Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 186 loop_ _publ_author_name 'Raymond Roulet' 'Katya Besancon' 'Serena Detti' 'Gabor Laurenczy' 'Tito Lumini' 'Kurt Schenk' _publ_contact_author_name 'Prof Raymond Roulet' _publ_contact_author_address ; EPFL Institute de chimie moleculaire et biologique ICMB-CH U Lausanne 1015 SWITZERLAND ; _publ_contact_author_email RAYMOND.ROULET@EPFL.CH _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Crystal Structure and Fluxional Behaviour in Solution of [Rh4(CO)6(m-Me2PCH2PMe2)3] ; data_Tito_7 _database_code_CSD 197240 #------------------------------------------------------------------------------ _audit_creation_date 'Friday, 11th October 2002' _audit_creation_method SHELXL-97 #------------------------------------------------------------------------------ _computing_data_collection 'ENRAF-NONIUS CAD4' _computing_cell_refinement 'ENRAF-NONIUS CAD4' _computing_data_reduction X-Ray-72 _computing_structure_solution 'DirDif 96' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'BRUKER SHELXTL' _computing_publication_material 'BRUKER SHELXTL' #------------------------------------------------------------------------------ _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C21 H40 O6 P6 Rh4 . CH2Cl2' _chemical_formula_sum 'C22 H42 Cl2 O6 P6 Rh4' _chemical_formula_weight 1070.92 #------------------------------------------------------------------------------ loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0015 0.0009 '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' O O 0.0056 0.0036 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.0667 0.0580 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Rh Rh -2.5280 0.5964 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.0998 0.0984 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #------------------------------------------------------------------------------ _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M Pnma loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z' '-x-1/2, y-1/2, z-1/2' _cell_length_a 17.340(4) _cell_length_b 17.788(4) _cell_length_c 12.037(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3712.7(13) _cell_formula_units_Z 4 _cell_measurement_temperature 130(1) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 7.5 _cell_measurement_theta_max 19.0 #------------------------------------------------------------------------------ _exptl_crystal_description irregular-globular _exptl_crystal_colour 'dark red brown' _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.916 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2104 _exptl_absorpt_coefficient_mu 1.144 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; #------------------------------------------------------------------------------ _diffrn_ambient_temperature 130(1) _diffrn_radiation_wavelength 0.56086 _diffrn_radiation_type AgK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type diffractometer _diffrn_measurement_method '\w : 2\q scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 180s _diffrn_standards_decay_% none _diffrn_reflns_number 16348 _diffrn_reflns_av_R_equivalents 0.0237 _diffrn_reflns_av_sigmaI/netI 0.0240 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.61 _diffrn_reflns_theta_max 26.97 _reflns_number_total 8415 _reflns_number_gt 6931 _reflns_threshold_expression >2sigma(I) _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 sigma _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00064(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 8415 _refine_ls_number_parameters 201 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0349 _refine_ls_R_factor_gt 0.0212 _refine_ls_wR_factor_ref 0.0471 _refine_ls_wR_factor_gt 0.0461 _refine_ls_goodness_of_fit_ref 2.089 _refine_ls_restrained_S_all 2.089 _refine_ls_shift/su_max 0.002 _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 Rh1 Rh 0.310577(7) 0.2500 0.562774(12) 0.01131(3) Uani 1 2 d S . . Rh2 Rh 0.184213(5) 0.323516(5) 0.476494(8) 0.01096(2) Uani 1 1 d . . . Rh3 Rh 0.273221(8) 0.2500 0.329098(12) 0.01334(3) Uani 1 2 d S . . P1 P 0.362581(19) 0.36581(2) 0.60704(3) 0.01996(7) Uani 1 1 d . . . P2 P 0.197671(18) 0.430236(19) 0.57930(3) 0.01730(6) Uani 1 1 d . . . P3 P 0.069477(18) 0.337303(19) 0.39324(3) 0.01567(6) Uani 1 1 d . . . O1 O 0.24095(10) 0.2500 0.79221(14) 0.0425(5) Uani 1 2 d S . . O2 O 0.43701(8) 0.2500 0.38795(13) 0.0333(4) Uani 1 2 d S . . O3 O 0.32837(10) 0.2500 0.09134(14) 0.0410(4) Uani 1 2 d S . . O4 O 0.25741(6) 0.41952(6) 0.29385(10) 0.0306(2) Uani 1 1 d . . . O5 O 0.08731(8) 0.2500 0.66109(11) 0.0215(3) Uani 1 2 d S . . C1 C 0.26149(11) 0.2500 0.70191(17) 0.0237(4) Uani 1 2 d S . . C2 C 0.37111(10) 0.2500 0.41400(15) 0.0186(3) Uani 1 2 d S . . C3 C 0.30858(10) 0.2500 0.18198(17) 0.0211(4) Uani 1 2 d S . . C4 C 0.24674(7) 0.36371(7) 0.34328(11) 0.0183(2) Uani 1 1 d . . . C5 C 0.13108(10) 0.2500 0.58557(14) 0.0149(3) Uani 1 2 d S . . C7 C 0.28720(8) 0.42807(8) 0.66287(14) 0.0275(3) Uani 1 1 d . . . H7A H 0.3075 0.4782 0.6680 0.0526(14) Uiso 1 1 d R . . H7B H 0.2746 0.4118 0.7367 0.0526(14) Uiso 1 1 d R . . C8 C 0.04145(11) 0.2500 0.32244(16) 0.0203(3) Uani 1 2 d S . . H8A H 0.0641 0.2500 0.2497 0.0526(14) Uiso 1 2 d SR . . H8B H -0.0136 0.2500 0.3133 0.0526(14) Uiso 1 2 d SR . . C11 C 0.43242(9) 0.36983(10) 0.72103(17) 0.0407(5) Uani 1 1 d . . . H11A H 0.4496 0.4207 0.7311 0.0526(14) Uiso 1 1 d R . . H11B H 0.4083 0.3524 0.7881 0.0526(14) Uiso 1 1 d R . . H11C H 0.4758 0.3384 0.7040 0.0526(14) Uiso 1 1 d R . . C12 C 0.40948(9) 0.42303(9) 0.50150(17) 0.0358(4) Uani 1 1 d . . . H12A H 0.4275 0.4690 0.5343 0.0526(14) Uiso 1 1 d R . . H12B H 0.4524 0.3959 0.4709 0.0526(14) Uiso 1 1 d R . . H12C H 0.3733 0.4344 0.4436 0.0526(14) Uiso 1 1 d R . . C21 C 0.12594(8) 0.45019(9) 0.68610(14) 0.0288(3) Uani 1 1 d . . . H21A H 0.1387 0.4965 0.7226 0.0526(14) Uiso 1 1 d R . . H21B H 0.0759 0.4544 0.6525 0.0526(14) Uiso 1 1 d R . . H21C H 0.1255 0.4101 0.7395 0.0526(14) Uiso 1 1 d R . . C22 C 0.20497(9) 0.52092(8) 0.50921(16) 0.0308(3) Uani 1 1 d . . . H22A H 0.2103 0.5600 0.5637 0.0526(14) Uiso 1 1 d R . . H22B H 0.2492 0.5210 0.4612 0.0526(14) Uiso 1 1 d R . . H22C H 0.1593 0.5296 0.4660 0.0526(14) Uiso 1 1 d R . . C31 C 0.05990(10) 0.40533(10) 0.28150(15) 0.0337(4) Uani 1 1 d . . . H31A H 0.0079 0.4049 0.2542 0.0526(14) Uiso 1 1 d R . . H31B H 0.0722 0.4546 0.3089 0.0526(14) Uiso 1 1 d R . . H31C H 0.0946 0.3924 0.2223 0.0526(14) Uiso 1 1 d R . . C32 C -0.01417(8) 0.36028(10) 0.47825(15) 0.0315(3) Uani 1 1 d . . . H32A H -0.0590 0.3645 0.4318 0.0526(14) Uiso 1 1 d R . . H32B H -0.0221 0.3212 0.5321 0.0526(14) Uiso 1 1 d R . . H32C H -0.0055 0.4071 0.5158 0.0526(14) Uiso 1 1 d R . . C40 C 0.08788(13) 0.2500 0.9455(2) 0.0341(5) Uani 1 2 d S . . Cl Cl 0.13190(4) 0.33192(4) 0.99693(6) 0.06778(18) Uani 1 1 d . . . #------------------------------------------------------------------------------ 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 Rh1 0.01018(5) 0.01207(6) 0.01168(6) 0.000 -0.00045(4) 0.000 Rh2 0.01017(4) 0.00948(4) 0.01322(4) -0.00018(3) -0.00029(3) 0.00060(3) Rh3 0.01283(6) 0.01547(6) 0.01170(6) 0.000 0.00191(5) 0.000 P1 0.01381(14) 0.01623(15) 0.02984(18) -0.00700(14) -0.00492(12) -0.00020(11) P2 0.01352(13) 0.01274(13) 0.02565(17) -0.00528(13) -0.00055(12) 0.00071(10) P3 0.01343(13) 0.01532(14) 0.01826(15) 0.00128(12) -0.00267(11) 0.00235(10) O1 0.0340(9) 0.0758(14) 0.0178(7) 0.000 0.0058(7) 0.000 O2 0.0156(6) 0.0628(12) 0.0215(7) 0.000 0.0042(5) 0.000 O3 0.0307(8) 0.0740(14) 0.0182(7) 0.000 0.0068(6) 0.000 O4 0.0327(5) 0.0216(5) 0.0373(6) 0.0135(5) 0.0122(5) 0.0031(4) O5 0.0197(6) 0.0268(7) 0.0179(6) 0.000 0.0062(5) 0.000 C1 0.0190(8) 0.0354(11) 0.0166(8) 0.000 0.0018(7) 0.000 C2 0.0170(7) 0.0234(9) 0.0153(7) 0.000 0.0010(6) 0.000 C3 0.0153(8) 0.0285(10) 0.0196(9) 0.000 0.0008(6) 0.000 C4 0.0159(5) 0.0176(5) 0.0214(6) 0.0036(5) 0.0021(4) 0.0002(4) C5 0.0155(7) 0.0156(7) 0.0136(7) 0.000 0.0001(6) 0.000 C7 0.0209(6) 0.0226(6) 0.0390(8) -0.0169(6) -0.0090(6) 0.0041(5) C8 0.0198(8) 0.0215(8) 0.0195(8) 0.000 -0.0049(7) 0.000 C11 0.0282(8) 0.0380(9) 0.0559(11) -0.0223(9) -0.0230(8) 0.0074(6) C12 0.0227(7) 0.0231(7) 0.0616(12) 0.0068(8) 0.0026(7) -0.0071(6) C21 0.0227(6) 0.0294(7) 0.0343(8) -0.0162(6) 0.0049(6) -0.0007(5) C22 0.0315(7) 0.0132(6) 0.0478(10) -0.0015(6) 0.0013(7) 0.0003(5) C31 0.0339(8) 0.0279(7) 0.0392(9) 0.0132(7) -0.0119(7) 0.0015(6) C32 0.0176(6) 0.0394(9) 0.0374(9) -0.0094(7) 0.0000(6) 0.0066(6) C40 0.0296(11) 0.0428(14) 0.0298(11) 0.000 0.0047(9) 0.000 Cl 0.0557(3) 0.0702(4) 0.0774(4) -0.0369(4) 0.0083(3) -0.0079(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 Rh1 C1 1.879(2) . ? Rh1 C2 2.0758(18) . ? Rh1 P1 2.3110(5) 7_565 ? Rh1 P1 2.3110(5) . ? Rh1 Rh2 2.7550(4) 7_565 ? Rh1 Rh2 2.7550(4) . ? Rh1 Rh3 2.8864(6) . ? Rh2 C4 2.0634(13) . ? Rh2 C5 2.0695(14) . ? Rh2 P3 2.2411(5) . ? Rh2 P2 2.2780(5) . ? Rh2 Rh2 2.6154(6) 7_565 ? Rh2 Rh3 2.6907(4) . ? Rh3 C3 1.874(2) . ? Rh3 C2 1.9813(18) . ? Rh3 C4 2.0811(14) 7_565 ? Rh3 C4 2.0812(14) . ? Rh3 Rh2 2.6907(4) 7_565 ? P1 C12 1.8197(18) . ? P1 C11 1.8314(16) . ? P1 C7 1.8403(14) . ? P2 C21 1.8237(15) . ? P2 C22 1.8248(17) . ? P2 C7 1.8502(15) . ? P3 C31 1.8168(16) . ? P3 C32 1.8215(15) . ? P3 C8 1.8369(11) . ? O1 C1 1.144(3) . ? O2 C2 1.185(2) . ? O3 C3 1.144(3) . ? O4 C4 1.1722(16) . ? O5 C5 1.184(2) . ? C5 Rh2 2.0695(14) 7_565 ? C8 P3 1.8369(11) 7_565 ? C40 Cl 1.7577(15) . ? C40 Cl 1.7577(15) 7_565 ? 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 Rh1 C2 176.57(8) . . ? C1 Rh1 P1 88.35(3) . 7_565 ? C2 Rh1 P1 90.09(3) . 7_565 ? C1 Rh1 P1 88.35(3) . . ? C2 Rh1 P1 90.09(3) . . ? P1 Rh1 P1 126.10(2) 7_565 . ? C1 Rh1 Rh2 88.61(5) . 7_565 ? C2 Rh1 Rh2 94.42(5) . 7_565 ? P1 Rh1 Rh2 88.518(15) 7_565 7_565 ? P1 Rh1 Rh2 145.123(9) . 7_565 ? C1 Rh1 Rh2 88.61(5) . . ? C2 Rh1 Rh2 94.41(5) . . ? P1 Rh1 Rh2 145.123(9) 7_565 . ? P1 Rh1 Rh2 88.519(15) . . ? Rh2 Rh1 Rh2 56.676(13) 7_565 . ? C1 Rh1 Rh3 140.09(6) . . ? C2 Rh1 Rh3 43.35(5) . . ? P1 Rh1 Rh3 108.196(11) 7_565 . ? P1 Rh1 Rh3 108.196(11) . . ? Rh2 Rh1 Rh3 56.918(5) 7_565 . ? Rh2 Rh1 Rh3 56.917(4) . . ? C4 Rh2 C5 161.06(5) . . ? C4 Rh2 P3 94.65(4) . . ? C5 Rh2 P3 87.57(5) . . ? C4 Rh2 P2 94.56(4) . . ? C5 Rh2 P2 103.15(4) . . ? P3 Rh2 P2 104.043(14) . . ? C4 Rh2 Rh2 110.27(4) . 7_565 ? C5 Rh2 Rh2 50.81(3) . 7_565 ? P3 Rh2 Rh2 96.283(9) . 7_565 ? P2 Rh2 Rh2 146.442(13) . 7_565 ? C4 Rh2 Rh3 49.81(4) . . ? C5 Rh2 Rh3 111.51(3) . . ? P3 Rh2 Rh3 105.518(16) . . ? P2 Rh2 Rh3 134.782(12) . . ? Rh2 Rh2 Rh3 60.922(6) 7_565 . ? C4 Rh2 Rh1 92.26(4) . . ? C5 Rh2 Rh1 79.34(4) . . ? P3 Rh2 Rh1 157.906(11) . . ? P2 Rh2 Rh1 96.275(13) . . ? Rh2 Rh2 Rh1 61.662(7) 7_565 . ? Rh3 Rh2 Rh1 64.002(13) . . ? C3 Rh3 C2 101.95(8) . . ? C3 Rh3 C4 98.61(4) . 7_565 ? C2 Rh3 C4 98.43(4) . 7_565 ? C3 Rh3 C4 98.61(4) . . ? C2 Rh3 C4 98.44(4) . . ? C4 Rh3 C4 152.77(7) 7_565 . ? C3 Rh3 Rh2 144.17(3) . . ? C2 Rh3 Rh2 98.70(5) . . ? C4 Rh3 Rh2 106.96(4) 7_565 . ? C4 Rh3 Rh2 49.23(4) . . ? C3 Rh3 Rh2 144.17(3) . 7_565 ? C2 Rh3 Rh2 98.70(5) . 7_565 ? C4 Rh3 Rh2 49.23(4) 7_565 7_565 ? C4 Rh3 Rh2 106.96(4) . 7_565 ? Rh2 Rh3 Rh2 58.157(13) . 7_565 ? C3 Rh3 Rh1 147.93(6) . . ? C2 Rh3 Rh1 45.98(5) . . ? C4 Rh3 Rh1 88.25(4) 7_565 . ? C4 Rh3 Rh1 88.26(4) . . ? Rh2 Rh3 Rh1 59.081(11) . . ? Rh2 Rh3 Rh1 59.080(11) 7_565 . ? C12 P1 C11 101.87(9) . . ? C12 P1 C7 103.64(8) . . ? C11 P1 C7 99.94(7) . . ? C12 P1 Rh1 120.80(6) . . ? C11 P1 Rh1 117.74(6) . . ? C7 P1 Rh1 110.09(5) . . ? C21 P2 C22 101.60(8) . . ? C21 P2 C7 101.13(8) . . ? C22 P2 C7 102.22(8) . . ? C21 P2 Rh2 118.38(5) . . ? C22 P2 Rh2 119.51(6) . . ? C7 P2 Rh2 111.34(4) . . ? C31 P3 C32 101.17(8) . . ? C31 P3 C8 101.27(8) . . ? C32 P3 C8 103.87(8) . . ? C31 P3 Rh2 119.02(5) . . ? C32 P3 Rh2 118.70(6) . . ? C8 P3 Rh2 110.48(5) . . ? O1 C1 Rh1 171.19(18) . . ? O2 C2 Rh3 133.61(15) . . ? O2 C2 Rh1 135.72(15) . . ? Rh3 C2 Rh1 90.67(7) . . ? O3 C3 Rh3 178.36(17) . . ? O4 C4 Rh2 140.43(11) . . ? O4 C4 Rh3 138.31(11) . . ? Rh2 C4 Rh3 80.96(5) . . ? O5 C5 Rh2 140.56(3) . . ? O5 C5 Rh2 140.56(3) . 7_565 ? Rh2 C5 Rh2 78.38(6) . 7_565 ? P1 C7 P2 114.21(8) . . ? P3 C8 P3 115.44(10) 7_565 . ? Cl C40 Cl 112.00(14) . 7_565 ? #------------------------------------------------------------------------------ _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.97 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.830 _refine_diff_density_min -0.893 _refine_diff_density_rms 0.107 #------------------------------------------------------------------------------