# Supplementary Material (ESI) for New Journal of Chemistry # This journal is (c) The Royal Society of Chemistry and # The Centre National de la Recherche Scientifique, 2006 data_global _journal_name_full 'New J.Chem.(Nouv.J.Chim.)' _journal_coden_Cambridge 0440 _publ_contact_author_name 'Sean McGrady' _publ_contact_author_address ; Department of Chemistry University of New Brunswick Fredericton, N.B. E3B 6E2 CANADA ; _publ_contact_author_email SMCGRADY@UNB.CA _publ_section_title ; Synthesis and structural characterisation of [TpMe2Nb(CH3)2(CH3CCCH3)] and [TpMe2NbCl(CH3)(CH3CCCH3)]: is there an intrinsic alpha-agostic interaction in alkyl complexes of the [TpMe2Nb(alkyne)] moiety? ; _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M.C., Polidori, G. and Camalli, M. (1994)., SIR92 program for automatic solution of crystal structures by direct methods. J. Appl. Cryst. 27, 435. DIFABS - N. Walker and D. Stuart, Acta Crystallogr., Sect A 1983, 39, 158-166. Farrugia, L. J., ORTEP3 for Windows, J. Appl. Crystallogr. 1997, 30, 565. Sheldrick, G. M. (1997). SHELXL97. Program for the refinement of Crystal Structures. University of G\"ottingen, Germany. Stoe, IPDS Manual. Version 2.75. Stoe & Cie, Darmstadt,1996, Germany. Stoe, X-RED, Data Reduction for STADI4 and IPDS, Revision 1.08. Stoe & Cie, Darmstadt, 1996, Germany. WINGX L.J. Farrugia, J. Appl. Cryst., 1999, 32, 837-838 ; loop_ _publ_author_name 'Emmanuelle Teuma' 'Sean McGrady' 'Michel Etienne' 'Bruno Donnadieu' # Attachment 'NbMe2; NbMeCl.cif' #**************************************** data_2 _database_code_depnum_ccdc_archive 'CCDC 286983' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C21 H34 B N6 Nb' _chemical_formula_weight 474.26 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' B B 0.0013 0.0007 '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' Nb Nb -2.0727 0.6215 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P c a 2(1)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y, z+1/2' 'x+1/2, -y, z' '-x, -y, z+1/2' _cell_length_a 10.1222(13) _cell_length_b 13.6129(13) _cell_length_c 16.5563(15) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2281.3(4) _cell_formula_units_Z 4 _cell_measurement_temperature 160(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 24.7 _exptl_crystal_description 'prism frag' _exptl_crystal_colour orange _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.381 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 992 _exptl_absorpt_coefficient_mu 0.547 _exptl_absorpt_correction_type refdelf _exptl_absorpt_correction_T_min 0.8110 _exptl_absorpt_correction_T_max 0.8986 _exptl_absorpt_process_details ? _exptl_special_details ; The data were collected on a Stoe Imaging Plate Diffraction System (IPDS). The crystal-to-detector distance was 0 mm. Coverage of the unique set was over 99.8% complete to at least 27.70\%. Crystal decay was monitored by measuring 200 reflexions per frame. ; _diffrn_ambient_temperature 160(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 'Stoe IPDS' _diffrn_measurement_method \f _diffrn_standards_number 200 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.1 _diffrn_reflns_number 15009 _diffrn_reflns_av_R_equivalents 0.0547 _diffrn_reflns_av_sigmaI/netI 0.0391 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.51 _diffrn_reflns_theta_max 24.70 _reflns_number_total 3828 _reflns_number_gt 3293 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Stoe IPDS software (Stoe, 1996)' _computing_data_reduction 'XRED (Stoe, 1.08, 1996)' _computing_cell_refinement 'Stoe IPDS software (Stoe, 1996)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP3 for Windows (Farrugia, 1997)' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' _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^)+(0.0500P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.03(5) _refine_ls_number_reflns 3828 _refine_ls_number_parameters 276 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0404 _refine_ls_R_factor_gt 0.0318 _refine_ls_wR_factor_ref 0.0776 _refine_ls_wR_factor_gt 0.0745 _refine_ls_goodness_of_fit_ref 1.002 _refine_ls_restrained_S_all 1.002 _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 Nb1 Nb 0.88059(2) 0.75427(2) 0.66475(4) 0.01945(10) Uani 1 1 d . . . B1 B 1.0588(4) 0.7346(3) 0.4895(2) 0.0161(8) Uani 1 1 d . . . N11 N 0.9361(3) 0.8675(2) 0.56401(19) 0.0191(7) Uani 1 1 d . . . N12 N 1.0103(3) 0.8404(2) 0.49754(18) 0.0180(6) Uani 1 1 d . . . N21 N 0.8553(3) 0.6546(2) 0.5509(2) 0.0200(7) Uani 1 1 d . . . N22 N 0.9413(3) 0.6633(2) 0.48714(18) 0.0168(6) Uani 1 1 d . . . N31 N 1.0968(3) 0.7101(2) 0.63820(18) 0.0196(7) Uani 1 1 d . . . N32 N 1.1494(3) 0.7119(2) 0.56139(18) 0.0156(6) Uani 1 1 d . . . C1 C 0.9596(4) 0.8532(3) 0.7441(2) 0.0259(9) Uani 1 1 d . . . C2 C 0.8550(4) 0.8145(3) 0.7773(3) 0.0279(9) Uani 1 1 d . . . C3 C 1.0703(4) 0.9218(3) 0.7583(3) 0.0340(10) Uani 1 1 d . . . H3A H 1.0581 0.9808 0.7253 0.051 Uiso 1 1 calc R . . H3B H 1.1537 0.8899 0.7436 0.051 Uiso 1 1 calc R . . H3C H 1.0725 0.9402 0.8155 0.051 Uiso 1 1 calc R . . C4 C 0.7755(5) 0.8153(3) 0.8536(3) 0.0442(12) Uani 1 1 d . . . H4A H 0.6846 0.8350 0.8415 0.066 Uiso 1 1 calc R . . H4B H 0.8145 0.8620 0.8919 0.066 Uiso 1 1 calc R . . H4C H 0.7756 0.7494 0.8775 0.066 Uiso 1 1 calc R . . C10 C 0.8703(4) 0.6130(3) 0.7300(3) 0.0301(9) Uani 1 1 d . . . H10A H 0.9065 0.5607 0.6959 0.045 Uiso 1 1 calc R . . H10B H 0.7781 0.5981 0.7431 0.045 Uiso 1 1 calc R . . H10C H 0.9219 0.6175 0.7800 0.045 Uiso 1 1 calc R . . C11 C 0.9155(4) 0.9647(2) 0.5560(2) 0.0237(8) Uani 1 1 d . . . C12 C 0.9780(4) 0.9990(3) 0.4875(2) 0.0259(8) Uani 1 1 d . . . H12 H 0.9802 1.0649 0.4688 0.031 Uiso 1 1 calc R . . C13 C 1.0361(3) 0.9193(3) 0.4519(2) 0.0224(8) Uani 1 1 d . . . C14 C 0.8340(4) 1.0238(3) 0.6140(3) 0.0325(9) Uani 1 1 d . . . H14A H 0.8373 0.9933 0.6675 0.049 Uiso 1 1 calc R . . H14B H 0.7422 1.0260 0.5951 0.049 Uiso 1 1 calc R . . H14C H 0.8691 1.0907 0.6172 0.049 Uiso 1 1 calc R . . C15 C 1.1200(4) 0.9124(3) 0.3776(3) 0.0341(10) Uani 1 1 d . . . H15A H 1.0765 0.8698 0.3379 0.051 Uiso 1 1 calc R . . H15B H 1.2063 0.8848 0.3917 0.051 Uiso 1 1 calc R . . H15C H 1.1318 0.9781 0.3545 0.051 Uiso 1 1 calc R . . C20 C 0.6758(4) 0.8021(3) 0.6398(3) 0.0342(10) Uani 1 1 d . . . H20A H 0.6137 0.7560 0.6649 0.051 Uiso 1 1 calc R . . H20B H 0.6610 0.8035 0.5813 0.051 Uiso 1 1 calc R . . H20C H 0.6619 0.8679 0.6622 0.051 Uiso 1 1 calc R . . C21 C 0.7648(3) 0.5875(2) 0.5278(3) 0.0245(8) Uani 1 1 d . . . C22 C 0.7911(4) 0.5559(3) 0.4508(3) 0.0285(9) Uani 1 1 d . . . H22 H 0.7415 0.5096 0.4204 0.034 Uiso 1 1 calc R . . C23 C 0.9032(3) 0.6041(3) 0.4260(2) 0.0219(8) Uani 1 1 d . . . C24 C 0.6544(4) 0.5540(3) 0.5814(3) 0.0343(10) Uani 1 1 d . . . H24A H 0.6292 0.6075 0.6179 0.051 Uiso 1 1 calc R . . H24B H 0.6835 0.4972 0.6131 0.051 Uiso 1 1 calc R . . H24C H 0.5782 0.5354 0.5482 0.051 Uiso 1 1 calc R . . C25 C 0.9725(4) 0.5987(3) 0.3469(2) 0.0284(9) Uani 1 1 d . . . H25A H 0.9799 0.6647 0.3238 0.043 Uiso 1 1 calc R . . H25B H 0.9223 0.5566 0.3100 0.043 Uiso 1 1 calc R . . H25C H 1.0610 0.5711 0.3548 0.043 Uiso 1 1 calc R . . C31 C 1.1993(4) 0.6924(3) 0.6882(2) 0.0214(8) Uani 1 1 d . . . C32 C 1.3142(3) 0.6847(3) 0.6441(2) 0.0216(9) Uani 1 1 d . . . H32 H 1.4002 0.6722 0.6647 0.026 Uiso 1 1 calc R . . C33 C 1.2804(3) 0.6987(2) 0.5647(2) 0.0189(7) Uani 1 1 d . . . C34 C 1.1836(4) 0.6797(3) 0.7774(2) 0.0312(10) Uani 1 1 d . . . H34A H 1.1126 0.7226 0.7968 0.047 Uiso 1 1 calc R . . H34B H 1.2664 0.6970 0.8045 0.047 Uiso 1 1 calc R . . H34C H 1.1613 0.6111 0.7893 0.047 Uiso 1 1 calc R . . C35 C 1.3672(3) 0.7027(3) 0.4912(2) 0.0246(8) Uani 1 1 d . . . H35A H 1.3505 0.7639 0.4617 0.037 Uiso 1 1 calc R . . H35B H 1.3478 0.6465 0.4562 0.037 Uiso 1 1 calc R . . H35C H 1.4601 0.7004 0.5078 0.037 Uiso 1 1 calc R . . H1 H 1.117(3) 0.727(3) 0.435(3) 0.018(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 Nb1 0.02048(15) 0.01915(15) 0.01871(15) -0.00024(17) 0.0053(2) 0.00085(13) B1 0.0175(19) 0.019(2) 0.0119(19) 0.0025(16) -0.0019(15) 0.0033(15) N11 0.0209(17) 0.0160(15) 0.0205(17) -0.0027(14) 0.0043(14) 0.0014(13) N12 0.0199(15) 0.0169(14) 0.0172(15) 0.0004(13) 0.0020(13) 0.0022(12) N21 0.0171(15) 0.0224(15) 0.0206(18) 0.0031(14) -0.0007(13) 0.0014(12) N22 0.0166(15) 0.0159(14) 0.0179(15) -0.0008(13) -0.0036(12) 0.0028(12) N31 0.0257(17) 0.0192(14) 0.0141(15) -0.0004(11) 0.0014(12) -0.0029(12) N32 0.0184(15) 0.0160(14) 0.0123(15) 0.0005(13) -0.0037(12) -0.0003(12) C1 0.030(2) 0.022(2) 0.026(2) -0.0042(17) -0.0005(17) 0.0035(17) C2 0.027(2) 0.025(2) 0.032(2) 0.0028(18) 0.0063(18) 0.0048(17) C3 0.034(2) 0.038(2) 0.030(2) -0.0040(19) 0.0023(18) -0.0071(19) C4 0.057(3) 0.039(3) 0.037(3) -0.011(2) 0.031(2) -0.018(2) C10 0.032(2) 0.029(2) 0.029(2) 0.0054(19) 0.0082(18) -0.0008(17) C11 0.0251(19) 0.0165(18) 0.029(2) -0.0042(17) 0.0016(17) 0.0047(16) C12 0.033(2) 0.0156(18) 0.029(2) 0.0043(16) -0.0004(18) 0.0040(15) C13 0.0240(19) 0.0217(19) 0.021(2) 0.0044(16) 0.0027(15) 0.0027(15) C14 0.040(2) 0.022(2) 0.036(2) -0.0030(19) 0.0063(19) 0.0077(18) C15 0.045(3) 0.027(2) 0.030(2) 0.0116(19) 0.0118(18) 0.0062(18) C20 0.023(2) 0.031(2) 0.049(3) -0.0041(18) 0.0013(18) 0.0018(17) C21 0.0183(19) 0.0145(17) 0.041(2) 0.0085(18) -0.0069(16) -0.0004(15) C22 0.025(2) 0.0194(18) 0.041(3) -0.0058(18) -0.0113(18) 0.0009(16) C23 0.0198(18) 0.0180(17) 0.028(2) -0.0025(16) -0.0081(15) 0.0065(14) C24 0.026(2) 0.025(2) 0.052(3) 0.0047(19) -0.0026(19) -0.0054(17) C25 0.0256(19) 0.034(2) 0.026(2) -0.0140(18) -0.0102(16) 0.0054(17) C31 0.030(2) 0.0192(17) 0.0154(19) -0.0001(13) -0.0070(14) -0.0030(15) C32 0.0152(17) 0.0261(18) 0.024(2) -0.0016(14) -0.0074(14) -0.0041(13) C33 0.0151(18) 0.0175(17) 0.024(2) -0.0010(16) -0.0003(15) -0.0020(14) C34 0.030(2) 0.044(3) 0.020(2) 0.002(2) -0.0041(18) -0.0008(19) C35 0.0158(18) 0.033(2) 0.025(2) -0.0007(17) 0.0001(16) 0.0012(15) _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 Nb1 C1 2.044(4) . ? Nb1 C2 2.053(4) . ? Nb1 C10 2.208(4) . ? Nb1 C20 2.212(4) . ? Nb1 N31 2.312(3) . ? Nb1 N21 2.337(3) . ? Nb1 N11 2.340(3) . ? B1 N12 1.527(4) . ? B1 N32 1.534(5) . ? B1 N22 1.535(5) . ? N11 C11 1.346(4) . ? N11 N12 1.383(4) . ? N12 C13 1.339(5) . ? N21 C21 1.350(5) . ? N21 N22 1.373(4) . ? N22 C23 1.350(5) . ? N31 C31 1.349(4) . ? N31 N32 1.379(4) . ? N32 C33 1.339(4) . ? C1 C2 1.305(6) . ? C1 C3 1.478(6) . ? C2 C4 1.497(6) . ? C11 C12 1.379(6) . ? C11 C14 1.500(5) . ? C12 C13 1.368(5) . ? C13 C15 1.497(5) . ? C21 C22 1.372(6) . ? C21 C24 1.498(5) . ? C22 C23 1.373(5) . ? C23 C25 1.488(6) . ? C31 C32 1.377(5) . ? C31 C34 1.496(5) . ? C32 C33 1.372(5) . ? C33 C35 1.501(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 C1 Nb1 C2 37.15(16) . . ? C1 Nb1 C10 106.13(17) . . ? C2 Nb1 C10 84.15(16) . . ? C1 Nb1 C20 107.04(16) . . ? C2 Nb1 C20 86.18(16) . . ? C10 Nb1 C20 107.67(16) . . ? C1 Nb1 N31 85.58(14) . . ? C2 Nb1 N31 113.35(14) . . ? C10 Nb1 N31 84.89(13) . . ? C20 Nb1 N31 158.19(14) . . ? C1 Nb1 N21 160.69(14) . . ? C2 Nb1 N21 161.93(13) . . ? C10 Nb1 N21 83.32(15) . . ? C20 Nb1 N21 85.27(14) . . ? N31 Nb1 N21 78.42(11) . . ? C1 Nb1 N11 85.99(13) . . ? C2 Nb1 N11 114.47(14) . . ? C10 Nb1 N11 159.05(13) . . ? C20 Nb1 N11 84.14(14) . . ? N31 Nb1 N11 78.98(11) . . ? N21 Nb1 N11 80.44(11) . . ? N12 B1 N32 108.3(3) . . ? N12 B1 N22 110.5(3) . . ? N32 B1 N22 110.8(3) . . ? C11 N11 N12 105.6(3) . . ? C11 N11 Nb1 132.9(3) . . ? N12 N11 Nb1 121.4(2) . . ? C13 N12 N11 109.9(3) . . ? C13 N12 B1 130.1(3) . . ? N11 N12 B1 119.8(3) . . ? C21 N21 N22 105.7(3) . . ? C21 N21 Nb1 134.2(3) . . ? N22 N21 Nb1 120.0(2) . . ? C23 N22 N21 110.1(3) . . ? C23 N22 B1 128.1(3) . . ? N21 N22 B1 121.8(3) . . ? C31 N31 N32 105.8(3) . . ? C31 N31 Nb1 131.1(2) . . ? N32 N31 Nb1 122.4(2) . . ? C33 N32 N31 110.0(3) . . ? C33 N32 B1 130.6(3) . . ? N31 N32 B1 119.2(3) . . ? C2 C1 C3 143.4(4) . . ? C2 C1 Nb1 71.8(3) . . ? C3 C1 Nb1 144.7(3) . . ? C1 C2 C4 142.1(4) . . ? C1 C2 Nb1 71.1(3) . . ? C4 C2 Nb1 146.8(3) . . ? N11 C11 C12 110.0(3) . . ? N11 C11 C14 123.3(3) . . ? C12 C11 C14 126.7(3) . . ? C13 C12 C11 106.5(3) . . ? N12 C13 C12 108.0(3) . . ? N12 C13 C15 121.6(3) . . ? C12 C13 C15 130.4(3) . . ? N21 C21 C22 110.1(3) . . ? N21 C21 C24 123.0(4) . . ? C22 C21 C24 126.9(3) . . ? C21 C22 C23 106.7(3) . . ? N22 C23 C22 107.3(3) . . ? N22 C23 C25 123.7(3) . . ? C22 C23 C25 128.9(3) . . ? N31 C31 C32 109.8(3) . . ? N31 C31 C34 123.0(3) . . ? C32 C31 C34 127.2(3) . . ? C33 C32 C31 106.7(3) . . ? N32 C33 C32 107.7(3) . . ? N32 C33 C35 122.8(3) . . ? C32 C33 C35 129.5(3) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 24.70 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.674 _refine_diff_density_min -0.540 _refine_diff_density_rms 0.067 #====END data_3 _database_code_depnum_ccdc_archive 'CCDC 286984' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H31 B Cl N6 Nb' _chemical_formula_weight 494.68 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' B B 0.0013 0.0007 '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' Nb Nb -2.0727 0.6215 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P c a 2(1)' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y, z+1/2' 'x+1/2, -y, z' '-x, -y, z+1/2' _cell_length_a 10.0681(14) _cell_length_b 13.6445(12) _cell_length_c 16.4959(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2266.1(4) _cell_formula_units_Z 4 _cell_measurement_temperature 160(2) _cell_measurement_reflns_used 5000 _cell_measurement_theta_min 2.5 _cell_measurement_theta_max 24.40 _exptl_crystal_description 'prism frag' _exptl_crystal_colour orange _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.450 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1024 _exptl_absorpt_coefficient_mu 0.667 _exptl_absorpt_correction_type refdelf _exptl_absorpt_correction_T_min 0.7761 _exptl_absorpt_correction_T_max 0.9674 _exptl_absorpt_process_details ? _exptl_special_details ; The data were collected on a Stoe Imaging Plate Diffraction System (IPDS). The crystal-to-detector distance was 0 mm. Coverage of the unique set was over 98.7% complete to at least 24.40\%. Crystal decay was monitored by measuring 200 reflexions per frame ; _diffrn_ambient_temperature 160(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 'Stoe IPDS' _diffrn_measurement_method \f _diffrn_standards_number 200 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.1 _diffrn_reflns_number 14461 _diffrn_reflns_av_R_equivalents 0.1253 _diffrn_reflns_av_sigmaI/netI 0.0977 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.51 _diffrn_reflns_theta_max 24.40 _reflns_number_total 3579 _reflns_number_gt 2337 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Stoe IPDS software (Stoe, 1996)' _computing_data_reduction 'XRED (Stoe, 1.08, 1996)' _computing_cell_refinement 'Stoe IPDS software (Stoe, 1996)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP3 for Windows (Farrugia, 1997)' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' _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^)+(0.0384P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.02(8) _refine_ls_number_reflns 3579 _refine_ls_number_parameters 277 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0863 _refine_ls_R_factor_gt 0.0473 _refine_ls_wR_factor_ref 0.1005 _refine_ls_wR_factor_gt 0.0892 _refine_ls_goodness_of_fit_ref 0.942 _refine_ls_restrained_S_all 0.942 _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 Nb1 Nb 0.37614(5) 0.24510(5) 0.27895(5) 0.02983(16) Uani 1 1 d . . . Cl1 Cl 0.3622(5) 0.3958(4) 0.3499(3) 0.0650(18) Uani 0.398(9) 1 d P A 1 C20 C 0.1483(3) 0.19709(19) 0.25857(19) 0.0436(13) Uani 0.398(9) 1 d P A 1 H20A H 0.1207 0.1531 0.3024 0.065 Uiso 0.398(9) 1 calc PR A 1 H20B H 0.1398 0.1632 0.2065 0.065 Uiso 0.398(9) 1 calc PR A 1 H20C H 0.0916 0.2555 0.2586 0.065 Uiso 0.398(9) 1 calc PR A 1 Cl2 Cl 0.1483(3) 0.19709(19) 0.25857(19) 0.0436(13) Uani 0.602(9) 1 d P A 2 C10 C 0.3622(5) 0.3958(4) 0.3499(3) 0.0650(18) Uani 0.602(9) 1 d P A 2 H10A H 0.2921 0.3917 0.3910 0.098 Uiso 0.602(9) 1 calc PR A 2 H10B H 0.3415 0.4487 0.3117 0.098 Uiso 0.602(9) 1 calc PR A 2 H10C H 0.4474 0.4094 0.3764 0.098 Uiso 0.602(9) 1 calc PR A 2 N11 N 0.5920(6) 0.2893(4) 0.2572(3) 0.0262(17) Uani 1 1 d . A . N12 N 0.6459(6) 0.2878(4) 0.1792(4) 0.0236(14) Uani 1 1 d . . . N21 N 0.3523(7) 0.3457(4) 0.1668(4) 0.0274(15) Uani 1 1 d . A . N22 N 0.4406(6) 0.3371(4) 0.1030(4) 0.0251(14) Uani 1 1 d . . . N31 N 0.4322(7) 0.1336(4) 0.1771(4) 0.0271(16) Uani 1 1 d . A . N32 N 0.5077(6) 0.1605(4) 0.1136(4) 0.0233(14) Uani 1 1 d . . . B1 B 0.5561(8) 0.2664(6) 0.1056(5) 0.0241(18) Uani 1 1 d . A . C1 C 0.4611(10) 0.1438(7) 0.3581(6) 0.038(2) Uani 1 1 d . A . C2 C 0.3574(9) 0.1859(6) 0.3927(6) 0.039(2) Uani 1 1 d . A . C3 C 0.5692(8) 0.0784(6) 0.3690(5) 0.0381(19) Uani 1 1 d . . . H3A H 0.6502 0.1080 0.3470 0.057 Uiso 1 1 calc R A . H3B H 0.5508 0.0169 0.3404 0.057 Uiso 1 1 calc R . . H3C H 0.5811 0.0651 0.4269 0.057 Uiso 1 1 calc R . . C4 C 0.2806(11) 0.1879(7) 0.4708(6) 0.066(3) Uani 1 1 d . . . H4A H 0.1863 0.1763 0.4596 0.099 Uiso 1 1 calc R A . H4B H 0.2912 0.2521 0.4967 0.099 Uiso 1 1 calc R . . H4C H 0.3141 0.1368 0.5072 0.099 Uiso 1 1 calc R . . C11 C 0.6911(8) 0.3068(5) 0.3083(4) 0.0311(19) Uani 1 1 d . . . C12 C 0.8079(6) 0.3128(5) 0.2643(5) 0.030(2) Uani 1 1 d . A . H12 H 0.8942 0.3236 0.2858 0.035 Uiso 1 1 calc R . . C13 C 0.7767(7) 0.3004(5) 0.1840(4) 0.0238(15) Uani 1 1 d . A . C14 C 0.6758(9) 0.3191(6) 0.3973(5) 0.039(2) Uani 1 1 d . A . H14A H 0.5830 0.3075 0.4125 0.058 Uiso 1 1 calc R . . H14B H 0.7012 0.3859 0.4127 0.058 Uiso 1 1 calc R . . H14C H 0.7330 0.2720 0.4255 0.058 Uiso 1 1 calc R . . C15 C 0.8679(8) 0.2959(5) 0.1118(4) 0.0317(16) Uani 1 1 d . . . H15A H 0.8315 0.2503 0.0716 0.047 Uiso 1 1 calc R A . H15B H 0.9558 0.2731 0.1291 0.047 Uiso 1 1 calc R . . H15C H 0.8758 0.3613 0.0877 0.047 Uiso 1 1 calc R . . C21 C 0.2594(7) 0.4132(5) 0.1427(5) 0.0332(19) Uani 1 1 d . . . C22 C 0.2883(8) 0.4444(5) 0.0656(5) 0.0344(19) Uani 1 1 d . A . H22 H 0.2386 0.4901 0.0345 0.041 Uiso 1 1 calc R . . C23 C 0.4031(6) 0.3969(4) 0.0417(5) 0.0246(17) Uani 1 1 d . A . C24 C 0.1479(8) 0.4469(5) 0.1968(5) 0.041(2) Uani 1 1 d . A . H24A H 0.1179 0.3921 0.2306 0.061 Uiso 1 1 calc R . . H24B H 0.0738 0.4703 0.1634 0.061 Uiso 1 1 calc R . . H24C H 0.1793 0.5003 0.2316 0.061 Uiso 1 1 calc R . . C25 C 0.4724(8) 0.4006(6) -0.0385(5) 0.036(2) Uani 1 1 d . . . H25A H 0.4826 0.3340 -0.0598 0.054 Uiso 1 1 calc R A . H25B H 0.5602 0.4305 -0.0317 0.054 Uiso 1 1 calc R . . H25C H 0.4199 0.4398 -0.0766 0.054 Uiso 1 1 calc R . . C31 C 0.4089(7) 0.0362(5) 0.1717(5) 0.0300(18) Uani 1 1 d . . . C32 C 0.4695(8) 0.0030(5) 0.1013(5) 0.034(2) Uani 1 1 d . A . H32 H 0.4678 -0.0621 0.0810 0.040 Uiso 1 1 calc R . . C33 C 0.5316(8) 0.0807(6) 0.0671(5) 0.036(2) Uani 1 1 d . A . C34 C 0.3251(9) -0.0216(5) 0.2283(6) 0.044(2) Uani 1 1 d . A . H34A H 0.3358 0.0039 0.2834 0.066 Uiso 1 1 calc R . . H34B H 0.3524 -0.0905 0.2267 0.066 Uiso 1 1 calc R . . H34C H 0.2318 -0.0162 0.2120 0.066 Uiso 1 1 calc R . . C35 C 0.6157(10) 0.0884(5) -0.0072(5) 0.043(2) Uani 1 1 d . . . H35A H 0.7016 0.1174 0.0069 0.065 Uiso 1 1 calc R A . H35B H 0.5709 0.1299 -0.0473 0.065 Uiso 1 1 calc R . . H35C H 0.6296 0.0229 -0.0301 0.065 Uiso 1 1 calc R . . H1 H 0.633(7) 0.276(4) 0.048(4) 0.032(19) 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 Nb1 0.0302(2) 0.0318(3) 0.0275(3) -0.0013(4) 0.0059(5) -0.0018(4) Cl1 0.069(4) 0.073(3) 0.054(3) -0.012(2) 0.013(3) -0.016(3) C20 0.0289(18) 0.0395(15) 0.062(3) 0.0056(12) -0.0057(14) -0.0003(11) Cl2 0.0289(18) 0.0395(15) 0.062(3) 0.0056(12) -0.0057(14) -0.0003(11) C10 0.069(4) 0.073(3) 0.054(3) -0.012(2) 0.013(3) -0.016(3) N11 0.023(3) 0.034(3) 0.022(5) 0.004(2) 0.000(2) 0.002(2) N12 0.023(4) 0.022(3) 0.026(4) 0.003(2) -0.006(3) 0.006(2) N21 0.028(4) 0.025(3) 0.029(4) -0.011(3) -0.006(3) -0.001(3) N22 0.020(3) 0.027(3) 0.028(4) -0.005(3) -0.006(3) -0.002(3) N31 0.027(4) 0.025(3) 0.029(4) 0.002(3) 0.008(3) 0.002(3) N32 0.031(4) 0.019(3) 0.020(4) 0.002(3) 0.000(3) -0.008(3) B1 0.028(4) 0.021(4) 0.023(4) 0.004(3) 0.001(3) -0.008(3) C1 0.044(6) 0.043(5) 0.028(6) -0.005(4) 0.013(4) -0.010(4) C2 0.029(5) 0.034(4) 0.054(6) 0.001(4) -0.006(4) -0.001(4) C3 0.038(5) 0.048(5) 0.028(5) 0.007(4) 0.000(3) 0.002(4) C4 0.084(8) 0.057(6) 0.058(7) 0.020(5) 0.052(6) 0.034(5) C11 0.049(5) 0.016(3) 0.028(5) -0.001(3) -0.007(4) 0.005(3) C12 0.015(3) 0.043(4) 0.031(6) 0.003(3) -0.017(3) 0.011(3) C13 0.017(4) 0.024(3) 0.031(4) -0.002(3) 0.003(3) 0.006(3) C14 0.038(6) 0.049(5) 0.030(5) 0.001(4) -0.005(4) 0.004(4) C15 0.020(4) 0.043(4) 0.032(4) -0.009(3) -0.003(4) -0.001(4) C21 0.017(4) 0.024(4) 0.059(6) -0.010(4) -0.012(3) 0.005(3) C22 0.034(5) 0.026(4) 0.043(6) 0.006(3) -0.014(4) 0.003(3) C23 0.019(4) 0.019(3) 0.036(5) 0.002(3) -0.011(3) -0.003(3) C24 0.032(5) 0.026(4) 0.063(6) -0.008(4) -0.001(4) 0.014(3) C25 0.028(5) 0.037(4) 0.044(6) 0.013(4) -0.010(4) -0.009(3) C31 0.023(4) 0.023(4) 0.044(5) 0.000(3) -0.002(3) -0.003(3) C32 0.048(6) 0.024(4) 0.029(5) 0.001(3) 0.001(4) -0.011(3) C33 0.048(5) 0.029(4) 0.032(5) -0.010(3) -0.006(4) -0.002(4) C34 0.052(6) 0.023(4) 0.056(6) 0.007(4) 0.012(4) -0.006(3) C35 0.052(5) 0.033(4) 0.045(6) -0.014(3) 0.009(5) -0.008(4) _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 Nb1 C2 2.051(10) . ? Nb1 C1 2.086(10) . ? Nb1 N11 2.284(6) . ? Nb1 N21 2.316(7) . ? Nb1 N31 2.336(7) . ? Nb1 Cl1 2.371(5) . ? Nb1 C20 2.410(3) . ? N11 C11 1.329(9) . ? N11 N12 1.395(8) . ? N12 C13 1.330(9) . ? N12 B1 1.542(10) . ? N21 C21 1.371(9) . ? N21 N22 1.383(9) . ? N22 C23 1.354(9) . ? N22 B1 1.511(10) . ? N31 N32 1.345(9) . ? N31 C31 1.353(8) . ? N32 C33 1.353(9) . ? N32 B1 1.531(9) . ? C1 C2 1.321(12) . ? C1 C3 1.418(12) . ? C2 C4 1.504(12) . ? C11 C12 1.385(10) . ? C11 C14 1.486(11) . ? C12 C13 1.372(11) . ? C13 C15 1.505(10) . ? C21 C22 1.372(11) . ? C21 C24 1.507(11) . ? C22 C23 1.383(10) . ? C23 C25 1.496(11) . ? C31 C32 1.387(11) . ? C31 C34 1.485(10) . ? C32 C33 1.354(11) . ? C33 C35 1.493(11) . ? 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 C2 Nb1 C1 37.2(3) . . ? C2 Nb1 N11 109.6(3) . . ? C1 Nb1 N11 83.3(3) . . ? C2 Nb1 N21 162.6(3) . . ? C1 Nb1 N21 159.3(3) . . ? N11 Nb1 N21 79.4(2) . . ? C2 Nb1 N31 115.1(3) . . ? C1 Nb1 N31 85.4(3) . . ? N11 Nb1 N31 80.1(2) . . ? N21 Nb1 N31 80.6(2) . . ? C2 Nb1 Cl1 83.4(3) . . ? C1 Nb1 Cl1 106.9(3) . . ? N11 Nb1 Cl1 84.5(2) . . ? N21 Nb1 Cl1 82.8(2) . . ? N31 Nb1 Cl1 159.14(19) . . ? C2 Nb1 C20 86.1(3) . . ? C1 Nb1 C20 107.3(3) . . ? N11 Nb1 C20 162.92(15) . . ? N21 Nb1 C20 87.20(18) . . ? N31 Nb1 C20 87.29(19) . . ? Cl1 Nb1 C20 104.39(15) . . ? C11 N11 N12 107.2(6) . . ? C11 N11 Nb1 131.5(5) . . ? N12 N11 Nb1 120.7(4) . . ? C13 N12 N11 109.2(6) . . ? C13 N12 B1 130.7(6) . . ? N11 N12 B1 120.0(6) . . ? C21 N21 N22 105.9(7) . . ? C21 N21 Nb1 134.5(6) . . ? N22 N21 Nb1 119.4(5) . . ? C23 N22 N21 109.8(6) . . ? C23 N22 B1 128.4(6) . . ? N21 N22 B1 121.8(6) . . ? N32 N31 C31 108.4(6) . . ? N32 N31 Nb1 121.3(4) . . ? C31 N31 Nb1 130.2(6) . . ? N31 N32 C33 108.8(6) . . ? N31 N32 B1 120.3(5) . . ? C33 N32 B1 130.9(6) . . ? N22 B1 N32 111.1(6) . . ? N22 B1 N12 110.7(6) . . ? N32 B1 N12 107.3(5) . . ? C2 C1 C3 145.7(10) . . ? C3 C1 Nb1 144.1(7) . . ? C1 C2 C4 141.7(9) . . ? C1 C2 Nb1 72.8(6) . . ? C4 C2 Nb1 145.5(7) . . ? N11 C11 C12 108.4(6) . . ? N11 C11 C14 124.7(7) . . ? C12 C11 C14 126.9(7) . . ? C13 C12 C11 107.7(6) . . ? N12 C13 C12 107.5(6) . . ? N12 C13 C15 123.5(7) . . ? C12 C13 C15 129.0(6) . . ? N21 C21 C22 109.5(7) . . ? N21 C21 C24 122.8(8) . . ? C22 C21 C24 127.7(7) . . ? C21 C22 C23 107.2(6) . . ? N22 C23 C22 107.6(7) . . ? N22 C23 C25 123.4(6) . . ? C22 C23 C25 128.8(6) . . ? N31 C31 C32 107.4(6) . . ? N31 C31 C34 125.4(7) . . ? C32 C31 C34 127.1(6) . . ? C33 C32 C31 107.3(7) . . ? N32 C33 C32 108.1(7) . . ? N32 C33 C35 120.7(7) . . ? C32 C33 C35 131.2(7) . . ? _diffrn_measured_fraction_theta_max 0.987 _diffrn_reflns_theta_full 24.40 _diffrn_measured_fraction_theta_full 0.987 _refine_diff_density_max 0.683 _refine_diff_density_min -0.482 _refine_diff_density_rms 0.079 #====END