# Electronic Supplementary Material (ESI) for CrystEngComm # 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_Co-ZIF-68 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety C10H7CoN5O2 _chemical_formula_sum 'C10 H7 Co N5 O2' _chemical_formula_weight 288.14 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M P63/mmc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x-y, x, z+1/2' '-y, x-y, z' '-x, -y, z+1/2' '-x+y, -x, z' 'y, -x+y, z+1/2' 'x-y, -y, -z' '-x, -x+y, -z' 'y, x, -z' '-y, -x, -z+1/2' '-x+y, y, -z+1/2' 'x, x-y, -z+1/2' '-x, -y, -z' '-x+y, -x, -z-1/2' 'y, -x+y, -z' 'x, y, -z-1/2' 'x-y, x, -z' '-y, x-y, -z-1/2' '-x+y, y, z' 'x, x-y, z' '-y, -x, z' 'y, x, z-1/2' 'x-y, -y, z-1/2' '-x, -x+y, z-1/2' _cell_length_a 26.674(2) _cell_length_b 26.674(2) _cell_length_c 18.4694(20) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 11380.5(19) _cell_formula_units_Z 24 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min 3.05 _cell_measurement_theta_max 29.26 _exptl_crystal_description Plate _exptl_crystal_colour Pink _exptl_crystal_size_max 0.31 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.009 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3480 _exptl_absorpt_coefficient_mu 0.905 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.755 _exptl_absorpt_correction_T_max 0.873 _exptl_absorpt_process_details 'Blessing, Acta Cryst. (1995) A51 33-58' _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 ? _diffrn_measurement_method SMART _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 37603 _diffrn_reflns_av_R_equivalents 0.0927 _diffrn_reflns_av_sigmaI/netI 0.0696 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 36 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 36 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 3.05 _diffrn_reflns_theta_max 29.26 _reflns_number_total 5153 _reflns_number_gt 2116 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'Bruker SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; We believe anisotropic distortion in the aromatic ring in Co-ZIF-68 structure appears due to static or dynamic disorder. As a result despite lowering the data collection temperature to 100 K this distortion remains persistent. Moreover, there is disorder by symmetry in the crystal structure of Co-ZIF-68. we have repeatedly collected the single crystal XRD data of Co-ZIF-68 at different temperature (100, 120, 150K). We would like to mention that each time during the refinement of crystal structure we encountered electron densities within the framework cavity. However, assigning these electron densities with isolated O, N and C atoms, leads to highly distorted atoms, although the refinement become stable with decreased R factor and goodness of fit. Hence, we believe that one DMF molecule reside inside the asymmetric unit of Co-ZIF-68, however, these atoms of DMF molecule have very high thermal parameters apart from Co-ZIF-68 frameworks with several IUCr checkcif errors. Hence we have decided to use the SQUEEZE routine to remove these unstable and highly distorted DMF molecules from the pores of Co-ZIF-68. It should be noted that SQUEEZE structure is very stable with minimal IUCr checkcif problems, less R factor and goodness of fit. Here we have provided the SQUEEZE applied cif file of Co-ZIF-68. 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^)+(0.2000P)^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 5153 _refine_ls_number_parameters 165 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1630 _refine_ls_R_factor_gt 0.0992 _refine_ls_wR_factor_ref 0.3300 _refine_ls_wR_factor_gt 0.2938 _refine_ls_goodness_of_fit_ref 0.884 _refine_ls_restrained_S_all 0.884 _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 C11 C 0.3593(3) 0.3143(3) 0.2844(5) 0.149(4) Uani 1 1 d . . . H11 H 0.3295 0.3123 0.3128 0.179 Uiso 1 1 calc R . . C12 C 0.4377(4) 0.3216(3) 0.2500 0.093(2) Uani 1 2 d S . . C8 C 0.3872(3) 0.3872(3) 0.5000 0.129(4) Uani 1 2 d S . . H8 H 0.4220 0.4220 0.5000 0.155 Uiso 1 2 calc SR . . N6 N 0.4908(3) 0.3261(2) 0.2500 0.112(3) Uani 1 2 d S . . C6 C 0.2943(3) 0.2407(3) 0.4623(5) 0.160(4) Uani 1 1 d . . . H6 H 0.3121 0.2227 0.4393 0.192 Uiso 1 1 calc R . . C10 C 0.55122(19) 0.44878(19) 0.4199(6) 0.124(4) Uani 1 2 d S . . C4 C 0.4407(3) 0.22036(14) 0.4149(3) 0.0691(16) Uani 1 2 d S . . H4 H 0.4457 0.2229 0.3649 0.083 Uiso 1 2 calc SR . . C2 C 0.4236(5) 0.2657(5) 0.5815(3) 0.188(5) Uani 1 1 d . . . H2 H 0.4218 0.2996 0.5803 0.225 Uiso 1 1 calc R . . C5 C 0.3248(3) 0.2985(3) 0.4816(4) 0.134(3) Uani 1 1 d . . . C9 C 0.5597(4) 0.3926(4) 0.4874(4) 0.157(4) Uani 1 1 d . . . H9 H 0.5531 0.3597 0.5128 0.188 Uiso 1 1 calc R . . C1 C 0.4307(3) 0.2408(3) 0.5224(3) 0.118(2) Uani 1 1 d . . . C7 C 0.2357(4) 0.2109(4) 0.4791(7) 0.217(7) Uani 1 1 d . . . H7 H 0.2127 0.1734 0.4619 0.260 Uiso 1 1 calc R . . Co1 Co 0.44102(3) 0.33220(3) 0.41260(5) 0.0979(5) Uani 1 1 d . . . N2 N 0.3820(2) 0.34044(18) 0.4677(3) 0.131(2) Uani 1 1 d . . . N4 N 0.5283(2) 0.4717(2) 0.3773(11) 0.251(9) Uani 1 2 d S . . N5 N 0.4080(2) 0.31763(19) 0.3113(3) 0.0976(13) Uani 1 1 d . . . N1 N 0.43719(19) 0.26113(19) 0.4502(2) 0.0884(12) Uani 1 1 d . . . N3 N 0.5201(3) 0.3957(2) 0.4461(4) 0.131(2) Uani 1 1 d . . . O1 O 0.4766(2) 0.4431(3) 0.3695(4) 0.1649(16) Uani 1 1 d . . . O2 O 0.5146(2) 0.3290(2) 0.3093(4) 0.1649(16) Uani 1 1 d . . . C3 C 0.4192(7) 0.2355(8) 0.6445(5) 0.340(16) Uani 1 1 d . . . H3 H 0.4161 0.2508 0.6885 0.408 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 C11 0.076(4) 0.108(5) 0.267(12) 0.001(5) 0.015(5) 0.049(4) C12 0.082(5) 0.054(4) 0.144(7) 0.000 0.000 0.036(4) C8 0.075(3) 0.075(3) 0.219(9) -0.046(3) 0.046(3) 0.024(4) N6 0.062(4) 0.042(3) 0.248(9) 0.000 0.000 0.039(3) C6 0.132(6) 0.070(4) 0.227(8) -0.045(4) 0.077(6) 0.011(4) C10 0.059(3) 0.059(3) 0.249(11) -0.032(3) 0.032(3) 0.026(4) C4 0.078(4) 0.074(3) 0.057(3) 0.0081(13) 0.016(3) 0.039(2) C2 0.307(14) 0.217(10) 0.059(3) 0.000(4) 0.047(5) 0.146(10) C5 0.095(4) 0.069(4) 0.208(7) -0.046(4) 0.039(4) 0.017(3) C9 0.127(6) 0.154(7) 0.123(5) 0.005(4) -0.005(4) 0.020(5) C1 0.136(5) 0.141(5) 0.084(3) -0.013(3) 0.031(3) 0.075(4) C7 0.095(5) 0.122(6) 0.347(16) -0.109(8) 0.071(7) -0.011(5) Co1 0.0784(6) 0.0584(5) 0.1597(9) -0.0182(3) 0.0296(4) 0.0362(4) N2 0.089(3) 0.060(3) 0.223(6) -0.043(3) 0.059(3) 0.021(2) N4 0.076(4) 0.076(4) 0.60(3) 0.034(5) -0.034(5) 0.037(5) N5 0.099(4) 0.078(3) 0.123(3) 0.002(2) 0.008(3) 0.050(3) N1 0.108(3) 0.087(3) 0.077(2) -0.004(2) 0.025(2) 0.053(3) N3 0.091(4) 0.076(3) 0.195(6) -0.035(4) 0.057(4) 0.018(3) O1 0.102(3) 0.132(3) 0.276(4) 0.007(3) -0.025(3) 0.069(2) O2 0.102(3) 0.132(3) 0.276(4) 0.007(3) -0.025(3) 0.069(2) C3 0.44(2) 0.48(4) 0.101(5) -0.038(10) 0.048(7) 0.23(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 C11 C11 1.272(17) 16_556 ? C11 N5 1.352(8) . ? C11 H11 0.9300 . ? C12 N5 1.355(6) . ? C12 N5 1.355(6) 16_556 ? C12 N6 1.360(10) . ? C8 N2 1.325(6) . ? C8 N2 1.325(6) 9_556 ? C8 H8 0.9300 . ? N6 O2 1.250(6) 16_556 ? N6 O2 1.250(6) . ? C6 C5 1.383(8) . ? C6 C7 1.388(9) . ? C6 H6 0.9300 . ? C10 N4 1.320(16) . ? C10 N3 1.324(8) 21_665 ? C10 N3 1.324(8) . ? C4 N1 1.311(4) . ? C4 N1 1.311(4) 20 ? C4 H4 0.9300 . ? C2 C1 1.339(8) . ? C2 C3 1.386(15) . ? C2 H2 0.9300 . ? C5 C5 1.390(12) 9_556 ? C5 N2 1.393(7) . ? C9 C9 1.275(16) 21_665 ? C9 N3 1.339(9) . ? C9 H9 0.9300 . ? C1 C1 1.355(13) 20 ? C1 N1 1.418(7) . ? C7 C7 1.382(16) 9_556 ? C7 H7 0.9300 . ? Co1 N1 1.973(4) . ? Co1 N2 1.977(4) . ? Co1 N5 2.021(5) . ? Co1 N3 2.031(6) . ? N4 O1 1.205(6) . ? N4 O1 1.205(6) 21_665 ? C3 C3 1.38(4) 20 ? C3 H3 0.9300 . ? 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 C11 C11 N5 111.5(4) 16_556 . ? C11 C11 H11 124.2 16_556 . ? N5 C11 H11 124.2 . . ? N5 C12 N5 113.3(7) . 16_556 ? N5 C12 N6 123.3(4) . . ? N5 C12 N6 123.3(4) 16_556 . ? N2 C8 N2 117.1(7) . 9_556 ? N2 C8 H8 121.4 . . ? N2 C8 H8 121.4 9_556 . ? O2 N6 O2 122.5(8) 16_556 . ? O2 N6 C12 118.7(4) 16_556 . ? O2 N6 C12 118.7(4) . . ? C5 C6 C7 116.5(7) . . ? C5 C6 H6 121.7 . . ? C7 C6 H6 121.7 . . ? N4 C10 N3 121.6(6) . 21_665 ? N4 C10 N3 121.7(6) . . ? N3 C10 N3 116.2(12) 21_665 . ? N1 C4 N1 119.9(5) . 20 ? N1 C4 H4 120.1 . . ? N1 C4 H4 120.1 20 . ? C1 C2 C3 112.9(11) . . ? C1 C2 H2 123.6 . . ? C3 C2 H2 123.6 . . ? C6 C5 C5 121.6(4) . 9_556 ? C6 C5 N2 130.1(5) . . ? C5 C5 N2 108.2(3) 9_556 . ? C9 C9 N3 111.3(4) 21_665 . ? C9 C9 H9 124.4 21_665 . ? N3 C9 H9 124.4 . . ? C2 C1 C1 124.5(5) . 20 ? C2 C1 N1 126.6(6) . . ? C1 C1 N1 108.8(3) 20 . ? C7 C7 C6 121.5(4) 9_556 . ? C7 C7 H7 119.3 9_556 . ? C6 C7 H7 119.3 . . ? N1 Co1 N2 105.3(2) . . ? N1 Co1 N5 109.43(17) . . ? N2 Co1 N5 101.8(3) . . ? N1 Co1 N3 103.2(3) . . ? N2 Co1 N3 107.60(19) . . ? N5 Co1 N3 127.8(3) . . ? C8 N2 C5 103.2(5) . . ? C8 N2 Co1 128.5(4) . . ? C5 N2 Co1 128.3(3) . . ? O1 N4 O1 125.3(11) . 21_665 ? O1 N4 C10 115.3(8) . . ? O1 N4 C10 115.3(8) 21_665 . ? C11 N5 C12 101.7(6) . . ? C11 N5 Co1 131.6(5) . . ? C12 N5 Co1 125.2(4) . . ? C4 N1 C1 101.2(4) . . ? C4 N1 Co1 129.2(3) . . ? C1 N1 Co1 129.6(3) . . ? C10 N3 C9 100.5(7) . . ? C10 N3 Co1 128.0(8) . . ? C9 N3 Co1 130.1(6) . . ? C3 C3 C2 122.5(8) 20 . ? C3 C3 H3 118.8 20 . ? C2 C3 H3 118.8 . . ? _diffrn_measured_fraction_theta_max 0.909 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 0.916 _refine_diff_density_min -0.565 _refine_diff_density_rms 0.092 _database_code_depnum_ccdc_archive 'CCDC 952993' ####################################################################### # # 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_Co-ZIF-69 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety C10H5Cl2CoN5O2 _chemical_formula_sum 'C10 H5 Cl2 Co N5 O2' _chemical_formula_weight 357.02 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' Co Co 0.3494 0.9721 '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' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M P63/mmc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x-y, x, z+1/2' '-y, x-y, z' '-x, -y, z+1/2' '-x+y, -x, z' 'y, -x+y, z+1/2' 'x-y, -y, -z' '-x, -x+y, -z' 'y, x, -z' '-y, -x, -z+1/2' '-x+y, y, -z+1/2' 'x, x-y, -z+1/2' '-x, -y, -z' '-x+y, -x, -z-1/2' 'y, -x+y, -z' 'x, y, -z-1/2' 'x-y, x, -z' '-y, x-y, -z-1/2' '-x+y, y, z' 'x, x-y, z' '-y, -x, z' 'y, x, z-1/2' 'x-y, -y, z-1/2' '-x, -x+y, z-1/2' _cell_length_a 26.113(2) _cell_length_b 26.113(2) _cell_length_c 19.6459(14) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 11601.2(16) _cell_formula_units_Z 24 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min 3.16 _cell_measurement_theta_max 29.17 _exptl_crystal_description Plate _exptl_crystal_colour Pink _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.226 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4248 _exptl_absorpt_coefficient_mu 1.168 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.732 _exptl_absorpt_correction_T_max 0.830 _exptl_absorpt_process_details 'Blessing, Acta Cryst. (1995) A51 33-58' _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 ? _diffrn_measurement_method SMART _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 38519 _diffrn_reflns_av_R_equivalents 0.0907 _diffrn_reflns_av_sigmaI/netI 0.0799 _diffrn_reflns_limit_h_min -34 _diffrn_reflns_limit_h_max 31 _diffrn_reflns_limit_k_min -35 _diffrn_reflns_limit_k_max 35 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 3.16 _diffrn_reflns_theta_max 29.17 _reflns_number_total 5174 _reflns_number_gt 2364 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'Bruker SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; We believe anisotropic distortion in the aromatic ring in Co-ZIF-69 structure appears due to static or dynamic disorder. As a result despite lowering the data collection temperature to 100 K this distortion remains persistent. Moreover, there is disorder by symmetry in the crystal structure of Co-ZIF-69. There is only one Cl atom per cobalt metal center in the crystal structure Co-ZIF-69. However, due to crystallographic disorder of chlorine atom Co-ZIF-69 shows two chlorine atoms with 1/2 occupancy factor per cobalt center. Hence, the formula used (C10H5Cl2CoN5O2) in the cif and crystallographic tables is the original one, generated from crystallographically. we have repeatedly collected the single crystal XRD data of Co-ZIF-69 at different temperature (100, 120, 150K). We would like to mention that each time during the refinement of crystal structure we encountered electron densities within the framework cavity. However, assigning these electron densities with isolated O, N and C atoms, leads to highly distorted atoms, although the refinement become stable with decreased R factor and goodness of fit. Hence, we believe that one DMF molecule reside inside the asymmetric unit of Co-ZIF-69, however, these atoms of DMF molecule have very high thermal parameters apart from Co-ZIF-69 frameworks with several IUCr checkcif errors. Hence we have decided to use the SQUEEZE routine to remove these unstable and highly distorted DMF molecules from the pores of Co-ZIF-69. It should be noted that SQUEEZE structure is very stable with minimal IUCr checkcif problems, less R factor and goodness of fit. Here we have provided the SQUEEZE applied cif file of Co-ZIF-69. 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^)+(0.1852P)^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 5174 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1765 _refine_ls_R_factor_gt 0.0997 _refine_ls_wR_factor_ref 0.3340 _refine_ls_wR_factor_gt 0.2862 _refine_ls_goodness_of_fit_ref 0.979 _refine_ls_restrained_S_all 0.979 _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 Co1 Co 0.66716(3) 0.10261(3) 0.40179(4) 0.0650(4) Uani 1 1 d . . . N6 N 0.6762(2) 0.1592(3) 0.2500 0.0632(16) Uani 1 2 d S . . C8 C 0.78285(16) 0.21715(16) 0.4010(3) 0.0570(18) Uani 1 2 d S . . H8 H 0.7813 0.2187 0.3538 0.068 Uiso 1 2 calc SR . . N2 N 0.74115(19) 0.17309(18) 0.4363(2) 0.0691(12) Uani 1 1 d . . . O1 O 0.67329(18) 0.17952(18) 0.30582(19) 0.0791(12) Uani 1 1 d . . . C10 C 0.54807(18) 0.0961(4) 0.4110(5) 0.072(2) Uani 1 2 d S . . C12 C 0.6774(3) 0.1063(3) 0.2500 0.0571(18) Uani 1 2 d S . . N1 N 0.65954(19) 0.0372(2) 0.4616(3) 0.0784(14) Uani 1 1 d . . . N5 N 0.6800(2) 0.0798(2) 0.3081(2) 0.0711(13) Uani 1 1 d . . . N3 N 0.6034(3) 0.1219(3) 0.4324(4) 0.120(2) Uani 1 1 d . . . C5 C 0.7582(3) 0.1863(3) 0.5034(3) 0.0805(17) Uani 1 1 d . . . C4 C 0.6137(3) 0.0000 0.5000 0.072(2) Uani 1 2 d S . . H4 H 0.5781 0.0000 0.5000 0.087 Uiso 1 2 calc SR . . C6 C 0.7343(4) 0.1562(4) 0.5649(4) 0.143(3) Uani 1 1 d . . . H6 H 0.6989 0.1203 0.5650 0.171 Uiso 1 1 calc R . . C11 C 0.6807(3) 0.0326(3) 0.2850(3) 0.099(2) Uani 1 1 d . . . H11 H 0.6811 0.0037 0.3121 0.118 Uiso 1 1 calc R . . Cl4 Cl 0.7197(4) 0.1348(3) 0.6950(3) 0.378(5) Uani 1 1 d . . . C1 C 0.7032(3) 0.0231(3) 0.4748(3) 0.094(2) Uani 1 1 d . . . Cl7 Cl 0.8562(3) 0.0302(5) 0.4399(7) 0.542(8) Uani 1 1 d . . . C3 C 0.7936(4) 0.0210(6) 0.4740(8) 0.212(7) Uani 1 1 d . . . C2 C 0.7605(3) 0.0455(4) 0.4499(6) 0.160(4) Uani 1 1 d . . . H2 H 0.7761 0.0759 0.4181 0.192 Uiso 1 1 calc R . . C7 C 0.7626(5) 0.1797(5) 0.6229(3) 0.174(5) Uani 1 1 d . . . O2 O 0.5535(4) 0.0254(5) 0.3552(8) 0.277(7) Uani 1 1 d . . . C9 C 0.6072(5) 0.1595(6) 0.4747(5) 0.176(5) Uani 1 1 d . . . H9 H 0.6400 0.1833 0.5015 0.211 Uiso 1 1 calc R . . N4 N 0.5216(4) 0.0433(8) 0.3742(7) 0.201(7) Uani 1 2 d S . . 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 Co1 0.0552(5) 0.0549(5) 0.0708(6) 0.0181(3) 0.0066(3) 0.0169(4) N6 0.047(3) 0.069(4) 0.052(4) 0.000 0.000 0.012(3) C8 0.063(3) 0.063(3) 0.032(3) 0.0036(15) -0.0036(15) 0.022(4) N2 0.071(3) 0.071(3) 0.041(2) 0.009(2) 0.008(2) 0.018(2) O1 0.093(3) 0.072(2) 0.059(2) -0.0102(18) 0.0039(19) 0.032(2) C10 0.061(4) 0.054(4) 0.100(7) 0.013(4) 0.007(2) 0.027(2) C12 0.048(4) 0.033(3) 0.075(5) 0.000 0.000 0.009(3) N1 0.061(3) 0.072(3) 0.095(4) 0.039(3) 0.012(2) 0.028(2) N5 0.063(3) 0.054(3) 0.082(3) 0.003(2) -0.009(2) 0.018(2) N3 0.114(5) 0.122(5) 0.131(6) 0.032(5) 0.014(5) 0.066(5) C5 0.090(4) 0.089(4) 0.051(3) 0.012(3) 0.011(3) 0.035(3) C4 0.060(3) 0.075(5) 0.087(6) 0.009(4) 0.004(2) 0.038(3) C6 0.169(8) 0.163(8) 0.051(4) 0.035(5) 0.024(5) 0.049(6) C11 0.132(6) 0.069(4) 0.110(5) 0.010(3) 0.000(4) 0.062(4) Cl4 0.468(11) 0.325(7) 0.146(3) 0.025(4) 0.014(5) 0.051(7) C1 0.072(4) 0.102(5) 0.111(5) 0.050(4) 0.028(4) 0.047(4) Cl7 0.249(7) 0.641(16) 0.812(19) 0.405(15) 0.253(10) 0.278(9) C3 0.082(6) 0.253(14) 0.329(19) 0.169(13) 0.083(8) 0.105(8) C2 0.076(5) 0.185(9) 0.215(11) 0.101(9) 0.045(6) 0.062(6) C7 0.225(11) 0.247(12) 0.034(3) 0.029(5) 0.019(5) 0.105(10) O2 0.134(7) 0.261(10) 0.466(18) -0.196(12) -0.053(9) 0.120(7) C9 0.162(9) 0.259(13) 0.123(8) -0.103(9) -0.032(6) 0.118(9) N4 0.244(15) 0.232(18) 0.123(10) -0.040(11) -0.020(5) 0.116(9) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Co1 N1 1.999(4) . ? Co1 N2 2.006(4) . ? Co1 N5 2.014(5) . ? Co1 N3 2.057(7) . ? N6 O1 1.236(5) 16_556 ? N6 O1 1.237(5) . ? N6 C12 1.399(9) . ? C8 N2 1.319(5) 21_665 ? C8 N2 1.319(5) . ? C8 H8 0.9300 . ? N2 C5 1.378(7) . ? C10 N3 1.320(8) 19_655 ? C10 N3 1.320(8) . ? C10 N4 1.397(17) . ? C10 C9 2.032(13) 19_655 ? C12 N5 1.353(6) 16_556 ? C12 N5 1.353(6) . ? N1 C4 1.335(5) . ? N1 C1 1.386(7) . ? N5 C11 1.321(8) . ? N3 C9 1.249(11) . ? C5 C6 1.407(8) . ? C5 C5 1.449(12) 21_665 ? C4 N1 1.335(5) 7_556 ? C4 H4 0.9300 . ? C6 C7 1.331(12) . ? C6 H6 0.9300 . ? C11 C11 1.374(13) 16_556 ? C11 H11 0.9300 . ? Cl4 C7 1.822(10) . ? Cl4 Cl4 2.162(10) 16_557 ? C1 C2 1.395(9) . ? C1 C1 1.440(11) 7_556 ? Cl7 C3 1.669(11) . ? C3 C2 1.390(10) . ? C3 C3 1.39(2) 7_556 ? C2 H2 0.9300 . ? C7 C7 1.51(2) 21_665 ? O2 N4 1.199(9) . ? C9 C9 1.44(2) 19_655 ? C9 H9 0.9300 . ? N4 O2 1.199(9) 19_655 ? 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 Co1 N2 102.94(19) . . ? N1 Co1 N5 104.2(2) . . ? N2 Co1 N5 110.74(17) . . ? N1 Co1 N3 106.9(2) . . ? N2 Co1 N3 101.7(3) . . ? N5 Co1 N3 127.9(3) . . ? O1 N6 O1 125.0(7) 16_556 . ? O1 N6 C12 117.4(4) 16_556 . ? O1 N6 C12 117.4(4) . . ? N2 C8 N2 116.2(5) 21_665 . ? N2 C8 H8 121.9 21_665 . ? N2 C8 H8 121.9 . . ? C8 N2 C5 105.2(4) . . ? C8 N2 Co1 128.2(3) . . ? C5 N2 Co1 126.5(3) . . ? N3 C10 N3 114.1(10) 19_655 . ? N3 C10 N4 122.9(5) 19_655 . ? N3 C10 N4 122.9(5) . . ? N3 C10 C9 36.5(5) 19_655 19_655 ? N3 C10 C9 77.9(7) . 19_655 ? N4 C10 C9 157.1(5) . 19_655 ? N5 C12 N5 115.0(7) 16_556 . ? N5 C12 N6 122.4(3) 16_556 . ? N5 C12 N6 122.4(3) . . ? C4 N1 C1 104.9(5) . . ? C4 N1 Co1 128.6(4) . . ? C1 N1 Co1 126.4(4) . . ? C11 N5 C12 102.3(5) . . ? C11 N5 Co1 132.2(4) . . ? C12 N5 Co1 124.2(4) . . ? C9 N3 C10 104.5(8) . . ? C9 N3 Co1 128.9(7) . . ? C10 N3 Co1 126.5(7) . . ? N2 C5 C6 133.1(6) . . ? N2 C5 C5 106.7(3) . 21_665 ? C6 C5 C5 120.1(5) . 21_665 ? N1 C4 N1 115.7(6) . 7_556 ? N1 C4 H4 122.2 . . ? N1 C4 H4 122.2 7_556 . ? C7 C6 C5 119.3(9) . . ? C7 C6 H6 120.4 . . ? C5 C6 H6 120.4 . . ? N5 C11 C11 110.1(4) . 16_556 ? N5 C11 H11 125.0 . . ? C11 C11 H11 125.0 16_556 . ? C7 Cl4 Cl4 140.9(4) . 16_557 ? N1 C1 C2 132.5(6) . . ? N1 C1 C1 107.2(3) . 7_556 ? C2 C1 C1 120.3(4) . 7_556 ? C2 C3 C3 121.4(6) . 7_556 ? C2 C3 Cl7 125.9(9) . . ? C3 C3 Cl7 112.3(5) 7_556 . ? C3 C2 C1 118.2(8) . . ? C3 C2 H2 120.9 . . ? C1 C2 H2 120.9 . . ? C6 C7 C7 120.6(6) . 21_665 ? C6 C7 Cl4 110.3(8) . . ? C7 C7 Cl4 129.0(4) 21_665 . ? N3 C9 C9 108.1(6) . 19_655 ? N3 C9 H9 125.9 . . ? C9 C9 H9 125.9 19_655 . ? O2 N4 O2 125.4(18) . 19_655 ? O2 N4 C10 116.7(10) . . ? O2 N4 C10 116.7(10) 19_655 . ? _diffrn_measured_fraction_theta_max 0.905 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.733 _refine_diff_density_min -0.566 _refine_diff_density_rms 0.107 _database_code_depnum_ccdc_archive 'CCDC 952994' ####################################################################### # # 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_Co-ZIF-81 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety C10H5Br2CoN5O2 _chemical_formula_sum 'C10 H5 Br2 Co N5 O2' _chemical_formula_weight 445.92 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' Co Co 0.3494 0.9721 '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 Hexagonal _symmetry_space_group_name_H-M P63/mmc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x-y, x, z+1/2' '-y, x-y, z' '-x, -y, z+1/2' '-x+y, -x, z' 'y, -x+y, z+1/2' 'x-y, -y, -z' '-x, -x+y, -z' 'y, x, -z' '-y, -x, -z+1/2' '-x+y, y, -z+1/2' 'x, x-y, -z+1/2' '-x, -y, -z' '-x+y, -x, -z-1/2' 'y, -x+y, -z' 'x, y, -z-1/2' 'x-y, x, -z' '-y, x-y, -z-1/2' '-x+y, y, z' 'x, x-y, z' '-y, -x, z' 'y, x, z-1/2' 'x-y, -y, z-1/2' '-x, -x+y, z-1/2' _cell_length_a 25.9949(12) _cell_length_b 25.9949(12) _cell_length_c 19.7757(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 11572.9(10) _cell_formula_units_Z 24 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min 3.13 _cell_measurement_theta_max 29.14 _exptl_crystal_description Plate _exptl_crystal_colour Pink _exptl_crystal_size_max 0.31 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.536 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5112 _exptl_absorpt_coefficient_mu 5.038 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.229 _exptl_absorpt_correction_T_max 0.425 _exptl_absorpt_process_details 'Blessing, Acta Cryst. (1995) A51 33-58' _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 ? _diffrn_measurement_method SMART _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 29226 _diffrn_reflns_av_R_equivalents 0.0903 _diffrn_reflns_av_sigmaI/netI 0.1268 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 35 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 35 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 3.13 _diffrn_reflns_theta_max 29.14 _reflns_number_total 4947 _reflns_number_gt 1471 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'Bruker SHELXTL' _computing_structure_refinement 'Bruker SHELXTL' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; We believe anisotropic distortion in the aromatic ring in Co-ZIF-81 structure appears due to static or dynamic disorder. As a result despite lowering the data collection temperature to 100 K this distortion remains persistent. Moreover, there is disorder by symmetry in the crystal structure of Co-ZIF-81. There is only one Br atom per cobalt metal center in the crystal structure Co-ZIF-81. However, due to crystallographic disorder of bromine atom Co-ZIF-81 shows two bromine atoms with 1/2 occupancy factor per cobalt center. Hence, the formula used (C10H5Br2CoN5O2) in the cif and crystallographic tables is the original one, generated from crystallographically. we have repeatedly collected the single crystal XRD data of Co-ZIF-81 at different temperature (100, 120, 150K). We would like to mention that each time during the refinement of crystal structure we encountered electron densities within the framework cavity. However, assigning these electron densities with isolated O, N and C atoms, leads to highly distorted atoms, although the refinement become stable with decreased R factor and goodness of fit. Hence, we believe that one DMF molecule reside inside the asymmetric unit of Co-ZIF-81, however, these atoms of DMF molecule have very high thermal parameters apart from Co-ZIF-81 frameworks with several IUCr checkcif errors. Hence we have decided to use the SQUEEZE routine to remove these unstable and highly distorted DMF molecules from the pores of Co-ZIF-81. It should be noted that SQUEEZE structure is very stable with minimal IUCr checkcif problems, less R factor and goodness of fit. Here we have provided the SQUEEZE applied cif file of Co-ZIF-81. 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^)+(0.2000P)^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 4947 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1975 _refine_ls_R_factor_gt 0.0995 _refine_ls_wR_factor_ref 0.3115 _refine_ls_wR_factor_gt 0.2545 _refine_ls_goodness_of_fit_ref 0.702 _refine_ls_restrained_S_all 0.702 _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 Co1 Co 0.43467(4) 0.10167(4) 0.59921(4) 0.0715(4) Uani 1 1 d . . . N2 N 0.4826(3) 0.1584(3) 0.7500 0.073(2) Uani 1 2 d S . . C9 C 0.4345(3) 0.21727(16) 0.6043(4) 0.0586(19) Uani 1 2 d S . . H9 H 0.4372 0.2186 0.6513 0.070 Uiso 1 2 calc SR . . C2 C 0.4268(4) 0.1033(3) 0.7500 0.079(3) Uani 1 2 d S . . N6 N 0.4323(3) 0.1734(2) 0.5660(2) 0.0809(15) Uani 1 1 d . . . O1 O 0.5056(2) 0.1778(2) 0.69430(19) 0.0882(13) Uani 1 1 d . . . C4 C 0.5469(3) 0.0937(6) 0.5905(3) 0.079(3) Uani 1 2 d S . . N1 N 0.4017(3) 0.0793(3) 0.6921(3) 0.0960(18) Uani 1 1 d . . . N5 N 0.3764(2) 0.0370(2) 0.5405(3) 0.0869(17) Uani 1 1 d . . . N3 N 0.5170(3) 0.1191(3) 0.5648(5) 0.134(3) Uani 1 1 d . . . C10 C 0.4304(3) 0.1891(3) 0.4968(4) 0.101(2) Uani 1 1 d . . . C6 C 0.3180(4) 0.0206(4) 0.5280(4) 0.121(3) Uani 1 1 d . . . C5 C 0.3864(4) 0.0000 0.5000 0.077(2) Uani 1 2 d S . . H5 H 0.4222 0.0000 0.5000 0.092 Uiso 1 2 calc SR . . C1 C 0.3503(4) 0.0320(3) 0.7136(4) 0.113(3) Uani 1 1 d . . . H1 H 0.3201 0.0043 0.6861 0.136 Uiso 1 1 calc R . . C3 C 0.5539(6) 0.1689(6) 0.5328(6) 0.181(5) Uani 1 1 d . . . H3 H 0.5460 0.1972 0.5146 0.217 Uiso 1 1 calc R . . Br2 Br 0.1682(2) 0.0295(3) 0.5637(4) 0.547(4) Uani 1 1 d . . . O2 O 0.5525(3) 0.0231(4) 0.6395(5) 0.182(3) Uani 1 1 d . . . C11 C 0.4295(5) 0.1608(5) 0.4309(7) 0.158(4) Uani 1 1 d . . . H11 H 0.4360 0.1290 0.4249 0.190 Uiso 1 1 calc R . . C7 C 0.2821(5) 0.0461(6) 0.5502(6) 0.188(5) Uani 1 1 d . . . H7 H 0.2970 0.0790 0.5785 0.225 Uiso 1 1 calc R . . C8 C 0.2233(5) 0.0174(8) 0.5260(9) 0.203(7) Uani 1 1 d . . . C12 C 0.4182(11) 0.1880(8) 0.3833(7) 0.265(11) Uani 1 1 d . . . N4 N 0.5184(4) 0.0368(7) 0.6247(8) 0.164(5) Uani 1 2 d S . . Br1 Br 0.4154(3) 0.13555(18) 0.30144(17) 0.484(4) 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 Co1 0.0941(7) 0.0660(6) 0.0635(6) -0.0157(3) -0.0093(4) 0.0468(5) N2 0.082(5) 0.060(4) 0.115(6) 0.000 0.000 0.063(4) C9 0.085(5) 0.051(3) 0.051(4) -0.0156(17) -0.031(3) 0.043(3) C2 0.077(6) 0.032(4) 0.101(8) 0.000 0.000 0.006(4) N6 0.144(5) 0.107(4) 0.022(2) 0.000(2) -0.001(2) 0.085(3) O1 0.112(3) 0.092(3) 0.055(2) 0.007(2) 0.011(2) 0.046(3) C4 0.112(5) 0.119(8) 0.009(3) -0.016(4) -0.0078(18) 0.060(4) N1 0.126(5) 0.095(4) 0.071(3) -0.007(3) -0.038(3) 0.058(4) N5 0.089(4) 0.065(3) 0.110(4) -0.047(3) -0.037(3) 0.041(3) N3 0.096(5) 0.090(5) 0.194(8) -0.039(6) -0.014(5) 0.031(4) C10 0.127(6) 0.098(4) 0.085(5) -0.035(4) -0.027(4) 0.062(4) C6 0.124(7) 0.128(7) 0.125(7) -0.056(5) -0.028(5) 0.074(5) C5 0.093(5) 0.072(5) 0.059(5) -0.021(4) -0.010(2) 0.036(3) C1 0.110(5) 0.057(4) 0.122(6) 0.004(3) 0.004(4) 0.004(4) C3 0.222(12) 0.176(11) 0.187(12) 0.074(9) 0.057(9) 0.131(10) Br2 0.348(4) 0.534(6) 0.875(11) -0.287(6) -0.075(5) 0.307(5) O2 0.084(4) 0.241(8) 0.231(9) 0.054(7) 0.022(4) 0.089(5) C11 0.159(9) 0.133(8) 0.174(12) -0.083(8) -0.017(8) 0.067(7) C7 0.160(9) 0.266(14) 0.212(12) -0.099(11) -0.010(9) 0.163(10) C8 0.113(8) 0.282(19) 0.29(2) -0.068(13) -0.043(8) 0.154(12) C12 0.55(3) 0.31(2) 0.119(9) -0.084(10) -0.045(13) 0.35(2) N4 0.124(7) 0.194(14) 0.198(14) -0.059(11) -0.029(6) 0.097(7) Br1 0.887(11) 0.349(4) 0.219(3) -0.017(2) -0.019(4) 0.311(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 Co1 N5 1.980(4) . ? Co1 N1 1.987(6) . ? Co1 N6 2.006(5) . ? Co1 N3 2.068(7) . ? N2 O1 1.234(5) 16_557 ? N2 O1 1.234(5) . ? N2 C2 1.441(10) . ? C9 N6 1.347(6) 20 ? C9 N6 1.347(6) . ? C9 H9 0.9300 . ? C2 N1 1.310(6) 16_557 ? C2 N1 1.310(6) . ? N6 C10 1.436(8) . ? C4 N3 1.346(9) . ? C4 N3 1.346(9) 19_655 ? C4 N4 1.449(17) . ? N1 C1 1.355(10) . ? N5 C5 1.372(7) . ? N5 C6 1.381(9) . ? N3 C3 1.324(12) . ? C10 C10 1.354(13) 20 ? C10 C11 1.492(12) . ? C6 C6 1.445(14) 7_556 ? C6 C7 1.456(11) . ? C5 N5 1.372(7) 7_556 ? C5 H5 0.9300 . ? C1 C1 1.440(15) 16_557 ? C1 H1 0.9300 . ? C3 C3 1.59(2) 19_655 ? C3 H3 0.9300 . ? Br2 C8 1.778(11) . ? O2 N4 1.146(10) . ? C11 C12 1.296(16) . ? C11 H11 0.9300 . ? C7 C8 1.409(13) . ? C7 H7 0.9300 . ? C8 C8 1.29(2) 7_556 ? C12 C12 1.10(2) 20 ? C12 Br1 2.095(11) . ? N4 O2 1.146(10) 19_655 ? Br1 Br1 2.035(7) 16_556 ? 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 N5 Co1 N1 105.0(3) . . ? N5 Co1 N6 103.4(2) . . ? N1 Co1 N6 111.4(2) . . ? N5 Co1 N3 105.1(3) . . ? N1 Co1 N3 128.0(4) . . ? N6 Co1 N3 101.4(3) . . ? O1 N2 O1 126.3(8) 16_557 . ? O1 N2 C2 116.6(4) 16_557 . ? O1 N2 C2 116.6(4) . . ? N6 C9 N6 111.3(6) 20 . ? N6 C9 H9 124.3 20 . ? N6 C9 H9 124.3 . . ? N1 C2 N1 121.8(9) 16_557 . ? N1 C2 N2 119.1(4) 16_557 . ? N1 C2 N2 119.1(4) . . ? C9 N6 C10 106.7(5) . . ? C9 N6 Co1 126.5(3) . . ? C10 N6 Co1 126.8(4) . . ? N3 C4 N3 110.8(11) . 19_655 ? N3 C4 N4 123.5(6) . . ? N3 C4 N4 123.5(6) 19_655 . ? C2 N1 C1 100.8(6) . . ? C2 N1 Co1 129.0(6) . . ? C1 N1 Co1 129.8(5) . . ? C5 N5 C6 104.1(5) . . ? C5 N5 Co1 127.3(5) . . ? C6 N5 Co1 128.5(4) . . ? C3 N3 C4 110.1(8) . . ? C3 N3 Co1 122.5(7) . . ? C4 N3 Co1 123.8(7) . . ? C10 C10 N6 107.6(3) 20 . ? C10 C10 C11 119.1(7) 20 . ? N6 C10 C11 133.3(8) . . ? N5 C6 C6 108.0(4) . 7_556 ? N5 C6 C7 131.5(8) . . ? C6 C6 C7 119.0(6) 7_556 . ? N5 C5 N5 114.8(8) 7_556 . ? N5 C5 H5 122.6 7_556 . ? N5 C5 H5 122.6 . . ? N1 C1 C1 108.3(4) . 16_557 ? N1 C1 H1 125.9 . . ? C1 C1 H1 125.9 16_557 . ? N3 C3 C3 103.7(6) . 19_655 ? N3 C3 H3 128.1 . . ? C3 C3 H3 128.1 19_655 . ? C12 C11 C10 108.4(10) . . ? C12 C11 H11 125.8 . . ? C10 C11 H11 125.8 . . ? C8 C7 C6 115.4(10) . . ? C8 C7 H7 122.3 . . ? C6 C7 H7 122.3 . . ? C8 C8 C7 123.3(8) 7_556 . ? C8 C8 Br2 115.3(5) 7_556 . ? C7 C8 Br2 121.3(9) . . ? C12 C12 C11 131.3(7) 20 . ? C12 C12 Br1 129.3(4) 20 . ? C11 C12 Br1 98.6(8) . . ? O2 N4 O2 136(2) . 19_655 ? O2 N4 C4 111.0(10) . . ? O2 N4 C4 111.0(10) 19_655 . ? Br1 Br1 C12 140.6(4) 16_556 . ? _diffrn_measured_fraction_theta_max 0.869 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.942 _refine_diff_density_max 0.657 _refine_diff_density_min -0.537 _refine_diff_density_rms 0.110 _database_code_depnum_ccdc_archive 'CCDC 952995'