# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_cambridge 0177 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_name 'Paolo Clerici' _publ_contact_author_email clerici.paolo@unibas.ch loop_ _publ_author_name 'Paolo Clerici' 'Helma Wennemers' data_1 _database_code_depnum_ccdc_archive 'CCDC 820405' #TrackingRef '4933_web_deposit_cif_file_0_PaoloClerici_1301991250.cif' _exptl_special_details ; The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K. Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105 107. ; _refine_special_details ; ? ; #--------------------------------------------------------------- # _oxford_ data items, April 2010: # There is some uncertainty about the correct way of forming local data # names, e.g. # _atom_site_special_shape_oxford # or # _oxford_atom_site_special_shape # see: # http://www.iucr.org/resources/cif/spec/version1.1/semantics#namespace # A reserved prefix, e.g. foo, must be used in the following way # " If the data file contains items defined in a DDL1 dictionary, the # local data names assigned under the reserved prefix must contain it as # their first component, e.g. _foo_atom_site_my_item. " # However, this seems to say the opposite: # http://www.iucr.org/__data/iucr/cif/standard/cifstd8.html # According to advice from the IUCr, CRYSTALS is correct #--------------------------------------------------------------- # End of 'script/refcif.dat' #end of refcif _cell_length_a 5.8120(5) _cell_length_b 6.7788(6) _cell_length_c 25.807(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1016.75(15) _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' _symmetry_space_group_name_Hall 'P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz x,y,z x+1/2,-y+1/2,-z -x,y+1/2,-z+1/2 -x+1/2,-y,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Br -0.2901 2.4595 17.1789 2.1723 5.2358 16.5796 5.6377 0.2609 3.9851 41.4328 2.9557 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C13 H14 Br1 N1 O4 # Dc = 2.14 Fooo = 520.00 Mu = 40.55 M = 328.16 # Found Formula = C10 H12 Br1 N1 O2 # Dc = 1.69 FOOO = 520.00 Mu = 40.16 M = 258.11 _chemical_formula_sum 'C10 H12 Br1 N1 O2' _chemical_formula_moiety 'C10 H10 Br N O, H2 O' _chemical_compound_source ? _chemical_formula_weight 258.11 _cell_measurement_reflns_used 9927 _cell_measurement_theta_min 3 _cell_measurement_theta_max 40 _cell_measurement_temperature 123 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_min 0.030 _exptl_crystal_size_mid 0.130 _exptl_crystal_size_max 0.170 _exptl_crystal_density_diffrn 1.686 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 520 _exptl_absorpt_coefficient_mu 4.016 # Sheldrick geometric approximatio 0.59 0.89 # No experimental values of Tmin/max available _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.59 _exptl_absorpt_correction_T_max 0.89 _diffrn_measurement_device_type 'Bruker Kappa Apex2' _diffrn_measurement_device Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f & \w scans' # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'Apex2 (Bruker AXS, 2006)' _computing_cell_refinement 'Apex2 (Bruker AXS, 2006)' _computing_data_reduction 'Apex2 (Bruker AXS, 2006)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 123 _diffrn_reflns_number 59191 _reflns_number_total 8055 _diffrn_reflns_av_R_equivalents 0.046 # Number of reflections without Friedels Law is 8055 # Number of reflections with Friedels Law is 4561 # Theoretical number of reflections is about 4010 _diffrn_reflns_theta_min 3.107 _diffrn_reflns_theta_max 44.202 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 44.202 _diffrn_measured_fraction_theta_full 0.999 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -50 _diffrn_reflns_limit_l_max 50 _reflns_limit_h_min -11 _reflns_limit_h_max 11 _reflns_limit_k_min 0 _reflns_limit_k_max 13 _reflns_limit_l_min 0 _reflns_limit_l_max 50 _oxford_diffrn_Wilson_B_factor 1.20 _oxford_diffrn_Wilson_scale 55.85 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.64 _refine_diff_density_max 0.70 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>3.0\s(I) _refine_ls_number_reflns 5286 _refine_ls_number_restraints 0 _refine_ls_number_parameters 128 _oxford_refine_ls_R_factor_ref 0.0209 _refine_ls_wR_factor_ref 0.0205 _refine_ls_goodness_of_fit_ref 1.0800 _refine_ls_shift/su_max 0.0016881 _refine_ls_shift/su_mean 0.0000615 # The values computed from all data _oxford_reflns_number_all 8050 _refine_ls_R_factor_all 0.0412 _refine_ls_wR_factor_all 0.0381 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 5607 _refine_ls_R_factor_gt 0.0221 _refine_ls_wR_factor_gt 0.0210 _refine_ls_abs_structure_Flack 0.005(5) _refine_ls_abs_structure_details 'Flack (1983), 0 Friedel-pairs' # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration ad _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment none # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 0.120 0.955E-01 0.559E-01 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Bruker Analytical X-ray Systems, Inc., 2006. Apex2, Version 2 User Manual, M86-E01078, Madison, WI. Flack, H. D. (1983). Acta Cryst. A39, 876-881. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994). Acta Cryst, A50, 411-437. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Br1 Br 0.591838(17) 0.007201(17) 0.602964(3) 0.0165 1.0000 Uani . . . . . . C1 C 0.62781(13) 0.00348(17) 0.52976(3) 0.0128 1.0000 Uani . . . . . . C2 C 0.83215(17) -0.06452(14) 0.50863(4) 0.0136 1.0000 Uani . . . . . . C3 C 0.86090(17) -0.05930(14) 0.45478(4) 0.0132 1.0000 Uani . . . . . . C4 C 0.68760(14) 0.01096(18) 0.42219(3) 0.0118 1.0000 Uani . . . . . . C5 C 0.48140(17) 0.07488(15) 0.44470(4) 0.0138 1.0000 Uani . . . . . . C6 C 0.45113(17) 0.07253(15) 0.49842(4) 0.0137 1.0000 Uani . . . . . . C7 C 0.6346(2) 0.20585(15) 0.33820(4) 0.0164 1.0000 Uani . . . . . . C8 C 0.72279(15) 0.01297(19) 0.36397(3) 0.0141 1.0000 Uani . . . . . . C9 C 0.5840(2) -0.15068(14) 0.33617(4) 0.0156 1.0000 Uani . . . . . . C10 C 0.38666(18) -0.04466(13) 0.30988(3) 0.0143 1.0000 Uani . . . . . . N1 N 0.42029(19) 0.14916(12) 0.31353(3) 0.0161 1.0000 Uani . . . . . . O1 O 0.22020(16) -0.12569(13) 0.28850(4) 0.0212 1.0000 Uani . . . . . . H1 H 0.3299 0.2368 0.2988 0.0197 1.0000 Uiso R . . . . . H41 H 0.9980 -0.1029 0.4402 0.0161 1.0000 Uiso R . . . . . H61 H 0.3137 0.1164 0.5136 0.0159 1.0000 Uiso R . . . . . H71 H 0.9486 -0.1118 0.5306 0.0166 1.0000 Uiso R . . . . . H81 H 0.3617 0.1233 0.4236 0.0171 1.0000 Uiso R . . . . . H121 H 0.8827 -0.0006 0.3572 0.0169 1.0000 Uiso R . . . . . H211 H 0.6719 -0.2165 0.3097 0.0201 1.0000 Uiso R . . . . . H212 H 0.5271 -0.2497 0.3602 0.0199 1.0000 Uiso R . . . . . H231 H 0.7428 0.2540 0.3128 0.0212 1.0000 Uiso R . . . . . H232 H 0.6093 0.3104 0.3629 0.0191 1.0000 Uiso R . . . . . O2 O 0.14280(16) 0.47059(12) 0.27617(3) 0.0220 1.0000 Uani . . . . . . H2 H 0.1781 0.5896 0.2802 0.0327 1.0000 Uiso R . . . . . H3 H 0.0318 0.4556 0.2561 0.0315 1.0000 Uiso 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 0.02114(3) 0.01803(3) 0.01043(2) -0.00057(4) 0.00129(3) -0.00114(5) C1 0.0154(3) 0.0122(3) 0.0107(2) 0.0000(3) 0.00012(18) -0.0006(4) C2 0.0140(4) 0.0146(3) 0.0121(3) 0.0007(2) -0.0023(3) 0.0019(3) C3 0.0125(4) 0.0139(3) 0.0132(3) -0.0004(2) -0.0005(2) 0.0025(3) C4 0.0116(3) 0.0130(3) 0.0109(2) 0.0000(3) -0.0004(2) -0.0001(3) C5 0.0119(3) 0.0165(4) 0.0130(3) 0.0011(3) -0.0010(3) 0.0018(3) C6 0.0126(4) 0.0154(3) 0.0131(3) 0.0003(3) 0.0012(2) 0.0013(3) C7 0.0202(5) 0.0156(4) 0.0134(3) 0.0021(3) -0.0022(3) -0.0037(3) C8 0.0136(3) 0.0175(4) 0.0113(2) 0.0002(3) 0.0001(2) -0.0001(4) C9 0.0194(4) 0.0139(3) 0.0136(3) -0.0010(3) -0.0010(3) 0.0018(4) C10 0.0166(4) 0.0140(3) 0.0123(3) -0.0013(2) -0.0020(3) 0.0007(3) N1 0.0197(4) 0.0136(3) 0.0149(3) 0.0005(2) -0.0039(3) -0.0008(3) O1 0.0224(4) 0.0178(3) 0.0234(4) -0.0023(3) -0.0096(3) -0.0018(3) O2 0.0274(4) 0.0153(4) 0.0232(3) 0.0016(2) -0.0107(3) -0.0001(2) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.14218(8) 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 Br1 . C1 . 1.9008(7) yes C1 . C2 . 1.3858(13) yes C1 . C6 . 1.3884(13) yes C2 . C3 . 1.4001(13) yes C2 . H71 . 0.939 no C3 . C4 . 1.3960(13) yes C3 . H41 . 0.929 no C4 . C5 . 1.4005(13) yes C4 . C8 . 1.5165(11) yes C5 . C6 . 1.3976(14) yes C5 . H81 . 0.943 no C6 . H61 . 0.938 no C7 . C8 . 1.5539(16) yes C7 . N1 . 1.4508(14) yes C7 . H231 . 0.965 no C7 . H232 . 0.964 no C8 . C9 . 1.5479(15) yes C8 . H121 . 0.950 no C9 . C10 . 1.5141(15) yes C9 . H211 . 0.963 no C9 . H212 . 0.972 no C10 . N1 . 1.3317(12) yes C10 . O1 . 1.2418(13) yes N1 . H1 . 0.879 no O2 . H2 . 0.838 no O2 . H3 . 0.833 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 Br1 . C1 . C2 . 119.33(6) yes Br1 . C1 . C6 . 119.55(6) yes C2 . C1 . C6 . 121.11(8) yes C1 . C2 . C3 . 118.98(8) yes C1 . C2 . H71 . 119.6 no C3 . C2 . H71 . 121.5 no C2 . C3 . C4 . 121.37(9) yes C2 . C3 . H41 . 119.8 no C4 . C3 . H41 . 118.9 no C3 . C4 . C5 . 118.23(8) yes C3 . C4 . C8 . 120.18(8) yes C5 . C4 . C8 . 121.57(8) yes C4 . C5 . C6 . 121.04(9) yes C4 . C5 . H81 . 119.9 no C6 . C5 . H81 . 119.0 no C5 . C6 . C1 . 119.25(8) yes C5 . C6 . H61 . 121.2 no C1 . C6 . H61 . 119.5 no C8 . C7 . N1 . 104.36(8) yes C8 . C7 . H231 . 111.1 no N1 . C7 . H231 . 110.6 no C8 . C7 . H232 . 112.7 no N1 . C7 . H232 . 110.7 no H231 . C7 . H232 . 107.4 no C7 . C8 . C4 . 112.78(10) yes C7 . C8 . C9 . 103.46(8) yes C4 . C8 . C9 . 112.49(9) yes C7 . C8 . H121 . 108.9 no C4 . C8 . H121 . 108.3 no C9 . C8 . H121 . 110.8 no C8 . C9 . C10 . 105.21(8) yes C8 . C9 . H211 . 112.6 no C10 . C9 . H211 . 107.7 no C8 . C9 . H212 . 112.1 no C10 . C9 . H212 . 110.9 no H211 . C9 . H212 . 108.2 no C9 . C10 . N1 . 108.99(9) yes C9 . C10 . O1 . 125.40(9) yes N1 . C10 . O1 . 125.61(10) yes C7 . N1 . C10 . 114.74(9) yes C7 . N1 . H1 . 121.6 no C10 . N1 . H1 . 123.2 no H2 . O2 . H3 . 112.5 no loop_ _geom_hbond_atom_site_label_D _geom_hbond_site_symmetry_D _geom_hbond_atom_site_label_H _geom_hbond_site_symmetry_H _geom_hbond_atom_site_label_A _geom_hbond_site_symmetry_A _geom_hbond_angle_DHA _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_publ_flag N1 . H1 . O2 . 169 0.88 2.01 2.8772(14) yes O2 . H2 . O1 1_565 173 0.84 1.96 2.7917(14) yes O2 . H3 . O1 3_555 171 0.83 1.94 2.7681(14) yes