# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name D.Freedman R.Chisnell T.McQueen Y.Lee C.Payen Nocera _publ_contact_author_name 'Dr D Nocera' _publ_contact_author_email NOCERA@MIT.EDU data_nives _database_code_depnum_ccdc_archive 'CCDC 837685' #TrackingRef '1a.cif' _audit_creation_method 'Created with Diamond(www.crystalimpact.com)' _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'H4 Ba2 Ni6 O20 V4' _chemical_formula_weight 1154.73 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Ni Ni -3.0730 0.4820 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ba Ba -1.1120 8.3000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' V V -0.0696 2.1370 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0320 0.0500 '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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z' _cell_length_a 10.213(6) _cell_length_b 5.816(3) _cell_length_c 7.888(4) _cell_angle_alpha 90.00(6) _cell_angle_beta 117.01(4) _cell_angle_gamma 90.00(8) _cell_volume 417.4(4) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 155 _cell_measurement_theta_min 5 _cell_measurement_theta_max 40 _exptl_crystal_description powder _exptl_crystal_colour yellow _exptl_crystal_size_max powder _exptl_crystal_size_mid powder _exptl_crystal_size_min powder _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 4.594 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 536 _exptl_absorpt_coefficient_mu 0.000 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min none _exptl_absorpt_correction_T_max none _exptl_absorpt_process_details none _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54060 _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 155 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0174 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 4 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 5 _diffrn_reflns_theta_min 6.29 _diffrn_reflns_theta_max 39.65 _reflns_number_total 147 _reflns_number_gt 145 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _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. ; _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^)+(0.1000P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 147 _refine_ls_number_parameters 23 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1325 _refine_ls_R_factor_gt 0.1306 _refine_ls_wR_factor_ref 0.3308 _refine_ls_wR_factor_gt 0.3297 _refine_ls_goodness_of_fit_ref 3.662 _refine_ls_restrained_S_all 3.647 _refine_ls_shift/su_max 1.149 _refine_ls_shift/su_mean 0.068 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 0.0000 0.0000 0.0000 0.023(6) Uiso 1 4 d S . . Ni2 Ni 0.2500 0.2500 0.0000 0.105(7) Uiso 1 2 d S . . Ba Ba 0.0000 0.0000 0.5000 0.011(4) Uiso 1 4 d S . . V1 V 0.0911(9) 0.5000 0.2727(16) 0.010(6) Uiso 1 2 d S . . O2 O 0.470(4) 0.247(5) 0.153(6) 0.081(15) Uiso 1 1 d . . . O3 O 0.209(4) 0.5000 0.176(6) 0.031(12) Uiso 1 2 d S . . O4 O -0.144(8) -0.5000 0.519(10) 0.09(2) Uiso 1 2 d S . . O1 O 0.206(3) 0.0000 0.128(5) 0.000(14) Uiso 1 2 d SD . . H1 H 0.27(4) 0.0000 0.237(19) 0.00(15) Uiso 1 2 d SD . . _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 O1 1.88(2) 5 ? Ni1 O1 1.88(2) . ? Ni1 O2 2.01(4) 8_455 ? Ni1 O2 2.01(4) 3_445 ? Ni1 O2 2.01(4) 4_545 ? Ni1 O2 2.01(4) 7 ? Ni1 Ni2 2.938(2) 3_445 ? Ni1 Ni2 2.938(2) 2 ? Ni1 Ni2 2.938(2) . ? Ni1 Ni2 2.938(2) 4_545 ? Ni2 O1 1.94(2) . ? Ni2 O1 1.94(2) 7 ? Ni2 O2 2.01(4) . ? Ni2 O2 2.01(4) 7 ? Ni2 O3 2.18(3) . ? Ni2 O3 2.18(3) 7 ? Ni2 Ni2 2.9078(17) 4_545 ? Ni2 Ni2 2.9078(17) 4 ? Ni2 Ni1 2.938(2) 3 ? Ni2 Ba 3.878(3) 1_554 ? Ni2 Ba 3.878(3) 3 ? Ba O3 2.91(4) 7_556 ? Ba O3 2.91(4) 3_445 ? Ba O2 3.00(4) 7_556 ? Ba O2 3.00(4) 4_546 ? Ba O2 3.00(4) 3_445 ? Ba O2 3.00(4) 8_455 ? Ba O4 3.29(3) 1_565 ? Ba O4 3.29(3) . ? Ba O4 3.29(3) 5_556 ? Ba O4 3.29(3) 5_546 ? Ba V1 3.722(9) 7_556 ? Ba V1 3.722(9) 3_445 ? V1 O4 1.48(7) 5_556 ? V1 O3 1.69(4) . ? V1 O2 1.85(4) 8_455 ? V1 O2 1.85(4) 3_455 ? V1 Ba 3.722(9) 3 ? V1 Ba 3.749(7) 1_565 ? O2 V1 1.85(4) 3_545 ? O2 Ni1 2.01(4) 3 ? O2 Ba 3.00(4) 3 ? O3 Ni2 2.18(3) 4 ? O3 Ba 2.91(4) 3 ? O4 V1 1.48(7) 5_556 ? O4 Ba 3.29(3) 1_545 ? O1 Ni2 1.94(2) 4_545 ? 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 O1 Ni1 O1 179.999(1) 5 . ? O1 Ni1 O2 83.4(12) 5 8_455 ? O1 Ni1 O2 96.6(12) . 8_455 ? O1 Ni1 O2 83.4(12) 5 3_445 ? O1 Ni1 O2 96.6(12) . 3_445 ? O2 Ni1 O2 94(2) 8_455 3_445 ? O1 Ni1 O2 96.6(12) 5 4_545 ? O1 Ni1 O2 83.4(12) . 4_545 ? O2 Ni1 O2 179.999(2) 8_455 4_545 ? O2 Ni1 O2 86(2) 3_445 4_545 ? O1 Ni1 O2 96.6(12) 5 7 ? O1 Ni1 O2 83.4(12) . 7 ? O2 Ni1 O2 86(2) 8_455 7 ? O2 Ni1 O2 179.999(2) 3_445 7 ? O2 Ni1 O2 94(2) 4_545 7 ? O1 Ni1 Ni2 40.4(7) 5 3_445 ? O1 Ni1 Ni2 139.6(7) . 3_445 ? O2 Ni1 Ni2 89.6(9) 8_455 3_445 ? O2 Ni1 Ni2 43.1(10) 3_445 3_445 ? O2 Ni1 Ni2 90.4(9) 4_545 3_445 ? O2 Ni1 Ni2 136.9(10) 7 3_445 ? O1 Ni1 Ni2 40.4(7) 5 2 ? O1 Ni1 Ni2 139.6(7) . 2 ? O2 Ni1 Ni2 43.1(10) 8_455 2 ? O2 Ni1 Ni2 89.6(9) 3_445 2 ? O2 Ni1 Ni2 136.9(10) 4_545 2 ? O2 Ni1 Ni2 90.4(9) 7 2 ? Ni2 Ni1 Ni2 59.32(4) 3_445 2 ? O1 Ni1 Ni2 139.6(7) 5 . ? O1 Ni1 Ni2 40.4(7) . . ? O2 Ni1 Ni2 90.4(9) 8_455 . ? O2 Ni1 Ni2 136.9(10) 3_445 . ? O2 Ni1 Ni2 89.6(9) 4_545 . ? O2 Ni1 Ni2 43.1(10) 7 . ? Ni2 Ni1 Ni2 180.0 3_445 . ? Ni2 Ni1 Ni2 120.68(4) 2 . ? O1 Ni1 Ni2 139.6(7) 5 4_545 ? O1 Ni1 Ni2 40.4(7) . 4_545 ? O2 Ni1 Ni2 136.9(10) 8_455 4_545 ? O2 Ni1 Ni2 90.4(9) 3_445 4_545 ? O2 Ni1 Ni2 43.1(10) 4_545 4_545 ? O2 Ni1 Ni2 89.6(9) 7 4_545 ? Ni2 Ni1 Ni2 120.68(4) 3_445 4_545 ? Ni2 Ni1 Ni2 180.0 2 4_545 ? Ni2 Ni1 Ni2 59.32(4) . 4_545 ? O1 Ni2 O1 179.999(2) . 7 ? O1 Ni2 O2 98.1(13) . . ? O1 Ni2 O2 81.9(13) 7 . ? O1 Ni2 O2 81.9(13) . 7 ? O1 Ni2 O2 98.1(13) 7 7 ? O2 Ni2 O2 179.999(2) . 7 ? O1 Ni2 O3 90.6(11) . . ? O1 Ni2 O3 89.4(11) 7 . ? O2 Ni2 O3 96.2(15) . . ? O2 Ni2 O3 83.8(15) 7 . ? O1 Ni2 O3 89.4(11) . 7 ? O1 Ni2 O3 90.6(11) 7 7 ? O2 Ni2 O3 83.8(15) . 7 ? O2 Ni2 O3 96.2(15) 7 7 ? O3 Ni2 O3 180.000(2) . 7 ? O1 Ni2 Ni2 41.4(7) . 4_545 ? O1 Ni2 Ni2 138.6(7) 7 4_545 ? O2 Ni2 Ni2 89.5(9) . 4_545 ? O2 Ni2 Ni2 90.5(9) 7 4_545 ? O3 Ni2 Ni2 131.8(8) . 4_545 ? O3 Ni2 Ni2 48.2(8) 7 4_545 ? O1 Ni2 Ni2 138.6(7) . 4 ? O1 Ni2 Ni2 41.4(7) 7 4 ? O2 Ni2 Ni2 90.5(9) . 4 ? O2 Ni2 Ni2 89.5(9) 7 4 ? O3 Ni2 Ni2 48.2(8) . 4 ? O3 Ni2 Ni2 131.8(8) 7 4 ? Ni2 Ni2 Ni2 179.999(1) 4_545 4 ? O1 Ni2 Ni1 38.9(8) . . ? O1 Ni2 Ni1 141.1(8) 7 . ? O2 Ni2 Ni1 136.9(10) . . ? O2 Ni2 Ni1 43.1(10) 7 . ? O3 Ni2 Ni1 84.9(8) . . ? O3 Ni2 Ni1 95.1(8) 7 . ? Ni2 Ni2 Ni1 60.34(6) 4_545 . ? Ni2 Ni2 Ni1 119.66(6) 4 . ? O1 Ni2 Ni1 141.1(8) . 3 ? O1 Ni2 Ni1 38.9(8) 7 3 ? O2 Ni2 Ni1 43.1(10) . 3 ? O2 Ni2 Ni1 136.9(10) 7 3 ? O3 Ni2 Ni1 95.1(8) . 3 ? O3 Ni2 Ni1 84.9(8) 7 3 ? Ni2 Ni2 Ni1 119.66(6) 4_545 3 ? Ni2 Ni2 Ni1 60.34(6) 4 3 ? Ni1 Ni2 Ni1 180.0 . 3 ? O1 Ni2 Ba 92.8(9) . 1_554 ? O1 Ni2 Ba 87.2(9) 7 1_554 ? O2 Ni2 Ba 130.4(11) . 1_554 ? O2 Ni2 Ba 49.6(11) 7 1_554 ? O3 Ni2 Ba 132.1(9) . 1_554 ? O3 Ni2 Ba 47.9(9) 7 1_554 ? Ni2 Ni2 Ba 67.98(7) 4_545 1_554 ? Ni2 Ni2 Ba 112.02(7) 4 1_554 ? Ni1 Ni2 Ba 69.13(5) . 1_554 ? Ni1 Ni2 Ba 110.87(6) 3 1_554 ? O1 Ni2 Ba 87.2(9) . 3 ? O1 Ni2 Ba 92.8(9) 7 3 ? O2 Ni2 Ba 49.6(11) . 3 ? O2 Ni2 Ba 130.4(11) 7 3 ? O3 Ni2 Ba 47.9(9) . 3 ? O3 Ni2 Ba 132.1(9) 7 3 ? Ni2 Ni2 Ba 112.02(7) 4_545 3 ? Ni2 Ni2 Ba 67.98(7) 4 3 ? Ni1 Ni2 Ba 110.87(5) . 3 ? Ni1 Ni2 Ba 69.13(6) 3 3 ? Ba Ni2 Ba 180.0 1_554 3 ? O3 Ba O3 179.999(1) 7_556 3_445 ? O3 Ba O2 63.8(10) 7_556 7_556 ? O3 Ba O2 116.2(10) 3_445 7_556 ? O3 Ba O2 63.8(10) 7_556 4_546 ? O3 Ba O2 116.2(10) 3_445 4_546 ? O2 Ba O2 58.8(13) 7_556 4_546 ? O3 Ba O2 116.2(10) 7_556 3_445 ? O3 Ba O2 63.8(10) 3_445 3_445 ? O2 Ba O2 179.999(2) 7_556 3_445 ? O2 Ba O2 121.2(13) 4_546 3_445 ? O3 Ba O2 116.2(10) 7_556 8_455 ? O3 Ba O2 63.8(10) 3_445 8_455 ? O2 Ba O2 121.2(13) 7_556 8_455 ? O2 Ba O2 179.999(2) 4_546 8_455 ? O2 Ba O2 58.8(13) 3_445 8_455 ? O3 Ba O4 105.1(12) 7_556 1_565 ? O3 Ba O4 74.9(12) 3_445 1_565 ? O2 Ba O4 52.3(15) 7_556 1_565 ? O2 Ba O4 104.8(14) 4_546 1_565 ? O2 Ba O4 127.7(15) 3_445 1_565 ? O2 Ba O4 75.2(14) 8_455 1_565 ? O3 Ba O4 105.1(12) 7_556 . ? O3 Ba O4 74.9(12) 3_445 . ? O2 Ba O4 104.8(14) 7_556 . ? O2 Ba O4 52.3(15) 4_546 . ? O2 Ba O4 75.2(14) 3_445 . ? O2 Ba O4 127.7(15) 8_455 . ? O4 Ba O4 124(2) 1_565 . ? O3 Ba O4 74.9(12) 7_556 5_556 ? O3 Ba O4 105.1(12) 3_445 5_556 ? O2 Ba O4 75.2(14) 7_556 5_556 ? O2 Ba O4 127.7(15) 4_546 5_556 ? O2 Ba O4 104.8(14) 3_445 5_556 ? O2 Ba O4 52.3(15) 8_455 5_556 ? O4 Ba O4 56(2) 1_565 5_556 ? O4 Ba O4 180.000(2) . 5_556 ? O3 Ba O4 74.9(12) 7_556 5_546 ? O3 Ba O4 105.1(12) 3_445 5_546 ? O2 Ba O4 127.7(15) 7_556 5_546 ? O2 Ba O4 75.2(14) 4_546 5_546 ? O2 Ba O4 52.3(15) 3_445 5_546 ? O2 Ba O4 104.8(14) 8_455 5_546 ? O4 Ba O4 180.000(2) 1_565 5_546 ? O4 Ba O4 56(2) . 5_546 ? O4 Ba O4 124(2) 5_556 5_546 ? O3 Ba V1 26.0(9) 7_556 7_556 ? O3 Ba V1 154.0(9) 3_445 7_556 ? O2 Ba V1 86.2(6) 7_556 7_556 ? O2 Ba V1 86.2(6) 4_546 7_556 ? O2 Ba V1 93.8(6) 3_445 7_556 ? O2 Ba V1 93.8(6) 8_455 7_556 ? O4 Ba V1 113.9(11) 1_565 7_556 ? O4 Ba V1 113.9(11) . 7_556 ? O4 Ba V1 66.1(11) 5_556 7_556 ? O4 Ba V1 66.1(11) 5_546 7_556 ? O3 Ba V1 154.0(9) 7_556 3_445 ? O3 Ba V1 26.0(9) 3_445 3_445 ? O2 Ba V1 93.8(6) 7_556 3_445 ? O2 Ba V1 93.8(6) 4_546 3_445 ? O2 Ba V1 86.2(6) 3_445 3_445 ? O2 Ba V1 86.2(6) 8_455 3_445 ? O4 Ba V1 66.1(11) 1_565 3_445 ? O4 Ba V1 66.1(11) . 3_445 ? O4 Ba V1 113.9(11) 5_556 3_445 ? O4 Ba V1 113.9(11) 5_546 3_445 ? V1 Ba V1 180.0 7_556 3_445 ? O4 V1 O3 122(3) 5_556 . ? O4 V1 O2 113(2) 5_556 8_455 ? O3 V1 O2 102.6(15) . 8_455 ? O4 V1 O2 113(2) 5_556 3_455 ? O3 V1 O2 102.6(15) . 3_455 ? O2 V1 O2 102(2) 8_455 3_455 ? O4 V1 Ba 73(3) 5_556 3 ? O3 V1 Ba 49.0(14) . 3 ? O2 V1 Ba 126.1(10) 8_455 3 ? O2 V1 Ba 126.1(10) 3_455 3 ? O4 V1 Ba 60.8(12) 5_556 1_565 ? O3 V1 Ba 126.7(4) . 1_565 ? O2 V1 Ba 126.3(10) 8_455 1_565 ? O2 V1 Ba 52.2(13) 3_455 1_565 ? Ba V1 Ba 103.7(2) 3 1_565 ? O4 V1 Ba 60.8(12) 5_556 . ? O3 V1 Ba 126.7(4) . . ? O2 V1 Ba 52.2(13) 8_455 . ? O2 V1 Ba 126.3(10) 3_455 . ? Ba V1 Ba 103.7(2) 3 . ? Ba V1 Ba 101.7(2) 1_565 . ? V1 O2 Ni2 128.2(17) 3_545 . ? V1 O2 Ni1 128.6(16) 3_545 3 ? Ni2 O2 Ni1 93.8(17) . 3 ? V1 O2 Ba 98.5(18) 3_545 3 ? Ni2 O2 Ba 99.6(12) . 3 ? Ni1 O2 Ba 102.1(12) 3 3 ? V1 O3 Ni2 132.0(10) . . ? V1 O3 Ni2 132.0(10) . 4 ? Ni2 O3 Ni2 83.6(16) . 4 ? V1 O3 Ba 105(2) . 3 ? Ni2 O3 Ba 98.3(10) . 3 ? Ni2 O3 Ba 98.3(10) 4 3 ? V1 O4 Ba 96.0(18) 5_556 . ? V1 O4 Ba 96.0(18) 5_556 1_545 ? Ba O4 Ba 124(2) . 1_545 ? Ni1 O1 Ni2 100.8(12) . . ? Ni1 O1 Ni2 100.8(12) . 4_545 ? Ni2 O1 Ni2 97.3(14) . 4_545 ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 39.65 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 4.090 _refine_diff_density_min -3.494 _refine_diff_density_rms 0.752