# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_ohj129_0m
_database_code_depnum_ccdc_archive 'CCDC 1025236'
_audit_update_record             
;
2014-09-19 deposited with the CCDC.
2015-01-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
'4-Bromobenzoic acid 2-Ethoxycarbonyl-2-[3-methylene-1-(toluene-4-sulfonyl)-piperidin-4-yl]-ethyl ester '
_chemical_name_common            ?
_chemical_melting_point          426-427
_chemical_formula_moiety         ?
_chemical_formula_sum            'C25 H28 Br N O6 S'
_chemical_formula_weight         550.45

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'
S S 0.1246 0.1234 '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           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/n

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

_cell_length_a                   19.1472(17)
_cell_length_b                   5.7177(5)
_cell_length_c                   22.9157(19)
_cell_angle_alpha                90.00
_cell_angle_beta                 98.010(5)
_cell_angle_gamma                90.00
_cell_volume                     2484.3(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    3690
_cell_measurement_theta_min      2.99
_cell_measurement_theta_max      22.92

_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.472
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1136
_exptl_absorpt_coefficient_mu    1.779
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5829
_exptl_absorpt_correction_T_max  0.9322
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean 100
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        0
_diffrn_reflns_number            24369
_diffrn_reflns_av_R_equivalents  0.0673
_diffrn_reflns_av_sigmaI/netI    0.1030
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         1.30
_diffrn_reflns_theta_max         27.50
_reflns_number_total             5697
_reflns_number_gt                3175
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_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 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)+(0.0376P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0012(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         5697
_refine_ls_number_parameters     310
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1169
_refine_ls_R_factor_gt           0.0440
_refine_ls_wR_factor_ref         0.0951
_refine_ls_wR_factor_gt          0.0751
_refine_ls_goodness_of_fit_ref   0.992
_refine_ls_restrained_S_all      0.992
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.674777(19) -0.58136(7) 0.811193(15) 0.03711(14) Uani 1 1 d . . .
S1 S 0.61317(4) 0.83073(13) 0.26756(3) 0.0182(2) Uani 1 1 d . . .
N1 N 0.62757(12) 0.6515(4) 0.32355(10) 0.0167(6) Uani 1 1 d . . .
O1 O 0.63519(10) -0.1706(3) 0.53067(9) 0.0199(5) Uani 1 1 d . . .
O2 O 0.56611(11) 0.0941(4) 0.56806(9) 0.0243(5) Uani 1 1 d . . .
O3 O 0.77151(10) -0.0488(4) 0.47693(9) 0.0232(5) Uani 1 1 d . . .
O4 O 0.76819(10) 0.2913(4) 0.52543(8) 0.0196(5) Uani 1 1 d . . .
O5 O 0.67755(10) 0.9567(3) 0.26598(8) 0.0222(5) Uani 1 1 d . . .
O6 O 0.54976(10) 0.9550(3) 0.27356(9) 0.0226(5) Uani 1 1 d . . .
C1 C 0.65185(16) -0.4303(6) 0.73727(14) 0.0243(8) Uani 1 1 d . . .
C2 C 0.60993(17) -0.2328(6) 0.73342(14) 0.0275(8) Uani 1 1 d . . .
H2 H 0.5914 -0.1758 0.7670 0.033 Uiso 1 1 calc R . .
C3 C 0.59549(15) -0.1198(5) 0.68007(13) 0.0213(8) Uani 1 1 d . . .
H3 H 0.5669 0.0167 0.6769 0.026 Uiso 1 1 calc R . .
C4 C 0.62236(15) -0.2038(5) 0.63053(13) 0.0175(7) Uani 1 1 d . . .
C5 C 0.66357(15) -0.4040(5) 0.63587(13) 0.0207(7) Uani 1 1 d . . .
H5 H 0.6815 -0.4640 0.6023 0.025 Uiso 1 1 calc R . .
C6 C 0.67888(16) -0.5172(6) 0.68901(14) 0.0244(8) Uani 1 1 d . . .
H6 H 0.7077 -0.6532 0.6924 0.029 Uiso 1 1 calc R . .
C7 C 0.60387(15) -0.0761(6) 0.57459(13) 0.0182(7) Uani 1 1 d . . .
C8 C 0.62026(16) -0.0584(5) 0.47355(12) 0.0189(7) Uani 1 1 d . . .
H8A H 0.5692 -0.0239 0.4651 0.023 Uiso 1 1 calc R . .
H8B H 0.6323 -0.1668 0.4428 0.023 Uiso 1 1 calc R . .
C9 C 0.66157(14) 0.1669(5) 0.47101(12) 0.0158(7) Uani 1 1 d . . .
H9 H 0.6447 0.2833 0.4985 0.019 Uiso 1 1 calc R . .
C10 C 0.64906(14) 0.2655(5) 0.40793(12) 0.0163(7) Uani 1 1 d . . .
H10 H 0.6457 0.1288 0.3805 0.020 Uiso 1 1 calc R . .
C11 C 0.58030(15) 0.3999(5) 0.39482(13) 0.0159(7) Uani 1 1 d . . .
C12 C 0.56652(15) 0.5030(5) 0.33422(13) 0.0185(7) Uani 1 1 d . . .
H12A H 0.5595 0.3763 0.3046 0.022 Uiso 1 1 calc R . .
H12B H 0.5231 0.5989 0.3304 0.022 Uiso 1 1 calc R . .
C13 C 0.69389(15) 0.5148(5) 0.32973(13) 0.0179(7) Uani 1 1 d . . .
H13A H 0.7332 0.6154 0.3209 0.021 Uiso 1 1 calc R . .
H13B H 0.6891 0.3828 0.3015 0.021 Uiso 1 1 calc R . .
C14 C 0.70936(15) 0.4227(5) 0.39216(12) 0.0183(7) Uani 1 1 d . . .
H14A H 0.7160 0.5561 0.4199 0.022 Uiso 1 1 calc R . .
H14B H 0.7538 0.3318 0.3965 0.022 Uiso 1 1 calc R . .
C15 C 0.59669(15) 0.6596(5) 0.20340(12) 0.0174(7) Uani 1 1 d . . .
C16 C 0.52832(17) 0.6236(6) 0.17708(15) 0.0339(9) Uani 1 1 d . . .
H16 H 0.4901 0.6936 0.1929 0.041 Uiso 1 1 calc R . .
C17 C 0.51604(19) 0.4853(7) 0.12756(16) 0.0494(12) Uani 1 1 d . . .
H17 H 0.4689 0.4616 0.1093 0.059 Uiso 1 1 calc R . .
C18 C 0.57092(18) 0.3793(6) 0.10362(15) 0.0368(10) Uani 1 1 d . . .
C19 C 0.63865(17) 0.4171(6) 0.13072(13) 0.0259(8) Uani 1 1 d . . .
H19 H 0.6768 0.3455 0.1151 0.031 Uiso 1 1 calc R . .
C20 C 0.65266(16) 0.5566(5) 0.18016(13) 0.0209(7) Uani 1 1 d . . .
H20 H 0.6998 0.5820 0.1981 0.025 Uiso 1 1 calc R . .
C21 C 0.5571(2) 0.2236(8) 0.05014(16) 0.0643(14) Uani 1 1 d . . .
H21A H 0.5559 0.0600 0.0627 0.096 Uiso 1 1 calc R . .
H21B H 0.5948 0.2444 0.0257 0.096 Uiso 1 1 calc R . .
H21C H 0.5117 0.2652 0.0273 0.096 Uiso 1 1 calc R . .
C22 C 0.73897(16) 0.1183(5) 0.49051(12) 0.0177(7) Uani 1 1 d . . .
C23 C 0.84370(15) 0.2751(6) 0.54350(13) 0.0260(8) Uani 1 1 d . . .
H23A H 0.8692 0.2855 0.5089 0.031 Uiso 1 1 calc R . .
H23B H 0.8559 0.1251 0.5640 0.031 Uiso 1 1 calc R . .
C24 C 0.86262(17) 0.4786(6) 0.58460(14) 0.0321(9) Uani 1 1 d . . .
H24A H 0.8391 0.4605 0.6197 0.048 Uiso 1 1 calc R . .
H24B H 0.8472 0.6247 0.5645 0.048 Uiso 1 1 calc R . .
H24C H 0.9138 0.4826 0.5963 0.048 Uiso 1 1 calc R . .
C25 C 0.53387(15) 0.4309(5) 0.43214(13) 0.0195(7) Uani 1 1 d . . .
H25A H 0.4921 0.5182 0.4204 0.023 Uiso 1 1 calc R . .
H25B H 0.5425 0.3657 0.4706 0.023 Uiso 1 1 calc R . .


_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 1.898(3) . ?
S1 O6 1.430(2) . ?
S1 O5 1.433(2) . ?
S1 N1 1.635(2) . ?
S1 C15 1.757(3) . ?
N1 C13 1.481(3) . ?
N1 C12 1.492(3) . ?
O1 C7 1.354(3) . ?
O1 C8 1.450(3) . ?
O2 C7 1.209(3) . ?
O3 C22 1.205(3) . ?
O4 C22 1.344(3) . ?
O4 C23 1.450(3) . ?
C1 C6 1.378(4) . ?
C1 C2 1.381(4) . ?
C2 C3 1.376(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.395(4) . ?
C3 H3 0.9500 . ?
C4 C5 1.386(4) . ?
C4 C7 1.475(4) . ?
C5 C6 1.374(4) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C8 C9 1.517(4) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C22 1.513(4) . ?
C9 C10 1.539(4) . ?
C9 H9 1.0000 . ?
C10 C11 1.518(4) . ?
C10 C14 1.545(4) . ?
C10 H10 1.0000 . ?
C11 C25 1.328(4) . ?
C11 C12 1.498(4) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 C14 1.514(4) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 C16 1.378(4) . ?
C15 C20 1.392(4) . ?
C16 C17 1.376(4) . ?
C16 H16 0.9500 . ?
C17 C18 1.390(5) . ?
C17 H17 0.9500 . ?
C18 C19 1.375(4) . ?
C18 C21 1.508(4) . ?
C19 C20 1.381(4) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C23 C24 1.509(4) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 H24A 0.9800 . ?
C24 H24B 0.9800 . ?
C24 H24C 0.9800 . ?
C25 H25A 0.9500 . ?
C25 H25B 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
O6 S1 O5 119.85(12) . . ?
O6 S1 N1 106.77(12) . . ?
O5 S1 N1 106.46(12) . . ?
O6 S1 C15 107.54(13) . . ?
O5 S1 C15 108.28(13) . . ?
N1 S1 C15 107.36(13) . . ?
C13 N1 C12 111.4(2) . . ?
C13 N1 S1 117.02(18) . . ?
C12 N1 S1 115.77(18) . . ?
C7 O1 C8 116.3(2) . . ?
C22 O4 C23 116.0(2) . . ?
C6 C1 C2 121.6(3) . . ?
C6 C1 Br1 119.1(2) . . ?
C2 C1 Br1 119.3(2) . . ?
C3 C2 C1 118.9(3) . . ?
C3 C2 H2 120.5 . . ?
C1 C2 H2 120.5 . . ?
C2 C3 C4 120.7(3) . . ?
C2 C3 H3 119.7 . . ?
C4 C3 H3 119.7 . . ?
C5 C4 C3 118.8(3) . . ?
C5 C4 C7 123.4(3) . . ?
C3 C4 C7 117.8(3) . . ?
C6 C5 C4 121.0(3) . . ?
C6 C5 H5 119.5 . . ?
C4 C5 H5 119.5 . . ?
C5 C6 C1 118.9(3) . . ?
C5 C6 H6 120.5 . . ?
C1 C6 H6 120.5 . . ?
O2 C7 O1 123.3(3) . . ?
O2 C7 C4 125.0(3) . . ?
O1 C7 C4 111.8(3) . . ?
O1 C8 C9 111.8(2) . . ?
O1 C8 H8A 109.2 . . ?
C9 C8 H8A 109.2 . . ?
O1 C8 H8B 109.2 . . ?
C9 C8 H8B 109.2 . . ?
H8A C8 H8B 107.9 . . ?
C22 C9 C8 109.1(2) . . ?
C22 C9 C10 111.3(2) . . ?
C8 C9 C10 109.5(2) . . ?
C22 C9 H9 109.0 . . ?
C8 C9 H9 109.0 . . ?
C10 C9 H9 109.0 . . ?
C11 C10 C9 112.9(2) . . ?
C11 C10 C14 108.4(2) . . ?
C9 C10 C14 114.2(2) . . ?
C11 C10 H10 107.0 . . ?
C9 C10 H10 107.0 . . ?
C14 C10 H10 107.0 . . ?
C25 C11 C12 119.8(3) . . ?
C25 C11 C10 125.4(3) . . ?
C12 C11 C10 114.7(2) . . ?
N1 C12 C11 109.6(2) . . ?
N1 C12 H12A 109.8 . . ?
C11 C12 H12A 109.8 . . ?
N1 C12 H12B 109.8 . . ?
C11 C12 H12B 109.8 . . ?
H12A C12 H12B 108.2 . . ?
N1 C13 C14 109.0(2) . . ?
N1 C13 H13A 109.9 . . ?
C14 C13 H13A 109.9 . . ?
N1 C13 H13B 109.9 . . ?
C14 C13 H13B 109.9 . . ?
H13A C13 H13B 108.3 . . ?
C13 C14 C10 111.7(2) . . ?
C13 C14 H14A 109.3 . . ?
C10 C14 H14A 109.3 . . ?
C13 C14 H14B 109.3 . . ?
C10 C14 H14B 109.3 . . ?
H14A C14 H14B 107.9 . . ?
C16 C15 C20 120.3(3) . . ?
C16 C15 S1 119.9(2) . . ?
C20 C15 S1 119.8(2) . . ?
C17 C16 C15 119.3(3) . . ?
C17 C16 H16 120.4 . . ?
C15 C16 H16 120.4 . . ?
C16 C17 C18 121.6(3) . . ?
C16 C17 H17 119.2 . . ?
C18 C17 H17 119.2 . . ?
C19 C18 C17 118.1(3) . . ?
C19 C18 C21 120.5(3) . . ?
C17 C18 C21 121.4(3) . . ?
C18 C19 C20 121.6(3) . . ?
C18 C19 H19 119.2 . . ?
C20 C19 H19 119.2 . . ?
C19 C20 C15 119.1(3) . . ?
C19 C20 H20 120.4 . . ?
C15 C20 H20 120.4 . . ?
C18 C21 H21A 109.5 . . ?
C18 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C18 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
O3 C22 O4 123.4(3) . . ?
O3 C22 C9 126.2(3) . . ?
O4 C22 C9 110.5(3) . . ?
O4 C23 C24 105.8(2) . . ?
O4 C23 H23A 110.6 . . ?
C24 C23 H23A 110.6 . . ?
O4 C23 H23B 110.6 . . ?
C24 C23 H23B 110.6 . . ?
H23A C23 H23B 108.7 . . ?
C23 C24 H24A 109.5 . . ?
C23 C24 H24B 109.5 . . ?
H24A C24 H24B 109.5 . . ?
C23 C24 H24C 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
C11 C25 H25A 120.0 . . ?
C11 C25 H25B 120.0 . . ?
H25A C25 H25B 120.0 . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.392
_refine_diff_density_min         -0.573
_refine_diff_density_rms         0.094
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: EtOAc'
