# Electronic Supplementary Material (ESI) for Chemical Science
# This journal is © The Royal Society of Chemistry 2012


data_global
_journal_name_full               'Chemical Science'
_journal_coden_cambridge         1475
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
_publ_contact_author_email       ads10@st-andrews.ac.uk
_publ_contact_author_name        'Andrew Smith'
loop_
_publ_author_name
'Louis Morrill'
'Alexandra M. Z. Slawin'
'Andrew D. Smith'

data_7
_database_code_depnum_ccdc_archive 'CCDC 863562'
#TrackingRef '7.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H15 Br N2 O2'
_chemical_formula_sum            'C21 H15 Br N2 O2'
_chemical_formula_weight         407.26

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'
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           Orthorhombic
_symmetry_space_group_name_H-M   P2(1)2(1)2(1)

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   8.712(2)
_cell_length_b                   12.244(3)
_cell_length_c                   16.510(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1761.2(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    6298
_cell_measurement_theta_min      2.1
_cell_measurement_theta_max      28.6

_exptl_crystal_description       Prism
_exptl_crystal_colour            Colorless
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.536
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             824
_exptl_absorpt_coefficient_mu    2.352
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.798
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  confocal
_diffrn_measurement_device_type  CCD
_diffrn_measurement_method       '\w and \f scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            11137
_diffrn_reflns_av_R_equivalents  0.0496
_diffrn_reflns_av_sigmaI/netI    0.0706
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.07
_diffrn_reflns_theta_max         25.33
_reflns_number_total             3207
_reflns_number_gt                2850
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrystalClear (Rigaku Corp., 2004)'
_computing_cell_refinement       'CrystalClear (Rigaku Corp., 2004)'
_computing_data_reduction        'CrystalClear (Rigaku Corp., 2004)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_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^)+(0.0249P)^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    constr
_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   0.013(10)
_refine_ls_number_reflns         3207
_refine_ls_number_parameters     235
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0456
_refine_ls_R_factor_gt           0.0379
_refine_ls_wR_factor_ref         0.0682
_refine_ls_wR_factor_gt          0.0650
_refine_ls_goodness_of_fit_ref   0.966
_refine_ls_restrained_S_all      0.966
_refine_ls_shift/su_max          0.000
_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
O1 O 0.8064(3) 0.33642(19) -0.26812(11) 0.0243(5) Uani 1 1 d . . .
C2 C 0.8435(4) 0.2672(2) -0.20361(15) 0.0176(7) Uani 1 1 d . . .
N3 N 0.9673(3) 0.2752(2) -0.16149(14) 0.0207(6) Uani 1 1 d . . .
N4 N 1.0649(3) 0.3606(2) -0.17879(14) 0.0198(6) Uani 1 1 d . . .
C5 C 0.9991(4) 0.4604(3) -0.21218(17) 0.0200(7) Uani 1 1 d . . .
H5A H 1.0843 0.5045 -0.2362 0.024 Uiso 1 1 calc R . .
C6 C 0.8890(4) 0.4303(3) -0.27969(18) 0.0232(8) Uani 1 1 d . . .
O6 O 0.8648(3) 0.48496(18) -0.33857(12) 0.0286(6) Uani 1 1 d . . .
C7 C 0.7360(4) 0.1769(3) -0.19146(17) 0.0204(8) Uani 1 1 d . . .
C8 C 0.6095(4) 0.1612(3) -0.24248(18) 0.0243(8) Uani 1 1 d . . .
H8A H 0.5896 0.2111 -0.2853 0.029 Uiso 1 1 calc R . .
C9 C 0.5131(4) 0.0721(3) -0.2302(2) 0.0299(9) Uani 1 1 d . . .
H9A H 0.4281 0.0607 -0.2652 0.036 Uiso 1 1 calc R . .
C10 C 0.5405(4) 0.0000(3) -0.1672(2) 0.0284(9) Uani 1 1 d . . .
H10A H 0.4741 -0.0606 -0.1591 0.034 Uiso 1 1 calc R . .
C11 C 0.6642(4) 0.0159(3) -0.1160(2) 0.0268(8) Uani 1 1 d . . .
H11A H 0.6819 -0.0333 -0.0726 0.032 Uiso 1 1 calc R . .
C12 C 0.7624(4) 0.1034(3) -0.12789(18) 0.0239(8) Uani 1 1 d . . .
H12A H 0.8477 0.1137 -0.0929 0.029 Uiso 1 1 calc R . .
C13 C 1.2040(4) 0.3628(3) -0.13420(16) 0.0196(8) Uani 1 1 d . . .
C14 C 1.2713(3) 0.2643(3) -0.11198(15) 0.0210(7) Uani 1 1 d . . .
H14A H 1.2214 0.1971 -0.1237 0.025 Uiso 1 1 calc R . .
C15 C 1.4126(3) 0.2649(3) -0.07238(16) 0.0247(8) Uani 1 1 d . . .
H15A H 1.4588 0.1977 -0.0571 0.030 Uiso 1 1 calc R . .
C16 C 1.4866(4) 0.3625(3) -0.05493(18) 0.0275(8) Uani 1 1 d . . .
H16A H 1.5835 0.3624 -0.0285 0.033 Uiso 1 1 calc R . .
C17 C 1.4177(4) 0.4597(3) -0.07646(18) 0.0264(8) Uani 1 1 d . . .
H17A H 1.4678 0.5267 -0.0645 0.032 Uiso 1 1 calc R . .
C18 C 1.2755(4) 0.4612(3) -0.11552(17) 0.0232(8) Uani 1 1 d . . .
H18A H 1.2282 0.5286 -0.1292 0.028 Uiso 1 1 calc R . .
C19 C 0.9129(4) 0.5325(3) -0.15200(16) 0.0172(7) Uani 1 1 d . . .
C20 C 0.8792(4) 0.4971(2) -0.07394(17) 0.0193(7) Uani 1 1 d . . .
H20A H 0.9136 0.4275 -0.0562 0.023 Uiso 1 1 calc R . .
C21 C 0.7960(4) 0.5629(3) -0.02209(19) 0.0217(7) Uani 1 1 d . . .
H21A H 0.7728 0.5385 0.0311 0.026 Uiso 1 1 calc R . .
C22 C 0.7463(4) 0.6646(3) -0.04792(17) 0.0229(8) Uani 1 1 d . . .
Br22 Br 0.63042(4) 0.75332(3) 0.023113(19) 0.03764(13) Uani 1 1 d . . .
C23 C 0.7789(4) 0.7019(3) -0.12544(16) 0.0227(8) Uani 1 1 d . . .
H23A H 0.7444 0.7716 -0.1430 0.027 Uiso 1 1 calc R . .
C24 C 0.8632(4) 0.6349(3) -0.17664(17) 0.0223(7) Uani 1 1 d . . .
H24A H 0.8873 0.6596 -0.2297 0.027 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
O1 0.0243(14) 0.0256(13) 0.0230(11) 0.0023(10) -0.0025(10) -0.0029(11)
C2 0.0198(18) 0.0167(17) 0.0163(13) -0.0031(14) 0.0041(12) 0.0000(16)
N3 0.0191(16) 0.0195(17) 0.0234(13) 0.0002(12) 0.0031(11) -0.0007(13)
N4 0.0204(16) 0.0170(16) 0.0219(14) 0.0002(12) 0.0006(12) 0.0002(13)
C5 0.021(2) 0.0206(18) 0.0184(15) 0.0000(15) 0.0012(14) -0.0007(16)
C6 0.023(2) 0.0249(19) 0.0214(16) -0.0022(16) 0.0040(14) 0.0041(17)
O6 0.0388(15) 0.0269(13) 0.0202(11) 0.0048(10) -0.0021(11) 0.0010(13)
C7 0.018(2) 0.0221(19) 0.0216(15) -0.0056(15) 0.0038(14) 0.0040(16)
C8 0.022(2) 0.0241(19) 0.0268(17) -0.0014(15) 0.0004(15) 0.0026(17)
C9 0.023(2) 0.032(2) 0.035(2) -0.0084(18) -0.0016(16) 0.0002(19)
C10 0.027(2) 0.021(2) 0.036(2) -0.0021(17) 0.0057(16) -0.0082(17)
C11 0.031(2) 0.0178(19) 0.0315(18) -0.0004(15) 0.0036(16) 0.0000(17)
C12 0.023(2) 0.0242(19) 0.0242(16) -0.0001(16) -0.0020(14) -0.0003(16)
C13 0.0172(18) 0.027(2) 0.0147(15) 0.0005(14) 0.0024(13) 0.0022(16)
C14 0.0224(18) 0.0193(19) 0.0213(14) -0.0026(16) 0.0020(12) 0.0018(17)
C15 0.0211(19) 0.030(2) 0.0229(15) 0.0063(17) 0.0027(13) 0.0059(17)
C16 0.020(2) 0.037(2) 0.0260(17) 0.0016(16) -0.0007(15) -0.0022(18)
C17 0.026(2) 0.024(2) 0.0300(18) -0.0001(16) -0.0012(16) -0.0050(16)
C18 0.022(2) 0.0216(19) 0.0257(17) 0.0011(15) -0.0009(15) -0.0031(16)
C19 0.0153(19) 0.0173(18) 0.0189(15) 0.0002(14) -0.0037(13) -0.0023(14)
C20 0.0213(19) 0.0153(16) 0.0213(16) 0.0012(14) 0.0000(14) -0.0024(16)
C21 0.0230(19) 0.0239(19) 0.0182(14) -0.0003(16) -0.0002(15) 0.0002(16)
C22 0.019(2) 0.0227(19) 0.0266(17) -0.0062(15) 0.0001(14) 0.0007(15)
Br22 0.0462(2) 0.0274(2) 0.0393(2) -0.0024(2) 0.01669(16) 0.0102(2)
C23 0.026(2) 0.0190(18) 0.0229(16) 0.0017(14) -0.0017(15) -0.0011(16)
C24 0.024(2) 0.0225(18) 0.0200(15) 0.0038(14) 0.0010(15) -0.0021(18)

_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
O1 C6 1.369(4) . ?
O1 C2 1.399(3) . ?
C2 N3 1.287(4) . ?
C2 C7 1.462(4) . ?
N3 N4 1.378(3) . ?
N4 C13 1.419(4) . ?
N4 C5 1.458(4) . ?
C5 C6 1.516(4) . ?
C5 C19 1.527(4) . ?
C5 H5A 1.0000 . ?
C6 O6 1.199(3) . ?
C7 C8 1.400(4) . ?
C7 C12 1.401(4) . ?
C8 C9 1.391(5) . ?
C8 H8A 0.9500 . ?
C9 C10 1.385(5) . ?
C9 H9A 0.9500 . ?
C10 C11 1.383(5) . ?
C10 H10A 0.9500 . ?
C11 C12 1.385(5) . ?
C11 H11A 0.9500 . ?
C12 H12A 0.9500 . ?
C13 C18 1.391(4) . ?
C13 C14 1.390(5) . ?
C14 C15 1.394(4) . ?
C14 H14A 0.9500 . ?
C15 C16 1.389(5) . ?
C15 H15A 0.9500 . ?
C16 C17 1.379(4) . ?
C16 H16A 0.9500 . ?
C17 C18 1.397(4) . ?
C17 H17A 0.9500 . ?
C18 H18A 0.9500 . ?
C19 C24 1.387(4) . ?
C19 C20 1.391(4) . ?
C20 C21 1.381(4) . ?
C20 H20A 0.9500 . ?
C21 C22 1.385(4) . ?
C21 H21A 0.9500 . ?
C22 C23 1.388(4) . ?
C22 Br22 1.890(3) . ?
C23 C24 1.388(4) . ?
C23 H23A 0.9500 . ?
C24 H24A 0.9500 . ?

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
C6 O1 C2 119.6(2) . . ?
N3 C2 O1 124.0(3) . . ?
N3 C2 C7 121.3(3) . . ?
O1 C2 C7 114.5(2) . . ?
C2 N3 N4 117.6(2) . . ?
N3 N4 C13 115.7(2) . . ?
N3 N4 C5 118.1(3) . . ?
C13 N4 C5 121.1(3) . . ?
N4 C5 C6 108.9(3) . . ?
N4 C5 C19 115.6(2) . . ?
C6 C5 C19 107.9(3) . . ?
N4 C5 H5A 108.1 . . ?
C6 C5 H5A 108.1 . . ?
C19 C5 H5A 108.1 . . ?
O6 C6 O1 119.3(3) . . ?
O6 C6 C5 124.9(3) . . ?
O1 C6 C5 115.7(3) . . ?
C8 C7 C12 119.4(3) . . ?
C8 C7 C2 121.7(3) . . ?
C12 C7 C2 118.9(3) . . ?
C9 C8 C7 119.7(3) . . ?
C9 C8 H8A 120.2 . . ?
C7 C8 H8A 120.2 . . ?
C10 C9 C8 120.4(3) . . ?
C10 C9 H9A 119.8 . . ?
C8 C9 H9A 119.8 . . ?
C9 C10 C11 120.2(3) . . ?
C9 C10 H10A 119.9 . . ?
C11 C10 H10A 119.9 . . ?
C12 C11 C10 120.2(3) . . ?
C12 C11 H11A 119.9 . . ?
C10 C11 H11A 119.9 . . ?
C11 C12 C7 120.1(3) . . ?
C11 C12 H12A 120.0 . . ?
C7 C12 H12A 120.0 . . ?
C18 C13 C14 120.3(3) . . ?
C18 C13 N4 120.9(3) . . ?
C14 C13 N4 118.7(3) . . ?
C15 C14 C13 119.4(3) . . ?
C15 C14 H14A 120.3 . . ?
C13 C14 H14A 120.3 . . ?
C16 C15 C14 120.8(3) . . ?
C16 C15 H15A 119.6 . . ?
C14 C15 H15A 119.6 . . ?
C17 C16 C15 119.1(3) . . ?
C17 C16 H16A 120.4 . . ?
C15 C16 H16A 120.4 . . ?
C16 C17 C18 121.1(3) . . ?
C16 C17 H17A 119.5 . . ?
C18 C17 H17A 119.5 . . ?
C13 C18 C17 119.2(3) . . ?
C13 C18 H18A 120.4 . . ?
C17 C18 H18A 120.4 . . ?
C24 C19 C20 119.2(3) . . ?
C24 C19 C5 119.1(3) . . ?
C20 C19 C5 121.8(3) . . ?
C21 C20 C19 120.2(3) . . ?
C21 C20 H20A 119.9 . . ?
C19 C20 H20A 119.9 . . ?
C20 C21 C22 119.8(3) . . ?
C20 C21 H21A 120.1 . . ?
C22 C21 H21A 120.1 . . ?
C23 C22 C21 121.0(3) . . ?
C23 C22 Br22 119.5(2) . . ?
C21 C22 Br22 119.5(2) . . ?
C22 C23 C24 118.4(3) . . ?
C22 C23 H23A 120.8 . . ?
C24 C23 H23A 120.8 . . ?
C23 C24 C19 121.4(3) . . ?
C23 C24 H24A 119.3 . . ?
C19 C24 H24A 119.3 . . ?

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 O1 C2 N3 -12.4(4) . . . . ?
C6 O1 C2 C7 172.8(3) . . . . ?
O1 C2 N3 N4 3.3(4) . . . . ?
C7 C2 N3 N4 177.8(2) . . . . ?
C2 N3 N4 C13 -176.5(3) . . . . ?
C2 N3 N4 C5 28.2(4) . . . . ?
N3 N4 C5 C6 -46.4(3) . . . . ?
C13 N4 C5 C6 159.7(3) . . . . ?
N3 N4 C5 C19 75.2(3) . . . . ?
C13 N4 C5 C19 -78.6(4) . . . . ?
C2 O1 C6 O6 174.2(3) . . . . ?
C2 O1 C6 C5 -9.6(4) . . . . ?
N4 C5 C6 O6 -148.0(3) . . . . ?
C19 C5 C6 O6 85.7(4) . . . . ?
N4 C5 C6 O1 36.0(4) . . . . ?
C19 C5 C6 O1 -90.2(3) . . . . ?
N3 C2 C7 C8 -173.2(3) . . . . ?
O1 C2 C7 C8 1.7(4) . . . . ?
N3 C2 C7 C12 5.6(4) . . . . ?
O1 C2 C7 C12 -179.5(3) . . . . ?
C12 C7 C8 C9 -0.9(4) . . . . ?
C2 C7 C8 C9 177.9(3) . . . . ?
C7 C8 C9 C10 0.9(5) . . . . ?
C8 C9 C10 C11 -0.1(5) . . . . ?
C9 C10 C11 C12 -0.6(5) . . . . ?
C10 C11 C12 C7 0.6(5) . . . . ?
C8 C7 C12 C11 0.2(5) . . . . ?
C2 C7 C12 C11 -178.7(3) . . . . ?
N3 N4 C13 C18 -149.3(3) . . . . ?
C5 N4 C13 C18 5.1(4) . . . . ?
N3 N4 C13 C14 33.1(4) . . . . ?
C5 N4 C13 C14 -172.5(3) . . . . ?
C18 C13 C14 C15 -1.4(4) . . . . ?
N4 C13 C14 C15 176.2(2) . . . . ?
C13 C14 C15 C16 0.0(4) . . . . ?
C14 C15 C16 C17 0.8(4) . . . . ?
C15 C16 C17 C18 -0.2(5) . . . . ?
C14 C13 C18 C17 2.0(4) . . . . ?
N4 C13 C18 C17 -175.6(3) . . . . ?
C16 C17 C18 C13 -1.2(5) . . . . ?
N4 C5 C19 C24 172.2(3) . . . . ?
C6 C5 C19 C24 -65.6(4) . . . . ?
N4 C5 C19 C20 -9.6(4) . . . . ?
C6 C5 C19 C20 112.5(3) . . . . ?
C24 C19 C20 C21 0.6(5) . . . . ?
C5 C19 C20 C21 -177.5(3) . . . . ?
C19 C20 C21 C22 -0.2(5) . . . . ?
C20 C21 C22 C23 0.0(5) . . . . ?
C20 C21 C22 Br22 179.3(2) . . . . ?
C21 C22 C23 C24 -0.2(5) . . . . ?
Br22 C22 C23 C24 -179.5(2) . . . . ?
C22 C23 C24 C19 0.7(5) . . . . ?
C20 C19 C24 C23 -0.9(5) . . . . ?
C5 C19 C24 C23 177.3(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        25.30
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.466
_refine_diff_density_min         -0.508
_refine_diff_density_rms         0.063