# Electronic Supplementary Material (ESI) for Green Chemistry.
# 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_S_44
_database_code_depnum_ccdc_archive 'CCDC 1512468'
_audit_update_record             
;
2016-10-28 deposited with the CCDC.
2016-12-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        '5-bromo-2,3-difluorophenyl 4-methoxybenzoate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H9 Br F2 O3'
_chemical_formula_sum            'C14 H9 Br F2 O3'
_chemical_formula_weight         343.12

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'
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'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -y, -z'

_cell_length_a                   6.6847(5)
_cell_length_b                   8.2593(7)
_cell_length_c                   12.7076(12)
_cell_angle_alpha                71.172(4)
_cell_angle_beta                 85.353(3)
_cell_angle_gamma                72.077(3)
_cell_volume                     631.70(9)
_cell_formula_units_Z            2
_cell_measurement_temperature    110(2)
_cell_measurement_reflns_used    9956
_cell_measurement_theta_min      2.72
_cell_measurement_theta_max      30.47

_exptl_crystal_description       PLATE
_exptl_crystal_colour            COLOURLESS
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.804
_exptl_crystal_F_000             340
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_exptl_absorpt_coefficient_mu    3.282
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.070
_exptl_absorpt_correction_T_max  0.100
_exptl_absorpt_process_details   'BRUKER SADABS'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      110(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            31984
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_av_R_equivalents  0.0604
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.724
_diffrn_reflns_theta_max         30.527
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3870
_reflns_number_gt                3420
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0191P)²+0.4475P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    RIDING
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3870
_refine_ls_number_parameters     182
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0282
_refine_ls_wR_factor_ref         0.0600
_refine_ls_wR_factor_gt          0.0575
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_restrained_S_all      1.061
_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 0.19919(3) 0.91529(2) 0.90334(2) 0.01984(6) Uani 1 1 d . . . . .
F1 F 0.26222(16) 0.23914(13) 1.01602(9) 0.0229(2) Uani 1 1 d . . . . .
F2 F 0.51146(16) 0.19046(13) 0.84338(9) 0.0230(2) Uani 1 1 d . . . . .
O1 O 0.61300(18) 0.46637(16) 0.69023(9) 0.0182(2) Uani 1 1 d . . . . .
O2 O 0.91125(19) 0.39038(18) 0.79037(10) 0.0223(3) Uani 1 1 d . . . . .
O3 O 1.26389(18) 0.11614(15) 0.37885(9) 0.0167(2) Uani 1 1 d . . . . .
C1 C 0.2980(2) 0.6869(2) 0.88320(13) 0.0137(3) Uani 1 1 d . . . . .
C2 C 0.2421(2) 0.5455(2) 0.96000(13) 0.0144(3) Uani 1 1 d . . . . .
H2 H 0.1567 0.5627 1.0213 0.017 Uiso 1 1 calc R U . . .
C3 C 0.3140(2) 0.3796(2) 0.94464(13) 0.0154(3) Uani 1 1 d . . . . .
C4 C 0.4410(2) 0.3533(2) 0.85637(14) 0.0155(3) Uani 1 1 d . . . . .
C5 C 0.4955(2) 0.4959(2) 0.78147(13) 0.0149(3) Uani 1 1 d . . . . .
C6 C 0.4241(2) 0.6656(2) 0.79321(13) 0.0144(3) Uani 1 1 d . . . . .
H6 H 0.4602 0.7640 0.7414 0.017 Uiso 1 1 calc R U . . .
C7 C 0.8281(2) 0.3948(2) 0.70876(13) 0.0139(3) Uani 1 1 d . . . . .
C8 C 0.9330(2) 0.3274(2) 0.61807(12) 0.0126(3) Uani 1 1 d . . . . .
C9 C 1.1526(2) 0.2583(2) 0.62318(13) 0.0140(3) Uani 1 1 d . . . . .
H9 H 1.2291 0.2596 0.6826 0.017 Uiso 1 1 calc R U . . .
C10 C 1.2585(2) 0.1881(2) 0.54223(13) 0.0149(3) Uani 1 1 d . . . . .
H10 H 1.4075 0.1410 0.5461 0.018 Uiso 1 1 calc R U . . .
C11 C 1.1460(2) 0.1867(2) 0.45462(13) 0.0131(3) Uani 1 1 d . . . . .
C12 C 0.9273(2) 0.2546(2) 0.44889(13) 0.0143(3) Uani 1 1 d . . . . .
H12 H 0.8509 0.2534 0.3895 0.017 Uiso 1 1 calc R U . . .
C13 C 0.8221(2) 0.3242(2) 0.53117(13) 0.0141(3) Uani 1 1 d . . . . .
H13 H 0.6730 0.3700 0.5279 0.017 Uiso 1 1 calc R U . . .
C14 C 1.1565(3) 0.1182(2) 0.28486(14) 0.0191(3) Uani 1 1 d . . . . .
H14A H 1.0525 0.0530 0.3108 0.029 Uiso 1 1 calc R U . . .
H14B H 1.2584 0.0606 0.2381 0.029 Uiso 1 1 calc R U . . .
H14C H 1.0851 0.2424 0.2415 0.029 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 1.8910(15) . ?
F1 C3 1.3437(18) . ?
F2 C4 1.3414(18) . ?
O1 C7 1.3836(19) . ?
O1 C5 1.3922(18) . ?
O2 C7 1.201(2) . ?
O3 C11 1.3581(18) . ?
O3 C14 1.4354(19) . ?
C1 C2 1.390(2) . ?
C1 C6 1.390(2) . ?
C2 C3 1.378(2) . ?
C2 H2 0.9500 . ?
C3 C4 1.384(2) . ?
C4 C5 1.382(2) . ?
C5 C6 1.388(2) . ?
C6 H6 0.9500 . ?
C7 C8 1.474(2) . ?
C8 C13 1.391(2) . ?
C8 C9 1.400(2) . ?
C9 C10 1.382(2) . ?
C9 H9 0.9500 . ?
C10 C11 1.398(2) . ?
C10 H10 0.9500 . ?
C11 C12 1.394(2) . ?
C12 C13 1.392(2) . ?
C12 H12 0.9500 . ?
C13 H13 0.9500 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 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
C7 O1 C5 115.61(12) . . ?
C11 O3 C14 117.71(12) . . ?
C2 C1 C6 122.27(14) . . ?
C2 C1 Br1 118.37(11) . . ?
C6 C1 Br1 119.36(12) . . ?
C3 C2 C1 118.08(14) . . ?
C3 C2 H2 121.0 . . ?
C1 C2 H2 121.0 . . ?
F1 C3 C2 120.27(14) . . ?
F1 C3 C4 118.56(14) . . ?
C2 C3 C4 121.17(15) . . ?
F2 C4 C5 120.00(14) . . ?
F2 C4 C3 120.36(15) . . ?
C5 C4 C3 119.65(14) . . ?
C4 C5 C6 120.95(14) . . ?
C4 C5 O1 117.85(14) . . ?
C6 C5 O1 121.08(14) . . ?
C5 C6 C1 117.88(14) . . ?
C5 C6 H6 121.1 . . ?
C1 C6 H6 121.1 . . ?
O2 C7 O1 121.92(14) . . ?
O2 C7 C8 126.52(15) . . ?
O1 C7 C8 111.56(13) . . ?
C13 C8 C9 119.50(14) . . ?
C13 C8 C7 122.55(14) . . ?
C9 C8 C7 117.90(14) . . ?
C10 C9 C8 120.31(14) . . ?
C10 C9 H9 119.8 . . ?
C8 C9 H9 119.8 . . ?
C9 C10 C11 119.85(14) . . ?
C9 C10 H10 120.1 . . ?
C11 C10 H10 120.1 . . ?
O3 C11 C12 124.11(14) . . ?
O3 C11 C10 115.55(13) . . ?
C12 C11 C10 120.34(14) . . ?
C13 C12 C11 119.33(14) . . ?
C13 C12 H12 120.3 . . ?
C11 C12 H12 120.3 . . ?
C8 C13 C12 120.66(14) . . ?
C8 C13 H13 119.7 . . ?
C12 C13 H13 119.7 . . ?
O3 C14 H14A 109.5 . . ?
O3 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
O3 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?

_refine_diff_density_max         0.375
_refine_diff_density_min         -0.577
_refine_diff_density_rms         0.094

_shelxl_version_number           2014-3


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: n-hexane'
