Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Juan Flores' _publ_contact_author_address ; Departamento de Quimica Inorganica Universidad de Alcala Campus Universitario Alcala de Henares Madrid 28871 SPAIN ; _publ_contact_author_email JUANC.FLORES@UAH.ES _publ_section_title ; Synthesis and 1H NMR Studies of Paramagnetic Nickel(II) Complexes Containing Bis(pyrazolyl)methane Ligands With Dendritic Substituents ; _publ_requested_category FM loop_ _publ_author_name 'Juan Flores' 'Jose M. Benito' 'E.de Jesus' 'F.J.de la Mata' 'Rafael Gomez' ; P.Gomez-Sal ; 'Alberto Sanchez-Mendez' data_import _database_code_depnum_ccdc_archive 'CCDC 606876' _audit_creation_date 2006-06-23T16:23:49-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.2 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C18 H22 Br2 N4 Ni1' _chemical_formula_sum 'C18 H22 Br2 N4 Ni' _chemical_formula_weight 512.93 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 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 8.8157(10) _cell_length_b 16.3175(9) _cell_length_c 14.3685(12) _cell_angle_alpha 90 _cell_angle_beta 97.294(8) _cell_angle_gamma 90 _cell_volume 2050.2(3) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 93 _cell_measurement_theta_min 5.092 _cell_measurement_theta_max 21.43 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description prism _exptl_crystal_colour purple-blue _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_diffrn 1.662 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1024 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 1 -6 10 0.063 -1 3 -5 0.096 15 3 -16 0.095 -5 1 2 0.245 -8 9 6 0.208 9 -8 -11 0.158 0 19 -1 0.089 0 -4 -1 0.234 0 2 -3 0.049 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 4.852 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; R.H. Blessing, Acta Cryst. (1995), A51, 33-38 ; _exptl_absorpt_correction_T_min 0.771 _exptl_absorpt_correction_T_max 2.003 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_source 'Enraf Nonius FR590' _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector 'CCD plate' _diffrn_orient_matrix_type X=UH _diffrn_orient_matrix_ub_11 0.01 _diffrn_orient_matrix_ub_12 0 _diffrn_orient_matrix_ub_13 0 _diffrn_orient_matrix_ub_21 0 _diffrn_orient_matrix_ub_22 0.01 _diffrn_orient_matrix_ub_23 0 _diffrn_orient_matrix_ub_31 0 _diffrn_orient_matrix_ub_32 0 _diffrn_orient_matrix_ub_33 0.01 _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method 'CCD rotation images, thick slices' _diffrn_reflns_av_R_equivalents 0.2191 _diffrn_reflns_av_unetI/netI 0.1692 _diffrn_reflns_number 13367 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.12 _diffrn_reflns_theta_max 25.51 _diffrn_reflns_theta_full 25.51 _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.997 _reflns_number_total 3814 _reflns_number_gt 2098 _reflns_threshold_expression >2sigma(I) _diffrn_reflns_reduction_process ; Scaled and merged with SORTAV R.H. Blessing, (1987) Cryst. Rev. 1, 3-58 R.H. Blessing, (1989) J. Appl. Cryst. 22, 396-397 ; #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Collect (Nonius BV, 1997-2000)' _computing_cell_refinement 'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)' _computing_data_reduction 'EvalCCD (Duisenberg & Schreurs 1990-2000)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0307P)^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_number_reflns 3814 _refine_ls_number_parameters 230 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1451 _refine_ls_R_factor_gt 0.0641 _refine_ls_wR_factor_ref 0.1252 _refine_ls_wR_factor_gt 0.1049 _refine_ls_goodness_of_fit_ref 0.973 _refine_ls_restrained_S_all 0.973 _refine_ls_shift/su_max 0.063 _refine_ls_shift/su_mean 0.01 _refine_diff_density_max 0.753 _refine_diff_density_min -0.931 _refine_diff_density_rms 0.151 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 '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' Ni Ni 0.3393 1.1124 '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' 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 Ni1 Ni 0.36780(10) -0.03912(7) 0.72319(7) 0.0230(3) Uani 1 1 d . . . Br1 Br 0.20155(9) 0.04215(7) 0.62020(6) 0.0401(3) Uani 1 1 d . . . Br3 Br 0.26015(9) -0.12261(6) 0.83326(6) 0.0317(3) Uani 1 1 d . . . C1 C 0.4920(8) -0.1832(5) 0.6247(5) 0.0182(19) Uani 1 1 d . . . C2 C 0.6320(8) -0.2110(5) 0.6013(5) 0.024(2) Uani 1 1 d . . . H2 H 0.6505 -0.2622 0.5765 0.028 Uiso 1 1 calc R . . C3 C 0.7356(8) -0.1508(5) 0.6210(5) 0.022(2) Uani 1 1 d . . . C4 C 0.3434(9) -0.2278(5) 0.6205(6) 0.029(2) Uani 1 1 d . . . H4A H 0.3378 -0.2552 0.6791 0.044 Uiso 1 1 calc R . . H4B H 0.3363 -0.2675 0.5707 0.044 Uiso 1 1 calc R . . H4C H 0.2605 -0.1895 0.6088 0.044 Uiso 1 1 calc R . . C5 C 0.9042(8) -0.1478(6) 0.6116(5) 0.031(2) Uani 1 1 d . . . H5A H 0.961 -0.1357 0.6715 0.046 Uiso 1 1 calc R . . H5B H 0.9227 -0.1059 0.5674 0.046 Uiso 1 1 calc R . . H5C H 0.9362 -0.1998 0.5897 0.046 Uiso 1 1 calc R . . C6 C 0.5480(8) 0.0638(5) 0.8718(5) 0.024(2) Uani 1 1 d . . . C7 C 0.7008(8) 0.0790(5) 0.9066(6) 0.028(2) Uani 1 1 d . . . H7 H 0.738 0.1017 0.9644 0.033 Uiso 1 1 calc R . . C8 C 0.7850(8) 0.0531(5) 0.8373(5) 0.0181(18) Uani 1 1 d . . . C9 C 0.4071(9) 0.0833(6) 0.9185(6) 0.036(2) Uani 1 1 d . . . H9A H 0.333 0.1108 0.8746 0.054 Uiso 1 1 calc R . . H9B H 0.4352 0.1181 0.9718 0.054 Uiso 1 1 calc R . . H9C H 0.3639 0.0333 0.9387 0.054 Uiso 1 1 calc R . . C10 C 0.9534(8) 0.0545(6) 0.8337(5) 0.027(2) Uani 1 1 d . . . H10A H 0.9874 0.0007 0.819 0.041 Uiso 1 1 calc R . . H10B H 1.0049 0.0713 0.8936 0.041 Uiso 1 1 calc R . . H10C H 0.9762 0.0924 0.7863 0.041 Uiso 1 1 calc R . . C11 C 0.7109(8) -0.0032(5) 0.6738(5) 0.0175(18) Uani 1 1 d . . . H11 H 0.8217 -0.0019 0.6722 0.021 Uiso 1 1 calc R . . C12 C 0.6370(8) 0.0551(5) 0.5968(5) 0.0184(18) Uani 1 1 d . . . H12A H 0.6619 0.0367 0.5364 0.022 Uiso 1 1 calc R . . H12B H 0.5267 0.053 0.5951 0.022 Uiso 1 1 calc R . . C13 C 0.6901(8) 0.1427(5) 0.6127(4) 0.0131(17) Uani 1 1 d . . . C14 C 0.8408(9) 0.1631(6) 0.6046(5) 0.027(2) Uani 1 1 d . . . H14 H 0.9081 0.1227 0.5898 0.032 Uiso 1 1 calc R . . C15 C 0.8923(9) 0.2431(6) 0.6180(6) 0.033(2) Uani 1 1 d . . . H15 H 0.9946 0.2554 0.6151 0.039 Uiso 1 1 calc R . . C16 C 0.7932(10) 0.3040(6) 0.6355(5) 0.033(2) Uani 1 1 d . . . H16 H 0.8274 0.3578 0.6427 0.04 Uiso 1 1 calc R . . C17 C 0.6426(10) 0.2854(6) 0.6425(5) 0.034(2) Uani 1 1 d . . . H17 H 0.5755 0.3269 0.6543 0.041 Uiso 1 1 calc R . . C18 C 0.5907(9) 0.2063(6) 0.6321(5) 0.028(2) Uani 1 1 d . . . H18 H 0.4891 0.1946 0.6379 0.034 Uiso 1 1 calc R . . N1 N 0.5081(6) -0.1074(4) 0.6567(4) 0.0186(15) Uani 1 1 d . . . N2 N 0.6601(6) -0.0869(4) 0.6545(4) 0.0182(16) Uani 1 1 d . . . N3 N 0.5363(6) 0.0296(4) 0.7881(4) 0.0177(15) Uani 1 1 d . . . N4 N 0.6832(6) 0.0219(4) 0.7667(4) 0.0173(15) 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 Ni1 0.0142(5) 0.0317(7) 0.0231(6) -0.0041(5) 0.0025(4) -0.0001(5) Br1 0.0235(4) 0.0639(8) 0.0333(5) 0.0133(5) 0.0049(4) 0.0145(5) Br3 0.0296(4) 0.0404(6) 0.0257(4) 0.0049(5) 0.0063(3) 0.0033(5) C1 0.022(4) 0.019(5) 0.013(4) 0.002(4) 0.000(3) -0.006(4) C2 0.023(4) 0.019(5) 0.028(5) -0.005(4) 0.000(4) -0.008(4) C3 0.019(4) 0.026(6) 0.023(4) -0.001(4) 0.004(3) 0.007(4) C4 0.034(5) 0.018(6) 0.037(5) -0.010(4) 0.008(4) -0.009(4) C5 0.024(4) 0.043(7) 0.026(5) -0.003(4) 0.005(4) 0.005(4) C6 0.028(5) 0.019(6) 0.027(5) -0.007(4) 0.012(4) 0.014(4) C7 0.025(4) 0.028(6) 0.032(5) -0.001(4) 0.006(4) -0.010(4) C8 0.026(4) 0.004(5) 0.024(4) 0.006(4) 0.002(3) 0.000(3) C9 0.041(5) 0.030(6) 0.040(5) -0.019(5) 0.014(4) -0.001(5) C10 0.020(4) 0.038(6) 0.023(4) -0.004(4) 0.000(3) -0.006(4) C11 0.015(4) 0.022(5) 0.017(4) -0.002(4) 0.007(3) -0.006(4) C12 0.020(4) 0.016(5) 0.019(4) -0.001(4) 0.001(3) 0.000(4) C13 0.020(4) 0.015(5) 0.004(3) 0.003(3) -0.001(3) 0.002(3) C14 0.026(5) 0.037(7) 0.019(4) 0.006(4) 0.007(3) 0.005(4) C15 0.022(5) 0.048(7) 0.027(5) 0.007(5) 0.001(4) -0.013(5) C16 0.047(6) 0.037(7) 0.014(4) -0.001(4) -0.002(4) -0.015(5) C17 0.045(6) 0.033(7) 0.025(5) -0.006(5) 0.005(4) 0.011(5) C18 0.019(4) 0.043(7) 0.024(5) 0.001(5) 0.007(4) 0.008(4) N1 0.015(3) 0.017(5) 0.023(4) 0.003(3) 0.002(3) -0.001(3) N2 0.015(3) 0.023(4) 0.016(3) 0.002(3) -0.002(3) -0.001(3) N3 0.014(3) 0.022(4) 0.019(3) -0.001(3) 0.008(2) -0.001(3) N4 0.014(3) 0.021(4) 0.018(3) 0.004(3) 0.004(3) 0.000(3) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 Ni1 N1 1.996(6) . ? Ni1 N3 1.996(6) . ? Ni1 Br1 2.3549(14) . ? Ni1 Br3 2.3747(14) . ? C1 N1 1.321(10) . ? C1 C2 1.397(10) . ? C1 C4 1.494(10) . ? C2 C3 1.347(11) . ? C2 H2 0.93 . ? C3 N2 1.358(10) . ? C3 C5 1.510(9) . ? C4 H4A 0.96 . ? C4 H4B 0.96 . ? C4 H4C 0.96 . ? C5 H5A 0.96 . ? C5 H5B 0.96 . ? C5 H5C 0.96 . ? C6 N3 1.318(9) . ? C6 C7 1.398(10) . ? C6 C9 1.519(10) . ? C7 C8 1.381(10) . ? C7 H7 0.93 . ? C8 N4 1.365(9) . ? C8 C10 1.492(9) . ? C9 H9A 0.96 . ? C9 H9B 0.96 . ? C9 H9C 0.96 . ? C10 H10A 0.96 . ? C10 H10B 0.96 . ? C10 H10C 0.96 . ? C11 N4 1.446(9) . ? C11 N2 1.453(10) . ? C11 C12 1.541(10) . ? C11 H11 0.98 . ? C12 C13 1.512(10) . ? C12 H12A 0.97 . ? C12 H12B 0.97 . ? C13 C14 1.389(10) . ? C13 C18 1.410(10) . ? C14 C15 1.387(12) . ? C14 H14 0.93 . ? C15 C16 1.366(12) . ? C15 H15 0.93 . ? C16 C17 1.378(11) . ? C16 H16 0.93 . ? C17 C18 1.370(12) . ? C17 H17 0.93 . ? C18 H18 0.93 . ? N1 N2 1.385(7) . ? N3 N4 1.374(7) . ? 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 Ni1 N3 93.9(2) . . ? N1 Ni1 Br1 112.81(17) . . ? N3 Ni1 Br1 110.12(19) . . ? N1 Ni1 Br3 108.85(19) . . ? N3 Ni1 Br3 110.37(17) . . ? Br1 Ni1 Br3 118.17(5) . . ? N1 C1 C2 109.2(7) . . ? N1 C1 C4 121.8(7) . . ? C2 C1 C4 129.0(8) . . ? C3 C2 C1 108.0(8) . . ? C3 C2 H2 126 . . ? C1 C2 H2 126 . . ? C2 C3 N2 106.5(7) . . ? C2 C3 C5 130.8(8) . . ? N2 C3 C5 122.6(7) . . ? C1 C4 H4A 109.5 . . ? C1 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C1 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C3 C5 H5A 109.5 . . ? C3 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C3 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? N3 C6 C7 111.2(7) . . ? N3 C6 C9 121.2(7) . . ? C7 C6 C9 127.6(7) . . ? C8 C7 C6 105.6(7) . . ? C8 C7 H7 127.2 . . ? C6 C7 H7 127.2 . . ? N4 C8 C7 106.7(6) . . ? N4 C8 C10 122.9(7) . . ? C7 C8 C10 130.4(7) . . ? C6 C9 H9A 109.5 . . ? C6 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C6 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C8 C10 H10A 109.5 . . ? C8 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C8 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N4 C11 N2 111.0(6) . . ? N4 C11 C12 112.4(6) . . ? N2 C11 C12 110.6(6) . . ? N4 C11 H11 107.5 . . ? N2 C11 H11 107.5 . . ? C12 C11 H11 107.5 . . ? C13 C12 C11 112.3(6) . . ? C13 C12 H12A 109.1 . . ? C11 C12 H12A 109.1 . . ? C13 C12 H12B 109.1 . . ? C11 C12 H12B 109.1 . . ? H12A C12 H12B 107.9 . . ? C14 C13 C18 117.7(8) . . ? C14 C13 C12 119.7(7) . . ? C18 C13 C12 122.5(7) . . ? C15 C14 C13 120.9(8) . . ? C15 C14 H14 119.5 . . ? C13 C14 H14 119.5 . . ? C16 C15 C14 120.2(8) . . ? C16 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? C15 C16 C17 119.9(9) . . ? C15 C16 H16 120.1 . . ? C17 C16 H16 120.1 . . ? C18 C17 C16 120.7(9) . . ? C18 C17 H17 119.6 . . ? C16 C17 H17 119.6 . . ? C17 C18 C13 120.5(8) . . ? C17 C18 H18 119.8 . . ? C13 C18 H18 119.7 . . ? C1 N1 N2 106.2(6) . . ? C1 N1 Ni1 130.0(5) . . ? N2 N1 Ni1 122.5(5) . . ? C3 N2 N1 110.0(6) . . ? C3 N2 C11 129.5(6) . . ? N1 N2 C11 119.9(6) . . ? C6 N3 N4 106.0(6) . . ? C6 N3 Ni1 129.2(5) . . ? N4 N3 Ni1 120.7(5) . . ? C8 N4 N3 110.4(6) . . ? C8 N4 C11 128.3(6) . . ? N3 N4 C11 120.4(6) . . ?