# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
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#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_shelxl

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C13 H13 Br Cl3 N O2'
_chemical_formula_weight         401.50

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 '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 21'

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

_cell_length_a                   12.1328(11)
_cell_length_b                   13.7151(15)
_cell_length_c                   10.0433(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1671.2(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    290(2)
_cell_measurement_reflns_used    1104
_cell_measurement_theta_min      3.6400
_cell_measurement_theta_max      69.4307

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.30
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.596
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             800
_exptl_absorpt_coefficient_mu    7.773
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.1663
_exptl_absorpt_correction_T_max  0.2039
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      290(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'Enhance Ultra (Cu) X-ray Source'
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device_type  'Gemini S Ultra, Agilent Technologies'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 15.9149
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            3506
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_sigmaI/netI    0.0392
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         4.87
_diffrn_reflns_theta_max         69.56
_reflns_number_total             2164
_reflns_number_gt                1714
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrysAlisPro (Agilent Technologies)'
_computing_cell_refinement       'CrysAlisPro (Agilent Technologies)'
_computing_data_reduction        'CrysAlisPro (Agilent Technologies)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Ortep-3 (L. J. Farrugia, 2001)'
_computing_publication_material  SHELXL-97

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² 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/[σ²(Fo²)+(0.0901P)²+0.5444P] where P=(Fo²+2Fc²)/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   ?
_refine_ls_number_reflns         2164
_refine_ls_number_parameters     182
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0596
_refine_ls_wR_factor_ref         0.1768
_refine_ls_wR_factor_gt          0.1598
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_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
Br1 Br -0.01024(9) 0.80211(10) 0.96569(16) 0.1162(5) Uani 1 1 d . . .
Cl1 Cl 0.2509(3) 1.00548(19) 0.9724(7) 0.1517(15) Uani 1 1 d . . .
Cl2 Cl 0.4444(3) 0.9387(3) 1.0985(3) 0.1319(13) Uani 1 1 d . . .
Cl3 Cl 0.4160(4) 0.9122(3) 0.8203(3) 0.171(2) Uani 1 1 d . . .
O2 O 0.2818(5) 0.7910(4) 1.1200(5) 0.0802(17) Uani 1 1 d . . .
N1 N 0.2475(5) 0.7712(4) 0.9026(5) 0.0585(14) Uani 1 1 d . . .
H1 H 0.2601 0.7930 0.8238 0.070 Uiso 1 1 calc R . .
C9 C 0.1807(5) 0.6848(5) 0.9190(7) 0.0577(15) Uani 1 1 d . . .
H9 H 0.1755 0.6706 1.0144 0.069 Uiso 1 1 calc R . .
C8 C 0.2273(6) 0.5967(5) 0.8506(8) 0.0653(17) Uani 1 1 d . . .
H8 H 0.1874 0.5391 0.8589 0.078 Uiso 1 1 calc R . .
O1 O 0.3029(12) 0.2483(8) 0.6322(12) 0.155(5) Uani 1 1 d . . .
C7 C 0.3175(6) 0.5924(6) 0.7811(7) 0.0644(17) Uani 1 1 d . . .
H7 H 0.3581 0.6498 0.7754 0.077 Uiso 1 1 calc R . .
C11 C 0.2890(6) 0.8166(5) 1.0053(6) 0.0567(15) Uani 1 1 d . . .
C12 C 0.3487(6) 0.9144(6) 0.9739(9) 0.0750(19) Uani 1 1 d . . .
C3 C 0.3634(7) 0.5073(8) 0.7102(8) 0.084(3) Uani 1 1 d . . .
C10 C 0.0649(6) 0.7013(7) 0.8664(8) 0.070(2) Uani 1 1 d . . .
H10A H 0.0234 0.6410 0.8726 0.084 Uiso 1 1 calc R . .
H10B H 0.0686 0.7198 0.7733 0.084 Uiso 1 1 calc R . .
C6 C 0.4425(15) 0.3542(12) 0.5585(13) 0.143(7) Uani 1 1 d . . .
H6 H 0.4683 0.3046 0.5036 0.172 Uiso 1 1 calc R . .
C2 C 0.3094(8) 0.4165(8) 0.7110(10) 0.091(3) Uani 1 1 d . . .
H2 H 0.2459 0.4090 0.7620 0.109 Uiso 1 1 calc R . .
C1 C 0.3481(11) 0.3377(10) 0.6377(12) 0.115(4) Uani 1 1 d . . .
C4 C 0.4575(9) 0.5199(10) 0.6368(9) 0.101(3) Uani 1 1 d . . .
H4 H 0.4943 0.5794 0.6377 0.122 Uiso 1 1 calc R . .
C5 C 0.4976(14) 0.4428(14) 0.5608(12) 0.140(7) Uani 1 1 d . . .
H5 H 0.5617 0.4508 0.5113 0.168 Uiso 1 1 calc R . .
C13 C 0.2235(15) 0.2268(10) 0.732(2) 0.145(7) Uani 1 1 d . . .
H13A H 0.1581 0.2646 0.7162 0.218 Uiso 1 1 calc R . .
H13B H 0.2531 0.2428 0.8178 0.218 Uiso 1 1 calc R . .
H13C H 0.2057 0.1587 0.7290 0.218 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 0.0946(7) 0.1253(9) 0.1288(10) -0.0244(9) 0.0148(7) 0.0335(6)
Cl1 0.130(2) 0.0742(13) 0.251(5) 0.041(2) -0.010(3) 0.0051(15)
Cl2 0.140(2) 0.129(2) 0.127(2) 0.0165(19) -0.056(2) -0.065(2)
Cl3 0.230(5) 0.180(4) 0.103(2) -0.026(2) 0.070(3) -0.134(4)
O2 0.107(4) 0.091(4) 0.043(3) 0.006(3) -0.004(3) -0.022(3)
N1 0.066(3) 0.067(3) 0.042(3) 0.007(2) 0.001(2) -0.007(3)
C9 0.057(3) 0.063(4) 0.053(3) 0.000(3) 0.000(3) 0.001(3)
C8 0.058(4) 0.064(4) 0.074(4) -0.008(4) -0.005(3) -0.003(3)
O1 0.207(11) 0.105(7) 0.154(9) -0.058(7) -0.038(9) 0.055(8)
C7 0.060(4) 0.070(4) 0.063(4) 0.001(4) -0.005(3) 0.001(3)
C11 0.064(4) 0.064(4) 0.043(3) -0.003(3) -0.005(3) -0.005(3)
C12 0.081(4) 0.074(5) 0.070(4) -0.003(4) -0.006(4) -0.018(4)
C3 0.075(5) 0.115(8) 0.061(4) 0.003(5) -0.006(4) 0.042(5)
C10 0.056(4) 0.088(5) 0.067(4) -0.008(4) 0.003(3) 0.002(4)
C6 0.186(16) 0.164(14) 0.080(6) -0.008(9) 0.003(9) 0.120(14)
C2 0.093(6) 0.098(7) 0.083(5) -0.019(5) -0.020(5) 0.037(6)
C1 0.122(9) 0.120(9) 0.104(8) -0.032(7) -0.035(7) 0.065(8)
C4 0.094(7) 0.128(9) 0.081(6) 0.016(6) 0.017(5) 0.051(6)
C5 0.154(12) 0.193(16) 0.072(6) 0.028(10) 0.021(7) 0.101(13)
C13 0.174(19) 0.085(8) 0.176(18) -0.031(10) -0.072(14) 0.020(9)

_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 C10 1.933(8) . ?
Cl1 C12 1.723(9) . ?
Cl2 C12 1.739(8) . ?
Cl3 C12 1.745(9) . ?
O2 C11 1.208(8) . ?
N1 C11 1.306(8) . ?
N1 C9 1.444(9) . ?
N1 H1 0.8600 . ?
C9 C8 1.501(10) . ?
C9 C10 1.517(10) . ?
C9 H9 0.9800 . ?
C8 C7 1.300(11) . ?
C8 H8 0.9300 . ?
O1 C1 1.345(18) . ?
O1 C13 1.42(2) . ?
C7 C3 1.477(12) . ?
C7 H7 0.9300 . ?
C11 C12 1.558(10) . ?
C3 C4 1.370(14) . ?
C3 C2 1.407(14) . ?
C10 H10A 0.9700 . ?
C10 H10B 0.9700 . ?
C6 C5 1.39(3) . ?
C6 C1 1.41(2) . ?
C6 H6 0.9300 . ?
C2 C1 1.389(13) . ?
C2 H2 0.9300 . ?
C4 C5 1.391(18) . ?
C4 H4 0.9300 . ?
C5 H5 0.9300 . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?

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
C11 N1 C9 121.2(5) . . ?
C11 N1 H1 119.4 . . ?
C9 N1 H1 119.4 . . ?
N1 C9 C8 113.4(6) . . ?
N1 C9 C10 111.0(6) . . ?
C8 C9 C10 108.0(6) . . ?
N1 C9 H9 108.1 . . ?
C8 C9 H9 108.1 . . ?
C10 C9 H9 108.1 . . ?
C7 C8 C9 126.8(7) . . ?
C7 C8 H8 116.6 . . ?
C9 C8 H8 116.6 . . ?
C1 O1 C13 115.8(11) . . ?
C8 C7 C3 127.7(8) . . ?
C8 C7 H7 116.1 . . ?
C3 C7 H7 116.1 . . ?
O2 C11 N1 126.0(7) . . ?
O2 C11 C12 118.5(7) . . ?
N1 C11 C12 115.5(6) . . ?
C11 C12 Cl1 107.8(5) . . ?
C11 C12 Cl2 109.3(6) . . ?
Cl1 C12 Cl2 109.1(5) . . ?
C11 C12 Cl3 112.4(6) . . ?
Cl1 C12 Cl3 109.1(6) . . ?
Cl2 C12 Cl3 109.1(5) . . ?
C4 C3 C2 120.2(10) . . ?
C4 C3 C7 118.3(11) . . ?
C2 C3 C7 121.4(8) . . ?
C9 C10 Br1 111.3(5) . . ?
C9 C10 H10A 109.4 . . ?
Br1 C10 H10A 109.4 . . ?
C9 C10 H10B 109.4 . . ?
Br1 C10 H10B 109.4 . . ?
H10A C10 H10B 108.0 . . ?
C5 C6 C1 121.4(12) . . ?
C5 C6 H6 119.3 . . ?
C1 C6 H6 119.3 . . ?
C1 C2 C3 121.9(12) . . ?
C1 C2 H2 119.1 . . ?
C3 C2 H2 119.1 . . ?
O1 C1 C2 126.4(14) . . ?
O1 C1 C6 116.9(13) . . ?
C2 C1 C6 116.6(14) . . ?
C3 C4 C5 119.4(15) . . ?
C3 C4 H4 120.3 . . ?
C5 C4 H4 120.3 . . ?
C6 C5 C4 120.4(14) . . ?
C6 C5 H5 119.8 . . ?
C4 C5 H5 119.8 . . ?
O1 C13 H13A 109.5 . . ?
O1 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
O1 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 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
C11 N1 C9 C8 -120.2(7) . . . . ?
C11 N1 C9 C10 118.0(7) . . . . ?
N1 C9 C8 C7 -0.5(11) . . . . ?
C10 C9 C8 C7 122.9(8) . . . . ?
C9 C8 C7 C3 -178.2(7) . . . . ?
C9 N1 C11 O2 3.7(12) . . . . ?
C9 N1 C11 C12 -173.8(6) . . . . ?
O2 C11 C12 Cl1 -91.7(9) . . . . ?
N1 C11 C12 Cl1 86.1(8) . . . . ?
O2 C11 C12 Cl2 26.8(10) . . . . ?
N1 C11 C12 Cl2 -155.4(6) . . . . ?
O2 C11 C12 Cl3 148.1(7) . . . . ?
N1 C11 C12 Cl3 -34.1(9) . . . . ?
C8 C7 C3 C4 176.8(8) . . . . ?
C8 C7 C3 C2 0.3(13) . . . . ?
N1 C9 C10 Br1 -63.1(7) . . . . ?
C8 C9 C10 Br1 172.0(5) . . . . ?
C4 C3 C2 C1 -0.6(14) . . . . ?
C7 C3 C2 C1 175.8(8) . . . . ?
C13 O1 C1 C2 -14.6(18) . . . . ?
C13 O1 C1 C6 167.3(11) . . . . ?
C3 C2 C1 O1 179.7(10) . . . . ?
C3 C2 C1 C6 -2.2(15) . . . . ?
C5 C6 C1 O1 -177.6(13) . . . . ?
C5 C6 C1 C2 4.1(18) . . . . ?
C2 C3 C4 C5 1.4(14) . . . . ?
C7 C3 C4 C5 -175.1(9) . . . . ?
C1 C6 C5 C4 -3(2) . . . . ?
C3 C4 C5 C6 0.5(18) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1 O2 0.86 2.11 2.873(7) 147.6 3_554

_diffrn_measured_fraction_theta_max 0.967
_diffrn_reflns_theta_full        69.56
_diffrn_measured_fraction_theta_full 0.967
_refine_diff_density_max         0.453
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.066
_database_code_depnum_ccdc_archive 'CCDC 986047'
