Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2003

data_global

_journal_coden_Cambridge         222

loop_
_publ_author_name
'Matthew Clarke'
A.Orpen
P.Pringle
'Edward Turley'

_publ_contact_author_name        'Dr Matthew Clarke'
_publ_contact_author_address     
;
School of Chemistry
University of St Andrews
St andrews
FIFE
KY16 9ST
UNITED KINGDOM
;

_publ_contact_author_email       MC28@ST-ANDREWS.AC.UK

_publ_requested_journal          'Dalton Transactions'

_publ_section_title              
;
Organometallic chemistry of bromodifluoromethyl
substituted phosphines.  The development of a novel nickel catalysed P-C
bond forming reaction.
;

data_sad
_database_code_CSD               220351

_audit_creation_method           SHELXL-97
_chemical_formula_moiety         'C23 H25 Br Cl2 F2 P Rh'
_chemical_formula_sum            'C23 H25 Br Cl2 F2 P Rh'
_chemical_formula_weight         624.12

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'
F F 0.0171 0.0103 '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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Rh Rh -1.1178 0.9187 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'C 2/c'
_symmetry_space_group_name_Hall  '-C 2yc'

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

_cell_length_a                   15.890(3)
_cell_length_b                   8.3668(18)
_cell_length_c                   36.119(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 92.679(4)
_cell_angle_gamma                90.00
_cell_volume                     4796.7(18)
_cell_formula_units_Z            8
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      0.622
_cell_measurement_theta_max      0.764

_exptl_crystal_description       cube
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.40
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.728
_exptl_crystal_density_method    none
_exptl_crystal_F_000             2480
_exptl_absorpt_coefficient_mu    2.692
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.405
_exptl_absorpt_correction_T_max  0.766
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1996)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(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       'Frames, each covering 0.3 \% in \w'
_diffrn_detector_area_resol_mean 8.2
_diffrn_standards_decay_%        0
_diffrn_reflns_number            24225
_diffrn_reflns_av_R_equivalents  0.0567
_diffrn_reflns_av_sigmaI/netI    0.0411
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_theta_min         1.13
_diffrn_reflns_theta_max         27.48
_reflns_number_total             5500
_reflns_number_gt                4609
_reflns_threshold_expression     >2\s(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_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^)+(0.0451P)^2^+58.5618P] 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_number_reflns         5500
_refine_ls_number_parameters     271
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0573
_refine_ls_wR_factor_ref         0.1342
_refine_ls_wR_factor_gt          0.1285
_refine_ls_goodness_of_fit_ref   1.143
_refine_ls_restrained_S_all      1.143
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Rh1 Rh 0.24450(3) 0.81120(5) 0.167083(11) 0.01943(12) Uani 1 1 d . . .
P1 P 0.25129(9) 0.83526(16) 0.10329(4) 0.0183(3) Uani 1 1 d . . .
Cl2 Cl 0.34874(10) 1.01777(17) 0.17815(4) 0.0311(3) Uani 1 1 d . . .
Cl1 Cl 0.13281(10) 1.00567(18) 0.16874(4) 0.0330(3) Uani 1 1 d . . .
C11 C 0.1609(4) 0.7435(7) 0.07881(14) 0.0223(11) Uani 1 1 d . . .
C18 C 0.3513(4) 0.7239(7) 0.04505(17) 0.0278(12) Uani 1 1 d . . .
H18A H 0.3026 0.7318 0.0289 0.033 Uiso 1 1 calc R . .
C2 C 0.2702(4) 0.5533(7) 0.16996(17) 0.0319(14) Uani 1 1 d . . .
C17 C 0.3466(3) 0.7647(7) 0.08286(14) 0.0217(11) Uani 1 1 d . . .
C22 C 0.4205(4) 0.7569(7) 0.10567(17) 0.0280(12) Uani 1 1 d . . .
H22A H 0.4191 0.7879 0.1309 0.034 Uiso 1 1 calc R . .
C12 C 0.0820(4) 0.8073(8) 0.08443(17) 0.0306(13) Uani 1 1 d . . .
H12A H 0.0775 0.9022 0.0986 0.037 Uiso 1 1 calc R . .
C1 C 0.3190(4) 0.6333(7) 0.19799(17) 0.0303(13) Uani 1 1 d . . .
C16 C 0.1668(4) 0.6000(7) 0.05874(15) 0.0266(12) Uani 1 1 d . . .
H16A H 0.2203 0.5536 0.0550 0.032 Uiso 1 1 calc R . .
C7 C 0.3025(6) 0.4406(8) 0.1413(2) 0.049(2) Uani 1 1 d . . .
H7A H 0.3064 0.3325 0.1517 0.074 Uiso 1 1 calc R . .
H7B H 0.3583 0.4756 0.1342 0.074 Uiso 1 1 calc R . .
H7C H 0.2636 0.4404 0.1194 0.074 Uiso 1 1 calc R . .
C19 C 0.4247(5) 0.6739(7) 0.03179(16) 0.0348(15) Uani 1 1 d . . .
H19A H 0.4272 0.6470 0.0063 0.042 Uiso 1 1 calc R . .
C13 C 0.0100(4) 0.7350(8) 0.06973(18) 0.0353(14) Uani 1 1 d . . .
H13A H -0.0434 0.7824 0.0732 0.042 Uiso 1 1 calc R . .
C15 C 0.0936(4) 0.5265(8) 0.04434(17) 0.0337(14) Uani 1 1 d . . .
H15A H 0.0975 0.4301 0.0306 0.040 Uiso 1 1 calc R . .
C4 C 0.1792(4) 0.6721(8) 0.20948(17) 0.0349(15) Uani 1 1 d . . .
C3 C 0.1822(4) 0.5828(8) 0.17570(17) 0.0335(14) Uani 1 1 d . . .
C5 C 0.2628(5) 0.7068(7) 0.22268(15) 0.0319(14) Uani 1 1 d . . .
C20 C 0.4976(4) 0.6609(8) 0.05534(19) 0.0342(14) Uani 1 1 d . . .
H20A H 0.5488 0.6221 0.0461 0.041 Uiso 1 1 calc R . .
C9 C 0.1000(5) 0.7181(11) 0.2282(2) 0.060(2) Uani 1 1 d . . .
H9A H 0.0858 0.6347 0.2459 0.090 Uiso 1 1 calc R . .
H9B H 0.0537 0.7301 0.2095 0.090 Uiso 1 1 calc R . .
H9C H 0.1090 0.8196 0.2414 0.090 Uiso 1 1 calc R . .
C10 C 0.2873(6) 0.7926(9) 0.25771(18) 0.056(2) Uani 1 1 d . . .
H10A H 0.2897 0.7166 0.2784 0.084 Uiso 1 1 calc R . .
H10B H 0.2456 0.8757 0.2623 0.084 Uiso 1 1 calc R . .
H10C H 0.3428 0.8419 0.2555 0.084 Uiso 1 1 calc R . .
C14 C 0.0150(4) 0.5930(8) 0.04983(18) 0.0356(15) Uani 1 1 d . . .
H14A H -0.0348 0.5422 0.0401 0.043 Uiso 1 1 calc R . .
C8 C 0.1083(6) 0.5073(11) 0.1553(2) 0.057(2) Uani 1 1 d . . .
H8A H 0.0957 0.4043 0.1667 0.086 Uiso 1 1 calc R . .
H8B H 0.1215 0.4905 0.1293 0.086 Uiso 1 1 calc R . .
H8C H 0.0592 0.5778 0.1564 0.086 Uiso 1 1 calc R . .
C6 C 0.4123(5) 0.6286(10) 0.2040(2) 0.051(2) Uani 1 1 d . . .
H6A H 0.4284 0.5344 0.2188 0.076 Uiso 1 1 calc R . .
H6B H 0.4315 0.7254 0.2171 0.076 Uiso 1 1 calc R . .
H6C H 0.4385 0.6227 0.1800 0.076 Uiso 1 1 calc R . .
Br1 Br 0.23558(5) 1.06291(8) 0.029431(18) 0.03882(18) Uani 1 1 d . . .
F1 F 0.1919(2) 1.1409(4) 0.09743(10) 0.0336(8) Uani 1 1 d . . .
F2 F 0.3266(2) 1.1174(4) 0.09175(10) 0.0334(8) Uani 1 1 d . . .
C23 C 0.2511(4) 1.0465(7) 0.08379(15) 0.0241(11) Uani 1 1 d . . .
C21 C 0.4936(4) 0.7056(8) 0.09202(18) 0.0344(14) Uani 1 1 d . . .
H21A H 0.5429 0.7002 0.1079 0.041 Uiso 1 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
Rh1 0.0270(2) 0.0162(2) 0.01497(19) -0.00067(15) -0.00007(14) 0.00121(17)
P1 0.0196(7) 0.0188(7) 0.0166(6) 0.0008(5) 0.0010(5) -0.0007(5)
Cl2 0.0421(9) 0.0210(7) 0.0298(7) -0.0022(5) -0.0052(6) -0.0058(6)
Cl1 0.0396(9) 0.0301(7) 0.0298(7) 0.0007(6) 0.0054(6) 0.0139(6)
C11 0.024(3) 0.026(3) 0.017(2) 0.002(2) -0.001(2) -0.006(2)
C18 0.028(3) 0.022(3) 0.033(3) 0.001(2) -0.004(2) -0.003(2)
C2 0.047(4) 0.017(3) 0.031(3) 0.005(2) 0.002(3) 0.008(3)
C17 0.023(3) 0.022(3) 0.020(2) 0.000(2) 0.006(2) 0.002(2)
C22 0.034(3) 0.019(3) 0.030(3) -0.003(2) -0.008(2) -0.001(2)
C12 0.026(3) 0.033(3) 0.033(3) -0.004(3) 0.003(2) -0.007(3)
C1 0.033(3) 0.022(3) 0.036(3) 0.009(2) -0.001(3) 0.003(2)
C16 0.027(3) 0.030(3) 0.023(3) 0.000(2) 0.002(2) -0.006(2)
C7 0.088(6) 0.015(3) 0.046(4) 0.003(3) 0.019(4) 0.014(3)
C19 0.058(4) 0.025(3) 0.022(3) -0.005(2) 0.011(3) -0.008(3)
C13 0.023(3) 0.043(4) 0.040(3) 0.006(3) 0.002(3) -0.005(3)
C15 0.045(4) 0.030(3) 0.025(3) -0.001(2) -0.002(3) -0.012(3)
C4 0.041(4) 0.032(3) 0.033(3) 0.016(3) 0.011(3) 0.011(3)
C3 0.045(4) 0.029(3) 0.026(3) 0.014(2) -0.002(3) -0.009(3)
C5 0.060(4) 0.019(3) 0.016(3) 0.003(2) 0.004(3) -0.001(3)
C20 0.026(3) 0.032(3) 0.045(4) -0.001(3) 0.010(3) 0.003(3)
C9 0.064(5) 0.060(5) 0.059(5) 0.026(4) 0.036(4) 0.025(4)
C10 0.110(7) 0.035(4) 0.022(3) -0.002(3) -0.007(4) -0.004(4)
C14 0.033(3) 0.041(4) 0.032(3) 0.001(3) -0.004(3) -0.016(3)
C8 0.064(5) 0.059(5) 0.049(4) 0.022(4) -0.006(4) -0.028(4)
C6 0.039(4) 0.050(4) 0.063(5) 0.027(4) -0.010(4) 0.008(3)
Br1 0.0498(4) 0.0386(4) 0.0282(3) 0.0073(3) 0.0031(3) 0.0029(3)
F1 0.035(2) 0.0250(18) 0.042(2) 0.0021(15) 0.0106(16) 0.0083(15)
F2 0.0271(18) 0.0246(18) 0.048(2) -0.0038(16) -0.0047(15) -0.0060(15)
C23 0.023(3) 0.023(3) 0.025(3) 0.002(2) 0.000(2) 0.000(2)
C21 0.035(3) 0.027(3) 0.040(3) 0.001(3) -0.002(3) -0.006(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 2.177(6) . ?
Rh1 C3 2.181(6) . ?
Rh1 C5 2.197(5) . ?
Rh1 C2 2.197(6) . ?
Rh1 C4 2.219(6) . ?
Rh1 P1 2.3206(14) . ?
Rh1 Cl1 2.4105(15) . ?
Rh1 Cl2 2.4143(15) . ?
P1 C17 1.814(5) . ?
P1 C11 1.821(6) . ?
P1 C23 1.902(6) . ?
C11 C12 1.386(8) . ?
C11 C16 1.408(8) . ?
C18 C19 1.347(9) . ?
C18 C17 1.413(8) . ?
C2 C1 1.415(9) . ?
C2 C3 1.443(10) . ?
C2 C7 1.507(9) . ?
C17 C22 1.404(8) . ?
C22 C21 1.354(9) . ?
C12 C13 1.378(9) . ?
C1 C5 1.431(9) . ?
C1 C6 1.489(9) . ?
C16 C15 1.395(8) . ?
C19 C20 1.410(10) . ?
C13 C14 1.393(10) . ?
C15 C14 1.390(10) . ?
C4 C5 1.420(10) . ?
C4 C3 1.434(9) . ?
C4 C9 1.506(9) . ?
C3 C8 1.498(10) . ?
C5 C10 1.491(8) . ?
C20 C21 1.381(9) . ?
Br1 C23 1.972(6) . ?
F1 C23 1.340(7) . ?
F2 C23 1.356(7) . ?

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 C3 64.4(2) . . ?
C1 Rh1 C5 38.2(2) . . ?
C3 Rh1 C5 64.1(2) . . ?
C1 Rh1 C2 37.7(2) . . ?
C3 Rh1 C2 38.5(3) . . ?
C5 Rh1 C2 63.3(2) . . ?
C1 Rh1 C4 63.2(2) . . ?
C3 Rh1 C4 38.0(2) . . ?
C5 Rh1 C4 37.5(3) . . ?
C2 Rh1 C4 62.9(2) . . ?
C1 Rh1 P1 121.26(18) . . ?
C3 Rh1 P1 105.08(17) . . ?
C5 Rh1 P1 158.74(17) . . ?
C2 Rh1 P1 96.60(16) . . ?
C4 Rh1 P1 140.87(19) . . ?
C1 Rh1 Cl1 146.32(17) . . ?
C3 Rh1 Cl1 104.40(19) . . ?
C5 Rh1 Cl1 108.17(18) . . ?
C2 Rh1 Cl1 142.84(19) . . ?
C4 Rh1 Cl1 88.18(17) . . ?
P1 Rh1 Cl1 91.98(5) . . ?
C1 Rh1 Cl2 92.97(17) . . ?
C3 Rh1 Cl2 156.33(17) . . ?
C5 Rh1 Cl2 94.18(17) . . ?
C2 Rh1 Cl2 124.79(19) . . ?
C4 Rh1 Cl2 126.89(19) . . ?
P1 Rh1 Cl2 92.23(5) . . ?
Cl1 Rh1 Cl2 90.74(6) . . ?
C17 P1 C11 108.7(3) . . ?
C17 P1 C23 98.0(3) . . ?
C11 P1 C23 103.0(3) . . ?
C17 P1 Rh1 117.01(18) . . ?
C11 P1 Rh1 111.91(18) . . ?
C23 P1 Rh1 116.67(18) . . ?
C12 C11 C16 119.1(5) . . ?
C12 C11 P1 117.7(4) . . ?
C16 C11 P1 122.6(4) . . ?
C19 C18 C17 120.3(6) . . ?
C1 C2 C3 108.6(5) . . ?
C1 C2 C7 126.5(7) . . ?
C3 C2 C7 124.6(7) . . ?
C1 C2 Rh1 70.4(3) . . ?
C3 C2 Rh1 70.1(3) . . ?
C7 C2 Rh1 130.6(4) . . ?
C22 C17 C18 118.3(5) . . ?
C22 C17 P1 117.9(4) . . ?
C18 C17 P1 123.7(4) . . ?
C21 C22 C17 120.7(6) . . ?
C13 C12 C11 121.0(6) . . ?
C2 C1 C5 108.1(6) . . ?
C2 C1 C6 126.9(7) . . ?
C5 C1 C6 124.6(7) . . ?
C2 C1 Rh1 71.9(3) . . ?
C5 C1 Rh1 71.6(3) . . ?
C6 C1 Rh1 127.4(5) . . ?
C15 C16 C11 119.6(6) . . ?
C18 C19 C20 120.7(6) . . ?
C12 C13 C14 120.5(6) . . ?
C14 C15 C16 120.7(6) . . ?
C5 C4 C3 108.9(6) . . ?
C5 C4 C9 125.8(7) . . ?
C3 C4 C9 125.2(7) . . ?
C5 C4 Rh1 70.4(3) . . ?
C3 C4 Rh1 69.6(3) . . ?
C9 C4 Rh1 127.1(5) . . ?
C4 C3 C2 106.4(6) . . ?
C4 C3 C8 125.6(7) . . ?
C2 C3 C8 126.9(7) . . ?
C4 C3 Rh1 72.4(4) . . ?
C2 C3 Rh1 71.4(3) . . ?
C8 C3 Rh1 130.5(5) . . ?
C4 C5 C1 107.8(5) . . ?
C4 C5 C10 125.9(7) . . ?
C1 C5 C10 126.1(7) . . ?
C4 C5 Rh1 72.1(3) . . ?
C1 C5 Rh1 70.2(3) . . ?
C10 C5 Rh1 127.1(4) . . ?
C21 C20 C19 119.0(6) . . ?
C15 C14 C13 119.2(6) . . ?
F1 C23 F2 107.0(5) . . ?
F1 C23 P1 113.6(4) . . ?
F2 C23 P1 110.0(4) . . ?
F1 C23 Br1 105.5(4) . . ?
F2 C23 Br1 104.4(4) . . ?
P1 C23 Br1 115.5(3) . . ?
C22 C21 C20 120.9(6) . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        27.48
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         1.462
_refine_diff_density_min         -1.414
_refine_diff_density_rms         0.150

data_cranksad
_database_code_CSD               220352

_audit_creation_method           SHELXL-97
_chemical_formula_moiety         'C36 H66 Br2 P2 Pd1'
_chemical_formula_sum            'C36 H66 Br2 P2 Pd1'
_chemical_formula_weight         827.05

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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Triclinic
_symmetry_space_group_name_H-M   P-1
_symmetry_space_group_name_Hall  '-P 1'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   9.9954(15)
_cell_length_b                   10.1866(15)
_cell_length_c                   10.7114(16)
_cell_angle_alpha                112.589(2)
_cell_angle_beta                 109.652(2)
_cell_angle_gamma                92.205(2)
_cell_volume                     930.5(2)
_cell_formula_units_Z            1
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       cube
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.476
_exptl_crystal_density_method    none
_exptl_crystal_F_000             428
_exptl_absorpt_coefficient_mu    2.755
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.542
_exptl_absorpt_correction_T_max  0.726
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1996)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(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       'Frames, each covering 0.3 \% in \w'
_diffrn_detector_area_resol_mean 8.2
_diffrn_standards_number         0
_diffrn_reflns_number            9717
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_sigmaI/netI    0.0399
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.20
_diffrn_reflns_theta_max         27.53
_reflns_number_total             4201
_reflns_number_gt                3440
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_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^)+(0.0581P)^2^+2.1044P] 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_number_reflns         4201
_refine_ls_number_parameters     187
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0392
_refine_ls_wR_factor_ref         0.1211
_refine_ls_wR_factor_gt          0.1172
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_restrained_S_all      1.100
_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
Pd1 Pd 0.5000 0.5000 0.0000 0.01370(12) Uani 1 2 d S . .
Br1 Br 0.34713(5) 0.42560(6) 0.10596(5) 0.03287(15) Uani 1 1 d . . .
P1 P 0.70520(11) 0.53311(10) 0.20813(11) 0.0150(2) Uani 1 1 d . . .
C1 C 0.8739(4) 0.6386(4) 0.2310(5) 0.0180(8) Uani 1 1 d . . .
H1A H 0.8745 0.6041 0.1303 0.022 Uiso 1 1 calc R . .
C2 C 0.8723(5) 0.8012(4) 0.2800(5) 0.0236(9) Uani 1 1 d . . .
H2A H 0.7799 0.8148 0.2183 0.028 Uiso 1 1 calc R . .
H2B H 0.8794 0.8446 0.3826 0.028 Uiso 1 1 calc R . .
C3 C 0.9981(5) 0.8772(5) 0.2676(6) 0.0346(11) Uani 1 1 d . . .
H3A H 0.9979 0.9824 0.3041 0.042 Uiso 1 1 calc R . .
H3B H 0.9853 0.8403 0.1635 0.042 Uiso 1 1 calc R . .
C4 C 1.1429(5) 0.8532(5) 0.3543(6) 0.0357(12) Uani 1 1 d . . .
H4A H 1.2212 0.8974 0.3374 0.043 Uiso 1 1 calc R . .
H4B H 1.1618 0.9010 0.4600 0.043 Uiso 1 1 calc R . .
C5 C 1.1429(5) 0.6934(5) 0.3093(6) 0.0314(10) Uani 1 1 d . . .
H5A H 1.2359 0.6806 0.3710 0.038 Uiso 1 1 calc R . .
H5B H 1.1350 0.6481 0.2065 0.038 Uiso 1 1 calc R . .
C6 C 1.0188(4) 0.6170(5) 0.3237(5) 0.0243(9) Uani 1 1 d . . .
H6A H 1.0298 0.6568 0.4274 0.029 Uiso 1 1 calc R . .
H6B H 1.0207 0.5122 0.2904 0.029 Uiso 1 1 calc R . .
C7 C 0.7555(4) 0.3569(4) 0.1966(4) 0.0175(8) Uani 1 1 d . . .
H7A H 0.8498 0.3786 0.2799 0.021 Uiso 1 1 calc R . .
C8 C 0.6484(5) 0.2584(4) 0.2110(5) 0.0241(9) Uani 1 1 d . . .
H8A H 0.5527 0.2361 0.1314 0.029 Uiso 1 1 calc R . .
H8B H 0.6374 0.3089 0.3054 0.029 Uiso 1 1 calc R . .
C9 C 0.7009(5) 0.1168(5) 0.2031(5) 0.0285(10) Uani 1 1 d . . .
H9A H 0.7930 0.1385 0.2871 0.034 Uiso 1 1 calc R . .
H9B H 0.6285 0.0532 0.2096 0.034 Uiso 1 1 calc R . .
C10 C 0.7235(5) 0.0385(5) 0.0613(5) 0.0286(10) Uani 1 1 d . . .
H10A H 0.6299 0.0105 -0.0225 0.034 Uiso 1 1 calc R . .
H10B H 0.7598 -0.0509 0.0597 0.034 Uiso 1 1 calc R . .
C11 C 0.8319(5) 0.1355(5) 0.0463(5) 0.0285(10) Uani 1 1 d . . .
H11A H 0.9279 0.1567 0.1253 0.034 Uiso 1 1 calc R . .
H11B H 0.8421 0.0845 -0.0485 0.034 Uiso 1 1 calc R . .
C12 C 0.7816(5) 0.2773(4) 0.0550(5) 0.0237(9) Uani 1 1 d . . .
H12A H 0.6908 0.2565 -0.0302 0.028 Uiso 1 1 calc R . .
H12B H 0.8557 0.3408 0.0505 0.028 Uiso 1 1 calc R . .
C13 C 0.6729(4) 0.6093(4) 0.3797(4) 0.0175(8) Uani 1 1 d . . .
H13A H 0.5977 0.5337 0.3690 0.021 Uiso 1 1 calc R . .
C14 C 0.6051(5) 0.7452(4) 0.4021(5) 0.0230(9) Uani 1 1 d . . .
H14A H 0.6767 0.8277 0.4217 0.028 Uiso 1 1 calc R . .
H14B H 0.5206 0.7279 0.3124 0.028 Uiso 1 1 calc R . .
C15 C 0.5573(5) 0.7814(5) 0.5311(5) 0.0286(10) Uani 1 1 d . . .
H15A H 0.5197 0.8727 0.5490 0.034 Uiso 1 1 calc R . .
H15B H 0.4774 0.7035 0.5056 0.034 Uiso 1 1 calc R . .
C16 C 0.6795(5) 0.7980(5) 0.6696(5) 0.0278(10) Uani 1 1 d . . .
H16A H 0.6413 0.8127 0.7472 0.033 Uiso 1 1 calc R . .
H16B H 0.7533 0.8847 0.7033 0.033 Uiso 1 1 calc R . .
C17 C 0.7495(5) 0.6652(5) 0.6445(5) 0.0276(9) Uani 1 1 d . . .
H17A H 0.6786 0.5806 0.6218 0.033 Uiso 1 1 calc R . .
H17B H 0.8327 0.6818 0.7349 0.033 Uiso 1 1 calc R . .
C18 C 0.8012(5) 0.6329(5) 0.5192(4) 0.0225(9) Uani 1 1 d . . .
H18A H 0.8445 0.5450 0.5035 0.027 Uiso 1 1 calc R . .
H18B H 0.8763 0.7149 0.5437 0.027 Uiso 1 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
Pd1 0.0122(2) 0.0172(2) 0.0110(2) 0.00637(15) 0.00326(15) 0.00231(15)
Br1 0.0268(3) 0.0474(3) 0.0268(3) 0.0198(2) 0.0086(2) 0.0034(2)
P1 0.0140(5) 0.0164(4) 0.0131(5) 0.0066(4) 0.0029(4) 0.0020(4)
C1 0.0144(18) 0.0200(19) 0.020(2) 0.0109(16) 0.0042(16) 0.0033(15)
C2 0.020(2) 0.021(2) 0.032(2) 0.0134(18) 0.0089(18) 0.0037(16)
C3 0.028(3) 0.030(2) 0.055(3) 0.027(2) 0.016(2) 0.0054(19)
C4 0.018(2) 0.034(3) 0.053(3) 0.022(2) 0.008(2) -0.0021(19)
C5 0.014(2) 0.036(3) 0.046(3) 0.023(2) 0.008(2) 0.0048(18)
C6 0.015(2) 0.027(2) 0.028(2) 0.0163(18) 0.0008(17) 0.0033(16)
C7 0.0192(19) 0.0159(17) 0.0157(19) 0.0072(15) 0.0039(16) 0.0030(15)
C8 0.027(2) 0.0198(19) 0.030(2) 0.0132(18) 0.0136(19) 0.0063(17)
C9 0.033(3) 0.021(2) 0.034(3) 0.0158(19) 0.010(2) 0.0058(18)
C10 0.030(2) 0.0157(19) 0.031(2) 0.0070(17) 0.005(2) 0.0028(17)
C11 0.031(2) 0.022(2) 0.029(2) 0.0060(18) 0.012(2) 0.0062(18)
C12 0.031(2) 0.0187(19) 0.022(2) 0.0067(16) 0.0120(18) 0.0047(17)
C13 0.0174(19) 0.0196(18) 0.0145(19) 0.0073(15) 0.0049(15) 0.0032(15)
C14 0.023(2) 0.022(2) 0.022(2) 0.0072(16) 0.0072(17) 0.0074(16)
C15 0.026(2) 0.031(2) 0.026(2) 0.0066(18) 0.0123(19) 0.0084(19)
C16 0.030(2) 0.029(2) 0.020(2) 0.0041(17) 0.0125(19) 0.0005(18)
C17 0.031(2) 0.033(2) 0.017(2) 0.0101(18) 0.0068(18) 0.0028(19)
C18 0.023(2) 0.028(2) 0.014(2) 0.0086(16) 0.0043(17) 0.0052(17)

_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
Pd1 P1 2.3631(10) 2_665 ?
Pd1 P1 2.3631(10) . ?
Pd1 Br1 2.4363(5) 2_665 ?
Pd1 Br1 2.4363(5) . ?
P1 C13 1.845(4) . ?
P1 C7 1.852(4) . ?
P1 C1 1.854(4) . ?
C1 C6 1.535(5) . ?
C1 C2 1.536(5) . ?
C2 C3 1.521(6) . ?
C3 C4 1.521(7) . ?
C4 C5 1.509(7) . ?
C5 C6 1.521(6) . ?
C7 C8 1.524(6) . ?
C7 C12 1.538(6) . ?
C8 C9 1.535(6) . ?
C9 C10 1.519(7) . ?
C10 C11 1.528(7) . ?
C11 C12 1.527(6) . ?
C13 C18 1.532(5) . ?
C13 C14 1.536(5) . ?
C14 C15 1.529(6) . ?
C15 C16 1.515(7) . ?
C16 C17 1.521(6) . ?
C17 C18 1.523(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 Pd1 P1 180.00(5) 2_665 . ?
P1 Pd1 Br1 89.15(3) 2_665 2_665 ?
P1 Pd1 Br1 90.85(3) . 2_665 ?
P1 Pd1 Br1 90.85(3) 2_665 . ?
P1 Pd1 Br1 89.15(3) . . ?
Br1 Pd1 Br1 180.0 2_665 . ?
C13 P1 C7 104.22(18) . . ?
C13 P1 C1 109.53(19) . . ?
C7 P1 C1 102.91(18) . . ?
C13 P1 Pd1 113.10(13) . . ?
C7 P1 Pd1 110.69(13) . . ?
C1 P1 Pd1 115.34(13) . . ?
C6 C1 C2 109.7(3) . . ?
C6 C1 P1 117.9(3) . . ?
C2 C1 P1 112.9(3) . . ?
C3 C2 C1 110.5(4) . . ?
C2 C3 C4 111.8(4) . . ?
C5 C4 C3 110.7(4) . . ?
C4 C5 C6 112.1(4) . . ?
C5 C6 C1 109.8(4) . . ?
C8 C7 C12 110.4(3) . . ?
C8 C7 P1 114.7(3) . . ?
C12 C7 P1 110.4(3) . . ?
C7 C8 C9 110.8(4) . . ?
C10 C9 C8 110.9(4) . . ?
C9 C10 C11 110.7(4) . . ?
C12 C11 C10 110.5(4) . . ?
C11 C12 C7 111.7(4) . . ?
C18 C13 C14 110.4(3) . . ?
C18 C13 P1 116.0(3) . . ?
C14 C13 P1 114.4(3) . . ?
C15 C14 C13 109.6(4) . . ?
C16 C15 C14 112.5(4) . . ?
C15 C16 C17 111.3(4) . . ?
C16 C17 C18 111.2(4) . . ?
C17 C18 C13 109.5(3) . . ?

_diffrn_measured_fraction_theta_max 0.983
_diffrn_reflns_theta_full        27.53
_diffrn_measured_fraction_theta_full 0.983
_refine_diff_density_max         1.428
_refine_diff_density_min         -1.457
_refine_diff_density_rms         0.123