# Copyright The Royal Society of Chemistry, 1998

# CRYSTALLOGRAPHIC INFORMATION FILE FOR THE STRUCTURE IN

# J.C.S. Dalton Transactions Paper No. 7/09121D

# Paper title:
# The X-ray crystal structure of triphenylphosphinesulfidediiodide;
# the first crystallographically characterised 1:1 molecular
# charge-transfer complex of a tertiary phosphine sulfide and
# diiodide.
# Authors: D.C. Apperley, N. Bricklebank, S.L. Burns, D.E. Hibbs,
# M.B. Hursthouse and K.M.A. Malik

# =================================================================

data_C18H15I2PS
 
_audit_creation_method            SHELXL-93
_chemical_name_systematic         'Triphenylphosphinesulfide-diiodide'
_chemical_name_common             ?
_chemical_formula_moiety          C18H15I2PS
_chemical_formula_structural      ? 
_chemical_formula_analytical      ? 
_chemical_formula_sum             'C18 H15 I2 P S' 
_chemical_formula_weight          548.13 
_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' 
 'P'  'P'   0.1023   0.0942 
 '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' 
 'I'  'I'  -0.4742   1.8119 
 '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)/n  (No. 14)'
 
loop_ 
 _symmetry_equiv_pos_as_xyz 
 'x, y, z' 
 '-x+1/2, y+1/2, -z+1/2' 
 '-x, -y, -z' 
 'x-1/2, -y-1/2, z-1/2' 
 
_cell_length_a                    12.618(2) 
_cell_length_b                    9.454(3) 
_cell_length_c                    15.930(6) 
_cell_angle_alpha                 90.00 
_cell_angle_beta                  97.400(8) 
_cell_angle_gamma                 90.00 
_cell_volume                      1884.5(10) 
_cell_formula_units_Z             4 
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     250
_cell_measurement_theta_min       1.94
_cell_measurement_theta_max       25.14
 
_exptl_crystal_description        block
_exptl_crystal_colour             red-brown
_exptl_crystal_size_max           0.10
_exptl_crystal_size_mid           0.08
_exptl_crystal_size_min           0.08
_exptl_crystal_density_meas       ? 
_exptl_crystal_density_diffrn     1.932 
_exptl_crystal_density_method     ? 
_exptl_crystal_F_000              1040 
_exptl_absorpt_coefficient_mu     3.527 
_exptl_absorpt_correction_type    'DIFABS (Walker & Stuart, 1983)'
_exptl_absorpt_correction_T_min   0.879
_exptl_absorpt_correction_T_max   0.988
 
_exptl_special_details 
; 
 ? 
; 
 
_diffrn_ambient_temperature       293(2)
_diffrn_radiation_wavelength      0.71069 
_diffrn_radiation_type            MoK\a 
_diffrn_radiation_source          'rotating anode generator, Mo anode)'
_diffrn_radiation_monochromator   graphite 
_diffrn_measurement_device        'FAST area detector diffractomer'
_diffrn_measurement_method        'Darr, Drake, Hursthose & Malik, 1993)'
_diffrn_standards_number          ? 
_diffrn_standards_interval_count  ? 
_diffrn_standards_interval_time   ? 
_diffrn_standards_decay_%         none
_diffrn_reflns_number             7642 
_diffrn_reflns_av_R_equivalents   0.0489 
_diffrn_reflns_av_sigmaI/netI     0.0621 
_diffrn_reflns_limit_h_min        -7 
_diffrn_reflns_limit_h_max        14 
_diffrn_reflns_limit_k_min        -10 
_diffrn_reflns_limit_k_max        11 
_diffrn_reflns_limit_l_min        -18 
_diffrn_reflns_limit_l_max        17 
_diffrn_reflns_theta_min          1.94 
_diffrn_reflns_theta_max          25.14 
_reflns_number_total              2875 
_reflns_number_observed           1878 
_reflns_observed_criterion        >2sigma(I) 
 
_computing_data_collection        MADNES
_computing_cell_refinement        'REFINE in MADNES'
_computing_data_reduction         'ABSMAD, Karaulov, 1991)'
_computing_structure_solution     'SHELXS-86 (Sheldrick, 1990)' 
_computing_structure_refinement   'SHELXL-93 (Sheldrick, 1993)'
_computing_molecular_graphics     'SNOOPI (Davies, 1983)'
_computing_publication_material   SHELXL-93
 
_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^)+(0.0185P)^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     'calculated positions, riding model'
_refine_ls_extinction_method      none 
_refine_ls_extinction_coef        ? 
_refine_ls_number_reflns          2875 
_refine_ls_number_parameters      199 
_refine_ls_number_restraints      0 
_refine_ls_R_factor_all           0.0485 
_refine_ls_R_factor_obs           0.0270 
_refine_ls_wR_factor_all          0.0572 
_refine_ls_wR_factor_obs          0.0543 
_refine_ls_goodness_of_fit_all    0.799 
_refine_ls_goodness_of_fit_obs    0.956 
_refine_ls_restrained_S_all       0.799 
_refine_ls_restrained_S_obs       0.956 
_refine_ls_shift/esd_max          -0.000 
_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 
S1 S 0.39231(12) 0.05966(13) 0.09861(8) 0.0568(4) Uani 1 d . . 
I1 I 0.31305(3) 0.06175(3) -0.07069(2) 0.05278(12) Uani 1 d . . 
I2 I 0.24358(3) 0.04730(4) -0.24617(2) 0.06686(14) Uani 1 d . . 
P1 P 0.33116(11) 0.22389(12) 0.15495(8) 0.0418(3) Uani 1 d . . 
C1 C 0.1879(4) 0.2158(4) 0.1506(3) 0.0397(12) Uani 1 d . . 
C2 C 0.1327(4) 0.0961(5) 0.1211(3) 0.0486(13) Uani 1 d . . 
H2 H 0.1699(4) 0.0183(5) 0.1011(3) 0.058 Uiso 1 calc R . 
C3 C 0.0235(5) 0.0893(5) 0.1207(4) 0.059(2) Uani 1 d . . 
H3 H -0.0143(5) 0.0074(5) 0.0991(4) 0.071 Uiso 1 calc R . 
C4 C -0.0311(4) 0.1997(5) 0.1510(3) 0.0567(15) Uani 1 d . . 
H4 H -0.1059(4) 0.1928(5) 0.1527(3) 0.068 Uiso 1 calc R . 
C5 C 0.0229(5) 0.3201(5) 0.1789(4) 0.061(2) Uani 1 d . . 
H5 H -0.0153(5) 0.3980(5) 0.1979(4) 0.073 Uiso 1 calc R . 
C6 C 0.1325(5) 0.3292(5) 0.1798(3) 0.056(2) Uani 1 d . . 
H6 H 0.1696(5) 0.4123(5) 0.2002(3) 0.067 Uiso 1 calc R . 
C7 C 0.3913(4) 0.2170(4) 0.2644(3) 0.0384(12) Uani 1 d . . 
C8 C 0.5004(4) 0.1991(4) 0.2804(3) 0.0484(14) Uani 1 d . . 
H8 H 0.5412(4) 0.1946(4) 0.2344(3) 0.058 Uiso 1 calc R . 
C9 C 0.5512(5) 0.1876(5) 0.3617(3) 0.0556(15) Uani 1 d . . 
H9 H 0.6265(5) 0.1755(5) 0.3716(3) 0.067 Uiso 1 calc R . 
C10 C 0.4929(5) 0.1936(5) 0.4286(3) 0.059(2) Uani 1 d . . 
H10 H 0.5275(5) 0.1848(5) 0.4849(3) 0.071 Uiso 1 calc R . 
C11 C 0.3835(6) 0.2125(5) 0.4133(3) 0.064(2) Uani 1 d . . 
H11 H 0.3432(6) 0.2192(5) 0.4596(3) 0.077 Uiso 1 calc R . 
C12 C 0.3317(5) 0.2217(5) 0.3311(3) 0.0522(14) Uani 1 d . . 
H12 H 0.2562(5) 0.2310(5) 0.3210(3) 0.063 Uiso 1 calc R . 
C13 C 0.3607(4) 0.3944(4) 0.1124(3) 0.0414(12) Uani 1 d . . 
C14 C 0.3110(4) 0.4312(5) 0.0318(3) 0.0536(14) Uani 1 d . . 
H14 H 0.2596(4) 0.3698(5) 0.0020(3) 0.064 Uiso 1 calc R . 
C15 C 0.3373(5) 0.5581(6) -0.0043(4) 0.066(2) Uani 1 d . . 
H15 H 0.3030(5) 0.5841(6) -0.0588(4) 0.079 Uiso 1 calc R . 
C16 C 0.4129(5) 0.6468(5) 0.0383(4) 0.062(2) Uani 1 d . . 
H16 H 0.4307(5) 0.7332(5) 0.0130(4) 0.074 Uiso 1 calc R . 
C17 C 0.4621(4) 0.6104(5) 0.1167(4) 0.0570(15) Uani 1 d . . 
H17 H 0.5138(4) 0.6717(5) 0.1461(4) 0.068 Uiso 1 calc R . 
C18 C 0.4367(4) 0.4839(5) 0.1537(3) 0.0519(14) Uani 1 d . . 
H18 H 0.4720(4) 0.4587(5) 0.2080(3) 0.062 Uiso 1 calc R . 
 
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 
S1 0.0581(10) 0.0570(7) 0.0537(9) -0.0134(7) 0.0017(7) 0.0214(8) 
I1 0.0460(2) 0.0540(2) 0.0602(2) -0.0077(2) 0.0141(2) 0.0048(2) 
I2 0.0607(3) 0.0894(3) 0.0526(2) -0.0042(2) 0.0157(2) -0.0001(2) 
P1 0.0415(9) 0.0402(6) 0.0437(8) -0.0029(6) 0.0050(7) 0.0034(7) 
C1 0.044(3) 0.034(2) 0.041(3) -0.000(2) 0.007(3) 0.004(2) 
C2 0.052(4) 0.043(3) 0.051(3) 0.003(2) 0.008(3) -0.001(3) 
C3 0.060(4) 0.046(3) 0.071(4) 0.002(3) 0.009(3) -0.018(3) 
C4 0.042(4) 0.063(3) 0.067(4) 0.011(3) 0.016(3) -0.009(3) 
C5 0.049(4) 0.052(3) 0.084(4) 0.012(3) 0.020(3) 0.016(3) 
C6 0.054(4) 0.039(3) 0.077(4) -0.005(3) 0.013(3) -0.004(3) 
C7 0.045(4) 0.033(2) 0.038(3) -0.000(2) 0.007(3) 0.001(3) 
C8 0.049(4) 0.053(3) 0.043(3) 0.005(2) 0.006(3) 0.001(3) 
C9 0.056(4) 0.060(3) 0.049(4) -0.002(3) -0.002(3) 0.006(3) 
C10 0.073(5) 0.056(3) 0.044(4) 0.002(3) -0.010(3) -0.008(3) 
C11 0.091(5) 0.062(3) 0.042(4) -0.008(3) 0.019(4) -0.018(4) 
C12 0.058(4) 0.051(3) 0.049(4) -0.002(3) 0.012(3) -0.011(3) 
C13 0.043(3) 0.049(3) 0.035(3) -0.001(2) 0.013(3) 0.010(3) 
C14 0.060(4) 0.060(3) 0.040(3) -0.005(3) 0.001(3) 0.001(3) 
C15 0.080(5) 0.061(3) 0.057(4) 0.014(3) 0.007(3) 0.017(4) 
C16 0.075(5) 0.050(3) 0.065(4) 0.014(3) 0.027(4) 0.002(3) 
C17 0.058(4) 0.055(3) 0.060(4) -0.003(3) 0.011(3) -0.013(3) 
C18 0.053(4) 0.057(3) 0.044(3) 0.005(3) 0.001(3) -0.012(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 
S1 P1 1.998(2) . ? 
S1 I1 2.753(2) . ? 
I1 I2 2.8230(11) . ? 
P1 C1 1.802(5) . ? 
P1 C13 1.806(5) . ? 
P1 C7 1.811(5) . ? 
C1 C2 1.379(6) . ? 
C1 C6 1.392(6) . ? 
C2 C3 1.378(7) . ? 
C3 C4 1.373(7) . ? 
C4 C5 1.370(6) . ? 
C5 C6 1.384(7) . ? 
C7 C8 1.378(7) . ? 
C7 C12 1.379(6) . ? 
C8 C9 1.373(6) . ? 
C9 C10 1.371(7) . ? 
C10 C11 1.382(8) . ? 
C11 C12 1.389(7) . ? 
C13 C18 1.381(6) . ? 
C13 C14 1.398(6) . ? 
C14 C15 1.390(6) . ? 
C15 C16 1.381(7) . ? 
C16 C17 1.366(7) . ? 
C17 C18 1.388(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 
P1 S1 I1 108.78(7) . . ? 
S1 I1 I2 175.51(3) . . ? 
C1 P1 C13 106.1(2) . . ? 
C1 P1 C7 109.2(2) . . ? 
C13 P1 C7 108.2(2) . . ? 
C1 P1 S1 113.2(2) . . ? 
C13 P1 S1 114.5(2) . . ? 
C7 P1 S1 105.5(2) . . ? 
C2 C1 C6 119.5(5) . . ? 
C2 C1 P1 120.5(4) . . ? 
C6 C1 P1 119.9(4) . . ? 
C3 C2 C1 120.1(5) . . ? 
C4 C3 C2 120.6(5) . . ? 
C5 C4 C3 119.7(5) . . ? 
C4 C5 C6 120.6(5) . . ? 
C5 C6 C1 119.5(5) . . ? 
C8 C7 C12 119.5(5) . . ? 
C8 C7 P1 117.9(4) . . ? 
C12 C7 P1 122.6(4) . . ? 
C9 C8 C7 121.2(5) . . ? 
C10 C9 C8 119.8(6) . . ? 
C9 C10 C11 119.5(5) . . ? 
C10 C11 C12 120.8(6) . . ? 
C7 C12 C11 119.2(6) . . ? 
C18 C13 C14 119.2(4) . . ? 
C18 C13 P1 122.2(4) . . ? 
C14 C13 P1 118.5(4) . . ? 
C15 C14 C13 119.5(5) . . ? 
C16 C15 C14 120.5(5) . . ? 
C17 C16 C15 120.0(5) . . ? 
C16 C17 C18 120.2(5) . . ? 
C13 C18 C17 120.6(5) . . ? 
 
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 
 P1 S1 I1 I2 169.8(4) . . . . ? 
 I1 S1 P1 C1 62.6(2) . . . . ? 
 I1 S1 P1 C13 -59.2(2) . . . . ? 
 I1 S1 P1 C7 -178.0(2) . . . . ? 
 C13 P1 C1 C2 134.8(4) . . . . ? 
 C7 P1 C1 C2 -108.8(4) . . . . ? 
 S1 P1 C1 C2 8.4(4) . . . . ? 
 C13 P1 C1 C6 -47.4(4) . . . . ? 
 C7 P1 C1 C6 69.1(4) . . . . ? 
 S1 P1 C1 C6 -173.8(3) . . . . ? 
 C6 C1 C2 C3 0.0(7) . . . . ? 
 P1 C1 C2 C3 177.9(4) . . . . ? 
 C1 C2 C3 C4 -1.4(8) . . . . ? 
 C2 C3 C4 C5 2.6(8) . . . . ? 
 C3 C4 C5 C6 -2.5(8) . . . . ? 
 C4 C5 C6 C1 1.1(8) . . . . ? 
 C2 C1 C6 C5 0.1(8) . . . . ? 
 P1 C1 C6 C5 -177.8(4) . . . . ? 
 C1 P1 C7 C8 169.8(3) . . . . ? 
 C13 P1 C7 C8 -75.1(4) . . . . ? 
 S1 P1 C7 C8 47.9(4) . . . . ? 
 C1 P1 C7 C12 -6.8(4) . . . . ? 
 C13 P1 C7 C12 108.4(4) . . . . ? 
 S1 P1 C7 C12 -128.7(4) . . . . ? 
 C12 C7 C8 C9 -0.9(7) . . . . ? 
 P1 C7 C8 C9 -177.5(3) . . . . ? 
 C7 C8 C9 C10 0.2(7) . . . . ? 
 C8 C9 C10 C11 -0.6(7) . . . . ? 
 C9 C10 C11 C12 1.7(8) . . . . ? 
 C8 C7 C12 C11 2.0(7) . . . . ? 
 P1 C7 C12 C11 178.5(3) . . . . ? 
 C10 C11 C12 C7 -2.4(7) . . . . ? 
 C1 P1 C13 C18 130.5(4) . . . . ? 
 C7 P1 C13 C18 13.4(5) . . . . ? 
 S1 P1 C13 C18 -103.9(4) . . . . ? 
 C1 P1 C13 C14 -54.8(4) . . . . ? 
 C7 P1 C13 C14 -171.9(4) . . . . ? 
 S1 P1 C13 C14 70.8(4) . . . . ? 
 C18 C13 C14 C15 -1.3(7) . . . . ? 
 P1 C13 C14 C15 -176.2(4) . . . . ? 
 C13 C14 C15 C16 0.8(8) . . . . ? 
 C14 C15 C16 C17 -0.3(8) . . . . ? 
 C15 C16 C17 C18 0.3(8) . . . . ? 
 C14 C13 C18 C17 1.3(7) . . . . ? 
 P1 C13 C18 C17 176.0(4) . . . . ? 
 C16 C17 C18 C13 -0.8(8) . . . . ? 
 
_refine_diff_density_max    0.704 
_refine_diff_density_min   -0.339 
_refine_diff_density_rms    0.080 

#======================================================