# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Bedford, Robin' _publ_contact_author_email r.bedford@bristol.ac.uk _publ_section_title ; Solvent-free aromatic C-H functionalisation/halogenation reactions ; loop_ _publ_author_name R.B.Bedford J.U.Engelhart M.F.Haddow C.J.Mitchell R.L.Webster # Attachment '- 7b.cif' data_rw_0m _database_code_depnum_ccdc_archive 'CCDC 780622' #TrackingRef '- 7b.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C9 H10 Br N O' _chemical_formula_sum 'C9 H10 Br N O' _chemical_formula_weight 228.09 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' O O 0.0106 0.0060 '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 monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 4.04010(10) _cell_length_b 23.7100(5) _cell_length_c 9.7444(2) _cell_angle_alpha 90.00 _cell_angle_beta 100.0070(10) _cell_angle_gamma 90.00 _cell_volume 919.22(4) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4512 _cell_measurement_theta_min 2.29 _cell_measurement_theta_max 32.25 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.48 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.648 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 456 _exptl_absorpt_coefficient_mu 4.422 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.3964 _exptl_absorpt_correction_T_max 0.7465 _exptl_absorpt_process_details 'SADABS V2008/1' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 'Bruker Apex II Kappa with CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 10973 _diffrn_reflns_av_R_equivalents 0.0320 _diffrn_reflns_av_sigmaI/netI 0.0327 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -34 _diffrn_reflns_limit_k_max 35 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.72 _diffrn_reflns_theta_max 32.94 _reflns_number_total 3192 _reflns_number_gt 2733 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker Apex II' _computing_cell_refinement 'Bruker Apex II' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _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^)+(0.0321P)^2^+0.3614P] 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 3192 _refine_ls_number_parameters 114 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0380 _refine_ls_R_factor_gt 0.0291 _refine_ls_wR_factor_ref 0.0694 _refine_ls_wR_factor_gt 0.0665 _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_restrained_S_all 1.054 _refine_ls_shift/su_max 0.004 _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 Br1 Br 0.34361(4) 0.519285(7) 0.777185(17) 0.02132(6) Uani 1 1 d . . . N1 N -0.1503(4) 0.27880(6) 0.81741(14) 0.0183(3) Uani 1 1 d . . . H1 H -0.193(6) 0.2709(9) 0.892(2) 0.022 Uiso 1 1 d . . . O1 O -0.2405(4) 0.24756(6) 0.59366(12) 0.0302(3) Uani 1 1 d . . . C1 C 0.1992(4) 0.44307(7) 0.78512(16) 0.0170(3) Uani 1 1 d . . . C2 C 0.0814(4) 0.42586(7) 0.90380(16) 0.0184(3) Uani 1 1 d . . . H2 H 0.0786 0.4514 0.9788 0.022 Uiso 1 1 calc R . . C3 C -0.0321(4) 0.37107(7) 0.91180(15) 0.0178(3) Uani 1 1 d . . . H3 H -0.1147 0.3589 0.9924 0.021 Uiso 1 1 calc R . . C4 C -0.0257(4) 0.33361(6) 0.80184(15) 0.0154(3) Uani 1 1 d . . . C5 C 0.1021(4) 0.35153(7) 0.68529(16) 0.0170(3) Uani 1 1 d . . . H5 H 0.1131 0.3256 0.6119 0.020 Uiso 1 1 calc R . . C6 C 0.2141(4) 0.40670(7) 0.67405(16) 0.0164(3) Uani 1 1 d . . . C7 C 0.3379(5) 0.42540(7) 0.54466(17) 0.0219(3) Uani 1 1 d . . . H7A H 0.1743 0.4513 0.4918 0.033 Uiso 1 1 calc R . . H7B H 0.3661 0.3924 0.4871 0.033 Uiso 1 1 calc R . . H7C H 0.5542 0.4447 0.5706 0.033 Uiso 1 1 calc R . . C8 C -0.2554(5) 0.24043(7) 0.71704(16) 0.0196(3) Uani 1 1 d . . . C9 C -0.3933(5) 0.18662(7) 0.76770(19) 0.0255(4) Uani 1 1 d . . . H9A H -0.5881 0.1742 0.7001 0.038 Uiso 1 1 calc R . . H9B H -0.4619 0.1934 0.8579 0.038 Uiso 1 1 calc R . . H9C H -0.2194 0.1574 0.7780 0.038 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 Br1 0.02175(10) 0.01582(8) 0.02515(9) -0.00018(6) 0.00058(6) -0.00249(6) N1 0.0282(7) 0.0149(6) 0.0115(5) 0.0006(4) 0.0033(5) -0.0003(5) O1 0.0522(9) 0.0239(6) 0.0161(5) -0.0055(5) 0.0104(6) -0.0091(6) C1 0.0151(7) 0.0144(6) 0.0198(7) 0.0004(5) -0.0012(5) 0.0015(6) C2 0.0215(8) 0.0164(7) 0.0160(6) -0.0032(5) -0.0004(6) 0.0018(6) C3 0.0226(8) 0.0173(7) 0.0129(6) -0.0011(5) 0.0013(6) 0.0016(6) C4 0.0185(7) 0.0134(6) 0.0131(6) 0.0002(5) -0.0007(5) 0.0017(5) C5 0.0213(7) 0.0161(7) 0.0129(6) -0.0005(5) 0.0012(5) 0.0018(6) C6 0.0154(7) 0.0167(7) 0.0161(6) 0.0013(5) 0.0002(5) 0.0026(5) C7 0.0253(8) 0.0203(7) 0.0208(7) 0.0017(6) 0.0062(6) 0.0002(6) C8 0.0256(8) 0.0151(7) 0.0177(7) -0.0014(5) 0.0030(6) 0.0014(6) C9 0.0343(10) 0.0186(7) 0.0237(8) -0.0014(6) 0.0055(7) -0.0052(7) _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 Br1 C1 1.9047(16) . ? N1 C8 1.349(2) . ? N1 C4 1.411(2) . ? N1 H1 0.80(2) . ? O1 C8 1.2258(19) . ? C1 C2 1.386(2) . ? C1 C6 1.393(2) . ? C2 C3 1.384(2) . ? C2 H2 0.9500 . ? C3 C4 1.396(2) . ? C3 H3 0.9500 . ? C4 C5 1.393(2) . ? C5 C6 1.395(2) . ? C5 H5 0.9500 . ? C6 C7 1.502(2) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 C9 1.509(2) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? 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 C8 N1 C4 128.03(14) . . ? C8 N1 H1 114.4(16) . . ? C4 N1 H1 116.7(16) . . ? C2 C1 C6 122.24(15) . . ? C2 C1 Br1 117.72(12) . . ? C6 C1 Br1 120.05(12) . . ? C3 C2 C1 119.22(14) . . ? C3 C2 H2 120.4 . . ? C1 C2 H2 120.4 . . ? C2 C3 C4 120.23(15) . . ? C2 C3 H3 119.9 . . ? C4 C3 H3 119.9 . . ? C5 C4 C3 119.39(14) . . ? C5 C4 N1 123.93(14) . . ? C3 C4 N1 116.68(14) . . ? C4 C5 C6 121.43(14) . . ? C4 C5 H5 119.3 . . ? C6 C5 H5 119.3 . . ? C1 C6 C5 117.45(15) . . ? C1 C6 C7 122.35(15) . . ? C5 C6 C7 120.19(14) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? O1 C8 N1 123.72(16) . . ? O1 C8 C9 121.42(15) . . ? N1 C8 C9 114.86(14) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 C1 C2 C3 -1.4(2) . . . . ? Br1 C1 C2 C3 178.67(12) . . . . ? C1 C2 C3 C4 0.4(2) . . . . ? C2 C3 C4 C5 1.3(2) . . . . ? C2 C3 C4 N1 -179.13(15) . . . . ? C8 N1 C4 C5 -19.8(3) . . . . ? C8 N1 C4 C3 160.57(17) . . . . ? C3 C4 C5 C6 -2.1(2) . . . . ? N1 C4 C5 C6 178.36(15) . . . . ? C2 C1 C6 C5 0.6(2) . . . . ? Br1 C1 C6 C5 -179.44(12) . . . . ? C2 C1 C6 C7 179.30(15) . . . . ? Br1 C1 C6 C7 -0.7(2) . . . . ? C4 C5 C6 C1 1.1(2) . . . . ? C4 C5 C6 C7 -177.60(15) . . . . ? C4 N1 C8 O1 3.8(3) . . . . ? C4 N1 C8 C9 -176.66(16) . . . . ? _diffrn_measured_fraction_theta_max 0.927 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.938 _refine_diff_density_min -0.738 _refine_diff_density_rms 0.089