Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_year ? _journal_page_first ? _publ_contact_author_name 'Goutam Lahiri' _publ_contact_author_address ; Department of Chemistry Indian Institute of Technology, Bombay Mumbai Maharashtra 400076 INDIA ; _publ_contact_author_email LAHIRI@CHEM.IITB.AC.IN _publ_section_title ; 3,6-Bis(2/-pyridyl)pyridazine (L) and its deprotonated form (L-H+)- as ligands for {(acac)2Run+} or {(bpy)2Rum+}: Investigation of mixed valency in [{(acac)2Ru}2(m-L-H+)-]+ and [{(bpy)2Ru}2(m-L-H+)-]3+ by spectroelectrochemistry and EPR ; loop_ _publ_author_name 'Goutam Lahiri' 'Jan Fiedler' 'Sandeep Ghumaan' W.Kaim 'Kumar Parimal' 'Srikanta Patra' ; B.Sarkar ; 'J.van Slageren' data_165a _database_code_depnum_ccdc_archive 'CCDC 256270' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C14 H10 N4' _chemical_formula_weight 234.26 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 'P n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y, z+1/2' _cell_length_a 5.7084(5) _cell_length_b 6.5938(4) _cell_length_c 15.3455(10) _cell_angle_alpha 90.00 _cell_angle_beta 91.693(6) _cell_angle_gamma 90.00 _cell_volume 577.35(7) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 9.6600 _cell_measurement_theta_max 14.1400 _exptl_crystal_description Block _exptl_crystal_colour Black _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.348 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 244 _exptl_absorpt_coefficient_mu 0.085 _exptl_absorpt_correction_type Psi-scan _exptl_absorpt_correction_T_min 0.9708 _exptl_absorpt_correction_T_max 0.9811 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.70930 _diffrn_radiation_type ' MoK\a' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf-Nonius CAD-4' _diffrn_measurement_method \w/q-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 3600 _diffrn_standards_decay_% <3% _diffrn_reflns_number 1122 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0236 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.65 _diffrn_reflns_theta_max 24.90 _reflns_number_total 1122 _reflns_number_gt 890 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Argus (Nonius, MACH3 software)' _computing_cell_refinement 'Argus (Nonius, MACH3 software)' _computing_data_reduction 'Maxus (Nonius software)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics Ortep _computing_publication_material Shelx97 _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 w=1/[\s^2^(Fo^2^)+(0.0505P)^2^+0.0443P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.032(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 2(3) _refine_ls_number_reflns 1122 _refine_ls_number_parameters 204 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0588 _refine_ls_R_factor_gt 0.0322 _refine_ls_wR_factor_ref 0.0888 _refine_ls_wR_factor_gt 0.0787 _refine_ls_goodness_of_fit_ref 1.018 _refine_ls_restrained_S_all 1.017 _refine_ls_shift/su_max 0.041 _refine_ls_shift/su_mean 0.011 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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.0486(7) 1.1471(5) 0.4766(3) 0.0609(10) Uani 1 d . . . C7 C 0.1595(6) 0.8239(6) 0.5887(2) 0.0470(10) Uani 1 d . . . C8 C 0.1919(6) 0.6541(6) 0.6378(3) 0.0486(11) Uani 1 d . . . N4 N 0.2192(6) 0.2817(5) 0.7256(2) 0.0494(9) Uani 1 d . . . C1 C 0.0141(8) 1.3152(7) 0.4283(3) 0.0696(14) Uani 1 d . . . C2 C -0.1744(8) 1.4432(7) 0.4381(3) 0.0591(13) Uani 1 d . . . C3 C -0.3374(7) 1.3948(7) 0.4984(3) 0.0538(11) Uani 1 d . . . C4 C -0.3076(7) 1.2216(6) 0.5481(3) 0.0505(10) Uani 1 d . . . C5 C -0.1104(6) 1.1034(6) 0.5359(2) 0.0436(10) Uani 1 d . . . C6 C -0.0614(6) 0.9145(6) 0.5875(2) 0.0393(9) Uani 1 d . . . N2 N -0.2394(5) 0.8399(5) 0.6325(2) 0.0475(9) Uani 1 d . . . N3 N -0.2072(5) 0.6689(5) 0.6789(2) 0.0481(10) Uani 1 d . . . C9 C 0.0012(7) 0.5767(6) 0.6815(2) 0.0416(9) Uani 1 d . . . C10 C 0.0189(6) 0.3877(6) 0.7332(2) 0.0406(9) Uani 1 d . . . C11 C -0.1626(7) 0.3205(6) 0.7843(3) 0.0526(10) Uani 1 d . . . C12 C 0.2401(10) 0.1101(7) 0.7723(4) 0.0644(13) Uani 1 d . . . C13 C 0.0737(9) 0.0387(7) 0.8262(3) 0.0670(14) Uani 1 d . . . C14 C -0.1322(8) 0.1459(7) 0.8320(3) 0.0645(13) Uani 1 d . . . H2 H -0.184(7) 1.568(7) 0.406(3) 0.074(14) Uiso 1 d . . . H14 H -0.252(7) 0.090(6) 0.863(3) 0.074(12) Uiso 1 d . . . H12 H 0.390(6) 0.042(6) 0.764(2) 0.050(10) Uiso 1 d . . . H3 H -0.470(7) 1.499(6) 0.509(2) 0.078(13) Uiso 1 d . . . H1 H 0.143(7) 1.338(5) 0.382(3) 0.072(11) Uiso 1 d . . . H11 H -0.298(7) 0.397(5) 0.788(2) 0.059(10) Uiso 1 d . . . H13 H 0.108(6) -0.078(6) 0.860(3) 0.059(12) Uiso 1 d . . . H4 H -0.418(6) 1.180(4) 0.5911(17) 0.041(8) Uiso 1 d . . . H7 H 0.283(5) 0.883(4) 0.5562(18) 0.047(8) Uiso 1 d . . . H8 H 0.328(6) 0.580(4) 0.6411(19) 0.049(9) Uiso 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 N1 0.0537(18) 0.063(2) 0.067(2) 0.0176(17) 0.0113(15) 0.0051(17) C7 0.034(2) 0.057(2) 0.050(2) 0.0069(19) 0.0075(17) -0.0002(18) C8 0.034(2) 0.054(2) 0.058(3) 0.0060(18) 0.0035(19) 0.0034(19) N4 0.0456(18) 0.0445(18) 0.058(2) 0.0027(17) -0.0065(14) 0.0028(15) C1 0.067(3) 0.074(3) 0.069(3) 0.022(2) 0.012(2) 0.004(2) C2 0.069(3) 0.048(2) 0.059(3) 0.007(2) -0.009(2) 0.003(2) C3 0.060(2) 0.051(2) 0.051(2) -0.006(2) -0.0061(19) 0.017(2) C4 0.050(2) 0.049(2) 0.052(3) -0.005(2) 0.0036(19) 0.0029(19) C5 0.043(2) 0.045(2) 0.042(2) -0.0017(17) -0.0019(17) -0.0042(18) C6 0.034(2) 0.043(2) 0.041(2) -0.0032(16) -0.0021(16) -0.0004(17) N2 0.0338(17) 0.047(2) 0.062(2) 0.0047(15) 0.0068(14) 0.0014(14) N3 0.0359(18) 0.0430(19) 0.066(2) 0.0072(16) 0.0061(15) 0.0017(14) C9 0.0344(19) 0.043(2) 0.047(2) -0.0055(16) 0.0000(17) -0.0014(18) C10 0.0396(19) 0.042(2) 0.039(2) -0.0053(15) -0.0047(16) -0.0022(16) C11 0.052(2) 0.053(2) 0.053(2) 0.0017(17) 0.0058(18) -0.005(2) C12 0.059(3) 0.049(3) 0.084(4) 0.004(2) -0.019(2) -0.002(2) C13 0.077(3) 0.054(3) 0.068(3) 0.019(2) -0.022(2) -0.014(3) C14 0.070(3) 0.065(3) 0.059(3) 0.011(2) 0.000(2) -0.019(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 C5 1.336(6) . ? N1 C1 1.345(5) . ? C7 C8 1.358(6) . ? C7 C6 1.395(5) . ? C7 H7 0.96(3) . ? C8 C9 1.393(6) . ? C8 H8 0.92(3) . ? N4 C12 1.343(6) . ? N4 C10 1.348(5) . ? C1 C2 1.379(7) . ? C1 H1 1.05(4) . ? C2 C3 1.368(6) . ? C2 H2 0.96(5) . ? C3 C4 1.381(6) . ? C3 H3 1.03(4) . ? C4 C5 1.386(6) . ? C4 H4 0.97(3) . ? C5 C6 1.498(5) . ? C6 N2 1.338(5) . ? N2 N3 1.344(4) . ? N3 C9 1.335(5) . ? C9 C10 1.479(5) . ? C10 C11 1.391(6) . ? C11 C14 1.372(6) . ? C11 H11 0.92(4) . ? C12 C13 1.362(7) . ? C12 H12 0.98(4) . ? C13 C14 1.377(7) . ? C13 H13 0.94(4) . ? C14 H14 0.92(4) . ? 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 C5 N1 C1 117.5(4) . . ? C8 C7 C6 117.9(4) . . ? C8 C7 H7 122.3(18) . . ? C6 C7 H7 119.8(18) . . ? C7 C8 C9 118.3(4) . . ? C7 C8 H8 125(2) . . ? C9 C8 H8 116.6(19) . . ? C12 N4 C10 117.0(4) . . ? N1 C1 C2 123.1(5) . . ? N1 C1 H1 113(2) . . ? C2 C1 H1 124(2) . . ? C3 C2 C1 118.6(4) . . ? C3 C2 H2 121(3) . . ? C1 C2 H2 120(3) . . ? C2 C3 C4 119.4(4) . . ? C2 C3 H3 117(2) . . ? C4 C3 H3 123(2) . . ? C3 C4 C5 118.5(4) . . ? C3 C4 H4 122.7(17) . . ? C5 C4 H4 118.8(17) . . ? N1 C5 C4 122.8(4) . . ? N1 C5 C6 114.8(3) . . ? C4 C5 C6 122.4(3) . . ? N2 C6 C7 122.4(3) . . ? N2 C6 C5 116.5(3) . . ? C7 C6 C5 121.2(3) . . ? C6 N2 N3 119.2(3) . . ? C9 N3 N2 120.4(3) . . ? N3 C9 C8 121.8(3) . . ? N3 C9 C10 116.5(3) . . ? C8 C9 C10 121.7(3) . . ? N4 C10 C11 122.1(3) . . ? N4 C10 C9 115.8(3) . . ? C11 C10 C9 122.0(3) . . ? C14 C11 C10 118.9(4) . . ? C14 C11 H11 121(2) . . ? C10 C11 H11 120(2) . . ? N4 C12 C13 124.2(5) . . ? N4 C12 H12 112(2) . . ? C13 C12 H12 123(2) . . ? C12 C13 C14 118.3(5) . . ? C12 C13 H13 118(2) . . ? C14 C13 H13 123(2) . . ? C11 C14 C13 119.4(5) . . ? C11 C14 H14 122(3) . . ? C13 C14 H14 118(3) . . ? 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 C6 C7 C8 C9 2.1(6) . . . . ? C5 N1 C1 C2 0.8(7) . . . . ? N1 C1 C2 C3 -1.7(8) . . . . ? C1 C2 C3 C4 0.8(6) . . . . ? C2 C3 C4 C5 0.8(6) . . . . ? C1 N1 C5 C4 0.9(6) . . . . ? C1 N1 C5 C6 -180.0(4) . . . . ? C3 C4 C5 N1 -1.7(6) . . . . ? C3 C4 C5 C6 179.2(4) . . . . ? C8 C7 C6 N2 -0.1(6) . . . . ? C8 C7 C6 C5 179.3(4) . . . . ? N1 C5 C6 N2 -165.0(4) . . . . ? C4 C5 C6 N2 14.1(5) . . . . ? N1 C5 C6 C7 15.6(5) . . . . ? C4 C5 C6 C7 -165.3(4) . . . . ? C7 C6 N2 N3 -1.7(5) . . . . ? C5 C6 N2 N3 178.9(3) . . . . ? C6 N2 N3 C9 1.3(5) . . . . ? N2 N3 C9 C8 0.8(6) . . . . ? N2 N3 C9 C10 -179.1(3) . . . . ? C7 C8 C9 N3 -2.6(6) . . . . ? C7 C8 C9 C10 177.3(3) . . . . ? C12 N4 C10 C11 -2.2(6) . . . . ? C12 N4 C10 C9 179.6(3) . . . . ? N3 C9 C10 N4 171.3(4) . . . . ? C8 C9 C10 N4 -8.6(5) . . . . ? N3 C9 C10 C11 -6.9(5) . . . . ? C8 C9 C10 C11 173.2(5) . . . . ? N4 C10 C11 C14 3.3(6) . . . . ? C9 C10 C11 C14 -178.7(4) . . . . ? C10 N4 C12 C13 -0.3(6) . . . . ? N4 C12 C13 C14 1.6(7) . . . . ? C10 C11 C14 C13 -1.8(7) . . . . ? C12 C13 C14 C11 -0.5(7) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 24.90 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.117 _refine_diff_density_min -0.132 _refine_diff_density_rms 0.027