#------------------------------------------------------------------------------
#$Date: 2016-03-22 11:34:44 +0200 (Tue, 22 Mar 2016) $
#$Revision: 178905 $
#$URL: svn://www.crystallography.net/cod/cif/4/11/34/4113426.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4113426
loop_
_publ_author_name
'David G. Churchill'
'Kevin E. Janak'
'Joshua S. Wittenberg'
'Gerard Parkin'
_publ_section_title
;
 Normal and Inverse Primary Kinetic Deuterium Isotope Effects for C-H Bond
 Reductive Elimination and Oxidative Addition Reactions of Molybdenocene
 and Tungstenocene Complexes: Evidence for Benzene σ-Complex
 Intermediates
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1403
_journal_page_last               1420
_journal_paper_doi               10.1021/ja027670k
_journal_volume                  125
_journal_year                    2003
_chemical_formula_sum            'C21 H34 Si W'
_chemical_formula_weight         498.42
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           62
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.257(3)
_cell_length_b                   14.744(6)
_cell_length_c                   13.261(5)
_cell_measurement_temperature    243(2)
_cell_volume                     2005.5(13)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      243(2)
_diffrn_measured_fraction_theta_full 0.952
_diffrn_measured_fraction_theta_max 0.952
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1108
_diffrn_reflns_av_sigmaI/netI    0.1140
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13447
_diffrn_reflns_theta_full        28.36
_diffrn_reflns_theta_max         28.36
_diffrn_reflns_theta_min         2.07
_exptl_absorpt_coefficient_mu    5.818
_exptl_absorpt_correction_T_max  0.5938
_exptl_absorpt_correction_T_min  0.3891
_exptl_crystal_density_diffrn    1.651
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_refine_diff_density_max         1.134
_refine_diff_density_min         -2.488
_refine_diff_density_rms         0.201
_refine_ls_extinction_coef       0.00076(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     116
_refine_ls_number_reflns         2474
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.1317
_refine_ls_R_factor_gt           0.0527
_refine_ls_shift/su_max          0.083
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0506P)²+5.5834P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1049
_refine_ls_wR_factor_ref         0.1266
_reflns_number_gt                1379
_reflns_number_total             2474
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja027670k-5_s1_2.cif
_cod_data_source_block           ds10
_cod_original_cell_volume        2005.6(13)
_cod_database_code               4113426
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z'
'x+1/2, -y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z'
'-x-1/2, y-1/2, z-1/2'
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
W W 0.13515(5) 0.2500 0.46430(4) 0.0381(2) Uani 1 2 d S
C1 C -0.0474(16) 0.3150(13) 0.3970(15) 0.039(5) Uiso 0.50 1 d P
H1A H -0.0404 0.3369 0.3283 0.059 Uiso 0.50 1 calc PR
H1B H 0.0261 0.3369 0.4361 0.059 Uiso 0.50 1 calc PR
H1C H -0.1279 0.3369 0.4267 0.059 Uiso 0.50 1 calc PR
C11 C 0.3483(11) 0.2500 0.4312(10) 0.034(3) Uani 1 2 d S
C12 C 0.2937(9) 0.3291(7) 0.3824(7) 0.041(3) Uani 1 1 d .
C13 C 0.2076(10) 0.2945(7) 0.3034(7) 0.049(3) Uani 1 1 d .
C21 C 0.2314(9) 0.2500 0.6156(9) 0.027(3) Uani 1 2 d S
C22 C 0.1461(9) 0.3271(6) 0.6114(7) 0.035(2) Uani 1 1 d .
C23 C 0.0170(10) 0.2995(8) 0.6084(8) 0.054(3) Uani 1 1 d .
C32 C 0.3343(10) 0.4274(8) 0.3924(9) 0.058(3) Uani 1 1 d .
H32A H 0.3777 0.4364 0.4566 0.087 Uiso 1 1 calc R
H32B H 0.2578 0.4659 0.3889 0.087 Uiso 1 1 calc R
H32C H 0.3935 0.4430 0.3380 0.087 Uiso 1 1 calc R
C33 C 0.1479(10) 0.3552(8) 0.2271(8) 0.063(3) Uani 1 1 d .
H33A H 0.2128 0.3716 0.1771 0.095 Uiso 1 1 calc R
H33B H 0.1158 0.4096 0.2599 0.095 Uiso 1 1 calc R
H33C H 0.0761 0.3242 0.1944 0.095 Uiso 1 1 calc R
C42 C 0.1812(11) 0.4255(8) 0.6312(9) 0.067(4) Uani 1 1 d .
H42A H 0.1298 0.4644 0.5876 0.100 Uiso 1 1 calc R
H42B H 0.2731 0.4348 0.6174 0.100 Uiso 1 1 calc R
H42C H 0.1632 0.4401 0.7011 0.100 Uiso 1 1 calc R
C43 C -0.1026(10) 0.3587(11) 0.6131(10) 0.097(5) Uani 1 1 d .
H43A H -0.1351 0.3604 0.6817 0.145 Uiso 1 1 calc R
H43B H -0.1693 0.3343 0.5689 0.145 Uiso 1 1 calc R
H43C H -0.0804 0.4197 0.5916 0.145 Uiso 1 1 calc R
C51 C 0.5061(10) 0.3474(9) 0.6003(9) 0.073(4) Uani 1 1 d .
H51A H 0.5333 0.3415 0.6700 0.110 Uiso 1 1 calc R
H51B H 0.4567 0.4030 0.5920 0.110 Uiso 1 1 calc R
H51C H 0.5823 0.3490 0.5570 0.110 Uiso 1 1 calc R
Si Si 0.4034(3) 0.2500 0.5657(3) 0.0401(10) Uani 1 2 d S
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'
Si Si 0.0817 0.0704 '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'
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
C11 W C21 75.1(4) . .
C11 W C22 97.0(4) . .
C21 W C22 37.2(3) . .
C11 W C22 97.0(4) . 7_565
C21 W C22 37.2(3) . 7_565
C22 W C22 60.4(5) . 7_565
C11 W C12 37.4(3) . .
C21 W C12 96.4(3) . .
C22 W C12 96.8(4) . .
C22 W C12 129.3(3) 7_565 .
C11 W C12 37.4(3) . 7_565
C21 W C12 96.4(3) . 7_565
C22 W C12 129.3(3) . 7_565
C22 W C12 96.8(4) 7_565 7_565
C12 W C12 61.6(5) . 7_565
C11 W C1 136.6(5) . 7_565
C21 W C1 135.4(5) . 7_565
C22 W C1 126.1(5) . 7_565
C22 W C1 99.6(5) 7_565 7_565
C12 W C1 127.9(5) . 7_565
C12 W C1 100.6(5) 7_565 7_565
C11 W C1 136.6(5) . .
C21 W C1 135.4(5) . .
C22 W C1 99.6(5) . .
C22 W C1 126.1(5) 7_565 .
C12 W C1 100.6(5) . .
C12 W C1 127.9(5) 7_565 .
C1 W C1 49.6(9) 7_565 .
C11 W C13 60.8(4) . 7_565
C21 W C13 132.4(4) . 7_565
C22 W C13 155.1(3) . 7_565
C22 W C13 128.8(4) 7_565 7_565
C12 W C13 59.0(3) . 7_565
C12 W C13 36.8(3) 7_565 7_565
C1 W C13 77.8(5) 7_565 7_565
C1 W C13 91.2(5) . 7_565
C11 W C13 60.8(4) . .
C21 W C13 132.4(4) . .
C22 W C13 128.8(4) . .
C22 W C13 155.1(3) 7_565 .
C12 W C13 36.8(3) . .
C12 W C13 59.0(3) 7_565 .
C1 W C13 91.2(5) 7_565 .
C1 W C13 77.8(5) . .
C13 W C13 32.4(5) 7_565 .
C11 W C23 131.2(4) . .
C21 W C23 60.3(4) . .
C22 W C23 34.7(3) . .
C22 W C23 59.1(3) 7_565 .
C12 W C23 126.2(4) . .
C12 W C23 154.8(4) 7_565 .
C1 W C23 91.4(5) 7_565 .
C1 W C23 76.5(5) . .
C13 W C23 167.3(4) 7_565 .
C13 W C23 143.5(4) . .
C11 W C23 131.2(4) . 7_565
C21 W C23 60.3(4) . 7_565
C22 W C23 59.1(3) . 7_565
C22 W C23 34.7(3) 7_565 7_565
C12 W C23 154.8(4) . 7_565
C12 W C23 126.2(4) 7_565 7_565
C1 W C23 76.5(5) 7_565 7_565
C1 W C23 91.4(5) . 7_565
C13 W C23 143.5(4) 7_565 7_565
C13 W C23 167.3(4) . 7_565
C23 W C23 35.8(6) . 7_565
C1 C1 W 65.2(5) 7_565 .
C12 C11 C12 107.5(12) 7_565 .
C12 C11 Si 122.9(6) 7_565 .
C12 C11 Si 122.9(6) . .
C12 C11 W 73.0(6) 7_565 .
C12 C11 W 73.0(6) . .
Si C11 W 96.2(5) . .
C11 C12 C13 105.8(9) . .
C11 C12 C32 128.8(9) . .
C13 C12 C32 124.3(9) . .
C11 C12 W 69.5(6) . .
C13 C12 W 74.5(6) . .
C32 C12 W 130.2(7) . .
C13 C13 C12 110.4(6) 7_565 .
C13 C13 C33 127.1(6) 7_565 .
C12 C13 C33 121.8(10) . .
C13 C13 W 73.8(2) 7_565 .
C12 C13 W 68.8(5) . .
C33 C13 W 131.0(7) . .
C22 C21 C22 104.7(10) 7_565 .
C22 C21 Si 123.9(6) 7_565 .
C22 C21 Si 123.9(6) . .
C22 C21 W 72.3(6) 7_565 .
C22 C21 W 72.3(6) . .
Si C21 W 95.7(5) . .
C23 C22 C21 110.6(8) . .
C23 C22 C42 120.8(9) . .
C21 C22 C42 127.3(9) . .
C23 C22 W 77.3(6) . .
C21 C22 W 70.5(6) . .
C42 C22 W 129.9(7) . .
C22 C23 C23 107.0(6) . 7_565
C22 C23 C43 127.4(11) . .
C23 C23 C43 125.4(8) 7_565 .
C22 C23 W 68.0(5) . .
C23 C23 W 72.1(3) 7_565 .
C43 C23 W 128.8(8) . .
C51 Si C51 102.7(8) . 7_565
C51 Si C11 114.3(4) . .
C51 Si C11 114.3(4) 7_565 .
C51 Si C21 116.7(4) . .
C51 Si C21 116.7(5) 7_565 .
C11 Si C21 93.0(5) . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
W C11 2.230(12) .
W C21 2.236(12) .
W C22 2.260(9) .
W C22 2.260(9) 7_565
W C12 2.276(9) .
W C12 2.276(9) 7_565
W C1 2.284(18) 7_565
W C1 2.284(18) .
W C13 2.353(10) 7_565
W C13 2.353(10) .
W C23 2.378(10) .
W C23 2.378(10) 7_565
C1 C1 1.92(4) 7_565
C11 C12 1.446(12) 7_565
C11 C12 1.446(12) .
C11 Si 1.871(13) .
C12 C13 1.463(14) .
C12 C32 1.515(14) .
C13 C13 1.31(2) 7_565
C13 C33 1.484(13) .
C21 C22 1.435(10) 7_565
C21 C22 1.435(10) .
C21 Si 1.884(11) .
C22 C23 1.386(13) .
C22 C42 1.517(14) .
C23 C23 1.46(2) 7_565
C23 C43 1.507(14) .
C51 Si 1.839(11) .
Si C51 1.839(11) 7_565
