Supplementary Material (ESI) for Dalton Transactions
This journal is (c) The Royal Society of Chemistry 2006

data_global

_journal_name_full               'Dalton Trans.'
_journal_coden_cambridge         0222
_publ_section_title              
;
A Combined Stopped-Flow, Electrospray Ionization Mass
Spectrometry and 31P NMR study on the Acetic Acid-Mediated Fragmentation
of the Hydroxo-Chalcogenide Cluster [W3Se4(OH)3(dmpe)3]+
(dmpe = 1,2-bis(dimethylphosphanyl)ethane) to yield the dinuclear
[W2Se2(m-Se)2(m-CH3CO2)(dmpe)2]+ complex
;
_publ_contact_author_name        'Rosa Llusar'
_publ_contact_author_address     'Campus Riu Sec, UJI 12071 Castellon (Spain)'
_publ_contact_author_email       llusar@exp.uji.es
_publ_contact_author_fax         34964728066
_publ_contact_author_phone       34964728086
loop_
_publ_author_name
'Andres G. Algarra'
'Manuel G. Basallote'
'C. Esther Castillo'
'Carolina Corao'
'Rosa Llusar'
'M. Jesus Fernandez-Trujillo'
'Cristian Vicent'

data_[W2Se4(dmpe)2(CH3CO2)]PF6
_database_code_depnum_ccdc_archive 'CCDC 616576'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            (W2Se4(dmpe)2(CH3CO2))PF6
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H35 F6 O2 P5 Se4 W2'
_chemical_formula_weight         1187.81

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'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Se Se -0.0929 2.2259 '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'
F F 0.0171 0.0103 '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)

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   8.446(5)
_cell_length_b                   12.795(7)
_cell_length_c                   14.728(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 91.892(14)
_cell_angle_gamma                90.00
_cell_volume                     1590.8(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       prism
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.480
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1096
_exptl_absorpt_coefficient_mu    12.100
_exptl_absorpt_correction_type   'Bruker SADABS'
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_Ratio_of_minimum_to_maximum_apparent_transmission 0.650835

_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            7512
_diffrn_reflns_av_R_equivalents  0.1017
_diffrn_reflns_av_sigmaI/netI    0.2389
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.11
_diffrn_reflns_theta_max         25.00
_reflns_number_total             5150
_reflns_number_gt                2565
_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^)+(0.0770P)^2^+0.0000P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.41(4)
_refine_ls_number_reflns         5150
_refine_ls_number_parameters     184
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.1822
_refine_ls_R_factor_gt           0.0803
_refine_ls_wR_factor_ref         0.2051
_refine_ls_wR_factor_gt          0.1601
_refine_ls_goodness_of_fit_ref   0.975
_refine_ls_restrained_S_all      0.975
_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 0.62688(18) 0.30006(12) 0.86009(9) 0.0384(4) Uani 1 1 d . . .
W2 W 0.56432(18) 0.11944(12) 0.75177(10) 0.0403(5) Uani 1 1 d . . .
Se1 Se 0.4805(5) 0.3094(4) 0.9866(3) 0.0663(13) Uani 1 1 d . . .
Se2 Se 0.7673(5) 0.1313(4) 0.8755(3) 0.0562(12) Uani 1 1 d . . .
Se3 Se 0.4308(4) 0.2913(4) 0.7309(2) 0.0483(11) Uani 1 1 d . . .
Se4 Se 0.3746(6) 0.0126(4) 0.8055(3) 0.0739(15) Uani 1 1 d . . .
P1 P 0.8649(14) 0.3663(9) 0.9516(7) 0.053(3) Uani 1 1 d . . .
P2 P 0.5996(13) 0.4951(8) 0.8367(7) 0.045(3) Uani 1 1 d . . .
P3 P 0.4587(15) 0.0831(9) 0.5917(7) 0.055(3) Uani 1 1 d . . .
P4 P 0.7212(14) -0.0392(9) 0.7084(8) 0.056(3) Uani 1 1 d . . .
C1 C 1.049(9) 0.379(6) 0.909(5) 0.18(3) Uiso 1 1 d . . .
H1A H 1.0831 0.3121 0.8870 0.270 Uiso 1 1 calc R . .
H1B H 1.1213 0.4025 0.9561 0.270 Uiso 1 1 calc R . .
H1C H 1.0453 0.4282 0.8602 0.270 Uiso 1 1 calc R . .
C2 C 0.890(7) 0.355(4) 1.067(4) 0.12(2) Uiso 1 1 d . . .
H2A H 0.7882 0.3549 1.0945 0.179 Uiso 1 1 calc R . .
H2B H 0.9518 0.4123 1.0903 0.179 Uiso 1 1 calc R . .
H2C H 0.9436 0.2903 1.0814 0.179 Uiso 1 1 calc R . .
C3 C 0.850(8) 0.492(5) 0.977(4) 0.14(2) Uiso 1 1 d . . .
H3A H 0.7902 0.5010 1.0320 0.165 Uiso 1 1 calc R . .
H3B H 0.9538 0.5228 0.9871 0.165 Uiso 1 1 calc R . .
C4 C 0.767(7) 0.541(5) 0.900(4) 0.11(2) Uiso 1 1 d . . .
H4A H 0.8475 0.5516 0.8551 0.131 Uiso 1 1 calc R . .
H4B H 0.7378 0.6098 0.9204 0.131 Uiso 1 1 calc R . .
C5 C 0.424(5) 0.548(3) 0.890(3) 0.067(13) Uiso 1 1 d . . .
H5A H 0.4205 0.5234 0.9514 0.101 Uiso 1 1 calc R . .
H5B H 0.3305 0.5243 0.8566 0.101 Uiso 1 1 calc R . .
H5C H 0.4277 0.6226 0.8891 0.101 Uiso 1 1 calc R . .
C6 C 0.591(5) 0.542(3) 0.725(2) 0.052(11) Uiso 1 1 d . . .
H6A H 0.6803 0.5153 0.6930 0.078 Uiso 1 1 calc R . .
H6B H 0.5945 0.6167 0.7253 0.078 Uiso 1 1 calc R . .
H6C H 0.4949 0.5186 0.6950 0.078 Uiso 1 1 calc R . .
C7 C 0.497(6) 0.185(3) 0.508(3) 0.070(14) Uiso 1 1 d . . .
H7A H 0.4445 0.2480 0.5245 0.105 Uiso 1 1 calc R . .
H7B H 0.4581 0.1623 0.4491 0.105 Uiso 1 1 calc R . .
H7C H 0.6091 0.1970 0.5060 0.105 Uiso 1 1 calc R . .
C8 C 0.257(9) 0.005(6) 0.578(5) 0.17(3) Uiso 1 1 d . . .
H8A H 0.2513 -0.0463 0.6250 0.260 Uiso 1 1 calc R . .
H8B H 0.2520 -0.0290 0.5197 0.260 Uiso 1 1 calc R . .
H8C H 0.1697 0.0527 0.5818 0.260 Uiso 1 1 calc R . .
C9 C 0.568(5) -0.024(4) 0.538(3) 0.081(15) Uiso 1 1 d D . .
H9A H 0.4951 -0.0697 0.5054 0.097 Uiso 1 1 calc R . .
H9B H 0.6414 0.0048 0.4950 0.097 Uiso 1 1 calc R . .
C10 C 0.654(6) -0.081(4) 0.608(3) 0.100(18) Uiso 1 1 d D . .
H10A H 0.7465 -0.1090 0.5786 0.121 Uiso 1 1 calc R . .
H10B H 0.5882 -0.1410 0.6208 0.121 Uiso 1 1 calc R . .
C11 C 0.928(6) -0.033(4) 0.706(3) 0.098(18) Uiso 1 1 d . . .
H11A H 0.9688 -0.0053 0.7629 0.148 Uiso 1 1 calc R . .
H11B H 0.9580 0.0122 0.6575 0.148 Uiso 1 1 calc R . .
H11C H 0.9698 -0.1015 0.6969 0.148 Uiso 1 1 calc R . .
C12 C 0.719(5) -0.144(3) 0.794(3) 0.061(13) Uiso 1 1 d . . .
H12A H 0.7566 -0.1166 0.8512 0.092 Uiso 1 1 calc R . .
H12B H 0.7862 -0.1997 0.7754 0.092 Uiso 1 1 calc R . .
H12C H 0.6127 -0.1689 0.7989 0.092 Uiso 1 1 calc R . .
C13 C 0.832(4) 0.283(3) 0.680(2) 0.036(9) Uiso 1 1 d . . .
C14 C 0.942(5) 0.325(4) 0.626(3) 0.076(15) Uiso 1 1 d . . .
H14A H 0.9682 0.2766 0.5798 0.115 Uiso 1 1 calc R . .
H14B H 1.0349 0.3416 0.6628 0.115 Uiso 1 1 calc R . .
H14C H 0.9003 0.3881 0.5991 0.115 Uiso 1 1 calc R . .
O1 O 0.787(4) 0.342(2) 0.7499(19) 0.074(10) Uani 1 1 d . . .
O2 O 0.746(3) 0.1845(19) 0.6723(18) 0.057(8) Uani 1 1 d . . .
P10 P 0.0856(16) 0.6495(11) 0.6497(8) 0.083(4) Uani 1 1 d G . .
F10 F 0.098(4) 0.616(3) 0.5438(10) 0.160(14) Uiso 1 1 d G . .
F11 F 0.071(4) 0.695(3) 0.7448(11) 0.21(2) Uiso 1 1 d G . .
F12 F -0.072(3) 0.701(3) 0.617(2) 0.188(19) Uiso 1 1 d G . .
F13 F 0.250(3) 0.596(3) 0.673(2) 0.31(3) Uiso 1 1 d G . .
F14 F -0.006(4) 0.5458(19) 0.674(2) 0.34(4) Uiso 1 1 d G . .
F15 F 0.175(4) 0.753(2) 0.615(2) 0.29(3) Uiso 1 1 d G . .

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 0.0406(10) 0.0422(10) 0.0323(9) 0.0010(9) 0.0000(7) -0.0010(10)
W2 0.0413(10) 0.0421(10) 0.0377(9) -0.0005(9) 0.0040(7) 0.0007(10)
Se1 0.075(3) 0.074(3) 0.051(2) -0.002(3) 0.016(2) -0.008(3)
Se2 0.065(3) 0.052(3) 0.051(2) 0.008(3) -0.008(2) 0.002(3)
Se3 0.040(2) 0.058(3) 0.046(2) -0.005(3) -0.0044(18) 0.011(3)
Se4 0.066(4) 0.085(4) 0.071(3) 0.009(3) 0.019(3) -0.016(3)
P1 0.055(8) 0.053(7) 0.049(7) 0.005(6) -0.019(6) -0.017(6)
P2 0.053(8) 0.032(6) 0.051(7) -0.011(5) 0.001(5) 0.003(5)
P3 0.073(9) 0.051(8) 0.041(6) -0.008(5) 0.001(6) -0.008(6)
P4 0.062(8) 0.049(7) 0.058(8) 0.008(6) 0.006(6) 0.001(6)
O1 0.10(2) 0.06(2) 0.07(2) -0.023(16) 0.059(18) -0.032(17)
O2 0.055(19) 0.045(17) 0.069(19) -0.019(15) -0.021(15) -0.011(14)
P10 0.074(10) 0.101(12) 0.073(9) -0.007(8) 0.011(7) 0.023(8)

_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 2.22(2) . ?
W1 P1 2.530(11) . ?
W1 Se2 2.471(5) . ?
W1 Se1 2.273(4) . ?
W1 P2 2.528(10) . ?
W1 Se3 2.483(4) . ?
W1 W2 2.848(2) . ?
W2 O2 2.13(3) . ?
W2 Se4 2.268(5) . ?
W2 Se2 2.465(5) . ?
W2 Se3 2.486(5) . ?
W2 P4 2.518(12) . ?
W2 P3 2.535(11) . ?
P1 C3 1.66(6) . ?
P1 C1 1.70(8) . ?
P1 C2 1.71(5) . ?
P2 C6 1.75(4) . ?
P2 C4 1.76(6) . ?
P2 C5 1.83(4) . ?
P3 C7 1.83(4) . ?
P3 C9 1.84(5) . ?
P3 C8 1.98(8) . ?
P4 C10 1.66(5) . ?
P4 C11 1.75(5) . ?
P4 C12 1.83(4) . ?
C3 C4 1.46(7) . ?
C9 C10 1.443(10) . ?
C13 C14 1.35(5) . ?
C13 O1 1.35(4) . ?
C13 O2 1.45(4) . ?
P10 F11 1.5246 . ?
P10 F12 1.5525 . ?
P10 F13 1.5732 . ?
P10 F14 1.5843 . ?
P10 F15 1.6122 . ?
P10 F10 1.6252 . ?

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 P1 79.2(9) . . ?
O1 W1 Se2 88.7(8) . . ?
P1 W1 Se2 82.7(3) . . ?
O1 W1 Se1 161.8(7) . . ?
P1 W1 Se1 89.4(3) . . ?
Se2 W1 Se1 104.06(18) . . ?
O1 W1 P2 73.4(8) . . ?
P1 W1 P2 79.0(4) . . ?
Se2 W1 P2 156.4(3) . . ?
Se1 W1 P2 90.6(3) . . ?
O1 W1 Se3 81.9(9) . . ?
P1 W1 Se3 157.2(3) . . ?
Se2 W1 Se3 109.69(17) . . ?
Se1 W1 Se3 105.26(16) . . ?
P2 W1 Se3 83.4(3) . . ?
O1 W1 W2 84.0(7) . . ?
P1 W1 W2 134.4(3) . . ?
Se2 W1 W2 54.67(12) . . ?
Se1 W1 W2 113.94(15) . . ?
P2 W1 W2 135.3(2) . . ?
Se3 W1 W2 55.08(12) . . ?
O2 W2 Se4 163.2(7) . . ?
O2 W2 Se2 83.4(7) . . ?
Se4 W2 Se2 105.14(19) . . ?
O2 W2 Se3 85.3(7) . . ?
Se4 W2 Se3 104.68(19) . . ?
Se2 W2 Se3 109.80(17) . . ?
O2 W2 P4 77.3(7) . . ?
Se4 W2 P4 89.2(3) . . ?
Se2 W2 P4 83.0(3) . . ?
Se3 W2 P4 157.3(3) . . ?
O2 W2 P3 78.4(7) . . ?
Se4 W2 P3 89.0(3) . . ?
Se2 W2 P3 156.0(3) . . ?
Se3 W2 P3 84.4(3) . . ?
P4 W2 P3 77.8(4) . . ?
O2 W2 W1 82.4(6) . . ?
Se4 W2 W1 114.44(15) . . ?
Se2 W2 W1 54.86(12) . . ?
Se3 W2 W1 54.99(10) . . ?
P4 W2 W1 135.0(3) . . ?
P3 W2 W1 136.3(3) . . ?
W1 Se2 W2 70.47(13) . . ?
W2 Se3 W1 69.93(12) . . ?
C3 P1 C1 94(3) . . ?
C3 P1 C2 82(3) . . ?
C1 P1 C2 107(3) . . ?
C3 P1 W1 112(2) . . ?
C1 P1 W1 124(3) . . ?
C2 P1 W1 125(2) . . ?
C6 P2 C4 113(2) . . ?
C6 P2 C5 105.6(19) . . ?
C4 P2 C5 108(2) . . ?
C6 P2 W1 117.7(13) . . ?
C4 P2 W1 101(2) . . ?
C5 P2 W1 112.1(15) . . ?
C7 P3 C9 98(2) . . ?
C7 P3 C8 117(3) . . ?
C9 P3 C8 91(3) . . ?
C7 P3 W2 115.6(16) . . ?
C9 P3 W2 111.6(14) . . ?
C8 P3 W2 118(2) . . ?
C10 P4 C11 108(3) . . ?
C10 P4 C12 111(2) . . ?
C11 P4 C12 95(2) . . ?
C10 P4 W2 108.8(18) . . ?
C11 P4 W2 120.0(19) . . ?
C12 P4 W2 113.3(14) . . ?
C4 C3 P1 106(5) . . ?
C3 C4 P2 129(5) . . ?
C10 C9 P3 109(4) . . ?
C9 C10 P4 128(4) . . ?
C14 C13 O1 115(3) . . ?
C14 C13 O2 131(3) . . ?
O1 C13 O2 113(3) . . ?
C13 O1 W1 128(2) . . ?
C13 O2 W2 132(2) . . ?
F11 P10 F12 91.8 . . ?
F11 P10 F13 93.6 . . ?
F12 P10 F13 174.4 . . ?
F11 P10 F14 93.1 . . ?
F12 P10 F14 90.2 . . ?
F13 P10 F14 91.3 . . ?
F11 P10 F15 92.0 . . ?
F12 P10 F15 87.8 . . ?
F13 P10 F15 90.2 . . ?
F14 P10 F15 174.6 . . ?
F11 P10 F10 173.0 . . ?
F12 P10 F10 84.0 . . ?
F13 P10 F10 90.6 . . ?
F14 P10 F10 92.4 . . ?
F15 P10 F10 82.4 . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         1.309
_refine_diff_density_min         -1.173
_refine_diff_density_rms         0.292