# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/1893 data_CRYSTALS_cif _audit_creation_date 99-06-16 _audit_creation_method CRYSTALS_ver_07-07-97 _publ_contact_author_name 'Michael Leech' _publ_contact_author_address ; Chemistry Department Durham University South Road Durham DH1 3LE ; _publ_contact_author_phone '(44) 191-3744704' _publ_contact_author_fax '(44) 191-3744737' _publ_contact_author_email 'm.a.leech@dur.ac.uk ' _publ_requested_journal ' ' _publ_requested_category 'FA' #choose from: FI FM FO CI CM CO AD# _publ_requested_coeditor_name ' ' _publ_section_exptl_refinement ; ? ; _publ_section_exptl_prep ; ? ; _publ_section_references # Add your own references - in alphabetic order ; Carruthers, J.R. and Watkin, D.J. (1979), Acta Cryst, A35, 698-699 Watkin, D.J., Prout, C.K. Carruthers, J.R. & Betteridge, P.W. (1996) CRYSTALS Issue 10. Chemical Crystallography Laboratory, OXFORD, UK. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. ; _computing_data_collection ; ? ; _computing_data_reduction ; ? ; _computing_cell_refinement ; ? ; _computing_structure_refinement ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_publication_material ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_molecular_graphics ; CAMERON (Watkin, Prout & Pearce, 1996) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' _chemical_name_systematic # IUPAC name, in full ; ? ; _chemical_melting_point 'not measured' _refine_ls_matrix_type full _atom_sites_solution_primary Direct_Methods _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _cell_length_a 16.584(3) _cell_angle_alpha 90 _cell_length_b 13.214(3) _cell_angle_beta 90 _cell_length_c 8.419(2) _cell_angle_gamma 90 _cell_volume 1844.9(6) _symmetry_cell_setting 'Orthorhombic' _symmetry_space_group_name_H-M 'P n m a' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' '-x,-y,-z' '-x+1/2,y+1/2,z+1/2' 'x+1/2,-y+1/2,-z+1/2' 'x,-y+1/2,z' '-x,y+1/2,-z' '-x+1/2,-y,z+1/2' 'x+1/2,y,-z+1/2' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_length_neutron _atom_type_scat_source 'Nb' 'Nb' 7.0540 'V.F. Sears, Neutron News, Vol. 3, 1992' 'Si' 'Si' 4.1490 'V.F. Sears, Neutron News, Vol. 3, 1992' 'Cl' 'Cl' 9.5770 'V.F. Sears, Neutron News, Vol. 3, 1992' 'O' 'O' 5.8030 'V.F. Sears, Neutron News, Vol. 3, 1992' 'N' 'N' 9.3600 'V.F. Sears, Neutron News, Vol. 3, 1992' 'C' 'C' 6.6460 'V.F. Sears, Neutron News, Vol. 3, 1992' 'H' 'H' -3.7390 'V.F. Sears, Neutron News, Vol. 3, 1992' _chemical_formula_sum 'C14 H23 Cl2 Nb1 Si2' _chemical_formula_moiety 'C14 H23 Cl2 Nb1 Si2' _chemical_compound_source ? _chemical_formula_weight 411.32 _cell_measurement_reflns_used 25 # see below (_exptl_special_details ) _cell_measurement_theta_min ? # see below (_exptl_special_details ) _cell_measurement_theta_max ? # see below (_exptl_special_details ) _cell_measurement_temperature 100 _cell_formula_units_Z 4.00 _exptl_crystal_description 'block' _exptl_crystal_colour 'pale beige' _exptl_crystal_size_min 1.00 _exptl_crystal_size_mid 2.00 _exptl_crystal_size_max 2.00 _exptl_crystal_density_diffrn 1.48 _exptl_crystal_density_meas 'not measured' _exptl_absorpt_coefficient_mu 0.206 # (mm^-1, at 1 Angstrom) _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.59 _exptl_absorpt_correction_T_max 0.84 _exptl_absorpt_process_details ; The linear absorption coefficient is wavelength dependent and it is calculated as: mu = 0.99 + 1.07 * lambda [cm^-1] ; _diffrn_radiation_wavelength 0.5-5.0 #see below (_exptl_special_details) _diffrn_radiation_type neutron _diffrn_radiation_source 'ISIS spallation source' _diffrn_radiation_monochromator none _diffrn_measurement_device 'SXD' _diffrn_measurement_method 'Time of flight LAUE diffraction' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number ? _diffrn_standards_decay_% ? _diffrn_ambient_temperature 100 _diffrn_reflns_number 8886 _reflns_number_total 1537 _diffrn_reflns_av_R_equivalents 0.0599 _reflns_threshold_expression >3sigma(I) _reflns_number_gt 1424 _diffrn_reflns_theta_min ? _diffrn_reflns_theta_max ? _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 28 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 14 _refine_diff_density_min 'not applicable' _refine_diff_density_max 'not applicable' _refine_ls_number_reflns 1537 _refine_ls_number_parameters 199 _refine_ls_R_factor_obs 0.062 _refine_ls_wR_factor_obs 0.098 _refine_ls_goodness_of_fit_obs 1.185 _refine_ls_shift/su_max 0.003 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Chebychev polynomial with 3 parameters (Carruthers & Watkin, 1979) 0.303 0.221 0.356E-01 ; _refine_ls_extinction_method 'Becker-Coppens Lorentzian model' _refine_ls_extinction_coef 103.3 _exptl_special_details ; For peak integration a local UB matrix refined for each frame, using approximately 25 reflections was used. Hence _cell_measurement_reflns_used 25 For final cell dimensions an average of all local cells was performed and estimated standard uncertainties were obtained from the spread of the local observations. Because of the nature of the experiment, it is not possible to give values of theta_min and theta_max for the cell determination. Instead, we can give values of _cell_measurement_sin(theta)/lambda_min 0.23 _cell_measurement_sin(theta)/lambda_max 0.60 The same applies for the wavelength used for the experiment. The full range of wavelengths for which data were collected was 0.5-5 Angstroms, BUT the bulk of the diffraction information is obtained from wavelength in the range 0.7-2.5 Angstroms. The extinction coefficient reported in _refine_ls_extinction_coef is in this case the refined value of the mosaic spread in units of 10^-4 rad^-1 The reference for the extinction method used is: Becker, P. & Coppens, P. (1974). Acta Cryst. A30, 129-148. ; # Uequiv = arithmetic mean of Ui # i.e. Ueqiv = (U1+U2+U3)/3 loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_thermal_displace_type Nb1 0.67855(17) 0.2500 0.4024(3) 0.0081 1.0000 Uani Cl1 0.65082(11) -0.05153(13) 0.3557(2) 0.0176 1.0000 Uani Si1 0.6132(2) 0.0938(2) 0.2624(4) 0.0098 1.0000 Uani C5 0.78783(14) 0.33784(19) 0.2734(3) 0.0169 1.0000 Uani C4 0.81529(15) 0.3036(2) 0.4246(3) 0.0170 1.0000 Uani C6 0.7699(2) 0.2500 0.1815(4) 0.0158 1.0000 Uani C2 0.67493(17) 0.1960(2) 0.6722(3) 0.0199 1.0000 Uani C1 0.60191(15) 0.16275(19) 0.6013(3) 0.0161 1.0000 Uani C3 0.5569(2) 0.2500 0.5563(4) 0.0144 1.0000 Uani C8 0.50056(15) 0.0826(2) 0.2775(3) 0.0187 1.0000 Uani C7 0.63450(17) 0.0770(2) 0.0448(3) 0.0194 1.0000 Uani H51 0.7858(4) 0.4157(5) 0.2345(9) 0.0371 1.0000 Uani H41 0.8332(4) 0.3523(5) 0.5234(8) 0.0399 1.0000 Uani H61 0.7482(6) 0.2500 0.059(1) 0.0371 1.0000 Uani H21 0.7214(4) 0.1481(6) 0.7180(7) 0.0371 1.0000 Uani H31 0.5821(5) 0.0844(4) 0.5904(8) 0.0383 1.0000 Uani H11 0.4978(5) 0.2500 0.500(1) 0.0318 1.0000 Uani H83 0.4777(4) 0.0789(6) 0.3993(8) 0.0423 1.0000 Uani H81 0.4721(4) 0.1465(6) 0.2170(11) 0.0457 1.0000 Uani H82 0.4815(4) 0.0145(6) 0.216(1) 0.0437 1.0000 Uani H73 0.6977(4) 0.0661(8) 0.0173(8) 0.0468 1.0000 Uani H72 0.6147(6) 0.1435(6) -0.0213(8) 0.0506 1.0000 Uani H71 0.6018(5) 0.0116(6) 0.0023(9) 0.0410 1.0000 Uani H1 0.6053(5) 0.2500 0.2419(9) 0.0264 1.0000 Uani 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 Nb1 0.010(1) 0.007(1) 0.0070(8) 0.0000 0.0009(9) 0.0000 Cl1 0.0235(7) 0.0104(6) 0.0188(6) 0.0004(5) -0.0012(6) 0.0024(6) Si1 0.0137(13) 0.0071(13) 0.0086(11) -0.001(1) 0.000(1) 0.0001(11 C5 0.0125(8) 0.017(1) 0.021(1) 0.0043(9) 0.0029(8) -0.0016(9) C4 0.0112(8) 0.017(1) 0.023(1) -0.0008(8) -0.0027(8) -0.0015(8) C6 0.0087(11) 0.0222(16) 0.0165(13) 0.0000 0.003(1) 0.0000 C2 0.0228(11) 0.0241(11) 0.0128(8) 0.0015(8) 0.0010(8) 0.004(1) C1 0.0214(11) 0.0143(9) 0.0126(8) 0.0013(8) 0.0043(8) -0.0012(9) C3 0.0133(12) 0.0197(15) 0.0102(11) 0.0000 0.003(1) 0.0000 C8 0.0128(8) 0.019(1) 0.0242(9) 0.0012(9) -0.0002(8) -0.0041(9) C7 0.0292(13) 0.0183(11) 0.0106(7) -0.0032(8) 0.0003(9) 0.000(1) H51 0.039(3) 0.023(2) 0.049(3) 0.016(3) 0.004(3) -0.004(3) H41 0.043(3) 0.038(3) 0.039(3) -0.014(3) -0.010(3) -0.005(3) H61 0.046(5) 0.049(5) 0.016(3) 0.0000 -0.006(3) 0.0000 H21 0.034(3) 0.047(4) 0.031(3) 0.007(3) -0.009(2) 0.005(3) H31 0.053(4) 0.019(2) 0.043(3) 0.005(2) 0.007(3) -0.013(2) H11 0.018(3) 0.051(5) 0.026(3) 0.0000 -0.001(3) 0.0000 H83 0.034(3) 0.058(4) 0.035(3) -0.007(3) 0.012(2) -0.016(3) H81 0.024(2) 0.042(4) 0.072(5) 0.017(4) -0.013(3) 0.001(3) H82 0.035(3) 0.044(4) 0.052(4) -0.011(3) 0.001(3) -0.018(3) H73 0.031(3) 0.074(6) 0.036(3) -0.015(3) 0.011(2) 0.001(3) H72 0.085(6) 0.045(4) 0.022(2) 0.011(2) 0.002(3) 0.009(4) H71 0.050(4) 0.033(3) 0.040(3) -0.019(3) 0.001(3) -0.009(3) H1 0.024(3) 0.031(4) 0.024(3) 0.0000 -0.009(3) 0.0000 loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Nb1 . Si1 . 2.612(4) yes Nb1 . Si1 5_555 2.612(4) yes Nb1 . C5 . 2.410(3) yes Nb1 . C5 5_555 2.410(3) yes Nb1 . C4 . 2.383(4) yes Nb1 . C4 5_555 2.383(4) yes Nb1 . C6 . 2.399(4) yes Nb1 . C2 . 2.382(3) yes Nb1 . C2 5_555 2.382(3) yes Nb1 . C1 . 2.398(3) yes Nb1 . C1 5_555 2.398(3) yes Nb1 . C3 . 2.397(4) yes Nb1 . H1 . 1.816(8) no Cl1 . Si1 . 2.166(4) yes Si1 . C8 . 1.878(4) yes Si1 . C7 . 1.879(4) yes Si1 . H1 . 2.076(3) no C5 . C4 . 1.425(3) yes C5 . C6 . 1.426(3) yes C5 . H51 . 1.081(6) no C4 . C4 5_555 1.416(5) yes C4 . H41 . 1.094(6) no C6 . H61 . 1.095(9) no C2 . C2 5_555 1.427(6) yes C2 . C1 . 1.420(4) yes C2 . H21 . 1.069(7) no C1 . C3 . 1.425(3) yes C1 . H31 . 1.090(6) no C3 . H11 . 1.087(9) no C8 . H83 . 1.095(7) no C8 . H81 . 1.094(8) no C8 . H82 . 1.083(8) no C7 . H73 . 1.083(7) no C7 . H72 . 1.091(8) no C7 . H71 . 1.081(7) no H83 . H81 . 1.778(11) no H83 . H82 . 1.76(1) no H81 . H82 . 1.752(11) no H73 . H72 . 1.746(13) no H73 . H71 . 1.750(11) no H72 . H71 . 1.767(11) no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag Si1 . Nb1 . Si1 5_555 104.42(18) yes Si1 . Nb1 . C5 . 119.29(14) yes Si1 5_555 Nb1 . C5 . 74.23(11) yes Si1 . Nb1 . C5 5_555 74.23(11) yes Si1 5_555 Nb1 . C5 5_555 119.29(14) yes C5 . Nb1 . C5 5_555 57.57(14) yes Si1 . Nb1 . C4 . 131.67(14) yes Si1 5_555 Nb1 . C4 . 101.26(11) yes C5 . Nb1 . C4 . 34.59(9) yes C5 5_555 Nb1 . C4 . 57.51(11) yes Si1 . Nb1 . C4 5_555 101.26(11) yes Si1 5_555 Nb1 . C4 5_555 131.67(14) yes C5 . Nb1 . C4 5_555 57.51(11) yes C5 5_555 Nb1 . C4 5_555 34.59(9) yes C4 . Nb1 . C4 5_555 34.57(13) yes Si1 . Nb1 . C6 . 84.97(11) yes Si1 5_555 Nb1 . C6 . 84.97(11) yes C5 . Nb1 . C6 . 34.50(9) yes C5 5_555 Nb1 . C6 . 34.50(9) yes C4 . Nb1 . C6 . 57.29(12) yes Si1 . Nb1 . C2 . 100.55(11) yes Si1 5_555 Nb1 . C2 . 131.03(14) yes C5 . Nb1 . C2 . 126.35(15) yes C5 5_555 Nb1 . C2 . 107.71(12) yes C4 . Nb1 . C2 . 92.19(13) yes Si1 . Nb1 . C2 5_555 131.03(14) yes Si1 5_555 Nb1 . C2 5_555 100.55(11) yes C5 . Nb1 . C2 5_555 107.71(12) yes C5 5_555 Nb1 . C2 5_555 126.35(15) yes C4 . Nb1 . C2 5_555 81.96(12) yes Si1 . Nb1 . C1 . 73.46(11) yes Si1 5_555 Nb1 . C1 . 118.37(15) yes C5 . Nb1 . C1 . 160.84(16) yes C5 5_555 Nb1 . C1 . 118.8(1) yes C4 . Nb1 . C1 . 126.33(14) yes Si1 . Nb1 . C1 5_555 118.37(15) yes Si1 5_555 Nb1 . C1 5_555 73.46(11) yes C5 . Nb1 . C1 5_555 118.8(1) yes C5 5_555 Nb1 . C1 5_555 160.84(16) yes C4 . Nb1 . C1 5_555 107.86(11) yes Si1 . Nb1 . C3 . 83.96(12) yes Si1 5_555 Nb1 . C3 . 83.96(12) yes C5 . Nb1 . C3 . 151.17(7) yes C5 5_555 Nb1 . C3 . 151.17(7) yes C4 . Nb1 . C3 . 139.31(14) yes Si1 . Nb1 . H1 . 52.21(9) no Si1 5_555 Nb1 . H1 . 52.21(9) no C5 . Nb1 . H1 . 99.7(3) no C5 5_555 Nb1 . H1 . 99.7(3) no C4 . Nb1 . H1 . 134.0(3) no C4 5_555 Nb1 . C6 . 57.29(12) yes C4 5_555 Nb1 . C2 . 81.96(12) yes C6 . Nb1 . C2 . 139.04(16) yes C4 5_555 Nb1 . C2 5_555 92.19(13) yes C6 . Nb1 . C2 5_555 139.04(16) yes C2 . Nb1 . C2 5_555 34.86(14) yes C4 5_555 Nb1 . C1 . 107.86(11) yes C6 . Nb1 . C1 . 151.20(7) yes C2 . Nb1 . C1 . 34.6(1) yes C2 5_555 Nb1 . C1 . 57.62(11) yes C4 5_555 Nb1 . C1 5_555 126.33(14) yes C6 . Nb1 . C1 5_555 151.20(7) yes C2 . Nb1 . C1 5_555 57.62(11) yes C2 5_555 Nb1 . C1 5_555 34.6(1) yes C1 . Nb1 . C1 5_555 57.48(13) yes C4 5_555 Nb1 . C3 . 139.31(14) yes C6 . Nb1 . C3 . 161.89(17) yes C2 . Nb1 . C3 . 57.55(12) yes C2 5_555 Nb1 . C3 . 57.55(12) yes C1 . Nb1 . C3 . 34.57(8) yes C4 5_555 Nb1 . H1 . 134.0(3) no C6 . Nb1 . H1 . 81.1(3) no C2 . Nb1 . H1 . 133.8(3) no C2 5_555 Nb1 . H1 . 133.8(3) no C1 . Nb1 . H1 . 99.5(3) no C1 5_555 Nb1 . C3 . 34.57(8) yes C1 5_555 Nb1 . H1 . 99.5(3) no C3 . Nb1 . H1 . 80.8(3) no Nb1 . Si1 . Cl1 . 114.69(15) yes Nb1 . Si1 . C8 . 116.38(18) yes Cl1 . Si1 . C8 . 101.08(18) yes Nb1 . Si1 . C7 . 117.07(19) yes Cl1 . Si1 . C7 . 101.23(17) yes C8 . Si1 . C7 . 104.1(2) yes Nb1 . Si1 . H1 . 43.8(2) no Cl1 . Si1 . H1 . 158.4(3) no C8 . Si1 . H1 . 91.2(3) no C7 . Si1 . H1 . 92.8(3) no Nb1 . C5 . C4 . 71.65(15) yes Nb1 . C5 . C6 . 72.32(16) yes C4 . C5 . C6 . 107.0(2) yes Nb1 . C5 . H51 . 124.8(4) no C4 . C5 . H51 . 125.7(5) no C6 . C5 . H51 . 127.2(5) no Nb1 . C4 . C5 . 73.76(15) yes Nb1 . C4 . C4 5_555 72.72(7) yes C5 . C4 . C4 5_555 108.52(15) yes Nb1 . C4 . H41 . 119.5(4) no C5 . C4 . H41 . 125.4(5) no C4 5_555 C4 . H41 . 126.1(4) no Nb1 . C6 . C5 . 73.18(16) yes Nb1 . C6 . C5 5_555 73.18(16) yes C5 . C6 . C5 5_555 108.9(3) yes Nb1 . C6 . H61 . 121.6(6) no C5 . C6 . H61 . 125.52(15) no C5 5_555 C6 . H61 . 125.52(15) no Nb1 . C2 . C2 5_555 72.57(7) yes Nb1 . C2 . C1 . 73.32(15) yes C2 5_555 C2 . C1 . 108.02(15) yes Nb1 . C2 . H21 . 120.2(4) no C2 5_555 C2 . H21 . 126.3(4) no C1 . C2 . H21 . 125.6(5) no Nb1 . C1 . C2 . 72.12(15) yes Nb1 . C1 . C3 . 72.70(16) yes C2 . C1 . C3 . 108.0(2) yes Nb1 . C1 . H31 . 123.9(4) no C2 . C1 . H31 . 125.9(5) no C3 . C1 . H31 . 126.0(5) no Nb1 . C3 . C1 . 72.73(16) yes Nb1 . C3 . C1 5_555 72.73(16) yes C1 . C3 . C1 5_555 108.0(3) yes Nb1 . C3 . H11 . 121.7(5) no C1 . C3 . H11 . 125.97(15) no C1 5_555 C3 . H11 . 125.97(15) no Si1 . C8 . H83 . 114.3(4) no Si1 . C8 . H81 . 109.7(4) no H83 . C8 . H81 . 108.7(7) no Si1 . C8 . H82 . 108.9(5) no H83 . C8 . H82 . 107.9(6) no H81 . C8 . H82 . 107.2(7) no Si1 . C7 . H73 . 113.9(4) no Si1 . C7 . H72 . 110.2(4) no H73 . C7 . H72 . 106.9(8) no Si1 . C7 . H71 . 108.9(5) no H73 . C7 . H71 . 107.9(7) no H72 . C7 . H71 . 108.9(7) no C8 . H83 . H81 . 35.6(4) no C8 . H83 . H82 . 35.9(4) no H81 . H83 . H82 . 59.3(5) no C8 . H81 . H83 . 35.7(4) no C8 . H81 . H82 . 36.2(4) no H83 . H81 . H82 . 59.8(4) no C8 . H82 . H83 . 36.3(4) no C8 . H82 . H81 . 36.6(4) no H83 . H82 . H81 . 60.8(5) no C7 . H73 . H72 . 36.7(4) no C7 . H73 . H71 . 36.0(4) no H72 . H73 . H71 . 60.7(5) no C7 . H72 . H73 . 36.4(4) no C7 . H72 . H71 . 35.4(4) no H73 . H72 . H71 . 59.8(5) no C7 . H71 . H73 . 36.1(4) no C7 . H71 . H72 . 35.7(4) no H73 . H71 . H72 . 59.5(5) no Nb1 . H1 . Si1 . 84.0(2) no Nb1 . H1 . Si1 5_555 84.0(2) no Si1 . H1 . Si1 5_555 168.0(4) no