Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_section_title ;bis(di-2-pyridyl-methanediol)copper(II) dihydrogentrifluoride: A structural and spectroscopic study of the H2F3-anion in a complex salt ; _publ_contact_author_name 'Jamie Manson' _publ_contact_author_email JMANSON@EWU.EDU loop_ _publ_author_name 'Jamie Manson' 'Janice L. Musfeldt' 'Ram Rai' 'Heather I. Southerland' 'Brendan Twamley' # Attachment '[Cu_py-methanediol_2]_H2F3_2.cif' data_bt994 _database_code_depnum_ccdc_archive 'CCDC 649636' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'C22 H20 Cu N4 O4, 4(F H), 2(F)' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H24 Cu F6 N4 O4' _chemical_formula_weight 585.99 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 '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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/n _symmetry_space_group_name_Hall '-P 2yn' 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 7.6534(2) _cell_length_b 15.3303(4) _cell_length_c 9.9870(2) _cell_angle_alpha 90.00 _cell_angle_beta 101.066(4) _cell_angle_gamma 90.00 _cell_volume 1149.98(5) _cell_formula_units_Z 2 _cell_measurement_temperature 90(2) _cell_measurement_reflns_used 7287 _cell_measurement_theta_min 2.46 _cell_measurement_theta_max 30.01 _exptl_crystal_description block _exptl_crystal_colour purple _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.692 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 598 _exptl_absorpt_coefficient_mu 1.037 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6468 _exptl_absorpt_correction_T_max 0.7815 _exptl_absorpt_process_details 'SADABS-2004/1 ; Bruker, 2004' _exptl_special_details ; ? ; _diffrn_ambient_temperature 90(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'normal-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker/Siemens SMART APEX' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8.3 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9860 _diffrn_reflns_av_R_equivalents 0.0138 _diffrn_reflns_av_sigmaI/netI 0.0126 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.47 _diffrn_reflns_theta_max 25.24 _reflns_number_total 2074 _reflns_number_gt 1965 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Bruker, 2006; SMART v. 5.632' _computing_cell_refinement 'Bruker, 2006; SAINT+ v. 7.23a' _computing_data_reduction 'Bruker, 2006; SAINT+ v. 7.23a' _computing_structure_solution 'Bruker, 2003; XS, SHELXTL v. 6.14' _computing_structure_refinement "Bruker, 2003; XL,SHELXTL v. 6.14'" _computing_molecular_graphics 'Bruker, 2003; XP, SHELXTL v. 6.14' _computing_publication_material 'Bruker, 2001; XCIF, SHELXTL, v. 6.14' _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^)+(0.0414P)^2^+1.0969P] 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 2074 _refine_ls_number_parameters 169 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0288 _refine_ls_R_factor_gt 0.0274 _refine_ls_wR_factor_ref 0.0778 _refine_ls_wR_factor_gt 0.0764 _refine_ls_goodness_of_fit_ref 1.091 _refine_ls_restrained_S_all 1.091 _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 Cu1 Cu 0.5000 0.5000 0.5000 0.01204(12) Uani 1 2 d S . . N1 N 0.2911(2) 0.45120(10) 0.56914(15) 0.0132(3) Uani 1 1 d . . . C2 C 0.2011(3) 0.49533(11) 0.6496(2) 0.0149(4) Uani 1 1 d . . . H2A H 0.2402 0.5521 0.6795 0.018 Uiso 1 1 calc R . . C3 C 0.0526(2) 0.46063(13) 0.69053(19) 0.0171(4) Uani 1 1 d . . . H3A H -0.0086 0.4929 0.7485 0.021 Uiso 1 1 calc R . . C4 C -0.0050(2) 0.37831(13) 0.64564(19) 0.0180(4) Uani 1 1 d . . . H4A H -0.1067 0.3534 0.6723 0.022 Uiso 1 1 calc R . . C5 C 0.0871(2) 0.33235(12) 0.56131(19) 0.0164(4) Uani 1 1 d . . . H5A H 0.0484 0.2762 0.5279 0.020 Uiso 1 1 calc R . . C6 C 0.2367(2) 0.37042(12) 0.52722(18) 0.0139(4) Uani 1 1 d . . . C7 C 0.3495(2) 0.32776(12) 0.43458(19) 0.0148(4) Uani 1 1 d . . . O8 O 0.30798(18) 0.24098(8) 0.40579(13) 0.0183(3) Uani 1 1 d . . . H8 H 0.3068 0.2149 0.4814 0.022 Uiso 1 1 d . . . O9 O 0.52943(17) 0.33984(9) 0.50144(12) 0.0147(3) Uani 1 1 d . . . H9 H 0.5931 0.3231 0.4445 0.018 Uiso 1 1 d . . . C10 C 0.3164(2) 0.37821(12) 0.30018(19) 0.0147(4) Uani 1 1 d . . . C11 C 0.2215(3) 0.34556(13) 0.1790(2) 0.0195(4) Uani 1 1 d . . . H11A H 0.1735 0.2882 0.1743 0.023 Uiso 1 1 calc R . . C12 C 0.1978(3) 0.39844(15) 0.0641(2) 0.0245(5) Uani 1 1 d . . . H12A H 0.1332 0.3776 -0.0207 0.029 Uiso 1 1 calc R . . C13 C 0.2691(3) 0.48189(14) 0.0739(2) 0.0223(4) Uani 1 1 d . . . H13A H 0.2556 0.5186 -0.0040 0.027 Uiso 1 1 calc R . . C14 C 0.3602(3) 0.51058(13) 0.1994(2) 0.0171(4) Uani 1 1 d . . . H14A H 0.4084 0.5679 0.2068 0.021 Uiso 1 1 calc R . . N15 N 0.3826(2) 0.46001(10) 0.31093(16) 0.0141(3) Uani 1 1 d . . . F1 F 0.72048(16) 0.28957(8) 0.32635(12) 0.0248(3) Uani 1 1 d . . . F2 F 0.79360(19) 0.34969(8) 0.13174(13) 0.0322(3) Uani 1 1 d . . . H2 H 0.7646 0.3215 0.2100 0.050 Uiso 1 1 d . . . F3 F 0.90457(19) 0.16307(9) 0.35681(15) 0.0386(3) Uani 1 1 d . . . H3 H 0.8190 0.2184 0.3366 0.050 Uiso 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 Cu1 0.01189(19) 0.01169(19) 0.01276(19) -0.00073(11) 0.00295(13) -0.00174(11) N1 0.0135(7) 0.0125(7) 0.0133(7) -0.0002(6) 0.0021(6) 0.0002(6) C2 0.0153(9) 0.0142(9) 0.0146(9) -0.0009(7) 0.0011(7) 0.0014(7) C3 0.0160(9) 0.0195(10) 0.0161(9) 0.0007(7) 0.0035(7) 0.0043(7) C4 0.0133(9) 0.0209(10) 0.0198(10) 0.0044(8) 0.0034(7) -0.0004(7) C5 0.0168(9) 0.0140(9) 0.0177(9) 0.0012(7) 0.0015(7) -0.0013(7) C6 0.0139(9) 0.0132(9) 0.0136(9) 0.0014(7) 0.0001(7) 0.0008(7) C7 0.0149(9) 0.0123(9) 0.0172(9) -0.0014(7) 0.0030(7) -0.0009(7) O8 0.0251(7) 0.0106(6) 0.0205(7) -0.0023(5) 0.0074(6) -0.0027(5) O9 0.0143(6) 0.0157(7) 0.0144(7) -0.0004(5) 0.0034(5) 0.0021(5) C10 0.0121(8) 0.0155(9) 0.0176(9) -0.0016(7) 0.0052(7) 0.0011(7) C11 0.0201(10) 0.0182(9) 0.0196(10) -0.0030(8) 0.0027(8) -0.0014(8) C12 0.0243(11) 0.0305(11) 0.0169(10) -0.0035(8) -0.0004(8) -0.0003(9) C13 0.0219(11) 0.0285(10) 0.0163(10) 0.0046(8) 0.0033(8) 0.0010(9) C14 0.0144(9) 0.0196(10) 0.0183(10) 0.0026(7) 0.0052(8) -0.0001(7) N15 0.0122(7) 0.0144(8) 0.0161(8) -0.0001(6) 0.0040(6) 0.0002(6) F1 0.0266(6) 0.0236(6) 0.0270(6) -0.0057(5) 0.0122(5) 0.0005(5) F2 0.0502(8) 0.0211(6) 0.0293(7) -0.0068(5) 0.0179(6) -0.0047(6) F3 0.0358(8) 0.0332(8) 0.0467(9) -0.0040(6) 0.0078(6) 0.0067(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 Cu1 N1 2.0040(15) . ? Cu1 N1 2.0040(15) 3_666 ? Cu1 N15 2.0243(15) . ? Cu1 N15 2.0243(15) 3_666 ? N1 C2 1.338(2) . ? N1 C6 1.347(2) . ? C2 C3 1.386(3) . ? C2 H2A 0.9500 . ? C3 C4 1.383(3) . ? C3 H3A 0.9500 . ? C4 C5 1.390(3) . ? C4 H4A 0.9500 . ? C5 C6 1.385(3) . ? C5 H5A 0.9500 . ? C6 C7 1.528(3) . ? C7 O8 1.385(2) . ? C7 O9 1.423(2) . ? C7 C10 1.528(3) . ? O8 H8 0.8567 . ? O9 H9 0.8568 . ? C10 N15 1.349(2) . ? C10 C11 1.380(3) . ? C11 C12 1.388(3) . ? C11 H11A 0.9500 . ? C12 C13 1.387(3) . ? C12 H12A 0.9500 . ? C13 C14 1.384(3) . ? C13 H13A 0.9500 . ? C14 N15 1.341(3) . ? C14 H14A 0.9500 . ? F1 H2 1.3618 . ? F1 H3 1.3190 . ? F2 H2 0.9558 . ? F3 H3 1.0669 . ? 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 Cu1 N1 180.0 . 3_666 ? N1 Cu1 N15 88.15(6) . . ? N1 Cu1 N15 91.85(6) 3_666 . ? N1 Cu1 N15 91.85(6) . 3_666 ? N1 Cu1 N15 88.15(6) 3_666 3_666 ? N15 Cu1 N15 180.0 . 3_666 ? C2 N1 C6 119.18(16) . . ? C2 N1 Cu1 123.70(12) . . ? C6 N1 Cu1 117.08(12) . . ? N1 C2 C3 121.94(17) . . ? N1 C2 H2A 119.0 . . ? C3 C2 H2A 119.0 . . ? C4 C3 C2 118.89(17) . . ? C4 C3 H3A 120.6 . . ? C2 C3 H3A 120.6 . . ? C3 C4 C5 119.48(18) . . ? C3 C4 H4A 120.3 . . ? C5 C4 H4A 120.3 . . ? C6 C5 C4 118.36(17) . . ? C6 C5 H5A 120.8 . . ? C4 C5 H5A 120.8 . . ? N1 C6 C5 122.12(17) . . ? N1 C6 C7 113.89(15) . . ? C5 C6 C7 123.94(17) . . ? O8 C7 O9 112.66(15) . . ? O8 C7 C10 108.13(15) . . ? O9 C7 C10 109.20(14) . . ? O8 C7 C6 113.77(15) . . ? O9 C7 C6 105.57(14) . . ? C10 C7 C6 107.32(15) . . ? C7 O8 H8 107.9 . . ? C7 O9 H9 105.8 . . ? N15 C10 C11 122.22(17) . . ? N15 C10 C7 113.85(16) . . ? C11 C10 C7 123.87(17) . . ? C10 C11 C12 118.45(18) . . ? C10 C11 H11A 120.8 . . ? C12 C11 H11A 120.8 . . ? C13 C12 C11 119.54(19) . . ? C13 C12 H12A 120.2 . . ? C11 C12 H12A 120.2 . . ? C14 C13 C12 118.70(19) . . ? C14 C13 H13A 120.7 . . ? C12 C13 H13A 120.7 . . ? N15 C14 C13 122.04(18) . . ? N15 C14 H14A 119.0 . . ? C13 C14 H14A 119.0 . . ? C14 N15 C10 119.03(16) . . ? C14 N15 Cu1 124.25(13) . . ? C10 N15 Cu1 116.64(12) . . ? H2 F1 H3 97.6 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O8 H8 F2 0.86 1.82 2.6705(18) 174.3 4_566 O9 H9 F1 0.86 1.75 2.6021(16) 179.1 . F3 H3 F1 1.07 1.32 2.3819(18) 173.4 . F2 H2 F1 0.96 1.36 2.3146(17) 174.2 . _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.24 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.390 _refine_diff_density_min -0.407 _refine_diff_density_rms 0.064