# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 182/1527 data_4s14cu _audit_creation_method SHELXL-97 _chemical_name_systematic ; [14]aneS~4~-6-oxy(trifluoro)borato-S,S,S,S,-mu-O-copper(II) tetrafluoroborate ; _chemical_name_common {Cu^II^[14]aneS~4~-OBF~3~}(BF~4~) _chemical_formula_moiety 'C10 H19 B2 Cu F7 O S4' _chemical_formula_sum 'C10 H19 B2 Cu F7 O S4' _chemical_formula_weight 501.65 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' 'B' 'B' 0.0013 0.0007 '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' 'F' 'F' 0.0171 0.0103 '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' 'Cu' 'Cu' 0.3201 1.2651 '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)/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' _cell_length_a 7.6090(6) _cell_length_b 11.0873(10) _cell_length_c 10.7640(9) _cell_angle_alpha 90.00 _cell_angle_beta 91.687(7) _cell_angle_gamma 90.00 _cell_volume 907.69(10) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 39 _cell_measurement_theta_min 12.5 _cell_measurement_theta_max 17 _exptl_crystal_description block _exptl_crystal_colour 'dark brown' _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.23 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.835 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 506 _exptl_absorpt_coefficient_mu 1.728 _exptl_absorpt_correction_type 'numerical' _exptl_absorpt_correction_T_min 0.672 _exptl_absorpt_correction_T_max 0.711 _exptl_special_details ; Sample obtained by slow diffusion of Et~2~O vapour into a MeNO~2~ solution of Cu(BF~4~)~2~ salt of [14]aneS~4~-6-OH. Crystal glued to a dual-stage fibre. ; _diffrn_ambient_temperature 298(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 'Stoe STADI-4 four-circle diffractometer' _diffrn_measurement_method 'omega-theta scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 'random variation +/-2' _diffrn_reflns_number 1783 _diffrn_reflns_av_R_equivalents 0.0727 _diffrn_reflns_av_sigmaI/netI 0.0226 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.64 _diffrn_reflns_theta_max 25.01 _reflns_number_total 1688 _reflns_number_gt 1432 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STADI-4 (v. 1.07, Stoe & Cie, 1997a)' _computing_cell_refinement 'STADI-4 (v. 1.07, Stoe & Cie, 1997a)' _computing_data_reduction 'X-RED (v. 1.09, Stoe & Cie, 1997b)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997a)' _computing_molecular_graphics 'SHELXTL/PC (Sheldrick, 1997b)' _computing_publication_material SHELXL-97 _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 non-H atoms, bar the F atoms in the minor part of the disorder about B1, were refined anisotropically. 38% disorder, 180 deg rotation about the B2-F3 vector was modelled as was 7% 180 deg rotation about B1-O6. Appropriate similarity restraints were placed on bond lengths and angles and anisotropic thermal parameters. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.061P)^2^+2.05P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary 'heavy atom methods' _atom_sites_solution_secondary 'from difference map' _atom_sites_solution_hydrogens 'placed geometrically' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1688 _refine_ls_number_parameters 143 _refine_ls_number_restraints 124 _refine_ls_R_factor_all 0.0586 _refine_ls_R_factor_gt 0.0464 _refine_ls_wR_factor_ref 0.1325 _refine_ls_wR_factor_gt 0.1182 _refine_ls_goodness_of_fit_ref 1.100 _refine_ls_restrained_S_all 1.263 _refine_ls_shift/su_max 0.001 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu Cu 0.70121(10) 0.7500 0.78801(8) 0.0363(3) Uani 1 d S . . S1 S 0.55417(18) 0.90118(13) 0.88160(13) 0.0456(4) Uani 1 d . . . C2 C 0.5789(8) 1.0125(5) 0.7613(6) 0.0525(15) Uani 1 d . . . H2A H 0.5232 0.9847 0.6843 0.063 Uiso 1 calc R . . H2B H 0.5238 1.0876 0.7850 0.063 Uiso 1 calc R . . C3 C 0.7742(8) 1.0317(5) 0.7439(7) 0.0582(16) Uani 1 d . . . H3A H 0.8253 1.0670 0.8191 0.070 Uiso 1 calc R . . H3B H 0.7896 1.0887 0.6767 0.070 Uiso 1 calc R . . S4 S 0.89142(17) 0.89397(13) 0.70921(15) 0.0498(4) Uani 1 d . . . C5 C 0.8420(9) 0.8644(6) 0.5453(6) 0.0613(17) Uani 1 d . . . H5A H 0.7757 0.9321 0.5111 0.074 Uiso 1 calc R . . H5B H 0.9517 0.8601 0.5019 0.074 Uiso 1 calc R . . O6 O 0.5826(6) 0.7500 0.5879(5) 0.0473(13) Uani 1 d SDU . . C6 C 0.7391(10) 0.7500 0.5194(7) 0.0454(18) Uani 1 d S . . H6A H 0.7047 0.7500 0.4310 0.054 Uiso 1 calc SR . . C13 C 0.2774(11) 0.7500 0.9364(9) 0.065(3) Uani 1 d S . . H13A H 0.1527 0.7500 0.9527 0.078 Uiso 1 calc SR . . H13B H 0.3403 0.7500 1.0161 0.078 Uiso 1 calc SR . . C14 C 0.3212(7) 0.8657(6) 0.8684(6) 0.0570(16) Uani 1 d . . . H14A H 0.2542 0.9317 0.9024 0.068 Uiso 1 calc R . . H14B H 0.2870 0.8574 0.7812 0.068 Uiso 1 calc R . . B1 B 0.4126(12) 0.7500 0.5251(8) 0.047(2) Uani 1 d SDU . . F1 F 0.4187(8) 0.7500 0.3990(5) 0.065(2) Uani 0.900(14) d SPDU A 1 F2 F 0.3224(7) 0.8495(6) 0.5586(5) 0.147(5) Uani 0.900(14) d PDU A 1 F1' F 0.285(2) 0.7500 0.610(2) 0.022(11) Uiso 0.100(14) d SPDU A 2 F2' F 0.392(3) 0.8490(9) 0.4530(17) 0.13(3) Uiso 0.100(14) d PDU A 2 B2 B 0.8418(11) 0.7500 1.1390(9) 0.061(3) Uani 1 d SDU . . F3 F 0.6636(7) 0.7500 1.1409(6) 0.0817(18) Uani 1 d SDU . . F4 F 0.9316(12) 0.7500 1.2479(7) 0.109(4) Uani 0.777(14) d SPDU B 1 F5 F 0.8976(7) 0.8498(5) 1.0684(6) 0.097(3) Uani 0.777(14) d PDU B 1 F4' F 0.903(3) 0.7500 1.0273(18) 0.110(13) Uiso 0.223(14) d SPDU B 2 F5' F 0.890(2) 0.8510(8) 1.2097(17) 0.132(13) Uiso 0.223(14) d PDU B 2 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 Cu 0.0286(5) 0.0319(5) 0.0483(6) 0.000 -0.0010(4) 0.000 S1 0.0420(7) 0.0469(8) 0.0476(8) -0.0121(6) -0.0048(6) 0.0080(6) C2 0.052(3) 0.031(3) 0.074(4) -0.003(3) -0.010(3) 0.010(2) C3 0.058(4) 0.031(3) 0.085(4) -0.002(3) -0.007(3) -0.003(3) S4 0.0320(7) 0.0403(8) 0.0770(10) 0.0025(7) -0.0009(6) -0.0058(6) C5 0.059(4) 0.058(4) 0.068(4) 0.009(3) 0.017(3) -0.007(3) O6 0.032(3) 0.066(4) 0.044(3) 0.000 -0.001(2) 0.000 C6 0.042(4) 0.052(5) 0.043(4) 0.000 0.009(3) 0.000 C13 0.041(5) 0.103(8) 0.052(5) 0.000 0.016(4) 0.000 C14 0.035(3) 0.076(4) 0.060(4) -0.011(3) 0.000(3) 0.010(3) B1 0.042(5) 0.057(5) 0.042(4) 0.000 -0.005(4) 0.000 F1 0.070(4) 0.082(5) 0.041(3) 0.000 -0.012(3) 0.000 F2 0.126(5) 0.201(9) 0.110(5) -0.086(5) -0.061(4) 0.114(6) B2 0.052(5) 0.066(6) 0.063(6) 0.000 -0.016(5) 0.000 F3 0.054(3) 0.094(5) 0.098(5) 0.000 0.021(3) 0.000 F4 0.112(7) 0.144(10) 0.069(5) 0.000 -0.029(5) 0.000 F5 0.064(3) 0.093(5) 0.135(6) 0.050(4) 0.002(3) -0.006(3) _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 Cu S1 2.2677(15) 4_575 ? Cu S1 2.2677(15) . Yes Cu O6 2.311(5) . Yes Cu S4 2.3312(15) . Yes Cu S4 2.3312(15) 4_575 ? S1 C2 1.802(6) . Yes S1 C14 1.817(6) . Yes C2 C3 1.518(8) . Yes C3 S4 1.813(6) . Yes S4 C5 1.823(7) . Yes C5 C6 1.512(8) . Yes O6 C6 1.419(9) . Yes O6 B1 1.441(10) . Yes C6 C5 1.512(8) 4_575 ? C13 C14 1.520(8) . Yes C13 C14 1.520(8) 4_575 ? B1 F1' 1.350(15) . ? B1 F2' 1.351(11) 4_575 ? B1 F2' 1.351(11) . ? B1 F2 1.354(7) 4_575 ? B1 F2 1.354(7) . Yes B1 F1 1.360(9) . Yes B2 F4' 1.302(14) . ? B2 F4 1.340(10) . Yes B2 F3 1.357(10) . Yes B2 F5' 1.397(11) . ? B2 F5' 1.397(11) 4_575 ? B2 F5 1.414(7) 4_575 ? B2 F5 1.414(7) . Yes 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 S1 Cu S1 95.32(8) 4_575 . Yes S1 Cu O6 103.29(9) 4_575 . ? S1 Cu O6 103.29(9) . . Yes S1 Cu S4 170.92(6) 4_575 . Yes S1 Cu S4 88.58(6) . . Yes O6 Cu S4 83.71(10) . . Yes S1 Cu S4 88.58(6) 4_575 4_575 ? S1 Cu S4 170.92(6) . 4_575 ? O6 Cu S4 83.71(10) . 4_575 ? S4 Cu S4 86.43(8) . 4_575 Yes C2 S1 C14 102.3(3) . . Yes C2 S1 Cu 97.1(2) . . Yes C14 S1 Cu 107.3(2) . . Yes C3 C2 S1 107.9(4) . . Yes C2 C3 S4 113.3(4) . . Yes C3 S4 C5 105.2(3) . . Yes C3 S4 Cu 100.8(2) . . Yes C5 S4 Cu 96.7(2) . . Yes C6 C5 S4 114.8(5) . . Yes C6 O6 B1 120.8(6) . . Yes C6 O6 Cu 100.0(4) . . Yes B1 O6 Cu 139.2(4) . . Yes O6 C6 C5 110.0(4) . . Yes O6 C6 C5 110.0(4) . 4_575 ? C5 C6 C5 114.0(7) . 4_575 ? C14 C13 C14 115.2(7) . 4_575 ? C13 C14 S1 111.9(5) . . Yes F1' B1 F2' 108.2(10) . 4_575 ? F1' B1 F2' 108.2(10) . . ? F2' B1 F2' 108.7(14) 4_575 . ? F1' B1 F2 56.0(5) . 4_575 ? F2' B1 F2 55.9(10) 4_575 4_575 ? F2' B1 F2 139.8(12) . 4_575 ? F1' B1 F2 56.0(5) . . ? F2' B1 F2 139.8(12) 4_575 . ? F2' B1 F2 55.9(10) . . ? F2 B1 F2 109.2(9) 4_575 . Yes F1' B1 F1 135.9(13) . . ? F2' B1 F1 55.5(8) 4_575 . ? F2' B1 F1 55.5(8) . . ? F2 B1 F1 107.3(5) 4_575 . ? F2 B1 F1 107.3(5) . . Yes F1' B1 O6 109.8(11) . . ? F2' B1 O6 110.9(10) 4_575 . ? F2' B1 O6 110.9(10) . . ? F2 B1 O6 109.3(5) 4_575 . ? F2 B1 O6 109.3(5) . . Yes F1 B1 O6 114.3(7) . . Yes F4' B2 F4 128.3(14) . . ? F4' B2 F3 113.6(12) . . ? F4 B2 F3 118.1(9) . . ? F4' B2 F5' 114.0(8) . . ? F4 B2 F5' 53.4(6) . . ? F3 B2 F5' 103.8(8) . . ? F4' B2 F5' 114.0(8) . 4_575 ? F4 B2 F5' 53.4(6) . 4_575 ? F3 B2 F5' 103.8(8) . 4_575 ? F5' B2 F5' 106.6(12) . 4_575 ? F4' B2 F5 51.9(4) . 4_575 ? F4 B2 F5 108.5(5) . 4_575 ? F3 B2 F5 108.9(5) . 4_575 ? F5' B2 F5 147.3(10) . 4_575 ? F5' B2 F5 65.6(8) 4_575 4_575 ? F4' B2 F5 51.9(4) . . ? F4 B2 F5 108.5(5) . . ? F3 B2 F5 108.9(5) . . ? F5' B2 F5 65.6(8) . . ? F5' B2 F5 147.3(10) 4_575 . ? F5 B2 F5 102.9(8) 4_575 . ? 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 S1 Cu S1 C2 -152.57(19) 4_575 . . . ? O6 Cu S1 C2 -47.5(2) . . . . ? S4 Cu S1 C2 35.7(2) . . . . ? S4 Cu S1 C2 92.3(4) 4_575 . . . ? S1 Cu S1 C14 -47.2(2) 4_575 . . . ? O6 Cu S1 C14 57.8(3) . . . . ? S4 Cu S1 C14 141.0(2) . . . . ? S4 Cu S1 C14 -162.4(4) 4_575 . . . ? C14 S1 C2 C3 -168.5(4) . . . . Yes Cu S1 C2 C3 -59.0(4) . . . . ? S1 C2 C3 S4 56.0(6) . . . . Yes C2 C3 S4 C5 78.0(5) . . . . Yes C2 C3 S4 Cu -22.1(5) . . . . ? S1 Cu S4 C3 -127.3(4) 4_575 . . . ? S1 Cu S4 C3 -11.7(2) . . . . ? O6 Cu S4 C3 91.8(2) . . . . ? S4 Cu S4 C3 175.9(2) 4_575 . . . ? S1 Cu S4 C5 125.8(4) 4_575 . . . ? S1 Cu S4 C5 -118.6(2) . . . . ? O6 Cu S4 C5 -15.1(2) . . . . ? S4 Cu S4 C5 69.0(2) 4_575 . . . ? C3 S4 C5 C6 -115.7(5) . . . . Yes Cu S4 C5 C6 -12.5(5) . . . . ? S1 Cu O6 C6 -130.58(5) 4_575 . . . ? S1 Cu O6 C6 130.58(5) . . . . ? S4 Cu O6 C6 43.54(4) . . . . ? S4 Cu O6 C6 -43.54(4) 4_575 . . . ? S1 Cu O6 B1 49.42(5) 4_575 . . . ? S1 Cu O6 B1 -49.42(5) . . . . ? S4 Cu O6 B1 -136.46(4) . . . . ? S4 Cu O6 B1 136.46(4) 4_575 . . . ? B1 O6 C6 C5 116.8(5) . . . . Yes Cu O6 C6 C5 -63.2(5) . . . . ? B1 O6 C6 C5 -116.8(5) . . . 4_575 Yes Cu O6 C6 C5 63.2(5) . . . 4_575 ? S4 C5 C6 O6 54.6(7) . . . . Yes S4 C5 C6 C5 -69.6(8) . . . 4_575 Yes C14 C13 C14 S1 -78.6(8) 4_575 . . . Yes C2 S1 C14 C13 164.6(5) . . . . Yes Cu S1 C14 C13 63.0(5) . . . . ? C6 O6 B1 F1' 180.000(4) . . . . ? Cu O6 B1 F1' 0.000(5) . . . . ? C6 O6 B1 F2' 60.4(9) . . . 4_575 ? Cu O6 B1 F2' -119.6(9) . . . 4_575 ? C6 O6 B1 F2' -60.4(9) . . . . ? Cu O6 B1 F2' 119.6(9) . . . . ? C6 O6 B1 F2 120.3(5) . . . 4_575 Yes Cu O6 B1 F2 -59.7(5) . . . 4_575 Yes C6 O6 B1 F2 -120.3(5) . . . . Yes Cu O6 B1 F2 59.7(5) . . . . Yes C6 O6 B1 F1 0.000(2) . . . . Yes Cu O6 B1 F1 180.000(2) . . . . Yes _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.01 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.813 _refine_diff_density_min -0.647 _refine_diff_density_rms 0.085