Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'Andrea Bencini' 'Carla Bazzicalupi' 'Emanuela Berni' 'Antonio Bianchi' 'Lucia Borsari' 'Claudia Giorgi' 'Joao C. Lima' 'Carlos Lodeiro' 'A.Jorge Parola' 'Fernando Pina' 'Barbara Valtancoli' _publ_contact_author_name 'Prof. Andrea Bencini' _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 andrea.bencini@unifi.it _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Protonation and coordination properties towards Zn(II), Cd(II) and Hg(II) of a phenanthroline-containing macrocycle with an ethylamino pendant arm. ; data_[HgL1Br]ClO4 _database_code_depnum_ccdc_archive 'CCDC 225564' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ; (C18 H21 Br Hg N5 +1), (Cl O4 1-) ; _chemical_formula_sum 'C18 H21 Br Cl Hg N5 O4' _chemical_formula_weight 687.35 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' Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Hg Hg -4.2923 7.6849 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n 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 8.315(5) _cell_length_b 23.272(5) _cell_length_c 11.1590(10) _cell_angle_alpha 90.00 _cell_angle_beta 96.53(2) _cell_angle_gamma 90.00 _cell_volume 2145.3(14) _cell_formula_units_Z 4 _cell_measurement_temperature 298 _cell_measurement_reflns_used 23 _cell_measurement_theta_min 10 _cell_measurement_theta_max 23 _exptl_crystal_description prismatic _exptl_crystal_colour colourless _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.128 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1312 _exptl_absorpt_coefficient_mu 16.511 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.17 _exptl_absorpt_correction_T_max 0.37 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 298 _diffrn_radiation_wavelength 1.54180 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'P4 Siemens' _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 3540 _diffrn_reflns_av_R_equivalents 0.0349 _diffrn_reflns_av_sigmaI/netI 0.0624 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 1 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 1 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.80 _diffrn_reflns_theta_max 59.90 _reflns_number_total 2682 _reflns_number_gt 2038 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'XSCANS Brucker' _computing_cell_refinement 'XSCANS Brucker' _computing_data_reduction 'XSCANS Brucker' _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^)+(0.0504P)^2^+7.8958P] 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 none _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2682 _refine_ls_number_parameters 271 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0630 _refine_ls_R_factor_gt 0.0396 _refine_ls_wR_factor_ref 0.1018 _refine_ls_wR_factor_gt 0.0891 _refine_ls_goodness_of_fit_ref 0.917 _refine_ls_restrained_S_all 0.917 _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 Hg Hg 0.20533(6) 0.14660(2) 0.14707(4) 0.05275(19) Uani 1 1 d . . . Br Br -0.05978(16) 0.20514(5) 0.12123(12) 0.0649(4) Uani 1 1 d . . . Cl1 Cl 0.7616(4) 0.11313(12) 0.5067(2) 0.0563(7) Uani 1 1 d . . . O11 O 0.7530(12) 0.1362(4) 0.3864(8) 0.092(3) Uani 1 1 d . . . O12 O 0.6688(12) 0.0620(4) 0.5051(8) 0.089(3) Uani 1 1 d . . . O13 O 0.6950(13) 0.1533(4) 0.5837(9) 0.102(3) Uani 1 1 d . . . O14 O 0.9243(11) 0.1014(5) 0.5483(8) 0.101(3) Uani 1 1 d . . . C7 C 0.3781(14) 0.0440(6) -0.1678(10) 0.061(3) Uani 1 1 d . . . N2 N 0.3337(11) 0.1200(4) -0.0254(7) 0.050(2) Uani 1 1 d . . . C11 C 0.4591(15) 0.1417(6) -0.2003(10) 0.069(4) Uani 1 1 d . . . H11 H 0.5067 0.1690 -0.2459 0.083 Uiso 1 1 calc R . . N5 N 0.1256(11) 0.0949(4) 0.3312(7) 0.053(2) Uani 1 1 d . . . H5 H 0.0372 0.1130 0.3541 0.064 Uiso 1 1 calc R . . C3 C 0.1704(15) -0.0700(5) 0.0690(11) 0.068(4) Uani 1 1 d . . . H3 H 0.1544 -0.1087 0.0506 0.082 Uiso 1 1 calc R . . C4 C 0.2421(14) -0.0352(5) -0.0114(10) 0.058(3) Uani 1 1 d . . . C2 C 0.1229(15) -0.0494(5) 0.1733(11) 0.061(3) Uani 1 1 d . . . H2 H 0.0796 -0.0738 0.2275 0.073 Uiso 1 1 calc R . . C14 C 0.4987(18) 0.2405(7) 0.1634(14) 0.090(4) Uani 1 1 d . . . H14A H 0.5423 0.2787 0.1532 0.108 Uiso 1 1 calc R . . H14B H 0.5844 0.2128 0.1566 0.108 Uiso 1 1 calc R . . N1 N 0.2025(10) 0.0442(4) 0.1214(7) 0.046(2) Uani 1 1 d . . . N4 N 0.3945(12) 0.1755(5) 0.3086(8) 0.067(3) Uani 1 1 d . . . H4 H 0.4840 0.1529 0.3096 0.080 Uiso 1 1 calc R . . C1 C 0.1409(13) 0.0095(5) 0.1969(9) 0.050(3) Uani 1 1 d . . . C9 C 0.2964(17) -0.0521(6) -0.1231(11) 0.075(4) Uani 1 1 d . . . H9 H 0.2871 -0.0904 -0.1466 0.091 Uiso 1 1 calc R . . C15 C 0.4412(19) 0.2358(6) 0.2857(13) 0.091(5) Uani 1 1 d . . . H15A H 0.5266 0.2479 0.3470 0.109 Uiso 1 1 calc R . . H15B H 0.3488 0.2609 0.2900 0.109 Uiso 1 1 calc R . . C5 C 0.2518(13) 0.0240(5) 0.0177(9) 0.047(3) Uani 1 1 d . . . C16 C 0.3197(16) 0.1652(6) 0.4211(11) 0.075(4) Uani 1 1 d . . . H16A H 0.3984 0.1728 0.4903 0.090 Uiso 1 1 calc R . . H16B H 0.2293 0.1913 0.4245 0.090 Uiso 1 1 calc R . . C18 C 0.0824(15) 0.0346(5) 0.3092(10) 0.062(3) Uani 1 1 d . . . H18A H -0.0344 0.0310 0.3028 0.074 Uiso 1 1 calc R . . H18B H 0.1272 0.0121 0.3783 0.074 Uiso 1 1 calc R . . C6 C 0.3221(13) 0.0640(5) -0.0593(8) 0.049(3) Uani 1 1 d . . . N3 N 0.3664(12) 0.2300(4) 0.0698(9) 0.061(3) Uani 1 1 d . . . H3A H 0.3014 0.2615 0.0650 0.073 Uiso 1 1 calc R . . C10 C 0.4007(14) 0.1575(5) -0.0919(10) 0.060(3) Uani 1 1 d . . . C8 C 0.3597(17) -0.0149(6) -0.1943(12) 0.076(4) Uani 1 1 d . . . H8 H 0.3938 -0.0284 -0.2657 0.092 Uiso 1 1 calc R . . C17 C 0.2623(15) 0.1052(6) 0.4262(10) 0.067(3) Uani 1 1 d . . . H17A H 0.3503 0.0791 0.4150 0.081 Uiso 1 1 calc R . . H17B H 0.2275 0.0977 0.5048 0.081 Uiso 1 1 calc R . . C13 C 0.4165(18) 0.2200(5) -0.0502(12) 0.080(4) Uani 1 1 d . . . H13A H 0.5284 0.2319 -0.0497 0.096 Uiso 1 1 calc R . . H13B H 0.3514 0.2440 -0.1081 0.096 Uiso 1 1 calc R . . C12 C 0.4456(17) 0.0860(7) -0.2385(11) 0.075(4) Uani 1 1 d . . . H12 H 0.4812 0.0756 -0.3115 0.090 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 Hg 0.0580(3) 0.0518(3) 0.0492(3) -0.0002(2) 0.0097(2) 0.0023(3) Br 0.0612(8) 0.0547(7) 0.0795(8) 0.0054(6) 0.0104(7) 0.0108(7) Cl1 0.065(2) 0.0561(17) 0.0506(15) 0.0048(13) 0.0186(14) 0.0055(16) O11 0.107(7) 0.107(8) 0.068(5) 0.030(5) 0.035(5) 0.028(6) O12 0.099(7) 0.076(6) 0.092(6) -0.003(5) 0.012(6) -0.020(6) O13 0.138(9) 0.079(7) 0.103(7) -0.027(6) 0.075(7) -0.010(6) O14 0.053(6) 0.166(10) 0.083(6) 0.028(7) 0.006(5) 0.003(6) C7 0.052(7) 0.082(9) 0.049(7) -0.012(7) 0.002(6) 0.017(7) N2 0.061(6) 0.052(5) 0.038(5) 0.007(4) 0.013(5) 0.005(5) C11 0.062(8) 0.093(10) 0.053(7) 0.019(7) 0.016(6) -0.002(8) N5 0.049(6) 0.072(7) 0.041(5) 0.000(5) 0.016(4) 0.007(5) C3 0.073(9) 0.055(8) 0.070(9) 0.006(7) -0.020(7) -0.010(7) C4 0.064(8) 0.056(7) 0.052(7) -0.017(6) -0.007(6) 0.026(7) C2 0.071(9) 0.048(7) 0.057(7) 0.006(6) -0.018(6) -0.001(6) C14 0.069(10) 0.091(11) 0.111(12) 0.005(9) 0.014(9) -0.007(9) N1 0.047(5) 0.048(5) 0.043(5) 0.003(4) 0.005(4) 0.005(5) N4 0.060(7) 0.075(7) 0.064(6) -0.004(5) 0.002(5) -0.004(6) C1 0.042(6) 0.058(7) 0.047(6) 0.009(6) -0.009(5) 0.005(6) C9 0.085(10) 0.065(9) 0.073(9) -0.019(7) -0.004(8) 0.025(8) C15 0.093(11) 0.074(10) 0.098(11) 0.004(8) -0.021(9) -0.011(9) C5 0.047(7) 0.055(7) 0.040(6) 0.006(5) 0.004(5) 0.006(6) C16 0.066(9) 0.100(11) 0.057(8) -0.017(7) 0.001(7) 0.015(8) C18 0.069(8) 0.064(8) 0.055(7) 0.018(6) 0.019(6) -0.006(7) C6 0.050(7) 0.066(8) 0.030(5) -0.006(5) -0.002(5) 0.011(6) N3 0.066(7) 0.048(6) 0.069(6) 0.000(5) 0.014(6) -0.002(5) C10 0.058(8) 0.073(9) 0.051(7) 0.011(6) 0.019(6) 0.002(7) C8 0.076(10) 0.091(11) 0.057(8) -0.026(8) -0.014(7) 0.022(9) C17 0.060(8) 0.087(10) 0.057(7) 0.008(7) 0.014(7) 0.005(8) C13 0.099(11) 0.060(8) 0.086(9) 0.015(7) 0.036(9) -0.004(8) C12 0.079(10) 0.104(12) 0.044(7) -0.009(7) 0.016(7) 0.005(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. Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric.Sci.(1965),15(II-A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d Plane 1 m1 = -0.86575(0.00120) m2 = 0.22755(0.00299) m3 = -0.44575(0.00278) D = -1.68031(0.01101) Atom d s d/s (d/s)**2 N1 * -0.0093 0.0083 -1.119 1.251 N2 * 0.0108 0.0089 1.207 1.456 N3 * -0.0077 0.0101 -0.762 0.581 N5 * 0.0058 0.0087 0.658 0.433 Hg 0.4133 0.0006 716.547 513439.938 #=========== Sum((d/s)**2) for starred atoms 3.721 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms does not deviate significantly from planarity Plane 2 m1 = 0.11131(0.00220) m2 = -0.70605(0.00210) m3 = -0.69936(0.00192) D = -4.37845(0.00660) Atom d s d/s (d/s)**2 Br * -0.0046 0.0013 -3.651 13.328 N3 * 0.3879 0.0094 41.376 1711.988 N4 * -0.5771 0.0099 -58.180 3384.907 N5 * 0.3212 0.0086 37.425 1400.650 Hg 0.9986 0.0005 2130.818 4540385.000 #=========== Sum((d/s)**2) for starred atoms 6510.873 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Plane 3 m1 = -0.86005(0.00112) m2 = 0.19959(0.00209) m3 = -0.46956(0.00170) D = -1.78955(0.00701) Atom d s d/s (d/s)**2 C9 * -0.0658 0.0136 -4.828 23.308 C8 * -0.0526 0.0139 -3.777 14.267 N3 * -0.0496 0.0101 -4.910 24.105 N5 * -0.0306 0.0087 -3.508 12.309 N1 * 0.0479 0.0083 5.782 33.431 N2 * 0.0647 0.0089 7.261 52.723 #=========== Sum((d/s)**2) for starred atoms 160.144 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Plane 4 m1 = 0.57749(0.00503) m2 = -0.74219(0.00237) m3 = -0.34009(0.00533) D = -2.52697(0.02942) Atom d s d/s (d/s)**2 N3 * 0.0000 0.0096 0.000 0.000 N4 * 0.0000 0.0103 0.000 0.000 N5 * 0.0000 0.0090 0.000 0.000 #=========== Sum((d/s)**2) for starred atoms 0.000 Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 86.86( 0.20) 93.14( 0.20) 1 3 2.13( 0.20) 177.87( 0.20) 1 4 58.85( 0.34) 121.15( 0.34) 2 3 84.74( 0.16) 95.26( 0.16) 2 4 34.30( 0.32) 145.70( 0.32) 3 4 60.98( 0.32) 119.02( 0.32) ; 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 Hg N4 2.353(9) . ? Hg N2 2.386(8) . ? Hg N1 2.399(8) . ? Hg N5 2.533(8) . ? Hg N3 2.562(9) . ? Hg Br 2.5796(18) . ? Cl1 O14 1.406(9) . ? Cl1 O12 1.418(9) . ? Cl1 O13 1.423(9) . ? Cl1 O11 1.441(8) . ? C7 C8 1.407(17) . ? C7 C12 1.411(17) . ? C7 C6 1.423(15) . ? N2 C10 1.310(13) . ? N2 C6 1.358(13) . ? C11 C12 1.366(17) . ? C11 C10 1.403(16) . ? N5 C18 1.462(14) . ? N5 C17 1.483(14) . ? C3 C2 1.358(17) . ? C3 C4 1.392(17) . ? C4 C5 1.415(15) . ? C4 C9 1.429(16) . ? C2 C1 1.402(15) . ? C14 N3 1.449(16) . ? C14 C15 1.501(19) . ? N1 C1 1.312(13) . ? N1 C5 1.356(12) . ? N4 C15 1.486(16) . ? N4 C16 1.483(15) . ? C1 C18 1.512(15) . ? C9 C8 1.324(18) . ? C5 C6 1.437(14) . ? C16 C17 1.479(18) . ? N3 C13 1.466(14) . ? C10 C13 1.528(16) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N4 Hg N2 111.8(3) . . ? N4 Hg N1 111.9(3) . . ? N2 Hg N1 69.2(3) . . ? N4 Hg N5 74.2(3) . . ? N2 Hg N5 135.5(3) . . ? N1 Hg N5 68.0(3) . . ? N4 Hg N3 73.2(3) . . ? N2 Hg N3 68.0(3) . . ? N1 Hg N3 135.3(3) . . ? N5 Hg N3 145.9(3) . . ? N4 Hg Br 115.0(3) . . ? N2 Hg Br 120.1(2) . . ? N1 Hg Br 121.0(2) . . ? N5 Hg Br 92.4(2) . . ? N3 Hg Br 92.0(2) . . ? O14 Cl1 O12 110.0(6) . . ? O14 Cl1 O13 110.7(7) . . ? O12 Cl1 O13 108.1(6) . . ? O14 Cl1 O11 108.9(6) . . ? O12 Cl1 O11 109.4(6) . . ? O13 Cl1 O11 109.7(6) . . ? C8 C7 C12 126.7(12) . . ? C8 C7 C6 117.3(12) . . ? C12 C7 C6 116.0(12) . . ? C10 N2 C6 120.2(9) . . ? C10 N2 Hg 122.8(8) . . ? C6 N2 Hg 116.7(7) . . ? C12 C11 C10 119.6(12) . . ? C18 N5 C17 115.4(9) . . ? C18 N5 Hg 113.7(6) . . ? C17 N5 Hg 104.7(6) . . ? C2 C3 C4 122.4(11) . . ? C3 C4 C5 115.8(11) . . ? C3 C4 C9 127.2(12) . . ? C5 C4 C9 116.9(12) . . ? C3 C2 C1 118.0(12) . . ? N3 C14 C15 110.4(12) . . ? C1 N1 C5 120.8(9) . . ? C1 N1 Hg 122.3(7) . . ? C5 N1 Hg 116.6(7) . . ? C15 N4 C16 116.2(11) . . ? C15 N4 Hg 107.6(7) . . ? C16 N4 Hg 107.1(7) . . ? N1 C1 C2 121.6(11) . . ? N1 C1 C18 118.7(10) . . ? C2 C1 C18 119.7(11) . . ? C8 C9 C4 122.1(13) . . ? N4 C15 C14 110.0(12) . . ? N1 C5 C4 121.3(10) . . ? N1 C5 C6 117.9(10) . . ? C4 C5 C6 120.7(10) . . ? C17 C16 N4 110.7(10) . . ? N5 C18 C1 114.4(9) . . ? N2 C6 C7 122.1(11) . . ? N2 C6 C5 118.5(9) . . ? C7 C6 C5 119.4(11) . . ? C14 N3 C13 114.4(11) . . ? C14 N3 Hg 105.6(8) . . ? C13 N3 Hg 113.7(7) . . ? N2 C10 C11 121.6(12) . . ? N2 C10 C13 119.3(10) . . ? C11 C10 C13 119.1(11) . . ? C9 C8 C7 123.5(13) . . ? N5 C17 C16 110.5(10) . . ? N3 C13 C10 113.9(9) . . ? C11 C12 C7 120.4(11) . . ? _diffrn_measured_fraction_theta_max 0.843 _diffrn_reflns_theta_full 59.90 _diffrn_measured_fraction_theta_full 0.843 _refine_diff_density_max 0.421 _refine_diff_density_min -1.411 _refine_diff_density_rms 0.119 #===END