.85(14) 11_666 . ? _diffrn_measured_fraction_theta_max 0.982 _diffrn_reflns_theta_full 25.25 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 1.113 _refine_diff_density_min -0.579 _refine_diff_density_rms 0.088