# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # 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_1.CIF _database_code_depnum_ccdc_archive 'CCDC 905260' _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common \1 _chemical_formula_moiety 'C44 H32 Cl4 Cu2 N8, 1.33(C H2 Cl2)' _chemical_formula_sum 'C22.66 H17.33 Cl3.33 Cu N4 O0' _exptl_crystal_recrystallization_method 'dichloromethane, methanol' _chemical_melting_point ? _exptl_crystal_description Rod _exptl_crystal_colour green _diffrn_ambient_temperature 100(2) _chemical_formula_weight 527.15 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'I b a 2' _symmetry_int_tables_number 45 _chemical_absolute_configuration ? _symmetry_space_group_name_Hall 'I 2 -2c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x, y, z+1/2' 'x, -y, z+1/2' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, z+1' 'x+1/2, -y+1/2, z+1' _cell_length_a 15.2832(9) _cell_length_b 23.1589(15) _cell_length_c 13.5599(8) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4799.4(5) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3461 _cell_measurement_theta_min 2.67 _cell_measurement_theta_max 24.80 _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.459 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2135 _exptl_absorpt_coefficient_mu 1.298 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5916 _exptl_absorpt_correction_T_max 0.9584 _exptl_absorpt_process_details 'SADABS, 2009' _exptl_special_details ; ? ; _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX CCD area -detector' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 14191 _diffrn_reflns_av_R_equivalents 0.0462 _diffrn_reflns_av_sigmaI/netI 0.0524 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -27 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.60 _diffrn_reflns_theta_max 25.12 _reflns_number_total 3651 _reflns_number_gt 2860 _reflns_threshold_expression >2\s(I) _computing_data_collection 'APEX2 (Bruker, 2009)' _computing_cell_refinement 'SAINT (Bruker, 2009)' _computing_data_reduction SAINT _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)' _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. ; _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^)+(0.0766P)^2^+4.4427P] 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 0.01(3) _refine_ls_number_reflns 3651 _refine_ls_number_parameters 309 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0694 _refine_ls_R_factor_gt 0.0485 _refine_ls_wR_factor_ref 0.1359 _refine_ls_wR_factor_gt 0.1221 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.053 _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 0.22204(4) 0.27807(3) 0.78342(7) 0.0354(2) Uani 1 1 d . . . Cl1 Cl 0.15377(11) 0.21398(7) 0.68410(12) 0.0456(4) Uani 1 1 d . . . N1 N 0.1446(3) 0.2668(2) 0.8958(4) 0.0376(13) Uani 1 1 d . . . Cl2 Cl 0.34178(10) 0.28633(9) 0.87769(13) 0.0556(5) Uani 1 1 d . . . C2 C 0.1596(4) 0.2858(3) 0.9881(4) 0.0368(16) Uani 1 1 d . . . H2 H 0.2110 0.3057 1.0081 0.044 Uiso 1 1 calc R . . N3 N 0.0932(3) 0.2730(2) 1.0476(4) 0.0377(13) Uani 1 1 d . . . C4 C 0.0304(4) 0.2456(3) 0.9939(5) 0.0433(16) Uani 1 1 d . . . H4 H -0.0246 0.2321 1.0170 0.052 Uiso 1 1 calc R . . C5 C 0.0627(4) 0.2414(3) 0.8985(5) 0.0385(15) Uani 1 1 d . . . H5 H 0.0335 0.2240 0.8443 0.046 Uiso 1 1 calc R . . C6 C 0.0863(4) 0.2901(3) 1.1526(5) 0.0421(16) Uani 1 1 d . . . H6A H 0.1433 0.2841 1.1858 0.051 Uiso 1 1 calc R . . H6B H 0.0422 0.2657 1.1861 0.051 Uiso 1 1 calc R . . C7 C 0.0602(4) 0.3525(3) 1.1601(4) 0.0384(15) Uani 1 1 d . . . C8 C 0.1240(5) 0.3945(3) 1.1620(5) 0.0413(17) Uani 1 1 d . A . H8 H 0.1839 0.3835 1.1628 0.050 Uiso 1 1 calc R . . C9 C 0.1019(4) 0.4526(3) 1.1627(5) 0.0401(16) Uani 1 1 d . . . C10 C 0.0115(4) 0.4687(3) 1.1624(5) 0.0423(18) Uani 1 1 d . . . C11 C -0.0518(4) 0.4260(3) 1.1626(5) 0.0458(18) Uani 1 1 d . . . C12 C -0.0275(4) 0.3681(3) 1.1621(5) 0.0428(16) Uani 1 1 d . A . H12 H -0.0713 0.3390 1.1630 0.051 Uiso 1 1 calc R . . C13 C 0.1574(7) 0.4925(6) 1.1644(9) 0.031(3) Uani 0.53 1 d P A 2 H13 H 0.2177 0.4827 1.1653 0.037 Uiso 0.53 1 calc PR A 2 C14 C 0.1349(7) 0.5494(6) 1.1650(9) 0.040(3) Uani 0.53 1 d P . 2 H14 H 0.1823 0.5759 1.1674 0.048 Uiso 0.53 1 calc PR . 2 N1' N 0.2700(3) 0.3246(2) 0.6739(4) 0.0399(13) Uani 1 1 d . . . C2' C 0.2457(4) 0.3216(3) 0.5802(5) 0.0392(15) Uani 1 1 d . . . H2' H 0.2044 0.2952 0.5537 0.047 Uiso 1 1 calc R . . N3' N 0.2899(4) 0.3628(3) 0.5278(5) 0.0518(15) Uani 1 1 d . . . C4' C 0.3421(6) 0.3918(4) 0.5910(6) 0.069(2) Uani 1 1 d . . . H4' H 0.3797 0.4231 0.5749 0.082 Uiso 1 1 calc R . . C5' C 0.3313(5) 0.3684(3) 0.6812(6) 0.062(2) Uani 1 1 d . . . H5' H 0.3608 0.3799 0.7397 0.075 Uiso 1 1 calc R . . C6' C 0.2719(5) 0.3769(4) 0.4226(5) 0.062(2) Uani 1 1 d . B . H6'1 H 0.2650 0.3407 0.3845 0.075 Uiso 1 1 calc R . . H6'2 H 0.3220 0.3985 0.3947 0.075 Uiso 1 1 calc R . . C8' C 0.1102(7) 0.3880(5) 0.4117(6) 0.069(3) Uani 1 1 d . B . H8' H 0.1067 0.3470 0.4118 0.083 Uiso 1 1 calc R . . C9' C 0.0313(8) 0.4198(4) 0.4091(6) 0.076(3) Uani 1 1 d . . . C10' C 0.0396(8) 0.4826(5) 0.4098(5) 0.083(4) Uani 1 1 d . . . C11' C 0.1233(8) 0.5080(5) 0.4109(6) 0.081(3) Uani 1 1 d . . . C12' C 0.1971(7) 0.4736(4) 0.4142(6) 0.072(3) Uani 1 1 d . B . H12' H 0.2533 0.4911 0.4166 0.086 Uiso 1 1 calc R . . C13' C -0.0391(13) 0.4021(6) 0.4098(11) 0.042(4) Uani 0.47 1 d P B -2 H13' H -0.0472 0.3614 0.4084 0.051 Uiso 0.47 1 calc PR B -2 C14' C -0.1136(12) 0.4377(7) 0.4126(10) 0.048(4) Uani 0.47 1 d P . -2 H14' H -0.1671 0.4169 0.4166 0.057 Uiso 0.47 1 calc PR . -2 C1A C 0.381(2) 0.5821(12) 0.5410(15) 0.229(19) Uani 0.663(10) 1 d P C 1 H1A1 H 0.3839 0.6246 0.5478 0.275 Uiso 0.663(10) 1 calc PR C 1 H1A2 H 0.3209 0.5724 0.5211 0.275 Uiso 0.663(10) 1 calc PR C 1 Cl2A Cl 0.4493(7) 0.5638(5) 0.4417(11) 0.354(11) Uani 0.663(10) 1 d P C 1 C7' C 0.1900(8) 0.4126(4) 0.4139(5) 0.067(2) Uani 1 1 d . . . Cl1A Cl 0.3962(7) 0.5547(4) 0.6537(12) 0.289(7) Uani 0.663(10) 1 d P C 1 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 0.0344(3) 0.0506(4) 0.0213(3) 0.0013(5) -0.0002(4) 0.0099(3) Cl1 0.0526(9) 0.0571(10) 0.0270(8) -0.0042(8) 0.0015(8) 0.0040(7) N1 0.037(3) 0.047(3) 0.028(3) 0.007(3) -0.002(2) 0.006(2) Cl2 0.0328(8) 0.1043(15) 0.0298(9) 0.0035(10) -0.0024(8) 0.0086(8) C2 0.030(3) 0.055(4) 0.025(4) -0.007(3) 0.004(3) 0.002(3) N3 0.037(3) 0.052(3) 0.024(3) 0.000(2) 0.000(2) 0.009(2) C4 0.027(3) 0.064(4) 0.039(4) 0.002(3) 0.004(3) 0.006(3) C5 0.034(3) 0.054(4) 0.028(4) -0.006(3) -0.002(3) 0.004(3) C6 0.047(4) 0.060(4) 0.019(3) -0.002(3) 0.006(3) 0.008(3) C7 0.044(4) 0.056(4) 0.015(3) 0.000(3) 0.002(3) 0.010(3) C8 0.043(4) 0.064(5) 0.017(3) 0.000(3) 0.000(3) 0.015(3) C9 0.047(4) 0.056(4) 0.018(4) 0.001(3) 0.001(3) 0.015(3) C10 0.050(4) 0.066(5) 0.011(3) 0.002(3) 0.001(3) 0.027(4) C11 0.044(4) 0.071(5) 0.022(4) 0.001(4) -0.008(3) 0.031(4) C12 0.048(4) 0.060(4) 0.021(3) 0.001(3) 0.006(3) 0.003(3) C13 0.023(5) 0.048(8) 0.021(6) 0.008(6) -0.005(5) 0.012(5) C14 0.026(6) 0.075(10) 0.018(7) 0.002(7) -0.002(5) -0.026(6) N1' 0.049(3) 0.052(3) 0.019(3) 0.003(3) -0.002(3) 0.005(2) C2' 0.043(3) 0.049(4) 0.026(3) -0.001(3) 0.010(3) 0.014(3) N3' 0.072(4) 0.049(3) 0.035(3) 0.007(3) 0.003(3) 0.014(3) C4' 0.097(6) 0.068(5) 0.041(5) 0.003(4) -0.002(5) -0.008(5) C5' 0.080(5) 0.077(5) 0.030(4) 0.008(4) -0.010(4) -0.025(4) C6' 0.103(6) 0.054(5) 0.031(4) 0.006(4) 0.012(4) 0.017(4) C8' 0.111(8) 0.076(6) 0.020(4) 0.007(4) 0.000(5) 0.046(6) C9' 0.138(10) 0.076(7) 0.013(4) -0.001(4) 0.009(5) 0.057(7) C10' 0.141(10) 0.100(8) 0.009(4) -0.001(5) -0.003(5) 0.070(7) C11' 0.144(10) 0.079(7) 0.020(4) -0.008(5) -0.016(6) 0.048(7) C12' 0.110(7) 0.079(7) 0.026(4) 0.006(4) -0.012(5) 0.031(5) C13' 0.079(12) 0.022(8) 0.026(8) -0.009(7) 0.017(9) -0.002(8) C14' 0.085(12) 0.038(9) 0.020(7) 0.008(7) 0.027(8) -0.001(8) C1A 0.36(4) 0.25(3) 0.081(15) -0.010(17) -0.03(2) 0.26(3) Cl2A 0.270(12) 0.310(13) 0.48(2) -0.300(14) -0.189(12) 0.135(9) C7' 0.124(8) 0.061(5) 0.015(3) 0.007(4) 0.004(5) 0.031(5) Cl1A 0.267(11) 0.137(6) 0.464(19) -0.051(11) -0.026(13) 0.011(6) _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 1.948(5) . ? Cu1 N1' 1.975(5) . ? Cu1 Cl2 2.2404(18) . ? Cu1 Cl1 2.2596(18) . ? N1 C2 1.347(8) . ? N1 C5 1.383(8) . ? C2 N3 1.331(8) . ? C2 H2 0.9500 . ? N3 C4 1.362(8) . ? N3 C6 1.482(8) . ? C4 C5 1.387(9) . ? C4 H4 0.9500 . ? C5 H5 0.9500 . ? C6 C7 1.503(8) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C7 C8 1.378(9) . ? C7 C12 1.389(8) . ? C8 C9 1.388(9) . ? C8 H8 0.9500 . ? C9 C13 1.255(14) . ? C9 C10 1.431(9) . ? C10 C11 1.385(10) . ? C10 C10 1.490(13) 2_565 ? C11 C14 1.391(14) 2_565 ? C11 C12 1.391(9) . ? C12 H12 0.9500 . ? C13 C14 1.362(18) . ? C13 H13 0.9500 . ? C14 C11 1.391(14) 2_565 ? C14 H14 0.9500 . ? N1' C2' 1.326(9) . ? N1' C5' 1.385(9) . ? C2' N3' 1.367(9) . ? C2' H2' 0.9500 . ? N3' C4' 1.351(10) . ? N3' C6' 1.488(9) . ? C4' C5' 1.347(11) . ? C4' H4' 0.9500 . ? C5' H5' 0.9500 . ? C6' C7' 1.505(12) . ? C6' H6'1 0.9900 . ? C6' H6'2 0.9900 . ? C8' C7' 1.347(13) . ? C8' C9' 1.414(13) . ? C8' H8' 0.9500 . ? C9' C13' 1.152(16) . ? C9' C10' 1.460(14) . ? C10' C11' 1.407(14) . ? C10' C10' 1.453(18) 2_565 ? C11' C14' 1.267(18) 2_565 ? C11' C12' 1.382(12) . ? C12' C7' 1.418(12) . ? C12' H12' 0.9500 . ? C13' C14' 1.41(2) . ? C13' H13' 0.9500 . ? C14' C11' 1.267(18) 2_565 ? C14' H14' 0.9500 . ? C1A Cl1A 1.67(2) . ? C1A Cl2A 1.75(3) . ? C1A H1A1 0.9900 . ? C1A H1A2 0.9900 . ? 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 N1' 152.5(2) . . ? N1 Cu1 Cl2 93.54(15) . . ? N1' Cu1 Cl2 94.54(15) . . ? N1 Cu1 Cl1 95.58(16) . . ? N1' Cu1 Cl1 94.69(16) . . ? Cl2 Cu1 Cl1 140.65(8) . . ? C2 N1 C5 105.6(5) . . ? C2 N1 Cu1 125.4(4) . . ? C5 N1 Cu1 128.9(4) . . ? N3 C2 N1 111.1(5) . . ? N3 C2 H2 124.4 . . ? N1 C2 H2 124.4 . . ? C2 N3 C4 108.5(5) . . ? C2 N3 C6 125.3(5) . . ? C4 N3 C6 126.1(5) . . ? N3 C4 C5 106.3(6) . . ? N3 C4 H4 126.9 . . ? C5 C4 H4 126.9 . . ? N1 C5 C4 108.5(6) . . ? N1 C5 H5 125.7 . . ? C4 C5 H5 125.7 . . ? N3 C6 C7 109.9(5) . . ? N3 C6 H6A 109.7 . . ? C7 C6 H6A 109.7 . . ? N3 C6 H6B 109.7 . . ? C7 C6 H6B 109.7 . . ? H6A C6 H6B 108.2 . . ? C8 C7 C12 119.9(6) . . ? C8 C7 C6 119.5(6) . . ? C12 C7 C6 120.6(6) . . ? C7 C8 C9 120.8(6) . . ? C7 C8 H8 119.6 . . ? C9 C8 H8 119.6 . . ? C13 C9 C8 123.4(8) . . ? C13 C9 C10 117.4(8) . . ? C8 C9 C10 119.3(7) . . ? C11 C10 C9 119.2(6) . . ? C11 C10 C10 121.9(8) . 2_565 ? C9 C10 C10 118.9(8) . 2_565 ? C10 C11 C14 110.2(8) . 2_565 ? C10 C11 C12 120.1(6) . . ? C14 C11 C12 129.6(8) 2_565 . ? C7 C12 C11 120.6(6) . . ? C7 C12 H12 119.7 . . ? C11 C12 H12 119.7 . . ? C9 C13 C14 122.8(10) . . ? C9 C13 H13 118.6 . . ? C14 C13 H13 118.6 . . ? C13 C14 C11 128.8(10) . 2_565 ? C13 C14 H14 115.6 . . ? C11 C14 H14 115.6 2_565 . ? C2' N1' C5' 107.2(6) . . ? C2' N1' Cu1 126.1(5) . . ? C5' N1' Cu1 126.7(5) . . ? N1' C2' N3' 108.9(6) . . ? N1' C2' H2' 125.5 . . ? N3' C2' H2' 125.5 . . ? C4' N3' C2' 108.0(6) . . ? C4' N3' C6' 127.5(7) . . ? C2' N3' C6' 124.0(7) . . ? C5' C4' N3' 107.7(7) . . ? C5' C4' H4' 126.2 . . ? N3' C4' H4' 126.2 . . ? C4' C5' N1' 108.3(7) . . ? C4' C5' H5' 125.9 . . ? N1' C5' H5' 125.9 . . ? N3' C6' C7' 110.4(6) . . ? N3' C6' H6'1 109.6 . . ? C7' C6' H6'1 109.6 . . ? N3' C6' H6'2 109.6 . . ? C7' C6' H6'2 109.6 . . ? H6'1 C6' H6'2 108.1 . . ? C7' C8' C9' 123.5(10) . . ? C7' C8' H8' 118.2 . . ? C9' C8' H8' 118.2 . . ? C13' C9' C8' 127.6(13) . . ? C13' C9' C10' 115.9(11) . . ? C8' C9' C10' 116.5(11) . . ? C11' C10' C10' 121.7(14) . 2_565 ? C11' C10' C9' 119.6(9) . . ? C10' C10' C9' 118.7(16) 2_565 . ? C14' C11' C12' 131.8(15) 2_565 . ? C14' C11' C10' 108.0(12) 2_565 . ? C12' C11' C10' 120.2(9) . . ? C11' C12' C7' 120.8(10) . . ? C11' C12' H12' 119.6 . . ? C7' C12' H12' 119.6 . . ? C9' C13' C14' 123.2(15) . . ? C9' C13' H13' 118.4 . . ? C14' C13' H13' 118.4 . . ? C11' C14' C13' 132.5(16) 2_565 . ? C11' C14' H14' 113.7 2_565 . ? C13' C14' H14' 113.7 . . ? Cl1A C1A Cl2A 122.1(11) . . ? Cl1A C1A H1A1 106.8 . . ? Cl2A C1A H1A1 106.8 . . ? Cl1A C1A H1A2 106.8 . . ? Cl2A C1A H1A2 106.8 . . ? H1A1 C1A H1A2 106.7 . . ? C8' C7' C12' 119.4(9) . . ? C8' C7' C6' 121.5(8) . . ? C12' C7' C6' 119.0(10) . . ? 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 N1 C2 -81.3(7) . . . . ? Cl2 Cu1 N1 C2 25.6(5) . . . . ? Cl1 Cu1 N1 C2 167.2(5) . . . . ? N1' Cu1 N1 C5 94.9(7) . . . . ? Cl2 Cu1 N1 C5 -158.2(5) . . . . ? Cl1 Cu1 N1 C5 -16.6(5) . . . . ? C5 N1 C2 N3 1.0(7) . . . . ? Cu1 N1 C2 N3 177.9(4) . . . . ? N1 C2 N3 C4 -1.3(7) . . . . ? N1 C2 N3 C6 -176.7(5) . . . . ? C2 N3 C4 C5 1.1(7) . . . . ? C6 N3 C4 C5 176.4(5) . . . . ? C2 N1 C5 C4 -0.2(7) . . . . ? Cu1 N1 C5 C4 -177.0(4) . . . . ? N3 C4 C5 N1 -0.5(7) . . . . ? C2 N3 C6 C7 77.4(7) . . . . ? C4 N3 C6 C7 -97.2(7) . . . . ? N3 C6 C7 C8 -89.2(7) . . . . ? N3 C6 C7 C12 88.8(7) . . . . ? C12 C7 C8 C9 -2.0(10) . . . . ? C6 C7 C8 C9 176.0(6) . . . . ? C7 C8 C9 C13 -179.9(9) . . . . ? C7 C8 C9 C10 0.6(10) . . . . ? C13 C9 C10 C11 -178.7(9) . . . . ? C8 C9 C10 C11 0.8(10) . . . . ? C13 C9 C10 C10 1.0(9) . . . 2_565 ? C8 C9 C10 C10 -179.5(4) . . . 2_565 ? C9 C10 C11 C14 178.3(7) . . . 2_565 ? C10 C10 C11 C14 -1.3(8) 2_565 . . 2_565 ? C9 C10 C11 C12 -0.8(10) . . . . ? C10 C10 C11 C12 179.6(4) 2_565 . . . ? C8 C7 C12 C11 2.1(10) . . . . ? C6 C7 C12 C11 -175.9(6) . . . . ? C10 C11 C12 C7 -0.7(11) . . . . ? C14 C11 C12 C7 -179.6(8) 2_565 . . . ? C8 C9 C13 C14 180.0(10) . . . . ? C10 C9 C13 C14 -0.6(16) . . . . ? C9 C13 C14 C11 -1(2) . . . 2_565 ? N1 Cu1 N1' C2' -97.9(6) . . . . ? Cl2 Cu1 N1' C2' 155.5(5) . . . . ? Cl1 Cu1 N1' C2' 13.8(5) . . . . ? N1 Cu1 N1' C5' 78.3(7) . . . . ? Cl2 Cu1 N1' C5' -28.4(6) . . . . ? Cl1 Cu1 N1' C5' -170.1(6) . . . . ? C5' N1' C2' N3' -0.4(7) . . . . ? Cu1 N1' C2' N3' 176.4(4) . . . . ? N1' C2' N3' C4' -0.3(7) . . . . ? N1' C2' N3' C6' -172.5(6) . . . . ? C2' N3' C4' C5' 0.9(9) . . . . ? C6' N3' C4' C5' 172.8(7) . . . . ? N3' C4' C5' N1' -1.1(10) . . . . ? C2' N1' C5' C4' 0.9(9) . . . . ? Cu1 N1' C5' C4' -175.9(5) . . . . ? C4' N3' C6' C7' -94.2(10) . . . . ? C2' N3' C6' C7' 76.5(9) . . . . ? C7' C8' C9' C13' -177.7(13) . . . . ? C7' C8' C9' C10' -0.5(12) . . . . ? C13' C9' C10' C11' 178.8(12) . . . . ? C8' C9' C10' C11' 1.3(11) . . . . ? C13' C9' C10' C10' -0.9(12) . . . 2_565 ? C8' C9' C10' C10' -178.4(5) . . . 2_565 ? C10' C10' C11' C14' 0.5(11) 2_565 . . 2_565 ? C9' C10' C11' C14' -179.2(9) . . . 2_565 ? C10' C10' C11' C12' 177.9(5) 2_565 . . . ? C9' C10' C11' C12' -1.9(12) . . . . ? C14' C11' C12' C7' 178.2(12) 2_565 . . . ? C10' C11' C12' C7' 1.6(12) . . . . ? C8' C9' C13' C14' 176.3(11) . . . . ? C10' C9' C13' C14' -1(2) . . . . ? C9' C13' C14' C11' 3(3) . . . 2_565 ? C9' C8' C7' C12' 0.3(12) . . . . ? C9' C8' C7' C6' 176.4(7) . . . . ? C11' C12' C7' C8' -0.8(12) . . . . ? C11' C12' C7' C6' -177.0(7) . . . . ? N3' C6' C7' C8' -83.8(10) . . . . ? N3' C6' C7' C12' 92.3(8) . . . . ? 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 C4 H4 Cl2 0.95 2.81 3.367(7) 118.0 8_454 C5 H5 Cl2 0.95 2.97 3.449(6) 112.2 8_454 _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 25.12 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.525 _refine_diff_density_min -0.325 _refine_diff_density_rms 0.089 data_L.CIF _database_code_depnum_ccdc_archive 'CCDC 905946' #TrackingRef '14691_web_deposit_cif_file_0_LeighLoots_1350297328.Ligand.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 1,1'-(phenanthrene-2,7-diyldimethanediyl)bis(1H-imidazole) ; _chemical_name_common L _chemical_melting_point ? _chemical_formula_moiety 'C22 H16 N4' _chemical_formula_sum 'C22 H16 N4' _chemical_formula_weight 336.39 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall '-P 2yn' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 6.3522(14) _cell_length_b 5.5996(13) _cell_length_c 23.548(5) _cell_angle_alpha 90.00 _cell_angle_beta 94.630(3) _cell_angle_gamma 90.00 _cell_volume 834.9(3) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 1241 _cell_measurement_theta_min 3.26 _cell_measurement_theta_max 25.06 _exptl_crystal_description shard _exptl_crystal_colour colourless _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.338 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 352 _exptl_absorpt_coefficient_mu 0.082 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9771 _exptl_absorpt_correction_T_max 0.9949 _exptl_absorpt_process_details 'Twinabs, 2008' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 APEX CCD area -detector' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 2799 _diffrn_reflns_av_R_equivalents 0.0674 _diffrn_reflns_av_sigmaI/netI 0.0723 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 3.26 _diffrn_reflns_theta_max 25.15 _reflns_number_total 1495 _reflns_number_gt 1061 _reflns_threshold_expression >2\s(I) _computing_data_collection 'APEX2 (Bruker, 2009)' _computing_cell_refinement 'SAINT (Bruker, 2009)' _computing_data_reduction SAINT _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)' _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. ; _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^)+(0.0792P)^2^+0.4090P] 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 1495 _refine_ls_number_parameters 128 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0957 _refine_ls_R_factor_gt 0.0641 _refine_ls_wR_factor_ref 0.1734 _refine_ls_wR_factor_gt 0.1606 _refine_ls_goodness_of_fit_ref 1.066 _refine_ls_restrained_S_all 1.066 _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 N1 N 1.0275(4) 0.0708(4) 0.19631(10) 0.0374(6) Uani 1 1 d . . . C2 C 0.8400(5) 0.0854(5) 0.16876(11) 0.0326(7) Uani 1 1 d . . . H2 H 0.7774 -0.0394 0.1459 0.039 Uiso 1 1 calc R . . N3 N 0.7454(3) 0.2992(4) 0.17666(8) 0.0278(6) Uani 1 1 d . . . C4 C 0.8841(4) 0.4294(5) 0.21193(11) 0.0323(7) Uani 1 1 d . . . H4 H 0.8640 0.5870 0.2254 0.039 Uiso 1 1 calc R . . C5 C 1.0561(4) 0.2880(5) 0.22375(11) 0.0327(7) Uani 1 1 d . . . H5 H 1.1781 0.3320 0.2474 0.039 Uiso 1 1 calc R . . C6 C 0.5329(4) 0.3697(5) 0.15539(11) 0.0346(7) Uani 1 1 d . . . H6A H 0.4581 0.4324 0.1875 0.041 Uiso 1 1 calc R . . H6B H 0.4555 0.2265 0.1405 0.041 Uiso 1 1 calc R . . C7 C 0.5271(4) 0.5562(5) 0.10910(10) 0.0317(7) Uani 1 1 d . . . C8 C 0.3577(5) 0.7154(5) 0.10289(11) 0.0379(7) Uani 1 1 d . A . H8 H 0.2492 0.7056 0.1283 0.045 Uiso 1 1 calc R . . C9 C 0.3443(5) 0.8887(5) 0.06011(12) 0.0432(8) Uani 1 1 d . . . C10 C 0.5049(6) 0.9079(5) 0.02210(11) 0.0442(8) Uani 1 1 d . . . C11 C 0.6756(5) 0.7458(5) 0.02844(11) 0.0399(8) Uani 1 1 d . . . C12 C 0.6851(5) 0.5734(5) 0.07115(11) 0.0373(7) Uani 1 1 d . A . H12 H 0.8007 0.4654 0.0746 0.045 Uiso 1 1 calc R . . C13 C 0.1964(8) 1.0499(10) 0.0501(2) 0.0284(12) Uani 0.50 1 d P A 1 H13 H 0.0840 1.0476 0.0744 0.034 Uiso 0.50 1 calc PR A 1 C14 C 0.1860(8) 1.2233(10) 0.00794(19) 0.0284(12) Uani 0.50 1 d P . 1 H14 H 0.0676 1.3275 0.0057 0.034 Uiso 0.50 1 calc PR . 1 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 N1 0.0396(15) 0.0356(15) 0.0373(13) 0.0007(11) 0.0056(11) 0.0017(12) C2 0.0414(17) 0.0280(15) 0.0283(13) -0.0035(12) 0.0026(12) 0.0012(13) N3 0.0332(13) 0.0257(12) 0.0246(11) -0.0007(9) 0.0024(9) -0.0018(10) C4 0.0399(17) 0.0297(15) 0.0274(13) -0.0017(11) 0.0025(12) -0.0055(13) C5 0.0309(16) 0.0372(16) 0.0299(14) 0.0042(13) 0.0013(11) -0.0034(13) C6 0.0337(16) 0.0335(16) 0.0356(15) -0.0015(12) -0.0022(12) -0.0003(13) C7 0.0410(16) 0.0273(15) 0.0255(13) -0.0027(11) -0.0053(11) -0.0023(13) C8 0.0459(18) 0.0345(16) 0.0315(14) -0.0038(13) -0.0078(12) -0.0011(14) C9 0.063(2) 0.0305(16) 0.0327(15) -0.0025(13) -0.0165(14) -0.0018(15) C10 0.074(2) 0.0295(16) 0.0265(14) -0.0030(12) -0.0162(15) -0.0080(16) C11 0.055(2) 0.0333(17) 0.0293(14) 0.0002(12) -0.0076(13) -0.0081(14) C12 0.0481(18) 0.0316(17) 0.0303(14) -0.0010(12) -0.0081(13) -0.0021(14) C13 0.018(3) 0.040(3) 0.027(3) -0.004(2) 0.003(2) 0.007(2) C14 0.023(3) 0.038(3) 0.025(2) -0.002(2) 0.004(2) 0.008(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 N1 C2 1.312(3) . ? N1 C5 1.382(4) . ? C2 N3 1.359(3) . ? C2 H2 0.9500 . ? N3 C4 1.371(3) . ? N3 C6 1.456(3) . ? C4 C5 1.360(4) . ? C4 H4 0.9500 . ? C5 H5 0.9500 . ? C6 C7 1.508(4) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C7 C8 1.396(4) . ? C7 C12 1.400(4) . ? C8 C9 1.397(4) . ? C8 H8 0.9500 . ? C9 C13 1.311(6) . ? C9 C10 1.414(5) . ? C10 C11 1.413(5) . ? C10 C10 1.463(6) 3_675 ? C11 C14 1.287(6) 3_675 ? C11 C12 1.392(4) . ? C12 H12 0.9500 . ? C13 C14 1.386(7) . ? C13 H13 0.9500 . ? C14 C11 1.287(6) 3_675 ? C14 H14 0.9500 . ? 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 C2 N1 C5 104.8(2) . . ? N1 C2 N3 112.4(2) . . ? N1 C2 H2 123.8 . . ? N3 C2 H2 123.8 . . ? C2 N3 C4 106.4(2) . . ? C2 N3 C6 126.8(2) . . ? C4 N3 C6 126.6(2) . . ? C5 C4 N3 106.3(2) . . ? C5 C4 H4 126.9 . . ? N3 C4 H4 126.9 . . ? C4 C5 N1 110.1(2) . . ? C4 C5 H5 125.0 . . ? N1 C5 H5 125.0 . . ? N3 C6 C7 113.8(2) . . ? N3 C6 H6A 108.8 . . ? C7 C6 H6A 108.8 . . ? N3 C6 H6B 108.8 . . ? C7 C6 H6B 108.8 . . ? H6A C6 H6B 107.7 . . ? C8 C7 C12 118.4(3) . . ? C8 C7 C6 119.4(3) . . ? C12 C7 C6 122.2(3) . . ? C7 C8 C9 121.4(3) . . ? C7 C8 H8 119.3 . . ? C9 C8 H8 119.3 . . ? C13 C9 C8 127.5(4) . . ? C13 C9 C10 112.2(3) . . ? C8 C9 C10 120.3(3) . . ? C11 C10 C9 118.1(3) . . ? C11 C10 C10 121.1(4) . 3_675 ? C9 C10 C10 120.8(4) . 3_675 ? C14 C11 C12 125.6(4) 3_675 . ? C14 C11 C10 113.8(3) 3_675 . ? C12 C11 C10 120.6(3) . . ? C11 C12 C7 121.2(3) . . ? C11 C12 H12 119.4 . . ? C7 C12 H12 119.4 . . ? C9 C13 C14 127.1(5) . . ? C9 C13 H13 116.5 . . ? C14 C13 H13 116.5 . . ? C11 C14 C13 125.1(5) 3_675 . ? C11 C14 H14 117.5 3_675 . ? C13 C14 H14 117.5 . . ? 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 C5 N1 C2 N3 0.1(3) . . . . ? N1 C2 N3 C4 0.0(3) . . . . ? N1 C2 N3 C6 -175.9(2) . . . . ? C2 N3 C4 C5 0.0(3) . . . . ? C6 N3 C4 C5 175.8(2) . . . . ? N3 C4 C5 N1 0.1(3) . . . . ? C2 N1 C5 C4 -0.1(3) . . . . ? C2 N3 C6 C7 -110.3(3) . . . . ? C4 N3 C6 C7 74.6(3) . . . . ? N3 C6 C7 C8 -150.9(2) . . . . ? N3 C6 C7 C12 30.2(4) . . . . ? C12 C7 C8 C9 -0.1(4) . . . . ? C6 C7 C8 C9 -179.1(2) . . . . ? C7 C8 C9 C13 -179.1(3) . . . . ? C7 C8 C9 C10 -0.5(4) . . . . ? C13 C9 C10 C11 179.5(3) . . . . ? C8 C9 C10 C11 0.7(4) . . . . ? C13 C9 C10 C10 0.1(5) . . . 3_675 ? C8 C9 C10 C10 -178.6(3) . . . 3_675 ? C9 C10 C11 C14 -180.0(3) . . . 3_675 ? C10 C10 C11 C14 -0.6(5) 3_675 . . 3_675 ? C9 C10 C11 C12 -0.3(4) . . . . ? C10 C10 C11 C12 179.1(3) 3_675 . . . ? C14 C11 C12 C7 179.3(4) 3_675 . . . ? C10 C11 C12 C7 -0.4(4) . . . . ? C8 C7 C12 C11 0.6(4) . . . . ? C6 C7 C12 C11 179.5(2) . . . . ? C8 C9 C13 C14 179.1(4) . . . . ? C10 C9 C13 C14 0.4(6) . . . . ? C9 C13 C14 C11 -0.5(8) . . . 3_675 ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.15 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.203 _refine_diff_density_min -0.225 _refine_diff_density_rms 0.053 data_P2.CIF _database_code_depnum_ccdc_archive 'CCDC 905947' #TrackingRef '14692_web_deposit_cif_file_2_LeighLoots_1350297328.Intermediate.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2,7-bis(bromomethyl)phenanthrene ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H12 Br2' _chemical_formula_sum 'C16 H12 Br2' _chemical_formula_weight 364.08 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall '-P 2ybc' 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 14.073(3) _cell_length_b 8.4828(15) _cell_length_c 11.281(2) _cell_angle_alpha 90.00 _cell_angle_beta 101.917(2) _cell_angle_gamma 90.00 _cell_volume 1317.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2212 _cell_measurement_theta_min 2.96 _cell_measurement_theta_max 26.16 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.835 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 712 _exptl_absorpt_coefficient_mu 6.129 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.3209 _exptl_absorpt_correction_T_max 0.6270 _exptl_absorpt_process_details 'SADABS, 2002' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 APEX CCD area -detector' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count . _diffrn_standards_interval_time . _diffrn_standards_decay_% ? _diffrn_reflns_number 7323 _diffrn_reflns_av_R_equivalents 0.0383 _diffrn_reflns_av_sigmaI/netI 0.0494 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.82 _diffrn_reflns_theta_max 26.28 _reflns_number_total 2666 _reflns_number_gt 2104 _reflns_threshold_expression >2/s(I) _computing_data_collection 'APEX2 (Bruker, 2009)' _computing_cell_refinement 'SAINT (Bruker, 2009)' _computing_data_reduction SAINT _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'X-Seed (BArbour,2001; Atwood & Barbour,2003)' _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. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0487P)^2^+0.4509P] 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 2666 _refine_ls_number_parameters 163 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0509 _refine_ls_R_factor_gt 0.0347 _refine_ls_wR_factor_ref 0.0932 _refine_ls_wR_factor_gt 0.0859 _refine_ls_goodness_of_fit_ref 1.025 _refine_ls_restrained_S_all 1.025 _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 Br1 Br 0.40606(3) 0.16865(5) 0.45904(4) 0.02736(15) Uani 1 1 d . . . Br2 Br -0.41523(3) 0.06563(5) 0.20841(4) 0.02884(15) Uani 1 1 d . . . C8 C -0.2251(3) 0.3910(4) 0.2766(3) 0.0138(8) Uani 1 1 d . . . H8 H -0.2563 0.4541 0.2104 0.017 Uiso 1 1 calc R . . C7 C -0.1237(3) 0.4026(4) 0.3169(3) 0.0120(8) Uani 1 1 d . . . C2 C 0.2349(3) 0.3171(4) 0.5095(3) 0.0154(8) Uani 1 1 d . . . C1 C 0.3424(3) 0.3253(5) 0.5456(4) 0.0207(9) Uani 1 1 d . . . H1A H 0.3623 0.3069 0.6339 0.025 Uiso 1 1 calc R . . H1B H 0.3642 0.4323 0.5283 0.025 Uiso 1 1 calc R . . C12 C -0.0758(3) 0.3057(4) 0.4140(3) 0.0105(7) Uani 1 1 d . . . C6 C -0.0671(3) 0.5078(4) 0.2601(3) 0.0132(8) Uani 1 1 d . . . H6 H -0.0990 0.5761 0.1977 0.016 Uiso 1 1 calc R . . C10 C -0.2326(3) 0.2018(4) 0.4318(3) 0.0157(8) Uani 1 1 d . . . H10 H -0.2698 0.1359 0.4730 0.019 Uiso 1 1 calc R . . C15 C 0.1816(3) 0.2155(4) 0.5693(3) 0.0146(8) Uani 1 1 d . . . H15 H 0.2152 0.1486 0.6315 0.017 Uiso 1 1 calc R . . C13 C 0.0288(3) 0.3084(4) 0.4478(3) 0.0114(8) Uani 1 1 d . . . C11 C -0.1343(3) 0.2087(4) 0.4713(3) 0.0145(8) Uani 1 1 d . . . H11 H -0.1046 0.1468 0.5390 0.017 Uiso 1 1 calc R . . C16 C -0.3862(3) 0.2739(5) 0.2847(4) 0.0207(9) Uani 1 1 d . . . H16A H -0.4092 0.3579 0.2247 0.025 Uiso 1 1 calc R . . H16B H -0.4207 0.2857 0.3524 0.025 Uiso 1 1 calc R . . C3 C 0.1840(3) 0.4135(4) 0.4181(3) 0.0140(8) Uani 1 1 d . . . H3 H 0.2188 0.4824 0.3761 0.017 Uiso 1 1 calc R . . C5 C 0.0305(3) 0.5120(4) 0.2934(3) 0.0121(8) Uani 1 1 d . . . H5 H 0.0658 0.5836 0.2542 0.014 Uiso 1 1 calc R . . C4 C 0.0822(3) 0.4106(4) 0.3868(3) 0.0111(8) Uani 1 1 d . . . C9 C -0.2802(3) 0.2903(4) 0.3310(3) 0.0158(8) Uani 1 1 d . . . C14 C 0.0828(3) 0.2105(4) 0.5401(3) 0.0134(8) Uani 1 1 d . . . H14 H 0.0491 0.1400 0.5823 0.016 Uiso 1 1 calc R . . 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 0.0199(3) 0.0249(2) 0.0391(3) -0.00913(19) 0.01017(19) 0.00126(18) Br2 0.0189(3) 0.0247(2) 0.0399(3) -0.00467(19) -0.00098(19) -0.00310(18) C8 0.019(2) 0.0066(17) 0.0151(18) -0.0023(14) 0.0031(16) 0.0018(15) C7 0.019(2) 0.0061(17) 0.0124(17) -0.0039(13) 0.0061(15) 0.0009(14) C2 0.015(2) 0.0139(19) 0.0171(18) -0.0072(15) 0.0040(16) -0.0014(15) C1 0.016(2) 0.021(2) 0.025(2) -0.0094(17) 0.0050(17) -0.0003(16) C12 0.017(2) 0.0084(17) 0.0065(15) -0.0032(13) 0.0043(14) -0.0015(14) C6 0.024(2) 0.0066(17) 0.0092(16) 0.0001(14) 0.0050(15) -0.0006(15) C10 0.019(2) 0.0101(18) 0.0200(19) 0.0004(15) 0.0089(16) -0.0026(15) C15 0.017(2) 0.0138(19) 0.0123(17) -0.0033(15) 0.0014(15) 0.0040(16) C13 0.020(2) 0.0056(17) 0.0102(16) -0.0043(13) 0.0072(15) -0.0009(14) C11 0.020(2) 0.0105(18) 0.0140(18) -0.0007(15) 0.0063(16) 0.0000(15) C16 0.019(2) 0.015(2) 0.028(2) -0.0010(17) 0.0036(17) 0.0016(17) C3 0.016(2) 0.0113(18) 0.0168(18) -0.0057(15) 0.0081(16) -0.0009(15) C5 0.020(2) 0.0082(17) 0.0103(17) 0.0003(13) 0.0081(16) -0.0017(15) C4 0.016(2) 0.0095(18) 0.0100(16) -0.0051(14) 0.0082(15) -0.0035(15) C9 0.016(2) 0.0109(18) 0.0207(19) -0.0050(15) 0.0049(16) 0.0012(15) C14 0.018(2) 0.0119(18) 0.0122(17) -0.0007(14) 0.0072(15) 0.0004(15) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 C1 1.971(4) . ? Br2 C16 1.971(4) . ? C8 C9 1.379(5) . ? C8 C7 1.409(5) . ? C8 H8 0.9500 . ? C7 C12 1.423(5) . ? C7 C6 1.432(5) . ? C2 C3 1.393(5) . ? C2 C15 1.402(5) . ? C2 C1 1.486(5) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C12 C11 1.412(5) . ? C12 C13 1.443(5) . ? C6 C5 1.347(5) . ? C6 H6 0.9500 . ? C10 C11 1.364(5) . ? C10 C9 1.411(5) . ? C10 H10 0.9500 . ? C15 C14 1.362(5) . ? C15 H15 0.9500 . ? C13 C4 1.416(5) . ? C13 C14 1.422(5) . ? C11 H11 0.9500 . ? C16 C9 1.483(5) . ? C16 H16A 0.9900 . ? C16 H16B 0.9900 . ? C3 C4 1.402(5) . ? C3 H3 0.9500 . ? C5 C4 1.437(5) . ? C5 H5 0.9500 . ? C14 H14 0.9500 . ? 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 C9 C8 C7 121.7(3) . . ? C9 C8 H8 119.2 . . ? C7 C8 H8 119.2 . . ? C8 C7 C12 119.7(3) . . ? C8 C7 C6 121.3(3) . . ? C12 C7 C6 119.1(3) . . ? C3 C2 C15 118.2(4) . . ? C3 C2 C1 120.9(3) . . ? C15 C2 C1 120.8(3) . . ? C2 C1 Br1 112.0(2) . . ? C2 C1 H1A 109.2 . . ? Br1 C1 H1A 109.2 . . ? C2 C1 H1B 109.2 . . ? Br1 C1 H1B 109.2 . . ? H1A C1 H1B 107.9 . . ? C11 C12 C7 117.4(3) . . ? C11 C12 C13 123.3(3) . . ? C7 C12 C13 119.3(3) . . ? C5 C6 C7 121.4(3) . . ? C5 C6 H6 119.3 . . ? C7 C6 H6 119.3 . . ? C11 C10 C9 121.4(3) . . ? C11 C10 H10 119.3 . . ? C9 C10 H10 119.3 . . ? C14 C15 C2 121.6(3) . . ? C14 C15 H15 119.2 . . ? C2 C15 H15 119.2 . . ? C4 C13 C14 117.2(3) . . ? C4 C13 C12 119.8(3) . . ? C14 C13 C12 123.0(3) . . ? C10 C11 C12 121.6(3) . . ? C10 C11 H11 119.2 . . ? C12 C11 H11 119.2 . . ? C9 C16 Br2 109.9(3) . . ? C9 C16 H16A 109.7 . . ? Br2 C16 H16A 109.7 . . ? C9 C16 H16B 109.7 . . ? Br2 C16 H16B 109.7 . . ? H16A C16 H16B 108.2 . . ? C2 C3 C4 121.2(3) . . ? C2 C3 H3 119.4 . . ? C4 C3 H3 119.4 . . ? C6 C5 C4 121.5(3) . . ? C6 C5 H5 119.3 . . ? C4 C5 H5 119.3 . . ? C3 C4 C13 120.4(3) . . ? C3 C4 C5 120.7(3) . . ? C13 C4 C5 118.9(3) . . ? C8 C9 C10 118.1(4) . . ? C8 C9 C16 121.3(3) . . ? C10 C9 C16 120.6(3) . . ? C15 C14 C13 121.5(3) . . ? C15 C14 H14 119.2 . . ? C13 C14 H14 119.2 . . ? 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 C9 C8 C7 C12 1.6(5) . . . . ? C9 C8 C7 C6 -179.8(3) . . . . ? C3 C2 C1 Br1 -93.8(4) . . . . ? C15 C2 C1 Br1 88.2(4) . . . . ? C8 C7 C12 C11 -4.2(5) . . . . ? C6 C7 C12 C11 177.2(3) . . . . ? C8 C7 C12 C13 174.7(3) . . . . ? C6 C7 C12 C13 -3.9(5) . . . . ? C8 C7 C6 C5 -175.8(3) . . . . ? C12 C7 C6 C5 2.8(5) . . . . ? C3 C2 C15 C14 -0.3(5) . . . . ? C1 C2 C15 C14 177.7(3) . . . . ? C11 C12 C13 C4 -179.2(3) . . . . ? C7 C12 C13 C4 2.0(5) . . . . ? C11 C12 C13 C14 1.7(5) . . . . ? C7 C12 C13 C14 -177.1(3) . . . . ? C9 C10 C11 C12 0.6(5) . . . . ? C7 C12 C11 C10 3.1(5) . . . . ? C13 C12 C11 C10 -175.7(3) . . . . ? C15 C2 C3 C4 0.5(5) . . . . ? C1 C2 C3 C4 -177.5(3) . . . . ? C7 C6 C5 C4 0.3(5) . . . . ? C2 C3 C4 C13 -0.2(5) . . . . ? C2 C3 C4 C5 179.2(3) . . . . ? C14 C13 C4 C3 -0.3(5) . . . . ? C12 C13 C4 C3 -179.5(3) . . . . ? C14 C13 C4 C5 -179.7(3) . . . . ? C12 C13 C4 C5 1.1(5) . . . . ? C6 C5 C4 C3 178.3(3) . . . . ? C6 C5 C4 C13 -2.3(5) . . . . ? C7 C8 C9 C10 2.1(5) . . . . ? C7 C8 C9 C16 -177.4(3) . . . . ? C11 C10 C9 C8 -3.2(5) . . . . ? C11 C10 C9 C16 176.3(3) . . . . ? Br2 C16 C9 C8 109.5(3) . . . . ? Br2 C16 C9 C10 -69.9(4) . . . . ? C2 C15 C14 C13 -0.2(5) . . . . ? C4 C13 C14 C15 0.5(5) . . . . ? C12 C13 C14 C15 179.6(3) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 26.28 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.590 _refine_diff_density_min -0.580 _refine_diff_density_rms 0.112