Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2001 data_for_compound_2+ _database_code_CSD 161685 _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name 'Alfonso, Montserrat' 'Berke, H.' 'Blacque, Olivier' 'Fernandez, Francisco J.' _publ_contact_author_name 'Prof H Berke' _publ_contact_author_address ; Prof H Berke Institute of Inorganic Chemistry University of Zurich Winterthurerstrasse 190 Zurich CH 8057 SWITZERLAND ; _publ_contact_author_email 'HBERKE@ACI.UNIZH.CH' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Trans,trans-bis(bis-(1,2-bisdimethylphosphinoethane)acetylide- manganese)-mu-1,3-butadiyne hexafluorophosphate ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C32 H66 F6 Mn2 P9' _chemical_formula_weight 953.46 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' 'Mn' 'Mn' 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 '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' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M 'I -4 c 2' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, z+1/2' '-x, -y, z' 'x, -y, z+1/2' 'y, x, -z+1/2' '-y, x, -z' 'y, -x, -z' '-y, -x, -z+1/2' 'x+1/2, y+1/2, z+1/2' '-x+1/2, y+1/2, z+1' '-x+1/2, -y+1/2, z+1/2' 'x+1/2, -y+1/2, z+1' 'y+1/2, x+1/2, -z+1' '-y+1/2, x+1/2, -z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-y+1/2, -x+1/2, -z+1' _cell_length_a 16.1403(9) _cell_length_b 16.1403(9) _cell_length_c 18.1409(14) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4725.9(5) _cell_formula_units_Z 4 _cell_measurement_temperature 183(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 1.90 _cell_measurement_theta_max 26.15 _exptl_crystal_description block _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas none _exptl_crystal_density_diffrn 1.340 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1988 _exptl_absorpt_coefficient_mu 0.884 _exptl_absorpt_correction_type numerical _exptl_absorpt_process_details 'Coppens et al. 1965' _exptl_absorpt_correction_T_min 0.7773 _exptl_absorpt_correction_T_max 0.8788 _exptl_special_details ; see text ; _diffrn_ambient_temperature 183(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 IPDS diffractometer' _diffrn_measurement_method '\f rotation scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number '50 to 200' _diffrn_standards_interval_count ' image' _diffrn_standards_interval_time 3.7 _diffrn_standards_decay_% 0 _diffrn_reflns_number 22664 _diffrn_reflns_unique 2924 _diffrn_reflns_av_R_equivalents 0.0905 _diffrn_reflns_av_sigmaI/netI 0.0553 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.52 _diffrn_reflns_theta_max 27.95 _reflns_number_total 1539 _reflns_number_gt 972 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Stoe IPDS software' _computing_cell_refinement 'Stoe IPDS software' _computing_data_reduction 'XRED (Stoe & Cie, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'PLATON97 (Spek, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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 'w=1/[\s^2^(Fo^2^)+(0.0714P)^2^+0.1172P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.40(10) _refine_ls_number_reflns 1539 _refine_ls_number_parameters 116 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0529 _refine_ls_R_factor_gt 0.0303 _refine_ls_wR_factor_ref 0.0777 _refine_ls_wR_factor_gt 0.0732 _refine_ls_goodness_of_fit_ref 0.807 _refine_ls_restrained_S_all 0.807 _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 Mn1 Mn 0.66459(3) 0.16459(3) 0.0000 0.02141(17) Uani 1 d S . . P1 P 0.7437(2) 0.0954(2) -0.0848(2) 0.0326(9) Uani 1 d . . . P2 P 0.7427(2) 0.0950(2) 0.0840(2) 0.0330(9) Uani 1 d . . . P3 P 1.0000 0.0000 -0.2500 0.0336(4) Uani 1 d S . . C1 C 0.58494(19) 0.08494(19) 0.0000 0.0272(10) Uani 1 d S . . C2 C 0.52863(19) 0.02863(19) 0.0000 0.0301(11) Uani 1 d S . . C3 C 0.7533(2) 0.2533(2) 0.0000 0.0300(10) Uani 1 d S . . C4 C 0.80545(18) 0.30545(18) 0.0000 0.0438(14) Uani 1 d S . . H4A H 0.8471 0.3471 0.0000 0.053 Uiso 1 calc SR . . C5 C 0.83400(18) 0.05215(18) -0.0355 0.0501(15) Uani 1 d R . . H5B H 0.8605 0.0087 -0.0660 0.060 Uiso 1 calc R . . H5A H 0.8752 0.0964 -0.0265 0.060 Uiso 1 calc R . . C6 C 0.8065(4) 0.0159(3) 0.0362(3) 0.0534(17) Uani 1 d . . . H6B H 0.8552 0.0011 0.0667 0.064 Uiso 1 calc R . . H6A H 0.7735 -0.0349 0.0276 0.064 Uiso 1 calc R . . C7 C 0.6951(10) 0.0148(9) -0.1381(8) 0.075(4) Uani 1 d . . . H7C H 0.7355 -0.0089 -0.1724 0.090 Uiso 1 calc R . . H7B H 0.6485 0.0381 -0.1659 0.090 Uiso 1 calc R . . H7A H 0.6747 -0.0286 -0.1050 0.090 Uiso 1 calc R . . C8 C 0.8043(10) 0.1484(10) -0.1522(8) 0.078(6) Uani 1 d . . . H8C H 0.8512 0.1135 -0.1668 0.094 Uiso 1 calc R . . H8B H 0.8250 0.2004 -0.1313 0.094 Uiso 1 calc R . . H8A H 0.7700 0.1603 -0.1955 0.094 Uiso 1 calc R . . C9 C 0.6934(10) 0.0195(11) 0.1461(9) 0.092(6) Uani 1 d . . . H9C H 0.7356 -0.0183 0.1656 0.111 Uiso 1 calc R . . H9B H 0.6518 -0.0122 0.1188 0.111 Uiso 1 calc R . . H9A H 0.6667 0.0488 0.1870 0.111 Uiso 1 calc R . . C10 C 0.8071(9) 0.1532(11) 0.1500(8) 0.075(5) Uani 1 d . . . H10C H 0.8343 0.1145 0.1838 0.090 Uiso 1 calc R . . H10B H 0.7720 0.1914 0.1782 0.090 Uiso 1 calc R . . H10A H 0.8492 0.1849 0.1231 0.090 Uiso 1 calc R . . F1 F 0.90128(13) -0.0003(8) -0.2507(6) 0.0592(7) Uani 1 d . . . F2 F 1.0000 0.0000 -0.16279(18) 0.0718(13) Uani 1 d S . . 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 Mn1 0.0206(2) 0.0206(2) 0.0231(3) 0.0011(10) -0.0011(10) -0.0018(3) P1 0.0337(19) 0.0299(19) 0.034(2) -0.0079(13) 0.0076(15) 0.0047(14) P2 0.038(2) 0.0308(19) 0.030(2) -0.0027(13) -0.0072(15) 0.0044(15) P3 0.0281(5) 0.0281(5) 0.0447(10) 0.000 0.000 -0.003(5) C1 0.0294(14) 0.0294(14) 0.023(2) 0.004(7) -0.004(7) -0.0030(19) C2 0.0329(16) 0.0329(16) 0.024(2) -0.008(6) 0.008(6) -0.0049(19) C3 0.0237(13) 0.0237(13) 0.043(2) -0.001(8) 0.001(8) 0.0029(18) C4 0.0280(15) 0.0280(15) 0.076(4) 0.003(9) -0.003(9) -0.003(2) C5 0.039(3) 0.053(4) 0.058(3) -0.009(3) 0.009(3) 0.020(3) C6 0.057(4) 0.036(3) 0.067(4) -0.002(3) -0.013(3) 0.016(3) C7 0.100(11) 0.052(7) 0.074(7) -0.036(6) 0.036(7) -0.006(6) C8 0.107(13) 0.040(7) 0.086(11) -0.005(7) 0.059(10) 0.008(7) C9 0.075(10) 0.111(12) 0.091(8) 0.079(8) -0.027(7) -0.032(8) C10 0.077(10) 0.072(10) 0.077(10) 0.009(8) -0.063(9) -0.010(8) F1 0.0294(11) 0.0488(13) 0.0994(18) -0.0206(14) -0.004(5) 0.006(6) F2 0.054(6) 0.118(8) 0.0433(18) 0.000 0.000 0.003(10) _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 Mn1 C1 1.818(4) . ? Mn1 C3 2.026(5) . ? Mn1 P2 2.275(3) 13_544 ? Mn1 P2 2.275(3) . ? Mn1 P1 2.290(3) . ? Mn1 P1 2.290(3) 13_544 ? P1 C8 1.783(14) . ? P1 C7 1.800(13) . ? P1 C5 1.848(4) . ? P2 C9 1.840(13) . ? P2 C10 1.842(13) . ? P2 C6 1.856(7) . ? P3 F2 1.582(3) 5_644 ? P3 F2 1.582(3) . ? P3 F1 1.593(2) . ? P3 F1 1.593(2) 8_664 ? P3 F1 1.593(2) 3_755 ? P3 F1 1.593(2) 5_644 ? C1 C2 1.285(6) . ? C2 C2 1.307(9) 3_655 ? C3 C4 1.189(6) . ? C5 C6 1.495(6) . ? 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 C1 Mn1 C3 180.0(2) . . ? C1 Mn1 P2 92.46(9) . 13_544 ? C3 Mn1 P2 87.54(9) . 13_544 ? C1 Mn1 P2 92.46(9) . . ? C3 Mn1 P2 87.54(9) . . ? P2 Mn1 P2 175.07(18) 13_544 . ? C1 Mn1 P1 92.82(8) . . ? C3 Mn1 P1 87.18(8) . . ? P2 Mn1 P1 95.44(3) 13_544 . ? P2 Mn1 P1 84.32(3) . . ? C1 Mn1 P1 92.82(8) . 13_544 ? C3 Mn1 P1 87.18(8) . 13_544 ? P2 Mn1 P1 84.32(3) 13_544 13_544 ? P2 Mn1 P1 95.44(3) . 13_544 ? P1 Mn1 P1 174.35(17) . 13_544 ? C8 P1 C7 102.6(7) . . ? C8 P1 C5 94.6(6) . . ? C7 P1 C5 109.3(6) . . ? C8 P1 Mn1 122.2(5) . . ? C7 P1 Mn1 118.1(5) . . ? C5 P1 Mn1 107.38(16) . . ? C9 P2 C10 100.6(8) . . ? C9 P2 C6 94.0(7) . . ? C10 P2 C6 110.0(6) . . ? C9 P2 Mn1 119.8(5) . . ? C10 P2 Mn1 119.8(5) . . ? C6 P2 Mn1 109.5(2) . . ? F2 P3 F2 180.0 5_644 . ? F2 P3 F1 89.5(4) 5_644 . ? F2 P3 F1 90.5(4) . . ? F2 P3 F1 90.5(4) 5_644 8_664 ? F2 P3 F1 89.5(4) . 8_664 ? F1 P3 F1 90.4(10) . 8_664 ? F2 P3 F1 89.5(4) 5_644 3_755 ? F2 P3 F1 90.5(4) . 3_755 ? F1 P3 F1 179.1(8) . 3_755 ? F1 P3 F1 89.6(10) 8_664 3_755 ? F2 P3 F1 90.5(4) 5_644 5_644 ? F2 P3 F1 89.5(4) . 5_644 ? F1 P3 F1 89.6(10) . 5_644 ? F1 P3 F1 179.1(8) 8_664 5_644 ? F1 P3 F1 90.4(10) 3_755 5_644 ? C2 C1 Mn1 180.0(4) . . ? C1 C2 C2 180.0(3) . 3_655 ? C4 C3 Mn1 180.0(4) . . ? C6 C5 P1 109.6(3) . . ? C5 C6 P2 107.6(3) . . ? 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 C1 Mn1 P1 C8 146.0(7) . . . . ? C3 Mn1 P1 C8 -34.0(7) . . . . ? P2 Mn1 P1 C8 53.2(7) 13_544 . . . ? P2 Mn1 P1 C8 -121.8(7) . . . . ? P1 Mn1 P1 C8 -34.0(7) 13_544 . . . ? C1 Mn1 P1 C7 17.2(7) . . . . ? C3 Mn1 P1 C7 -162.8(7) . . . . ? P2 Mn1 P1 C7 -75.6(7) 13_544 . . . ? P2 Mn1 P1 C7 109.4(7) . . . . ? P1 Mn1 P1 C7 -162.8(7) 13_544 . . . ? C1 Mn1 P1 C5 -106.84(18) . . . . ? C3 Mn1 P1 C5 73.16(18) . . . . ? P2 Mn1 P1 C5 160.4(2) 13_544 . . . ? P2 Mn1 P1 C5 -14.64(14) . . . . ? P1 Mn1 P1 C5 73.16(18) 13_544 . . . ? C1 Mn1 P2 C9 -23.4(8) . . . . ? C3 Mn1 P2 C9 156.6(8) . . . . ? P2 Mn1 P2 C9 156.6(8) 13_544 . . . ? P1 Mn1 P2 C9 -116.0(8) . . . . ? P1 Mn1 P2 C9 69.7(8) 13_544 . . . ? C1 Mn1 P2 C10 -148.3(6) . . . . ? C3 Mn1 P2 C10 31.7(6) . . . . ? P2 Mn1 P2 C10 31.7(6) 13_544 . . . ? P1 Mn1 P2 C10 119.1(7) . . . . ? P1 Mn1 P2 C10 -55.2(6) 13_544 . . . ? C1 Mn1 P2 C6 83.4(2) . . . . ? C3 Mn1 P2 C6 -96.6(2) . . . . ? P2 Mn1 P2 C6 -96.6(2) 13_544 . . . ? P1 Mn1 P2 C6 -9.2(2) . . . . ? P1 Mn1 P2 C6 176.4(3) 13_544 . . . ? C3 Mn1 C1 C2 0(100) . . . . ? P2 Mn1 C1 C2 -42(100) 13_544 . . . ? P2 Mn1 C1 C2 138(100) . . . . ? P1 Mn1 C1 C2 -138(100) . . . . ? P1 Mn1 C1 C2 42(100) 13_544 . . . ? Mn1 C1 C2 C2 0(100) . . . 3_655 ? C1 Mn1 C3 C4 0(100) . . . . ? P2 Mn1 C3 C4 42(100) 13_544 . . . ? P2 Mn1 C3 C4 -138(100) . . . . ? P1 Mn1 C3 C4 138(100) . . . . ? P1 Mn1 C3 C4 -42(100) 13_544 . . . ? C8 P1 C5 C6 168.5(6) . . . . ? C7 P1 C5 C6 -86.4(6) . . . . ? Mn1 P1 C5 C6 42.8(3) . . . . ? P1 C5 C6 P2 -50.3(4) . . . . ? C9 P2 C6 C5 161.1(6) . . . . ? C10 P2 C6 C5 -96.1(6) . . . . ? Mn1 P2 C6 C5 37.4(4) . . . . ? _diffrn_measured_fraction_theta_max 0.499 _diffrn_reflns_theta_full 27.95 _diffrn_measured_fraction_theta_full 0.499 _refine_diff_density_max 0.385 _refine_diff_density_min -0.251 _refine_diff_density_rms 0.070