# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and # The Centre National de la Recherche Scientifique, 2004 data_global _journal_coden_Cambridge 440 _journal_volume ? _journal_year ? _journal_page_first ? #------------------ SUBMISSION DETAILS --------------------------------------# # Name and address of author for correspondence _publ_contact_author_name 'Dr. Daniel J. Price' _publ_contact_author_address ;School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom ; _publ_contact_author_email daniel.price@soton.ac.uk _publ_contact_author_fax +44(0)2380596805 _publ_requested_journal 'New Journal of Chemistry' #------------------ TITLE AND AUTHOR LIST------------------------------------# _publ_section_title ; Ferromagnetic coupling in a heptanuclear nickel cluster with a vertex-shared dicubane structure ; loop_ _publ_author_name _publ_author_address 'Tony D. Keene' ;School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom ; 'Michael B. Hursthouse' ;School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom ; 'Daniel J. Price' ;School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom ; #------------------ ----------------------------------------------------# data_1 _database_code_depnum_ccdc_archive 'CCDC 232102' _audit_creation_method SHELXL-97 _chemical_name_systematic ; catena-(octakis(\m ~3~-hydroxo)-tris((\m ~2~-oxalato-O,O') -(piperazine-N,N'))-hepta-nickel) ; _chemical_name_common ? _chemical_melting_point N/A _chemical_formula_moiety 'C18 H38 N6 Ni7 O20' _chemical_formula_sum 'C18 H38 N6 Ni7 O20' _chemical_formula_weight 1069.37 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' O O 0.0106 0.0060 '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' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M 'R -3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 14.6951(12) _cell_length_b 14.6951(12) _cell_length_c 12.813(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 2396.2(5) _cell_formula_units_Z 3 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 15034 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour green _exptl_crystal_size_max 0.06 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.223 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1632 _exptl_absorpt_coefficient_mu 4.130 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.48349 _exptl_absorpt_correction_T_max 0.94362 _exptl_absorpt_process_details 'SORTAV (Blessing, 1997)' _exptl_special_details ; PLEASE NOTE cell_measurement_fields are not relavent to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range. ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Nonius FR591 rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD Area Detector' _diffrn_measurement_method '\f and \w scans to fill Ewald Sphere' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7605 _diffrn_reflns_av_R_equivalents 0.1981 _diffrn_reflns_av_sigmaI/netI 0.1159 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.56 _diffrn_reflns_theta_max 27.48 _reflns_number_total 1225 _reflns_number_gt 826 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'DENZO (Otwinowski and Minor, 1997)' _computing_cell_refinement 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_data_reduction 'DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998)' _computing_structure_solution ;SHELXS-97 (Sheldrick, 1997a) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_structure_refinement ;SHELXS-97 (Sheldrick, 1997a) in WINGX (L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; _computing_molecular_graphics 'Diamond (Brandenburg, 1997)' _computing_publication_material ? _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. All hydrogen atoms were fixed in calculated positions and refined in riding mode ; _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^)+(0.0455P)^2^+2.1926P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1225 _refine_ls_number_parameters 78 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1032 _refine_ls_R_factor_gt 0.0575 _refine_ls_wR_factor_ref 0.1318 _refine_ls_wR_factor_gt 0.1164 _refine_ls_goodness_of_fit_ref 1.033 _refine_ls_restrained_S_all 1.033 _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 O3 O 0.1422(3) 0.2460(3) 0.2297(3) 0.0186(9) Uani 1 1 d . . . O4 O 0.2802(3) 0.4069(3) 0.2576(3) 0.0201(10) Uani 1 1 d . . . N1 N -0.1014(4) 0.1347(4) 0.2261(4) 0.0195(11) Uani 1 1 d . . . H3 H -0.1516 0.0658 0.2211 0.023 Uiso 1 1 calc R . . C1 C -0.0791(5) 0.1697(5) 0.1156(4) 0.0206(13) Uani 1 1 d . . . H1A H -0.0488 0.1324 0.0808 0.025 Uiso 1 1 calc R . . H1B H -0.0277 0.2441 0.1136 0.025 Uiso 1 1 calc R . . C3 C 0.1931(5) 0.3308(5) 0.2817(4) 0.0197(13) Uani 1 1 d . . . C2 C -0.1562(5) 0.1829(5) 0.2764(5) 0.0235(14) Uani 1 1 d . . . H2A H -0.1086 0.2580 0.2820 0.028 Uiso 1 1 calc R . . H2B H -0.1758 0.1551 0.3466 0.028 Uiso 1 1 calc R . . Ni1 Ni 0.0000 0.0000 0.5000 0.0160(4) Uani 1 6 d S . . Ni2 Ni 0.01604(6) 0.13136(6) 0.31294(6) 0.0169(3) Uani 1 1 d . . . O2 O 0.0000 0.0000 0.2316(5) 0.0176(15) Uani 1 3 d S . . H5 H 0.0000 0.0000 0.1551 0.021 Uiso 1 3 calc SR . . O1 O -0.1000(3) 0.0151(3) 0.4004(3) 0.0155(9) Uani 1 1 d . . . H4 H -0.1577 0.0235 0.4278 0.019 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 O3 0.021(2) 0.019(2) 0.013(2) 0.0001(17) 0.0012(17) 0.0086(18) O4 0.022(2) 0.017(2) 0.021(2) 0.0002(18) 0.0028(18) 0.0093(19) N1 0.019(3) 0.021(3) 0.019(3) -0.003(2) 0.000(2) 0.011(2) C1 0.026(3) 0.027(3) 0.014(3) 0.002(3) 0.000(3) 0.017(3) C3 0.018(3) 0.027(3) 0.021(3) -0.001(3) -0.001(3) 0.016(3) C2 0.024(3) 0.033(4) 0.019(3) -0.002(3) -0.002(3) 0.018(3) Ni1 0.0178(6) 0.0178(6) 0.0124(10) 0.000 0.000 0.0089(3) Ni2 0.0177(4) 0.0179(4) 0.0153(4) 0.0007(3) -0.0003(3) 0.0090(3) O2 0.022(2) 0.022(2) 0.009(3) 0.000 0.000 0.0108(12) O1 0.017(2) 0.016(2) 0.016(2) -0.0015(17) 0.0012(17) 0.0099(18) _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 O3 C3 1.275(7) . ? O3 Ni2 2.072(4) . ? O4 C3 1.246(7) . ? O4 Ni2 2.085(4) 16 ? N1 C2 1.461(7) . ? N1 C1 1.486(7) . ? N1 Ni2 2.074(5) . ? N1 H3 0.9100 . ? C1 C2 1.522(8) 13_455 ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C3 C3 1.554(11) 16 ? C2 C1 1.522(8) 13_455 ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? Ni1 O1 2.041(4) . ? Ni2 O1 2.042(4) . ? Ni2 O1 2.064(4) 3 ? Ni2 O4 2.085(4) 16 ? Ni2 O2 2.101(3) . ? O2 Ni2 2.101(3) 2 ? O2 Ni2 2.101(3) 3 ? O2 H5 0.9800 . ? O1 Ni2 2.064(4) 2 ? O1 H4 0.9800 . ? 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 C3 O3 Ni2 112.0(4) . . ? C3 O4 Ni2 110.6(4) . 16 ? C2 N1 C1 109.4(4) . . ? C2 N1 Ni2 116.2(4) . . ? C1 N1 Ni2 118.5(3) . . ? C2 N1 H3 103.5 . . ? C1 N1 H3 103.5 . . ? Ni2 N1 H3 103.5 . . ? N1 C1 C2 112.4(5) . 13_455 ? N1 C1 H1A 109.1 . . ? C2 C1 H1A 109.1 13_455 . ? N1 C1 H1B 109.1 . . ? C2 C1 H1B 109.1 13_455 . ? H1A C1 H1B 107.8 . . ? O4 C3 O3 125.8(5) . . ? O4 C3 C3 118.8(6) . 16 ? O3 C3 C3 115.4(6) . 16 ? N1 C2 C1 113.1(5) . 13_455 ? N1 C2 H2A 109.0 . . ? C1 C2 H2A 109.0 13_455 . ? N1 C2 H2B 109.0 . . ? C1 C2 H2B 109.0 13_455 . ? H2A C2 H2B 107.8 . . ? O1 Ni1 O1 94.93(15) 11_556 . ? O1 Ni1 O1 180.00(15) 11_556 2 ? O1 Ni1 O1 85.07(15) . 2 ? O1 Ni1 O1 85.07(15) 11_556 12_556 ? O1 Ni1 O1 94.93(15) . 12_556 ? O1 Ni1 O1 94.93(15) 2 12_556 ? O1 Ni1 O1 85.07(15) 11_556 10_556 ? O1 Ni1 O1 180.000(1) . 10_556 ? O1 Ni1 O1 94.93(15) 2 10_556 ? O1 Ni1 O1 85.07(15) 12_556 10_556 ? O1 Ni1 O1 94.93(15) 11_556 3 ? O1 Ni1 O1 85.07(15) . 3 ? O1 Ni1 O1 85.07(15) 2 3 ? O1 Ni1 O1 180.0(2) 12_556 3 ? O1 Ni1 O1 94.93(15) 10_556 3 ? O1 Ni2 O1 84.4(2) . 3 ? O1 Ni2 O3 175.36(15) . . ? O1 Ni2 O3 90.97(15) 3 . ? O1 Ni2 N1 87.56(17) . . ? O1 Ni2 N1 169.99(17) 3 . ? O3 Ni2 N1 96.94(17) . . ? O1 Ni2 O4 99.41(14) . 16 ? O1 Ni2 O4 89.22(15) 3 16 ? O3 Ni2 O4 81.11(15) . 16 ? N1 Ni2 O4 98.03(17) . 16 ? O1 Ni2 O2 80.86(15) . . ? O1 Ni2 O2 80.34(15) 3 . ? O3 Ni2 O2 97.78(15) . . ? N1 Ni2 O2 92.47(16) . . ? O4 Ni2 O2 169.50(15) 16 . ? Ni2 O2 Ni2 97.50(19) . 2 ? Ni2 O2 Ni2 97.50(19) . 3 ? Ni2 O2 Ni2 97.50(19) 2 3 ? Ni2 O2 H5 119.8 . . ? Ni2 O2 H5 119.8 2 . ? Ni2 O2 H5 119.8 3 . ? Ni1 O1 Ni2 95.06(15) . . ? Ni1 O1 Ni2 94.38(15) . 2 ? Ni2 O1 Ni2 100.58(16) . 2 ? Ni1 O1 H4 120.3 . . ? Ni2 O1 H4 120.3 . . ? Ni2 O1 H4 120.3 2 . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.708 _refine_diff_density_min -0.916 _refine_diff_density_rms 0.192