# Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry, 1999
# CCDC Number: 186/1555

# CIF for complex 7 only 
# Hard copy data for the other 3 structures is available from the CCDC
 
data_Cpd7 

_publ_requested_journal           'J Chem Soc, Dalton Transactions' 
 
_publ_contact_author              
;
Ang How Ghee
Department of Chemistry, National University of Singapore, Kent Ridge,
Singapore 119260
;

_publ_contact_author_email        chmanghg@nus.edu.sg

_publ_section_title
;
Reactions of trifluoromethyl phosphine and arsine with ruthenium 
carbonyl cluster: synthesis, characterization and the reactivity 
of cluster derivatives capped by trifluoromethyl phosphinidene and 
arsinidene moieties
;

_audit_creation_method            SHELXL 
_chemical_name_systematic 
; 
 ? 
; 
_chemical_name_common             ? 
_chemical_formula_moiety          ? 
_chemical_formula_structural      ? 
_chemical_formula_analytical      ? 
_chemical_formula_sum             'C14 H2 As F3 O13 Ru4' 
_chemical_formula_weight          914.36 
_chemical_melting_point           ? 
_chemical_compound_source         ? 
  
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' 
 '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' 
 'As'  'As'   0.0499   2.0058 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
 'Ru'  'Ru'  -1.2594   0.8363 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
  
_symmetry_cell_setting            Orthorhombic 
_symmetry_space_group_name_H-M    Pbca 
  
loop_ 
 _symmetry_equiv_pos_as_xyz 
 'x, y, z' 
 '-x+1/2, -y, z+1/2' 
 '-x, y+1/2, -z+1/2' 
 'x+1/2, -y+1/2, -z' 
 '-x, -y, -z' 
 'x-1/2, y, -z-1/2' 
 'x, -y-1/2, z-1/2' 
 '-x-1/2, y-1/2, z' 
  
_cell_length_a                    17.3431(2) 
_cell_length_b                    15.46710(10) 
_cell_length_c                    18.0049(2) 
_cell_angle_alpha                 90.00 
_cell_angle_beta                  90.00 
_cell_angle_gamma                 90.00 
_cell_volume                      4829.77(8) 
_cell_formula_units_Z             8 
_cell_measurement_temperature     293(2) 
_cell_measurement_reflns_used     ? 
_cell_measurement_theta_min       ? 
_cell_measurement_theta_max       ? 
  
_exptl_crystal_description        'Rectangular block' 
_exptl_crystal_colour             Orange 
_exptl_crystal_size_max           0.50 
_exptl_crystal_size_mid           0.40 
_exptl_crystal_size_min           0.40 
_exptl_crystal_density_meas       ? 
_exptl_crystal_density_diffrn     2.515 
_exptl_crystal_density_method     ? 
_exptl_crystal_F_000              3408 
_exptl_absorpt_coefficient_mu     3.896 
_exptl_absorpt_correction_type    SADABS 
_exptl_absorpt_correction_T_min   ? 
_exptl_absorpt_correction_T_max   ? 
  
_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        'Siemens P4' 
_diffrn_measurement_method        '\w scans' 
_diffrn_standards_number          ? 
_diffrn_standards_interval_count  ? 
_diffrn_standards_interval_time   ? 
_diffrn_standards_decay_%         ? 
_diffrn_reflns_number             29612 
_diffrn_reflns_av_R_equivalents   0.0286 
_diffrn_reflns_av_sigmaI/netI     0.0220 
_diffrn_reflns_limit_h_min        -16 
_diffrn_reflns_limit_h_max        23 
_diffrn_reflns_limit_k_min        -20 
_diffrn_reflns_limit_k_max        16 
_diffrn_reflns_limit_l_min        -24 
_diffrn_reflns_limit_l_max        22 
_diffrn_reflns_theta_min          2.10 
_diffrn_reflns_theta_max          29.49 
_reflns_number_total              6243 
_reflns_number_observed           5124 
_reflns_observed_criterion        >2sigma(I) 
  
_computing_data_collection        'Siemens XSCANS' 
_computing_cell_refinement        'Siemens XSCANS' 
_computing_data_reduction         'Siemens SHELXTL' 
_computing_structure_solution     'SHELXS-86 (Sheldrick, 1990)' 
_computing_structure_refinement   'SHELXL-93 (Sheldrick, 1993)' 
_computing_molecular_graphics     'Siemens SHELXTL' 
_computing_publication_material   'Siemens SHELXTL' 
  
_refine_special_details 
; 
 Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ 
 or flagged by the user for potential systematic errors.  Weighted R-factors 
 wR and all goodnesses 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 observed criterion 
 of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0094P)^2^+5.2140P] 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     ? 
_refine_ls_extinction_method      SHELXL 
_refine_ls_extinction_coef        0.00098(2) 
_refine_ls_extinction_expression 
 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' 
_refine_ls_number_reflns          6243 
_refine_ls_number_parameters      325 
_refine_ls_number_restraints      0 
_refine_ls_R_factor_all           0.0375 
_refine_ls_R_factor_obs           0.0252 
_refine_ls_wR_factor_all          0.0498 
_refine_ls_wR_factor_obs          0.0448 
_refine_ls_goodness_of_fit_all    1.130 
_refine_ls_goodness_of_fit_obs    1.130 
_refine_ls_restrained_S_all       1.130 
_refine_ls_restrained_S_obs       1.130 
_refine_ls_shift/esd_max          -0.001 
_refine_ls_shift/esd_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_thermal_displace_type 
 _atom_site_occupancy 
 _atom_site_calc_flag 
 _atom_site_refinement_flags 
 _atom_site_disorder_group 
Ru1 Ru 0.049213(14) 0.33620(2) 0.180632(13) 0.03986(7) Uani 1 d . . 
C11 C -0.0589(2) 0.3472(3) 0.1609(2) 0.0582(9) Uani 1 d . . 
O11 O -0.1233(2) 0.3541(2) 0.1524(2) 0.0906(10) Uani 1 d . . 
C12 C 0.0521(2) 0.4310(3) 0.2462(2) 0.0590(9) Uani 1 d . . 
O12 O 0.0492(2) 0.4903(2) 0.2833(2) 0.0924(10) Uani 1 d . . 
C13 C 0.0420(2) 0.2522(3) 0.2567(2) 0.0636(10) Uani 1 d . . 
O13 O 0.0355(2) 0.2035(2) 0.3034(2) 0.1022(12) Uani 1 d . . 
Ru2 Ru 0.154872(14) 0.433932(15) 0.076072(14) 0.03725(6) Uani 1 d . . 
C21 C 0.1437(2) 0.5516(2) 0.1153(2) 0.0531(9) Uani 1 d . . 
O21 O 0.1384(2) 0.6167(2) 0.1420(2) 0.0789(9) Uani 1 d . . 
C22 C 0.1054(2) 0.4500(2) -0.0183(2) 0.0539(9) Uani 1 d . . 
O22 O 0.0789(2) 0.4617(2) -0.0745(2) 0.0889(10) Uani 1 d . . 
C23 C 0.2541(2) 0.4523(2) 0.0329(2) 0.0546(9) Uani 1 d . . 
O23 O 0.3136(2) 0.4630(2) 0.0093(2) 0.0875(10) Uani 1 d . . 
Ru3 Ru 0.040186(14) 0.19088(2) 0.074111(14) 0.04084(7) Uani 1 d . . 
C31 C -0.0070(2) 0.2807(2) 0.0144(2) 0.0524(8) Uani 1 d . . 
O31 O -0.0349(2) 0.3319(2) -0.0209(2) 0.0766(9) Uani 1 d . . 
C32 C 0.0516(2) 0.1154(3) -0.0114(2) 0.0652(10) Uani 1 d . . 
O32 O 0.0545(2) 0.0726(2) -0.0612(2) 0.1105(13) Uani 1 d . . 
C33 C -0.0610(2) 0.1554(2) 0.1112(2) 0.0613(10) Uani 1 d . . 
O33 O -0.1191(2) 0.1364(2) 0.1327(2) 0.0948(11) Uani 1 d . . 
C34 C 0.0915(2) 0.1087(2) 0.1399(2) 0.0570(9) Uani 1 d . . 
O34 O 0.1211(2) 0.0588(2) 0.1752(2) 0.0883(10) Uani 1 d . . 
Ru4 Ru 0.213532(14) 0.32303(2) 0.194780(14) 0.03950(7) Uani 1 d . . 
C41 C 0.2167(2) 0.3915(3) 0.2856(2) 0.0570(9) Uani 1 d . . 
O41 O 0.2192(2) 0.4338(2) 0.3367(2) 0.0854(10) Uani 1 d . . 
C42 C 0.3218(2) 0.3247(2) 0.1715(2) 0.0528(8) Uani 1 d . . 
O42 O 0.3848(2) 0.3270(2) 0.1575(2) 0.0800(9) Uani 1 d . . 
C43 C 0.2187(2) 0.2153(3) 0.2454(2) 0.0574(9) Uani 1 d . . 
O43 O 0.2241(2) 0.1525(2) 0.2773(2) 0.0866(10) Uani 1 d . . 
As As 0.16132(2) 0.27544(2) 0.07675(2) 0.03337(7) Uani 1 d . . 
C C 0.2348(2) 0.2315(2) -0.0013(2) 0.0477(8) Uani 1 d . . 
F1 F 0.2456(2) 0.14677(13) 0.00309(14) 0.0775(7) Uani 1 d . . 
F2 F 0.2098(2) 0.2474(2) -0.06937(12) 0.0944(9) Uani 1 d . . 
F3 F 0.30471(13) 0.2671(2) 0.00351(15) 0.0801(7) Uani 1 d . . 
H1 H 0.0616(19) 0.4185(21) 0.1099(18) 0.056(10) Uiso 1 d . . 
H2 H 0.2062(22) 0.4295(24) 0.1610(21) 0.074(12) Uiso 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 
Ru1 0.03431(12) 0.04762(15) 0.03765(13) 0.00408(11) 0.00503(9) 0.00948(10) 
C11 0.044(2) 0.073(3) 0.057(2) 0.010(2) 0.013(2) 0.011(2) 
O11 0.038(2) 0.132(3) 0.102(2) 0.013(2) 0.0063(15) 0.018(2) 
C12 0.057(2) 0.070(3) 0.050(2) -0.005(2) 0.004(2) 0.020(2) 
O12 0.110(3) 0.091(2) 0.076(2) -0.038(2) -0.002(2) 0.029(2) 
C13 0.056(2) 0.074(3) 0.060(2) 0.019(2) 0.017(2) 0.018(2) 
O13 0.107(3) 0.114(3) 0.086(2) 0.055(2) 0.035(2) 0.031(2) 
Ru2 0.03832(13) 0.03165(12) 0.04179(13) 0.00374(10) -0.00084(10) 0.00232(9) 
C21 0.056(2) 0.040(2) 0.063(2) 0.004(2) -0.011(2) 0.003(2) 
O21 0.102(2) 0.046(2) 0.089(2) -0.0155(15) -0.021(2) 0.012(2) 
C22 0.062(2) 0.044(2) 0.056(2) 0.012(2) -0.005(2) -0.002(2) 
O22 0.114(3) 0.092(2) 0.060(2) 0.025(2) -0.029(2) -0.008(2) 
C23 0.059(2) 0.038(2) 0.067(2) 0.006(2) 0.010(2) -0.002(2) 
O23 0.064(2) 0.070(2) 0.128(3) 0.008(2) 0.038(2) -0.010(2) 
Ru3 0.03619(13) 0.03870(13) 0.04764(14) 0.00591(11) -0.00305(10) -0.00275(10) 
C31 0.042(2) 0.056(2) 0.059(2) 0.008(2) -0.008(2) -0.006(2) 
O31 0.071(2) 0.073(2) 0.087(2) 0.026(2) -0.029(2) 0.0025(15) 
C32 0.065(2) 0.061(2) 0.070(3) -0.010(2) -0.010(2) 0.000(2) 
O32 0.131(3) 0.105(3) 0.095(3) -0.047(2) -0.022(2) 0.017(2) 
C33 0.049(2) 0.060(2) 0.075(3) 0.023(2) -0.005(2) -0.005(2) 
O33 0.048(2) 0.106(3) 0.130(3) 0.046(2) 0.011(2) -0.013(2) 
C34 0.055(2) 0.045(2) 0.070(2) 0.010(2) -0.005(2) -0.005(2) 
O34 0.097(2) 0.061(2) 0.107(3) 0.030(2) -0.027(2) 0.004(2) 
Ru4 0.03581(12) 0.04500(14) 0.03767(13) 0.00000(11) -0.00563(9) 0.00831(10) 
C41 0.053(2) 0.069(2) 0.049(2) -0.002(2) -0.011(2) 0.018(2) 
O41 0.096(2) 0.100(2) 0.060(2) -0.029(2) -0.019(2) 0.029(2) 
C42 0.042(2) 0.060(2) 0.056(2) -0.004(2) -0.011(2) 0.008(2) 
O42 0.0389(15) 0.104(2) 0.097(2) -0.005(2) -0.0026(14) 0.0040(15) 
C43 0.055(2) 0.063(2) 0.054(2) 0.006(2) -0.010(2) 0.010(2) 
O43 0.105(3) 0.070(2) 0.085(2) 0.027(2) -0.023(2) 0.011(2) 
As 0.03225(14) 0.03262(15) 0.03524(15) 0.00290(12) 0.00030(11) 0.00193(11) 
C 0.051(2) 0.046(2) 0.046(2) 0.0027(15) 0.0084(15) 0.0057(15) 
F1 0.094(2) 0.0428(12) 0.095(2) -0.0051(12) 0.0272(14) 0.0170(11) 
F2 0.112(2) 0.130(2) 0.0414(12) 0.0060(14) 0.0104(12) 0.040(2) 
F3 0.0544(13) 0.081(2) 0.105(2) -0.0183(14) 0.0347(13) -0.0078(12) 
  
_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 
Ru1 C12 1.883(4) . ? 
Ru1 C13 1.892(4) . ? 
Ru1 C11 1.916(4) . ? 
Ru1 As 2.8568(4) . ? 
Ru1 Ru4 2.8684(3) . ? 
Ru1 Ru3 2.9588(4) . ? 
Ru1 Ru2 3.0310(3) . ? 
C11 O11 1.133(4) . ? 
C12 O12 1.136(4) . ? 
C13 O13 1.134(4) . ? 
Ru2 C23 1.910(4) . ? 
Ru2 C22 1.920(4) . ? 
Ru2 C21 1.961(4) . ? 
Ru2 As 2.4540(4) . ? 
Ru2 Ru4 2.9233(3) . ? 
C21 O21 1.120(4) . ? 
C22 O22 1.125(4) . ? 
C23 O23 1.128(4) . ? 
Ru3 C31 1.938(4) . ? 
Ru3 C32 1.942(4) . ? 
Ru3 C34 1.952(4) . ? 
Ru3 C33 1.956(4) . ? 
Ru3 As 2.4751(4) . ? 
C31 O31 1.125(4) . ? 
C32 O32 1.116(5) . ? 
C33 O33 1.118(4) . ? 
C34 O34 1.124(4) . ? 
Ru4 C43 1.902(4) . ? 
Ru4 C42 1.924(4) . ? 
Ru4 C41 1.948(4) . ? 
Ru4 As 2.4245(4) . ? 
C41 O41 1.130(4) . ? 
C42 O42 1.123(4) . ? 
C43 O43 1.132(4) . ? 
As C 2.015(3) . ? 
C F2 1.323(4) . ? 
C F1 1.326(4) . ? 
C F3 1.334(4) . ? 
  
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 
C12 Ru1 C13 94.7(2) . . ? 
C12 Ru1 C11 94.2(2) . . ? 
C13 Ru1 C11 97.5(2) . . ? 
C12 Ru1 As 130.42(12) . . ? 
C13 Ru1 As 107.04(11) . . ? 
C11 Ru1 As 125.01(11) . . ? 
C12 Ru1 Ru4 88.45(11) . . ? 
C13 Ru1 Ru4 87.31(12) . . ? 
C11 Ru1 Ru4 174.31(11) . . ? 
As Ru1 Ru4 50.107(8) . . ? 
C12 Ru1 Ru3 177.80(11) . . ? 
C13 Ru1 Ru3 86.77(13) . . ? 
C11 Ru1 Ru3 83.99(12) . . ? 
As Ru1 Ru3 50.338(9) . . ? 
Ru4 Ru1 Ru3 93.221(10) . . ? 
C12 Ru1 Ru2 89.14(12) . . ? 
C13 Ru1 Ru2 146.33(11) . . ? 
C11 Ru1 Ru2 115.61(11) . . ? 
As Ru1 Ru2 49.155(8) . . ? 
Ru4 Ru1 Ru2 59.332(8) . . ? 
Ru3 Ru1 Ru2 90.473(9) . . ? 
O11 C11 Ru1 177.1(4) . . ? 
O12 C12 Ru1 175.0(3) . . ? 
O13 C13 Ru1 177.5(3) . . ? 
C23 Ru2 C22 91.3(2) . . ? 
C23 Ru2 C21 95.6(2) . . ? 
C22 Ru2 C21 98.88(15) . . ? 
C23 Ru2 As 96.31(10) . . ? 
C22 Ru2 As 98.86(10) . . ? 
C21 Ru2 As 158.35(11) . . ? 
C23 Ru2 Ru4 94.11(11) . . ? 
C22 Ru2 Ru4 151.48(10) . . ? 
C21 Ru2 Ru4 108.40(10) . . ? 
As Ru2 Ru4 52.723(10) . . ? 
C23 Ru2 Ru1 150.70(11) . . ? 
C22 Ru2 Ru1 110.13(11) . . ? 
C21 Ru2 Ru1 100.34(11) . . ? 
As Ru2 Ru1 61.721(10) . . ? 
Ru4 Ru2 Ru1 57.563(8) . . ? 
O21 C21 Ru2 175.6(3) . . ? 
O22 C22 Ru2 177.1(3) . . ? 
O23 C23 Ru2 178.0(4) . . ? 
C31 Ru3 C32 92.0(2) . . ? 
C31 Ru3 C34 174.8(2) . . ? 
C32 Ru3 C34 92.5(2) . . ? 
C31 Ru3 C33 90.68(15) . . ? 
C32 Ru3 C33 101.1(2) . . ? 
C34 Ru3 C33 91.08(15) . . ? 
C31 Ru3 As 89.42(10) . . ? 
C32 Ru3 As 104.27(13) . . ? 
C34 Ru3 As 86.89(11) . . ? 
C33 Ru3 As 154.56(13) . . ? 
C31 Ru3 Ru1 80.62(11) . . ? 
C32 Ru3 Ru1 164.82(13) . . ? 
C34 Ru3 Ru1 94.41(12) . . ? 
C33 Ru3 Ru1 92.24(13) . . ? 
As Ru3 Ru1 62.693(10) . . ? 
O31 C31 Ru3 178.9(3) . . ? 
O32 C32 Ru3 176.6(4) . . ? 
O33 C33 Ru3 179.0(4) . . ? 
O34 C34 Ru3 176.8(4) . . ? 
C43 Ru4 C42 94.0(2) . . ? 
C43 Ru4 C41 94.2(2) . . ? 
C42 Ru4 C41 98.5(2) . . ? 
C43 Ru4 As 99.89(11) . . ? 
C42 Ru4 As 100.24(10) . . ? 
C41 Ru4 As 155.65(10) . . ? 
C43 Ru4 Ru1 98.74(11) . . ? 
C42 Ru4 Ru1 161.67(11) . . ? 
C41 Ru4 Ru1 93.68(11) . . ? 
As Ru4 Ru1 64.699(10) . . ? 
C43 Ru4 Ru2 151.79(11) . . ? 
C42 Ru4 Ru2 99.93(11) . . ? 
C41 Ru4 Ru2 107.73(11) . . ? 
As Ru4 Ru2 53.651(9) . . ? 
Ru1 Ru4 Ru2 63.105(8) . . ? 
O41 C41 Ru4 177.4(4) . . ? 
O42 C42 Ru4 178.9(4) . . ? 
O43 C43 Ru4 177.2(3) . . ? 
C As Ru4 118.51(10) . . ? 
C As Ru2 111.25(10) . . ? 
Ru4 As Ru2 73.625(12) . . ? 
C As Ru3 110.19(10) . . ? 
Ru4 As Ru3 119.622(14) . . ? 
Ru2 As Ru3 119.282(14) . . ? 
C As Ru1 176.29(10) . . ? 
Ru4 As Ru1 65.194(10) . . ? 
Ru2 As Ru1 69.124(11) . . ? 
Ru3 As Ru1 66.968(11) . . ? 
F2 C F1 106.6(3) . . ? 
F2 C F3 106.3(3) . . ? 
F1 C F3 106.0(3) . . ? 
F2 C As 112.1(2) . . ? 
F1 C As 112.4(2) . . ? 
F3 C As 113.0(2) . . ? 
  
_refine_diff_density_max    0.789 
_refine_diff_density_min   -0.707 
_refine_diff_density_rms    0.082