Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 222 _journal_volume ? _journal_year ? _journal_page_first ? _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name 'Barbara Valtancoli' 'Carla Bazzicalupi' 'Andrea Bencini' 'Antonio Bianchi' 'Celia Duce' 'Patrizia Fornasari' 'Claudia Giorgi' 'Piero Paoletti' 'Rodolfo Pardini' 'Maria Rosaria Tine' _publ_contact_author_name 'Dr. Barbara Valtancoli' _publ_contact_author_address ; Department of Chemistry, POlo Scientifico, University of Florence via della Lastruccia 3 I-50019 Sesto Fiorentino, Firenze, Italy ; _publ_contact_author_email barbara.valtancoli@unifi.it _publ_section_title ; Coordination features of ditopic oxa-azamacrocycles toward Ni(II) and Co(II). Dioxygen uptake by their dinuclear Co(II) complexes. ; data_[Ni2L1Br2(H2O)4]Br2.2H2O _database_code_depnum_ccdc_archive 'CCDC 221797' _audit_creation_method SHELXL-97 _chemical_name_systematic ; [Ni2L1Br2(H2O)4]Br2.2H2O (L1=1,4,7,16,19,22-hexaza-10,13,25,28-tetraoxacyclotriacontane) ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ; (C20 H54 Br2 N6 Ni2 O8 2+), (Br 1-)2, (H2 O)2 ; _chemical_formula_sum 'C20 H58 Br4 N6 Ni2 O10' _chemical_formula_weight 979.78 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni -3.0029 0.5091 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 8.354(3) _cell_length_b 18.862(3) _cell_length_c 12.057(4) _cell_angle_alpha 90.00 _cell_angle_beta 100.95(3) _cell_angle_gamma 90.00 _cell_volume 1865.3(10) _cell_formula_units_Z 2 _cell_measurement_temperature 298 _cell_measurement_reflns_used 20 _cell_measurement_theta_min 17 _cell_measurement_theta_max 25 _exptl_crystal_description prismatic _exptl_crystal_colour green _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.744 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 992 _exptl_absorpt_coefficient_mu 6.716 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.27 _exptl_absorpt_correction_T_max 0.82 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 298 _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'siemens P4' _diffrn_measurement_method \q/2\q _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 200 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3535 _diffrn_reflns_av_R_equivalents 0.0686 _diffrn_reflns_av_sigmaI/netI 0.0562 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 1 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 1 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 4.41 _diffrn_reflns_theta_max 60.04 _reflns_number_total 2690 _reflns_number_gt 2162 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'XSCANS BRUKER' _computing_cell_refinement 'XSCANS BRUKER' _computing_data_reduction 'XSCANS BRUKER' _computing_structure_solution 'SIR97(Altomare, 1999)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP3 Ver. 1.01\b (Farrugia, 1997)' _computing_publication_material 'PARST93 (Nardelli, 1993)' _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^)+(0.1117P)^2^+7.1138P] 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 refU _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2690 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0667 _refine_ls_R_factor_gt 0.0542 _refine_ls_wR_factor_ref 0.1638 _refine_ls_wR_factor_gt 0.1477 _refine_ls_goodness_of_fit_ref 0.943 _refine_ls_restrained_S_all 0.943 _refine_ls_shift/su_max 0.071 _refine_ls_shift/su_mean 0.018 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 -0.09470(9) 0.13963(4) 0.31711(6) 0.0390(3) Uani 1 1 d . . . Br2 Br -0.24456(10) -0.11786(4) 0.16226(7) 0.0476(3) Uani 1 1 d . . . Ni Ni 0.12540(12) 0.10415(5) 0.20495(8) 0.0241(3) Uani 1 1 d . . . O10 O 0.0443(6) 0.0009(2) 0.1736(4) 0.0359(11) Uani 1 1 d . . . O20 O 0.3063(6) 0.0681(3) 0.1093(4) 0.0426(12) Uani 1 1 d . . . N1 N -0.0122(7) 0.1415(3) 0.0488(4) 0.0300(12) Uani 1 1 d . . . H1 H 0.0333 0.1228 -0.0075 0.050(5) Uiso 1 1 calc R . . C1 C 0.0162(10) 0.2194(3) 0.0494(6) 0.0444(18) Uani 1 1 d . . . H1A H -0.0565 0.2429 0.0916 0.050(5) Uiso 1 1 calc R . . H1B H -0.0064 0.2374 -0.0274 0.050(5) Uiso 1 1 calc R . . C2 C 0.1915(10) 0.2349(4) 0.1031(6) 0.0473(19) Uani 1 1 d . . . H2A H 0.2645 0.2143 0.0583 0.050(5) Uiso 1 1 calc R . . H2B H 0.2097 0.2857 0.1073 0.050(5) Uiso 1 1 calc R . . N2 N 0.2229(7) 0.2042(3) 0.2172(4) 0.0313(12) Uani 1 1 d . . . H2 H 0.1699 0.2307 0.2619 0.050(5) Uiso 1 1 calc R . . C3 C 0.3940(9) 0.1983(4) 0.2719(7) 0.0475(19) Uani 1 1 d . . . H3A H 0.4401 0.2450 0.2908 0.050(5) Uiso 1 1 calc R . . H3B H 0.4562 0.1751 0.2221 0.050(5) Uiso 1 1 calc R . . C4 C 0.3986(9) 0.1551(4) 0.3772(6) 0.0423(17) Uani 1 1 d . . . H4A H 0.5112 0.1455 0.4114 0.050(5) Uiso 1 1 calc R . . H4B H 0.3507 0.1824 0.4308 0.050(5) Uiso 1 1 calc R . . N3 N 0.3104(6) 0.0876(3) 0.3547(4) 0.0288(12) Uani 1 1 d . . . H3 H 0.3832 0.0570 0.3331 0.050(5) Uiso 1 1 calc R . . C5 C 0.2751(9) 0.0580(4) 0.4607(5) 0.0398(17) Uani 1 1 d . . . H5A H 0.2075 0.0912 0.4925 0.050(5) Uiso 1 1 calc R . . H5B H 0.3766 0.0525 0.5145 0.050(5) Uiso 1 1 calc R . . C6 C 0.1912(9) -0.0112(4) 0.4442(5) 0.0392(16) Uani 1 1 d . . . H6A H 0.1788 -0.0307 0.5165 0.050(5) Uiso 1 1 calc R . . H6B H 0.0837 -0.0055 0.3977 0.050(5) Uiso 1 1 calc R . . O1 O 0.2873(6) -0.0575(2) 0.3902(4) 0.0387(11) Uani 1 1 d . . . C7 C 0.2220(10) -0.1256(3) 0.3699(6) 0.0374(16) Uani 1 1 d . . . H7A H 0.1044 -0.1226 0.3474 0.050(5) Uiso 1 1 calc R . . H7B H 0.2471 -0.1536 0.4384 0.050(5) Uiso 1 1 calc R . . C8 C 0.2910(9) -0.1598(3) 0.2800(5) 0.0370(16) Uani 1 1 d . . . H8A H 0.4087 -0.1546 0.2949 0.050(5) Uiso 1 1 calc R . . H8B H 0.2650 -0.2099 0.2764 0.050(5) Uiso 1 1 calc R . . O2 O 0.2220(6) -0.1262(2) 0.1759(4) 0.0377(11) Uani 1 1 d . . . C9 C 0.2856(9) -0.1532(4) 0.0836(6) 0.0422(17) Uani 1 1 d . . . H9A H 0.2785 -0.2046 0.0823 0.050(5) Uiso 1 1 calc R . . H9B H 0.3994 -0.1400 0.0911 0.050(5) Uiso 1 1 calc R . . C10 C 0.1888(8) -0.1232(4) -0.0241(6) 0.0382(17) Uani 1 1 d . . . H10A H 0.1989 -0.0720 -0.0212 0.050(5) Uiso 1 1 calc R . . H10B H 0.2372 -0.1396 -0.0865 0.050(5) Uiso 1 1 calc R . . O100 O 0.5932(6) 0.0289(3) 0.2406(5) 0.0562(14) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Br1 0.0448(5) 0.0417(5) 0.0320(4) -0.0023(3) 0.0113(3) 0.0003(3) Br2 0.0425(5) 0.0510(5) 0.0501(5) -0.0005(3) 0.0106(4) -0.0076(3) Ni 0.0286(6) 0.0213(6) 0.0205(5) 0.0007(4) -0.0003(4) -0.0004(4) O10 0.040(3) 0.023(2) 0.041(3) 0.0007(19) 0.000(2) -0.005(2) O20 0.042(3) 0.048(3) 0.037(3) 0.000(2) 0.007(2) 0.012(2) N1 0.032(3) 0.033(3) 0.024(3) 0.002(2) 0.002(2) 0.004(2) C1 0.061(5) 0.023(3) 0.045(4) 0.011(3) 0.001(4) 0.009(3) C2 0.063(5) 0.034(4) 0.045(4) 0.011(3) 0.010(4) -0.004(4) N2 0.039(3) 0.022(3) 0.031(3) 0.003(2) 0.003(2) 0.000(2) C3 0.044(4) 0.041(4) 0.054(5) 0.000(3) 0.000(4) -0.013(3) C4 0.043(4) 0.037(4) 0.042(4) -0.010(3) -0.006(3) -0.005(3) N3 0.031(3) 0.029(3) 0.025(3) -0.003(2) 0.001(2) 0.002(2) C5 0.056(5) 0.042(4) 0.017(3) -0.003(3) -0.003(3) 0.008(3) C6 0.050(4) 0.041(4) 0.027(3) 0.006(3) 0.009(3) 0.004(3) O1 0.041(3) 0.034(2) 0.042(3) -0.001(2) 0.009(2) -0.002(2) C7 0.046(4) 0.033(4) 0.030(3) 0.005(3) -0.001(3) -0.006(3) C8 0.046(4) 0.026(3) 0.033(3) 0.008(3) -0.005(3) 0.008(3) O2 0.046(3) 0.040(3) 0.023(2) 0.0019(18) -0.006(2) 0.012(2) C9 0.037(4) 0.053(4) 0.032(4) 0.003(3) -0.004(3) 0.017(3) C10 0.030(4) 0.057(5) 0.028(3) 0.009(3) 0.006(3) 0.003(3) O100 0.038(3) 0.062(3) 0.067(4) -0.004(3) 0.006(3) 0.009(3) _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 Ni 2.5695(15) . ? Ni N2 2.049(5) . ? Ni O10 2.073(4) . ? Ni N1 2.131(5) . ? Ni N3 2.165(5) . ? Ni O20 2.177(5) . ? N1 C10 1.489(9) 3 ? N1 C1 1.488(8) . ? C1 C2 1.513(11) . ? C2 N2 1.469(9) . ? N2 C3 1.461(9) . ? C3 C4 1.504(11) . ? C4 N3 1.471(9) . ? N3 C5 1.475(8) . ? C5 C6 1.478(10) . ? C6 O1 1.424(8) . ? O1 C7 1.399(8) . ? C7 C8 1.470(10) . ? C8 O2 1.426(8) . ? O2 C9 1.416(9) . ? C9 C10 1.504(9) . ? C10 N1 1.489(9) 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 N2 Ni O10 171.8(2) . . ? N2 Ni N1 84.2(2) . . ? O10 Ni N1 92.68(19) . . ? N2 Ni N3 82.1(2) . . ? O10 Ni N3 99.98(19) . . ? N1 Ni N3 164.7(2) . . ? N2 Ni O20 91.1(2) . . ? O10 Ni O20 81.12(19) . . ? N1 Ni O20 87.0(2) . . ? N3 Ni O20 86.52(19) . . ? N2 Ni Br1 92.10(16) . . ? O10 Ni Br1 95.68(14) . . ? N1 Ni Br1 93.38(15) . . ? N3 Ni Br1 93.88(14) . . ? O20 Ni Br1 176.79(14) . . ? C10 N1 C1 112.4(5) 3 . ? C10 N1 Ni 116.6(4) 3 . ? C1 N1 Ni 105.3(4) . . ? N1 C1 C2 109.5(6) . . ? N2 C2 C1 108.1(6) . . ? C3 N2 C2 116.0(6) . . ? C3 N2 Ni 107.7(4) . . ? C2 N2 Ni 107.4(4) . . ? N2 C3 C4 106.8(6) . . ? N3 C4 C3 112.5(6) . . ? C4 N3 C5 110.0(5) . . ? C4 N3 Ni 106.4(4) . . ? C5 N3 Ni 123.3(4) . . ? N3 C5 C6 112.6(5) . . ? O1 C6 C5 108.0(6) . . ? C7 O1 C6 114.1(6) . . ? O1 C7 C8 109.7(6) . . ? O2 C8 C7 107.8(5) . . ? C9 O2 C8 112.5(5) . . ? O2 C9 C10 108.8(5) . . ? N1 C10 C9 115.8(6) 3 . ? _diffrn_measured_fraction_theta_max 0.973 _diffrn_reflns_theta_full 60.04 _diffrn_measured_fraction_theta_full 0.973 _refine_diff_density_max 0.840 _refine_diff_density_min -1.221 _refine_diff_density_rms 0.166 #===END