Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2004 data_global _publ_contact_author_email RRHERNAN@ULL.ES _publ_contact_author_name 'Prof Rita Hernandez-Molina' _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_address ; Department of Inorganic Chemistry University of La Laguna Av. Francisco Sanchez, S/N La Laguna Tenerife 38204 SPAIN ; _publ_section_title ; Aqueous solution chemistry of [Mo3CuSe4]n+ (n = 4, 5) and [W3CuQ4]5+ (Q = S, Se) clusters ; loop_ _publ_author_name 'Rita Hernandez-Molina' 'Pedro Esparza' 'Rosa Llusar' 'Maxim Sokolov' 'Cristian Vicent' data_[W3S4CuCl(H2O)6Cl3]Cl2(CUC).12H2O _database_code_depnum_ccdc_archive 'CCDC 221043' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H42 Cl5 Cu N12 O18 S4 W3' _chemical_formula_weight 1635.22 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 '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' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Rhombohedral _symmetry_space_group_name_H-M R-3m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'y, x, -z' 'x-y, -y, -z' '-x, -x+y, -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' 'y+2/3, x+1/3, -z+1/3' 'x-y+2/3, -y+1/3, -z+1/3' '-x+2/3, -x+y+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' 'y+1/3, x+2/3, -z+2/3' 'x-y+1/3, -y+2/3, -z+2/3' '-x+1/3, -x+y+2/3, -z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-y, -x, z' '-x+y, y, z' 'x, x-y, 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' '-y+2/3, -x+1/3, z+1/3' '-x+y+2/3, y+1/3, z+1/3' 'x+2/3, x-y+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' '-y+1/3, -x+2/3, z+2/3' '-x+y+1/3, y+2/3, z+2/3' 'x+1/3, x-y+2/3, z+2/3' _cell_length_a 16.276(3) _cell_length_b 16.276(3) _cell_length_c 32.367(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 7425(3) _cell_formula_units_Z 6 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.194 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 4668 _exptl_absorpt_coefficient_mu 7.883 _exptl_absorpt_correction_type 'Bruker SADABS' _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? #_exptl_absorpt_Ratio of minimum to maximum apparent transmission 0.869813 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14302 _diffrn_reflns_av_R_equivalents 0.0901 _diffrn_reflns_av_sigmaI/netI 0.0466 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -38 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.58 _diffrn_reflns_theta_max 24.99 _reflns_number_total 1628 _reflns_number_gt 1319 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0823P)^2^+331.3788P] 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 1628 _refine_ls_number_parameters 109 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0797 _refine_ls_R_factor_gt 0.0609 _refine_ls_wR_factor_ref 0.1827 _refine_ls_wR_factor_gt 0.1634 _refine_ls_goodness_of_fit_ref 1.224 _refine_ls_restrained_S_all 1.224 _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 W1 W 0.72285(3) 0.27715(3) 0.03483(2) 0.0361(3) Uani 1 2 d S . . Cu1 Cu 0.6667 0.3333 0.10826(14) 0.0518(13) Uani 1 6 d S . . Cl1 Cl 0.7999(2) 0.2001(2) 0.0709(2) 0.0715(19) Uani 1 2 d S . . Cl2 Cl 0.6667 0.3333 0.1752(4) 0.142(8) Uani 1 6 d S . . S1 S 0.6667 0.3333 -0.0190(3) 0.047(2) Uani 1 6 d S . . S2 S 0.5927(2) 0.1855(4) 0.07690(18) 0.0470(14) Uani 1 2 d S . . C1 C 0.4727(8) -0.0546(17) 0.2254(7) 0.056(6) Uani 1 2 d S . . C2 C 0.4653(14) 0.0243(11) 0.1658(5) 0.064(5) Uani 1 1 d . . . H2 H 0.4760 0.0891 0.1664 0.077 Uiso 1 1 calc R . . C3 C 0.3332(16) -0.0298(13) 0.1131(5) 0.070(6) Uani 1 1 d . . . H3A H 0.3319 -0.0343 0.0832 0.084 Uiso 1 1 calc R . . H3B H 0.3326 0.0276 0.1205 0.084 Uiso 1 1 calc R . . C4 C 0.4751(8) -0.0499(16) 0.1064(7) 0.057(7) Uani 1 2 d S . . N1 N 0.4181(14) -0.0271(11) 0.2034(4) 0.069(5) Uani 1 1 d . . . N2 N 0.4178(12) -0.0242(10) 0.1280(4) 0.060(4) Uani 1 1 d . . . O1 O 0.6765(8) 0.1551(8) -0.0042(3) 0.057(3) Uani 1 1 d . . . O2 O 0.4527(7) -0.0946(14) 0.2586(5) 0.065(5) Uani 1 2 d S . . O3 O 0.4558(6) -0.0885(13) 0.0724(5) 0.061(4) Uani 1 2 d S . . Cl10 Cl 0.7152(12) 0.0000 0.0000 0.055(4) Uani 0.33 2 d SP . . O100 O 0.7920(15) 0.2080(15) 0.1763(13) 0.203(17) Uiso 1 2 d S . . O101 O 0.166(4) -0.005(3) 0.0667(15) 0.158(18) Uiso 0.50 1 d P . . 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 W1 0.0419(5) 0.0419(5) 0.0284(5) -0.00174(17) 0.00174(17) 0.0239(4) Cu1 0.066(2) 0.066(2) 0.024(2) 0.000 0.000 0.0329(10) Cl1 0.075(4) 0.075(4) 0.083(5) 0.0092(17) -0.0092(17) 0.050(4) Cl2 0.203(13) 0.203(13) 0.020(6) 0.000 0.000 0.101(7) S1 0.060(4) 0.060(4) 0.023(5) 0.000 0.000 0.030(2) S2 0.051(3) 0.043(3) 0.044(3) 0.011(3) 0.0056(13) 0.0214(16) C1 0.074(14) 0.042(14) 0.041(14) -0.004(11) -0.002(5) 0.021(7) C2 0.108(15) 0.026(8) 0.039(9) -0.004(7) -0.001(9) 0.019(9) C3 0.117(18) 0.060(12) 0.035(10) 0.006(8) -0.001(10) 0.046(13) C4 0.085(16) 0.035(13) 0.034(13) 0.018(10) 0.009(5) 0.017(6) N1 0.120(15) 0.057(10) 0.036(8) 0.005(7) 0.005(8) 0.049(10) N2 0.101(13) 0.044(8) 0.032(7) 0.007(6) 0.005(7) 0.034(8) O1 0.072(8) 0.061(8) 0.044(6) -0.019(5) -0.006(5) 0.036(7) O2 0.070(8) 0.093(14) 0.040(9) 0.016(9) 0.008(5) 0.047(7) O3 0.074(9) 0.068(12) 0.039(9) 0.007(8) 0.004(4) 0.034(6) Cl10 0.065(9) 0.042(9) 0.050(10) 0.003(8) 0.002(4) 0.021(5) _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 W1 O1 2.148(11) . ? W1 O1 2.148(11) 22_665 ? W1 S2 2.325(4) 2_655 ? W1 S2 2.325(4) . ? W1 S1 2.353(7) . ? W1 Cl1 2.465(6) . ? W1 W1 2.7432(15) 2_655 ? W1 W1 2.7432(15) 3_665 ? W1 Cu1 2.856(4) . ? Cu1 Cl2 2.167(13) . ? Cu1 S2 2.318(6) . ? Cu1 S2 2.318(6) 2_655 ? Cu1 S2 2.318(6) 3_665 ? Cu1 W1 2.856(4) 3_665 ? Cu1 W1 2.856(4) 2_655 ? S1 W1 2.353(7) 2_655 ? S1 W1 2.353(7) 3_665 ? S2 W1 2.325(4) 3_665 ? C1 O2 1.21(3) . ? C1 N1 1.38(2) 23_655 ? C1 N1 1.38(2) . ? C2 N2 1.45(2) . ? C2 N1 1.46(2) . ? C2 C2 1.52(4) 23_655 ? C3 N2 1.42(2) . ? C3 N1 1.46(3) 12 ? C4 O3 1.23(3) . ? C4 N2 1.39(2) . ? C4 N2 1.39(2) 23_655 ? N1 C3 1.46(2) 12 ? 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 W1 O1 79.3(6) . 22_665 ? O1 W1 S2 162.9(3) . 2_655 ? O1 W1 S2 88.0(4) 22_665 2_655 ? O1 W1 S2 88.0(4) . . ? O1 W1 S2 162.9(3) 22_665 . ? S2 W1 S2 101.8(3) 2_655 . ? O1 W1 S1 84.2(4) . . ? O1 W1 S1 84.2(4) 22_665 . ? S2 W1 S1 106.04(13) 2_655 . ? S2 W1 S1 106.04(13) . . ? O1 W1 Cl1 80.8(4) . . ? O1 W1 Cl1 80.8(4) 22_665 . ? S2 W1 Cl1 85.89(14) 2_655 . ? S2 W1 Cl1 85.89(14) . . ? S1 W1 Cl1 160.5(2) . . ? O1 W1 W1 138.5(3) . 2_655 ? O1 W1 W1 96.4(3) 22_665 2_655 ? S2 W1 W1 53.84(8) 2_655 2_655 ? S2 W1 W1 100.74(12) . 2_655 ? S1 W1 W1 54.35(11) . 2_655 ? Cl1 W1 W1 139.73(12) . 2_655 ? O1 W1 W1 96.4(3) . 3_665 ? O1 W1 W1 138.5(3) 22_665 3_665 ? S2 W1 W1 100.74(12) 2_655 3_665 ? S2 W1 W1 53.84(8) . 3_665 ? S1 W1 W1 54.35(11) . 3_665 ? Cl1 W1 W1 139.73(12) . 3_665 ? W1 W1 W1 60.0 2_655 3_665 ? O1 W1 Cu1 139.9(3) . . ? O1 W1 Cu1 139.9(3) 22_665 . ? S2 W1 Cu1 51.93(15) 2_655 . ? S2 W1 Cu1 51.93(15) . . ? S1 W1 Cu1 104.02(16) . . ? Cl1 W1 Cu1 95.46(19) . . ? W1 W1 Cu1 61.30(4) 2_655 . ? W1 W1 Cu1 61.30(4) 3_665 . ? Cl2 Cu1 S2 115.97(17) . . ? Cl2 Cu1 S2 115.97(17) . 2_655 ? S2 Cu1 S2 102.3(2) . 2_655 ? Cl2 Cu1 S2 115.97(17) . 3_665 ? S2 Cu1 S2 102.3(2) . 3_665 ? S2 Cu1 S2 102.3(2) 2_655 3_665 ? Cl2 Cu1 W1 146.32(5) . . ? S2 Cu1 W1 52.15(13) . . ? S2 Cu1 W1 52.15(13) 2_655 . ? S2 Cu1 W1 97.7(2) 3_665 . ? Cl2 Cu1 W1 146.32(5) . 3_665 ? S2 Cu1 W1 52.15(13) . 3_665 ? S2 Cu1 W1 97.7(2) 2_655 3_665 ? S2 Cu1 W1 52.15(13) 3_665 3_665 ? W1 Cu1 W1 57.41(9) . 3_665 ? Cl2 Cu1 W1 146.32(5) . 2_655 ? S2 Cu1 W1 97.7(2) . 2_655 ? S2 Cu1 W1 52.15(13) 2_655 2_655 ? S2 Cu1 W1 52.15(13) 3_665 2_655 ? W1 Cu1 W1 57.41(9) . 2_655 ? W1 Cu1 W1 57.41(9) 3_665 2_655 ? W1 S1 W1 71.3(2) . 2_655 ? W1 S1 W1 71.3(2) . 3_665 ? W1 S1 W1 71.3(2) 2_655 3_665 ? Cu1 S2 W1 75.93(19) . 3_665 ? Cu1 S2 W1 75.93(19) . . ? W1 S2 W1 72.31(16) 3_665 . ? O2 C1 N1 126.1(11) . 23_655 ? O2 C1 N1 126.1(11) . . ? N1 C1 N1 108(2) 23_655 . ? N2 C2 N1 114.0(14) . . ? N2 C2 C2 105.1(11) . 23_655 ? N1 C2 C2 103.9(11) . 23_655 ? N2 C3 N1 111.9(15) . 12 ? O3 C4 N2 124.7(11) . . ? O3 C4 N2 124.7(11) . 23_655 ? N2 C4 N2 111(2) . 23_655 ? C1 N1 C2 112.2(18) . . ? C1 N1 C3 123.3(14) . 12 ? C2 N1 C3 123.1(16) . 12 ? C4 N2 C3 125.7(15) . . ? C4 N2 C2 109.6(17) . . ? C3 N2 C2 124.0(15) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 2.503 _refine_diff_density_min -2.835 _refine_diff_density_rms 0.313