# Supplementary Material (ESI) for Perkin Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 188/215 data_global #======================================================================= # 1. SUBMISSION DETAILS _publ_contact_author_name 'Brian K. Shull' _publ_contact_author_address ;Glycosyn Pharmaceuticals, Inc. Cary, North Carolina, 27513 USA ; _publ_contact_author_phone 1(919)4012323 _publ_contact_author_fax ? _publ_contact_author_email ? _publ_requested_journal 'Perkin Transactions 2' _publ_requested_category ? _publ_requested_coeditor_name ? _publ_contact_letter ; This is the CIF for manuscript A906038C ; #======================================================================= # 2. PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_date_printers_first ? _journal_date_printers_final ? _journal_date_proofs_out ? _journal_date_proofs_in ? _journal_coeditor_name ? _journal_coeditor_code ? _journal_coeditor_notes ; ? ; _journal_techeditor_code ? _journal_techeditor_notes ; ? ; _journal_coden_ASTM ? _journal_name_full ? _journal_year ? _journal_volume ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? #======================================================================= # 3. TITLE AND AUTHOR LIST _publ_section_title ; Evidence for Spontaneous, Reversible Paracyclophane Formation. Aprotic Solution Structure of the Boron Neutron Capture Therapy Drug, L-p-Boronophenylalanine ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address 'Shull, Brian K.' ;Glycosyn Pharmaceuticals, Inc. Cary, North Carolina, 27513 USA ; 'Spielvogel, David E.' ;New Concept Therapeutics, Inc. Cary, North Carolina, 27513 USA ; 'Gopalaswamy, Ramesh' ;Glycosyn Pharmaceuticals, Inc. Cary, North Carolina, 27513 USA ; 'Sankar, Sabapathy' ;Department of Chemistry North Carolina State University Raleigh, NC 27695-8204 ; 'Boyle, Paul D.' ;Department of Chemistry North Carolina State University Raleigh, NC 27695-8204 ; 'Head, Gerald' ;New Concept Therapeutics, Inc. Cary, North Carolina, 27513 USA ; 'Devito, Kevin' ;Glycosyn Pharmaceuticals, Inc. Cary, North Carolina, 27513 USA ; #======================================================================= # 4. TEXT _publ_section_exptl_refinement ; Structure Solution and Refinement. The data were reduced using routines from the NRCVAX set of programs. The structure was solved using SIR92. All non-H atom positions were recovered from the initial E-map. Although subsequent difference Fourier maps yielded peaks suggestive of hydrogen atom positions. However, the hydrogen atoms were placed at idealized calculated positions and were allowed to refine isotropically. All non-H atoms were allowed to refine with anisotropic displacement parameters refined smoothly using the NRCVAX LSTSQ routine to give R final factors of R = 0.031 and Rw = 0.043. The calculated structure factors were fit to the data using full matrix least-squares based on F. parameters (ADP's). The calculated structure factors included corrections for anomalous dispersion from the usual tabulation (International Tables for X-ray Crystallography, Vol. IV, (1974), Table 2.3.1, Kynoch Press, Birmingham, England). However, due to the small magnitude of the anomalous scattering terms, no absolute structure refinement was attempted. A secondary extinction correction was included in the final cycles of refinement. ; #======================================================================= # If more than one structure is reported, sections 5-10 should be filled in # per structure. For each data set, replace the ? in the data_? line below # by a unique identifier. data_BPA #======================================================================= # 5. CHEMICAL DATA _chemical_name_systematic ; L-p-boronophenylalanine ; _chemical_name_common ? _chemical_formula_moiety 'C9 H12 B N O4 ' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C9 H12 B N O4 ' _chemical_formula_weight 209.01 _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C ? .003 .002 'International Tables Vol. IV Table 2.2B' H ? .000 .000 'International Tables Vol. IV Table 2.2B' B ? .001 .001 'International Tables Vol. IV Table 2.2B' N ? .006 .003 'International Tables Vol. IV Table 2.2B' O ? .011 .006 'International Tables Vol. IV Table 2.2B' #======================================================================= # 6. CRYSTAL DATA _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,1/2+y,-z _cell_length_a 5.3472(3) _cell_length_b 7.3229(6) _cell_length_c 12.1705(7) _cell_angle_alpha 90.0 _cell_angle_beta 102.379(5) _cell_angle_gamma 90.0 _cell_volume 465.48(5) _cell_formula_units_Z 2 _cell_measurement_temperature 293 _cell_measurement_reflns_used 24 _cell_measurement_theta_min 17.00 _cell_measurement_theta_max 18.00 _cell_special_details ; ? #Insert any comments here. ; _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max .40 _exptl_crystal_size_mid .32 _exptl_crystal_size_min .19 _exptl_crystal_size_rad ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.491 _exptl_crystal_density_method ? _exptl_crystal_F_000 220.16 _exptl_absorpt_coefficient_mu .11 _exptl_absorpt_correction_type none #_exptl_absorpt_process_details 'NRCVAX ABSORP' #_exptl_absorpt_correction_T_min 1.0000 #_exptl_absorpt_correction_T_max 1.0000 #======================================================================= # 7. EXPERIMENTAL DATA _exptl_special_details ; Bijvoet pairs were collected pairwise using a negative theta setting. ; _diffrn_ambient_temperature 293 _diffrn_radiation_wavelength .71073 _diffrn_radiation_type 'Molybdenum K\a' _diffrn_radiation_source 'xray tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Nonius CAD-4 ' _diffrn_measurement_method 'Theta/2theta scan b/P/b ' _diffrn_standards_number 3 _diffrn_standards_interval_time 80 _diffrn_standards_decay_% 1.1 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 2 -2 -5 1 -1 6 -1 2 -5 _diffrn_reflns_number 2874 _diffrn_reflns_av_R_equivalents .008 _diffrn_reflns_av_sigmaI/netI ? _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.50 _diffrn_reflns_theta_max 30.00 _diffrn_reflns_reduction_process ? _reflns_number_total 2677 _reflns_number_observed 2602 _reflns_observed_criterion 'Inet > 1.0\s(Inet)' _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction 'NRCVAX DATRD2' _computing_structure_solution 'SIR92' _computing_structure_refinement 'NRCVAX LSTSQ' _computing_molecular_graphics 'NRCVAX' _computing_publication_material 'NRCVAX TABLES Jan 94 Version' #======================================================================= # 8. REFINEMENT DATA _refine_special_details ; ? #Insert any special details here. ; _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_weighting_details '1/(\s^2^(F)+ .0005F^2^) ' _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method Larson _refine_ls_extinction_coef 0.12(5) _refine_ls_number_reflns 2602 _refine_ls_number_parameters 184 _refine_ls_number_restraints ? _refine_ls_number_constraints ? _refine_ls_R_factor_all .031 _refine_ls_R_factor_obs .031 _refine_ls_wR_factor_all .043 _refine_ls_wR_factor_obs .043 _refine_ls_goodness_of_fit_all ? _refine_ls_goodness_of_fit_obs 1.60 _refine_ls_restrained_S_all ? _refine_ls_restrained_S_obs ? _refine_ls_shift/esd_max .003 _refine_ls_shift/esd_mean ? _refine_diff_density_max .28 _refine_diff_density_min -.17 _refine_ls_abs_structure_details ; The small magnitude of the anomalous dispersion terms precluded a successful refinement of the either the Rodgers or Flack parameters despite the fact that full set of Bijvoet pairs were collected. ; #======================================================================= # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS _atoms_sites_solution_primary direct _atoms_sites_solution_secondary geom loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_calc_flag _atom_site_refinement_flags _atom_site_type_symbol O(1) -.18635(15) .80987(18) .49088(7) .0307(4) Uani ? . O O(2) .22949(16) .8259(2) .57367(6) .0387(5) Uani ? . O O(3) .12862(16) .78510 -.22362(6) .0323(4) Uani ? . O O(4) .5067(2) .6140(2) -.17858(8) .0389(5) Uani ? . O N(1) .33817(17) 1.00847(18) .39311(7) .0238(4) Uani ? . N B(1) .3094(2) .7035(2) -.14509(9) .0233(5) Uani ? . B C(1) .04523(18) .83949(20) .49156(8) .0222(4) Uani ? . C C(2) .10948(18) .88513(19) .37729(8) .0196(4) Uani ? . C C(3) .1620(2) .70298(19) .32388(8) .0247(4) Uani ? . C C(4) .20716(18) .71382(18) .20586(7) .0201(4) Uani ? . C C(5) .03415(18) .80108(19) .11892(8) .0227(4) Uani ? . C C(6) .07038(17) .79866(19) .00897(8) .0222(4) Uani ? . C C(7) .28077(19) .70865(18) -.01850(7) .0203(4) Uani ? . C C(8) .45550(19) .62552(20) .06948(8) .0236(4) Uani ? . C C(9) .42016(19) .62774(20) .17977(8) .0244(4) Uani ? . C H(1a) .316(4) 1.107(4) .4288(17) .053(5) Uiso ? . H H(1b) .401(3) 1.043(3) .3216(16) .046(5) Uiso ? . H H(1c) .489(3) .948(3) .4372(15) .040(4) Uiso ? . H H(2) -.030(3) .945(2) .3361(13) .020(3) Uiso ? . H H(3) .152(4) .793(3) -.2937(17) .058(5) Uiso ? . H H(4) .591(4) .573(4) -.132(2) .060(7) Uiso ? . H H(3a) .318(4) .639(3) .3732(19) .053(5) Uiso ? . H H(3b) .003(3) .625(3) .3176(14) .043(4) Uiso ? . H H(5) -.099(3) .865(2) .1356(13) .026(3) Uiso ? . H H(6) -.055(3) .859(2) -.0470(12) .025(3) Uiso ? . H H(8) .600(3) .567(2) .0608(12) .023(3) Uiso ? . H H(9) .541(3) .573(2) .2437(13) .032(4) Uiso ? . H loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 _atom_site_aniso_type_symbol O(1) .0286(3) .0365(4) .0302(4) .0001(3) .0135(3) .0086(3) O O(2) .0340(4) .0671(6) .0157(3) -.0011(4) .0064(3) .0085(4) O O(3) .0388(4) .0419(5) .0178(3) .0076(4) .0100(3) .0037(3) O O(4) .0448(5) .0523(6) .0226(4) .0178(5) .0137(3) .0008(4) O N(1) .0296(4) .0250(4) .0190(4) -.0030(3) .0098(3) -.0003(3) N B(1) .0314(5) .0215(5) .0188(4) -.0025(4) .0092(4) -.0018(4) B C(1) .0290(5) .0244(4) .0154(4) .0013(3) .0100(3) .0024(3) C C(2) .0244(4) .0226(4) .0128(4) -.0005(3) .0065(3) .0012(3) C C(3) .0390(5) .0221(4) .0149(4) -.0002(4) .0101(3) -.0003(3) C C(4) .0270(4) .0189(4) .0149(4) -.0012(3) .0058(3) -.0016(3) C C(5) .0250(4) .0261(5) .0184(4) .0035(4) .0080(3) -.0012(4) C C(6) .0252(4) .0257(5) .0159(4) .0030(4) .0050(3) .0014(3) C C(7) .0263(4) .0204(4) .0156(4) -.0015(3) .0078(3) -.0021(3) C C(8) .0247(4) .0257(4) .0214(4) .0037(4) .0073(3) -.0011(4) C C(9) .0275(4) .0266(4) .0184(4) .0052(4) .0031(3) .0006(4) C #======================================================================= # 10. MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag O(1) C(1) 1.2554(12) ? ? ? O(2) C(1) 1.2479(13) ? ? ? O(3) B(1) 1.3448(14) ? ? ? O(3) H(3) .89(2) ? ? ? O(4) B(1) 1.3761(16) ? ? ? O(4) H(4) .71(3) ? ? ? N(1) C(2) 1.4991(15) ? ? ? N(1) H(1a) .87(3) ? ? ? N(1) H(1b) 1.027(18) ? ? ? N(1) H(1c) .975(19) ? ? ? B(1) C(7) 1.5810(13) ? ? ? C(1) C(2) 1.5391(13) ? ? ? C(2) C(3) 1.5359(18) ? ? ? C(2) H(2) .918(15) ? ? ? C(3) C(4) 1.5087(13) ? ? ? C(3) H(3a) 1.03(2) ? ? ? C(3) H(3b) 1.010(20) ? ? ? C(4) C(5) 1.4015(15) ? ? ? C(4) C(9) 1.3966(15) ? ? ? C(5) C(6) 1.3928(13) ? ? ? C(5) H(5) .911(16) ? ? ? C(6) C(7) 1.4047(14) ? ? ? C(6) H(6) .954(15) ? ? ? C(7) C(8) 1.4004(15) ? ? ? C(8) C(9) 1.3952(13) ? ? ? C(8) H(8) .910(15) ? ? ? C(9) H(9) .984(17) ? ? ? H(1a) H(1b) 1.54(3) ? ? ? H(1a) H(1c) 1.48(3) ? ? ? H(1b) H(1c) 1.55(3) ? ? ? 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag B(1) O(3) H(3) 118.8(14) ? ? ? ? B(1) O(4) H(4) 111.0(19) ? ? ? ? C(2) N(1) H(1a) 112.0(14) ? ? ? ? C(2) N(1) H(1b) 116.3(11) ? ? ? ? C(2) N(1) H(1c) 110.6(11) ? ? ? ? H(1a) N(1) H(1b) 108.9(18) ? ? ? ? H(1a) N(1) H(1c) 106.9(18) ? ? ? ? H(1b) N(1) H(1c) 101.4(14) ? ? ? ? O(3) B(1) O(4) 118.76(9) ? ? ? ? O(3) B(1) C(7) 118.49(10) ? ? ? ? O(4) B(1) C(7) 122.72(10) ? ? ? ? O(1) C(1) O(2) 126.86(9) ? ? ? ? O(1) C(1) C(2) 116.26(9) ? ? ? ? O(2) C(1) C(2) 116.75(8) ? ? ? ? N(1) C(2) C(1) 110.41(8) ? ? ? ? N(1) C(2) C(3) 111.06(8) ? ? ? ? N(1) C(2) H(2) 109.1(9) ? ? ? ? C(1) C(2) C(3) 106.88(10) ? ? ? ? C(1) C(2) H(2) 106.5(9) ? ? ? ? C(3) C(2) H(2) 112.7(10) ? ? ? ? C(2) C(3) C(4) 116.00(10) ? ? ? ? C(2) C(3) H(3a) 110.3(13) ? ? ? ? C(2) C(3) H(3b) 107.1(11) ? ? ? ? C(4) C(3) H(3a) 107.7(12) ? ? ? ? C(4) C(3) H(3b) 105.1(9) ? ? ? ? H(3a) C(3) H(3b) 110.5(18) ? ? ? ? C(3) C(4) C(5) 121.89(9) ? ? ? ? C(3) C(4) C(9) 119.83(9) ? ? ? ? C(5) C(4) C(9) 118.21(8) ? ? ? ? C(4) C(5) C(6) 120.95(9) ? ? ? ? C(4) C(5) H(5) 119.1(10) ? ? ? ? C(6) C(5) H(5) 119.9(10) ? ? ? ? C(5) C(6) C(7) 121.21(9) ? ? ? ? C(5) C(6) H(6) 117.3(9) ? ? ? ? C(7) C(6) H(6) 121.5(9) ? ? ? ? B(1) C(7) C(6) 119.53(9) ? ? ? ? B(1) C(7) C(8) 123.14(9) ? ? ? ? C(6) C(7) C(8) 117.33(8) ? ? ? ? C(7) C(8) C(9) 121.66(9) ? ? ? ? C(7) C(8) H(8) 124.1(9) ? ? ? ? C(9) C(8) H(8) 114.2(9) ? ? ? ? C(4) C(9) C(8) 120.61(10) ? ? ? ? C(4) C(9) H(9) 115.7(9) ? ? ? ? C(8) C(9) H(9) 123.7(9) ? ? ? ? N(1) H(1a) H(1b) 39.0(12) ? ? ? ? N(1) H(1a) H(1c) 39.1(13) ? ? ? ? H(1b) H(1a) H(1c) 61.6(14) ? ? ? ? N(1) H(1b) H(1a) 32.1(12) ? ? ? ? N(1) H(1b) H(1c) 38.1(9) ? ? ? ? H(1a) H(1b) H(1c) 57.2(13) ? ? ? ? N(1) H(1c) H(1a) 34.0(11) ? ? ? ? N(1) H(1c) H(1b) 40.5(10) ? ? ? ? H(1a) H(1c) H(1b) 61.2(13) ? ? ? ? #======================================================================= # Additional structures (sections 5-10 and associated data_? identifiers) # may be added at this point. #======================================================================= # The following lines are used to test the character set of files sent by # network email or other means. They are not part of the CIF data set. # abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789 # !@#$%^&*()_+{}:"~<>?|-=[];,./