Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004

data_global

_journal_coden_Cambridge         222

loop_
_publ_author_name
'Alexander Hopkins'
'Felipe Garcia'
'Mary McPartlin'
'Michael C. Rogers'
'Dominic S. Wright'

_publ_contact_author_name        'Dr Alexander Hopkins'
_publ_contact_author_address     
;
Chemistry Department
Cambridge University
Lensfield Road
Cambridge
Cambridgeshire
CB2 1EW
UNITED KINGDOM
;

_publ_contact_author_email       ADH1002@CAM.AC.UK

_publ_requested_journal          'Dalton Transactions'

_publ_section_title              
;
The First Example of a Si-Bridged Tris(pyridyl)
Ligand; Synthesis and Structure of [MeSi(2-C5H4N)3LiX] (X= 0.2Br, 0.8Cl)
;

data_dw0312
_database_code_depnum_ccdc_archive 'CCDC 225454'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C16 H15 Br0.20 Cl0.80 Li N3 Si'
_chemical_formula_sum            'C16 H15 Br0.20 Cl0.80 Li N3 Si'
_chemical_formula_weight         328.68

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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.0817 0.0704 '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'
Li Li -0.0003 0.0001 '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'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Pnma

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

_cell_length_a                   15.9893(6)
_cell_length_b                   12.8602(4)
_cell_length_c                   8.4619(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1739.98(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    6490
_cell_measurement_theta_min      1.02
_cell_measurement_theta_max      27.48

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             678
_exptl_absorpt_coefficient_mu    0.714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.925
_exptl_absorpt_correction_T_max  0.996
_exptl_absorpt_process_details   
;
multi-scan from symmetry-related measurements
Sortav (Blessing 1995)
;

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      180(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  'Nonius Kappa CCD'
_diffrn_measurement_method       'Thin slice \w and \f scans'
_diffrn_reflns_number            8753
_diffrn_reflns_av_R_equivalents  0.0529
_diffrn_reflns_av_sigmaI/netI    0.0513
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         3.85
_diffrn_reflns_theta_max         27.57
_reflns_number_total             2069
_reflns_number_gt                1502
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Collect (Nonius B.V. 1998)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
;
HKL Denzo and Scalepack (Otwinowski & Minor 1997)
;
_computing_structure_solution    'SIR-92 (Altomare et al. 1994)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick 1997)'

_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^)+(0.0329P)^2^+0.8894P] 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         2069
_refine_ls_number_parameters     151
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0764
_refine_ls_R_factor_gt           0.0463
_refine_ls_wR_factor_ref         0.0982
_refine_ls_wR_factor_gt          0.0872
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_restrained_S_all      1.044
_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
Si1 Si 0.55057(5) 0.2500 0.53134(9) 0.0353(2) Uani 1 2 d S . .
Li1 Li 0.7445(3) 0.2500 0.5597(6) 0.0371(12) Uani 1 2 d S . .
Cl1 Cl 0.88558(4) 0.2500 0.57488(7) 0.03867(19) Uani 0.80 2 d SP A 1
Br1 Br 0.88558(4) 0.2500 0.57488(7) 0.03867(19) Uani 0.20 2 d SP A 2
N1 N 0.67494(11) 0.37076(15) 0.6573(2) 0.0384(5) Uani 1 1 d . A .
N2 N 0.69040(16) 0.2500 0.3401(3) 0.0369(6) Uani 1 2 d S A .
C1 C 0.59041(14) 0.36510(17) 0.6469(2) 0.0347(5) Uani 1 1 d . . .
C3 C 0.70861(18) 0.4461(2) 0.7457(3) 0.0481(6) Uani 1 1 d . . .
H3 H 0.7689(16) 0.4455(19) 0.748(3) 0.048(7) Uiso 1 1 d . . .
C4 C 0.6621(2) 0.5176(2) 0.8288(3) 0.0579(8) Uani 1 1 d . A .
H4 H 0.6905(17) 0.568(2) 0.893(3) 0.063(8) Uiso 1 1 d . . .
C5 C 0.5768(2) 0.5125(2) 0.8199(3) 0.0592(8) Uani 1 1 d . . .
H5 H 0.5430(18) 0.560(2) 0.880(3) 0.073(9) Uiso 1 1 d . . .
C6 C 0.53997(18) 0.4359(2) 0.7278(3) 0.0463(6) Uani 1 1 d . A .
H6 H 0.4800(16) 0.4289(18) 0.716(3) 0.044(7) Uiso 1 1 d . . .
C7 C 0.60547(19) 0.2500 0.3344(3) 0.0336(7) Uani 1 2 d S . .
C9 C 0.7328(2) 0.2500 0.2037(4) 0.0405(8) Uani 1 2 d S . .
H9 H 0.795(2) 0.2500 0.212(3) 0.032(8) Uiso 1 2 d S . .
C10 C 0.6945(3) 0.2500 0.0573(4) 0.0484(9) Uani 1 2 d S A .
H10 H 0.725(2) 0.2500 -0.037(4) 0.038(8) Uiso 1 2 d S . .
C11 C 0.6087(2) 0.2500 0.0505(4) 0.0476(9) Uani 1 2 d S . .
H11 H 0.580(2) 0.2500 -0.049(4) 0.047(9) Uiso 1 2 d S . .
C12 C 0.5636(2) 0.2500 0.1906(4) 0.0408(8) Uani 1 2 d S A .
H12 H 0.501(2) 0.2500 0.190(3) 0.038(9) Uiso 1 2 d S . .
C13 C 0.4361(2) 0.2500 0.5054(5) 0.0534(10) Uani 1 2 d S . .
H13A H 0.413(3) 0.2500 0.610(6) 0.087(15) Uiso 1 2 d S . .
H13B H 0.4189(19) 0.187(2) 0.445(4) 0.083(10) Uiso 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
Si1 0.0328(5) 0.0459(6) 0.0273(4) 0.000 -0.0017(3) 0.000
Li1 0.042(3) 0.039(3) 0.031(3) 0.000 -0.004(2) 0.000
Cl1 0.0313(3) 0.0451(4) 0.0396(3) 0.000 -0.0037(2) 0.000
Br1 0.0313(3) 0.0451(4) 0.0396(3) 0.000 -0.0037(2) 0.000
N1 0.0446(11) 0.0376(11) 0.0329(10) -0.0028(8) -0.0015(8) -0.0038(9)
N2 0.0391(15) 0.0449(17) 0.0266(13) 0.000 0.0021(11) 0.000
C1 0.0433(13) 0.0336(12) 0.0271(10) 0.0057(8) 0.0017(9) 0.0039(10)
C3 0.0574(17) 0.0444(15) 0.0424(13) -0.0047(11) 0.0014(12) -0.0099(13)
C4 0.087(2) 0.0398(16) 0.0468(15) -0.0082(12) 0.0074(15) -0.0153(16)
C5 0.091(2) 0.0354(16) 0.0514(16) -0.0028(12) 0.0177(15) 0.0092(16)
C6 0.0518(16) 0.0409(15) 0.0461(14) 0.0046(11) 0.0079(12) 0.0082(12)
C7 0.0372(17) 0.0368(18) 0.0270(15) 0.000 -0.0028(13) 0.000
C9 0.039(2) 0.048(2) 0.0343(18) 0.000 0.0068(14) 0.000
C10 0.069(3) 0.048(2) 0.0279(18) 0.000 0.0099(17) 0.000
C11 0.065(3) 0.052(2) 0.0263(17) 0.000 -0.0082(17) 0.000
C12 0.045(2) 0.046(2) 0.0314(17) 0.000 -0.0063(14) 0.000
C13 0.0324(18) 0.086(3) 0.042(2) 0.000 -0.0026(16) 0.000

_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
Si1 C13 1.843(4) . ?
Si1 C1 1.885(2) . ?
Si1 C1 1.885(2) 7_565 ?
Si1 C7 1.884(3) . ?
Si1 Li1 3.110(5) . ?
Li1 N2 2.050(5) . ?
Li1 N1 2.081(4) . ?
Li1 N1 2.081(4) 7_565 ?
Li1 Cl1 2.260(5) . ?
N1 C3 1.338(3) . ?
N1 C1 1.356(3) . ?
N2 C9 1.339(4) . ?
N2 C7 1.359(4) . ?
C1 C6 1.396(3) . ?
C3 C4 1.376(4) . ?
C4 C5 1.366(4) . ?
C5 C6 1.388(4) . ?
C7 C12 1.389(4) . ?
C9 C10 1.383(5) . ?
C10 C11 1.373(5) . ?
C11 C12 1.388(5) . ?

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
C13 Si1 C1 113.41(10) . . ?
C13 Si1 C1 113.41(10) . 7_565 ?
C1 Si1 C1 103.51(13) . 7_565 ?
C13 Si1 C7 110.93(16) . . ?
C1 Si1 C7 107.54(9) . . ?
C1 Si1 C7 107.54(9) 7_565 . ?
C13 Si1 Li1 177.59(16) . . ?
C1 Si1 Li1 67.85(8) . . ?
C1 Si1 Li1 67.85(8) 7_565 . ?
C7 Si1 Li1 66.66(13) . . ?
N2 Li1 N1 97.71(19) . . ?
N2 Li1 N1 97.71(19) . 7_565 ?
N1 Li1 N1 96.6(2) . 7_565 ?
N2 Li1 Cl1 118.2(2) . . ?
N1 Li1 Cl1 120.73(16) . . ?
N1 Li1 Cl1 120.73(16) 7_565 . ?
N2 Li1 Si1 60.62(15) . . ?
N1 Li1 Si1 59.86(14) . . ?
N1 Li1 Si1 59.86(14) 7_565 . ?
Cl1 Li1 Si1 178.8(2) . . ?
C3 N1 C1 118.4(2) . . ?
C3 N1 Li1 123.2(2) . . ?
C1 N1 Li1 117.82(19) . . ?
C9 N2 C7 118.4(3) . . ?
C9 N2 Li1 124.6(3) . . ?
C7 N2 Li1 117.0(2) . . ?
N1 C1 C6 120.6(2) . . ?
N1 C1 Si1 114.37(16) . . ?
C6 C1 Si1 124.85(18) . . ?
N1 C3 C4 123.5(3) . . ?
C5 C4 C3 118.7(3) . . ?
C4 C5 C6 119.2(3) . . ?
C5 C6 C1 119.6(3) . . ?
N2 C7 C12 120.8(3) . . ?
N2 C7 Si1 115.7(2) . . ?
C12 C7 Si1 123.4(2) . . ?
N2 C9 C10 123.2(3) . . ?
C11 C10 C9 118.7(3) . . ?
C10 C11 C12 118.9(3) . . ?
C11 C12 C7 119.9(3) . . ?

_diffrn_measured_fraction_theta_max 0.985
_diffrn_reflns_theta_full        27.57
_diffrn_measured_fraction_theta_full 0.985
_refine_diff_density_max         0.318
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.057