# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_4h
_database_code_depnum_ccdc_archive 'CCDC 1510157'
_audit_update_record             
;
2016-10-17 deposited with the CCDC.
2016-11-10 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        4h
_chemical_name_common            4h
_chemical_melting_point          ?
_chemical_formula_moiety         'C21 H23 Br F3 N O6'
_chemical_formula_sum            'C21 H23 Br F3 N O6'
_chemical_formula_weight         522.31

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'
F F 0.0171 0.0103 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_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                   8.6647(6)
_cell_length_b                   15.3884(11)
_cell_length_c                   17.0772(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2277.0(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4748
_cell_measurement_theta_min      2.39
_cell_measurement_theta_max      25.58

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_F_000             1064
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.280
_exptl_crystal_size_min          0.270
_exptl_absorpt_coefficient_mu    1.866
_shelx_estimated_absorpt_T_min   0.587
_shelx_estimated_absorpt_T_max   0.633
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5811
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Incoatec microsource'
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            35125
_diffrn_reflns_av_unetI/netI     0.0654
_diffrn_reflns_av_R_equivalents  0.0588
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         1.781
_diffrn_reflns_theta_max         30.907
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.965
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             6794
_reflns_number_gt                5571
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.743
_reflns_Friedel_fraction_max     0.912
_reflns_Friedel_fraction_full    0.998

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    SHELXS-97
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 w=1/[σ²(Fo²)+(0.0296P)²]
 where P=(Fo²+2Fc²)/3
;
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_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 x determined using 2122 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.015(5)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         6794
_refine_ls_number_parameters     292
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0367
_refine_ls_wR_factor_ref         0.0837
_refine_ls_wR_factor_gt          0.0797
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_restrained_S_all      1.032
_refine_ls_shift/su_max          0.001
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.51070(4) 0.33206(3) 0.63767(2) 0.03856(12) Uani 1 1 d . . . . .
F1 F 0.3812(2) 0.11404(10) 0.28621(10) 0.0208(4) Uani 1 1 d . . . . .
F2 F 0.22079(19) 0.14929(10) 0.19445(10) 0.0194(4) Uani 1 1 d . . . . .
F3 F 0.46243(19) 0.13346(10) 0.16829(9) 0.0193(4) Uani 1 1 d . . . . .
O1 O 0.7318(2) 0.24114(12) 0.11065(12) 0.0176(4) Uani 1 1 d . . . . .
O2 O 0.5409(2) 0.27841(13) 0.02741(11) 0.0164(4) Uani 1 1 d . . . . .
O4 O 0.6520(2) 0.45378(12) 0.07807(12) 0.0179(4) Uani 1 1 d . . . . .
O3 O 0.4052(2) 0.47638(13) 0.11361(12) 0.0205(4) Uani 1 1 d . . . . .
O5 O 1.1163(2) 0.39281(13) 0.25207(14) 0.0230(5) Uani 1 1 d . . . . .
O6 O 1.0541(2) 0.53101(12) 0.28156(12) 0.0163(4) Uani 1 1 d . . . . .
N1 N 0.3801(3) 0.31031(14) 0.16912(13) 0.0123(4) Uani 1 1 d . . . . .
H1 H 0.2962 0.3195 0.1413 0.015 Uiso 1 1 calc R U . . .
C1 C 0.5201(3) 0.3127(2) 0.52785(16) 0.0230(7) Uani 1 1 d . . . . .
C2 C 0.4516(4) 0.3726(2) 0.47854(17) 0.0250(7) Uani 1 1 d . . . . .
H2 H 0.3982 0.4215 0.4991 0.030 Uiso 1 1 calc R U . . .
C3 C 0.4625(4) 0.35975(19) 0.39803(17) 0.0215(6) Uani 1 1 d . . . . .
H3 H 0.4154 0.4003 0.3636 0.026 Uiso 1 1 calc R U . . .
C4 C 0.5410(3) 0.28873(17) 0.36697(16) 0.0132(5) Uani 1 1 d . . . . .
C5 C 0.6076(3) 0.2300(2) 0.41831(18) 0.0208(6) Uani 1 1 d . . . . .
H5 H 0.6611 0.1809 0.3982 0.025 Uiso 1 1 calc R U . . .
C6 C 0.5971(4) 0.2420(2) 0.49930(19) 0.0277(7) Uani 1 1 d . . . . .
H6 H 0.6431 0.2015 0.5341 0.033 Uiso 1 1 calc R U . . .
C7 C 0.5497(3) 0.27473(17) 0.27898(15) 0.0116(5) Uani 1 1 d . . . . .
H7 H 0.6169 0.2233 0.2681 0.014 Uiso 1 1 calc R U . . .
C8 C 0.3885(3) 0.25929(16) 0.24105(15) 0.0121(5) Uani 1 1 d . . . . .
H8 H 0.3063 0.2794 0.2780 0.014 Uiso 1 1 calc R U . . .
C9 C 0.5334(3) 0.34348(16) 0.15108(14) 0.0106(5) Uani 1 1 d . . . . .
C10 C 0.6126(3) 0.35396(16) 0.23294(15) 0.0109(5) Uani 1 1 d . . . . .
H10 H 0.5675 0.4071 0.2577 0.013 Uiso 1 1 calc R U . . .
C11 C 0.3631(3) 0.16441(18) 0.22220(15) 0.0141(5) Uani 1 1 d . . . . .
C12 C 0.6169(3) 0.28116(17) 0.09513(16) 0.0138(5) Uani 1 1 d . . . . .
C13 C 0.6064(4) 0.22325(19) -0.03438(17) 0.0201(6) Uani 1 1 d . . . . .
H13A H 0.7204 0.2261 -0.0322 0.024 Uiso 1 1 calc R U . . .
H13B H 0.5731 0.2452 -0.0862 0.024 Uiso 1 1 calc R U . . .
C14 C 0.5551(4) 0.1306(2) -0.02500(19) 0.0278(7) Uani 1 1 d . . . . .
H14A H 0.5953 0.1074 0.0244 0.042 Uiso 1 1 calc R U . . .
H14B H 0.5945 0.0959 -0.0688 0.042 Uiso 1 1 calc R U . . .
H14C H 0.4421 0.1282 -0.0245 0.042 Uiso 1 1 calc R U . . .
C15 C 0.5191(3) 0.43252(17) 0.11185(14) 0.0136(5) Uani 1 1 d . . . . .
C16 C 0.6595(4) 0.53594(19) 0.03677(18) 0.0254(7) Uani 1 1 d . . . . .
H16A H 0.7677 0.5565 0.0353 0.031 Uiso 1 1 calc R U . . .
H16B H 0.5972 0.5798 0.0651 0.031 Uiso 1 1 calc R U . . .
C17 C 0.6002(7) 0.5268(3) -0.0448(2) 0.0572(14) Uani 1 1 d . . . . .
H17A H 0.6631 0.4842 -0.0732 0.086 Uiso 1 1 calc R U . . .
H17B H 0.6059 0.5830 -0.0715 0.086 Uiso 1 1 calc R U . . .
H17C H 0.4927 0.5070 -0.0434 0.086 Uiso 1 1 calc R U . . .
C18 C 0.7849(3) 0.36366(17) 0.23643(15) 0.0122(5) Uani 1 1 d . . . . .
H18 H 0.8481 0.3147 0.2254 0.015 Uiso 1 1 calc R U . . .
C19 C 0.8509(3) 0.43850(17) 0.25444(16) 0.0135(5) Uani 1 1 d . . . . .
H19 H 0.7870 0.4876 0.2635 0.016 Uiso 1 1 calc R U . . .
C20 C 1.0200(3) 0.44892(16) 0.26111(15) 0.0129(5) Uani 1 1 d . . . . .
C21 C 1.2155(3) 0.55076(19) 0.2921(2) 0.0237(7) Uani 1 1 d . . . . .
H21A H 1.2557 0.5179 0.3369 0.036 Uiso 1 1 calc R U . . .
H21B H 1.2278 0.6131 0.3020 0.036 Uiso 1 1 calc R U . . .
H21C H 1.2727 0.5347 0.2448 0.036 Uiso 1 1 calc R U . . .


_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 1.900(3) . ?
F1 C11 1.349(3) . ?
F2 C11 1.342(3) . ?
F3 C11 1.347(3) . ?
O1 C12 1.200(3) . ?
O2 C12 1.332(3) . ?
O2 C13 1.468(3) . ?
O4 C15 1.330(3) . ?
O4 C16 1.449(3) . ?
O3 C15 1.196(3) . ?
O5 C20 1.211(3) . ?
O6 C20 1.343(3) . ?
O6 C21 1.443(3) . ?
N1 C9 1.456(3) . ?
N1 C8 1.460(3) . ?
N1 H1 0.8800 . ?
C1 C6 1.367(5) . ?
C1 C2 1.382(5) . ?
C2 C3 1.392(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.392(4) . ?
C3 H3 0.9500 . ?
C4 C5 1.385(4) . ?
C4 C7 1.520(4) . ?
C5 C6 1.398(4) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C7 C10 1.550(3) . ?
C7 C8 1.558(4) . ?
C7 H7 1.0000 . ?
C8 C11 1.511(4) . ?
C8 H8 1.0000 . ?
C9 C15 1.530(4) . ?
C9 C12 1.535(4) . ?
C9 C10 1.566(3) . ?
C10 C18 1.501(4) . ?
C10 H10 1.0000 . ?
C13 C14 1.501(4) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C16 C17 1.492(5) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 0.9800 . ?
C18 C19 1.322(4) . ?
C18 H18 0.9500 . ?
C19 C20 1.478(4) . ?
C19 H19 0.9500 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 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
C12 O2 C13 116.8(2) . . ?
C15 O4 C16 117.7(2) . . ?
C20 O6 C21 116.4(2) . . ?
C9 N1 C8 108.7(2) . . ?
C9 N1 H1 125.6 . . ?
C8 N1 H1 125.6 . . ?
C6 C1 C2 121.5(3) . . ?
C6 C1 Br1 119.8(2) . . ?
C2 C1 Br1 118.6(2) . . ?
C1 C2 C3 118.5(3) . . ?
C1 C2 H2 120.7 . . ?
C3 C2 H2 120.7 . . ?
C2 C3 C4 121.4(3) . . ?
C2 C3 H3 119.3 . . ?
C4 C3 H3 119.3 . . ?
C5 C4 C3 118.3(3) . . ?
C5 C4 C7 120.8(2) . . ?
C3 C4 C7 120.8(2) . . ?
C4 C5 C6 120.8(3) . . ?
C4 C5 H5 119.6 . . ?
C6 C5 H5 119.6 . . ?
C1 C6 C5 119.4(3) . . ?
C1 C6 H6 120.3 . . ?
C5 C6 H6 120.3 . . ?
C4 C7 C10 114.0(2) . . ?
C4 C7 C8 112.8(2) . . ?
C10 C7 C8 103.0(2) . . ?
C4 C7 H7 108.9 . . ?
C10 C7 H7 108.9 . . ?
C8 C7 H7 108.9 . . ?
N1 C8 C11 109.5(2) . . ?
N1 C8 C7 108.2(2) . . ?
C11 C8 C7 111.5(2) . . ?
N1 C8 H8 109.2 . . ?
C11 C8 H8 109.2 . . ?
C7 C8 H8 109.2 . . ?
N1 C9 C15 109.4(2) . . ?
N1 C9 C12 110.1(2) . . ?
C15 C9 C12 109.0(2) . . ?
N1 C9 C10 104.31(19) . . ?
C15 C9 C10 109.5(2) . . ?
C12 C9 C10 114.4(2) . . ?
C18 C10 C7 114.0(2) . . ?
C18 C10 C9 118.8(2) . . ?
C7 C10 C9 102.58(19) . . ?
C18 C10 H10 106.9 . . ?
C7 C10 H10 106.9 . . ?
C9 C10 H10 106.9 . . ?
F2 C11 F3 106.5(2) . . ?
F2 C11 F1 107.0(2) . . ?
F3 C11 F1 106.1(2) . . ?
F2 C11 C8 112.1(2) . . ?
F3 C11 C8 113.2(2) . . ?
F1 C11 C8 111.4(2) . . ?
O1 C12 O2 125.9(2) . . ?
O1 C12 C9 125.1(2) . . ?
O2 C12 C9 109.1(2) . . ?
O2 C13 C14 111.0(2) . . ?
O2 C13 H13A 109.4 . . ?
C14 C13 H13A 109.4 . . ?
O2 C13 H13B 109.4 . . ?
C14 C13 H13B 109.4 . . ?
H13A C13 H13B 108.0 . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
O3 C15 O4 126.0(2) . . ?
O3 C15 C9 124.1(2) . . ?
O4 C15 C9 109.9(2) . . ?
O4 C16 C17 110.9(3) . . ?
O4 C16 H16A 109.5 . . ?
C17 C16 H16A 109.5 . . ?
O4 C16 H16B 109.5 . . ?
C17 C16 H16B 109.5 . . ?
H16A C16 H16B 108.0 . . ?
C16 C17 H17A 109.5 . . ?
C16 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C16 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C19 C18 C10 121.7(2) . . ?
C19 C18 H18 119.1 . . ?
C10 C18 H18 119.1 . . ?
C18 C19 C20 122.8(2) . . ?
C18 C19 H19 118.6 . . ?
C20 C19 H19 118.6 . . ?
O5 C20 O6 123.5(3) . . ?
O5 C20 C19 126.6(2) . . ?
O6 C20 C19 109.9(2) . . ?
O6 C21 H21A 109.5 . . ?
O6 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
O6 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?

_refine_diff_density_max         0.541
_refine_diff_density_min         -0.648
_refine_diff_density_rms         0.066

_shelxl_version_number           2013-2

