# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 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_dm14071
_database_code_depnum_ccdc_archive 'CCDC 1012761'
_audit_update_record             
;
2014-07-08 deposited with the CCDC.
2016-11-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C19 H23 Br N O3 P'
_chemical_formula_weight         424.26

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_H-M_alt        'P 21 21 2'
_space_group_name_Hall           'P 2 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+1/2, -z'
'-x+1/2, y+1/2, -z'
'-x, -y, z'

_cell_length_a                   9.8916(7)
_cell_length_b                   26.4389(19)
_cell_length_c                   7.7778(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2034.1(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    133(2)
_cell_measurement_reflns_used    5660
_cell_measurement_theta_min      2.57
_cell_measurement_theta_max      28.15

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_F_000             872
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    2.116
_shelx_estimated_absorpt_T_min   0.569
_shelx_estimated_absorpt_T_max   0.816
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5154
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      133(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            20495
_diffrn_reflns_av_unetI/netI     0.0589
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         1.540
_diffrn_reflns_theta_max         30.535
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             6186
_reflns_number_gt                4962
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_max     0.992
_reflns_Friedel_fraction_full    0.992

_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-2013 (Sheldrick, 2013)'
_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)+(0.0464P)²+0.7163P] 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 1804 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.024(5)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         6186
_refine_ls_number_parameters     228
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0629
_refine_ls_R_factor_gt           0.0454
_refine_ls_wR_factor_ref         0.1145
_refine_ls_wR_factor_gt          0.1077
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_restrained_S_all      1.108
_refine_ls_shift/su_max          0.096
_refine_ls_shift/su_mean         0.005

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 0.91017(5) 1.12838(2) 0.39195(7) 0.04247(15) Uani 1 1 d . . . . .
P1 P 0.62768(12) 0.88397(4) 0.85683(12) 0.0302(2) Uani 1 1 d . . . . .
O3 O 0.6263(4) 0.82455(12) 0.8544(4) 0.0404(8) Uani 1 1 d . . . . .
O2 O 0.7825(3) 0.89609(15) 0.8494(4) 0.0466(9) Uani 1 1 d . . . . .
O1 O 0.5528(4) 0.90601(13) 1.0011(4) 0.0411(9) Uani 1 1 d . . . . .
C3 C 0.6487(4) 0.88626(14) 0.4904(4) 0.0230(7) Uani 1 1 d . . . . .
H3 H 0.7459 0.8814 0.5215 0.028 Uiso 1 1 calc R U . . .
C14 C 0.8492(4) 1.02912(16) 0.5068(6) 0.0305(9) Uani 1 1 d . . . . .
H14 H 0.9065 1.0376 0.6004 0.037 Uiso 1 1 calc R U . . .
C8 C 0.6306(6) 0.74968(17) 0.3430(6) 0.0429(11) Uani 1 1 d . . . . .
H8 H 0.6914 0.7225 0.3228 0.051 Uiso 1 1 calc R U . . .
C15 C 0.7890(4) 0.98199(15) 0.5001(5) 0.0274(8) Uani 1 1 d . . . . .
H15 H 0.8046 0.9583 0.5896 0.033 Uiso 1 1 calc R U . . .
C11 C 0.6842(4) 1.00478(16) 0.2323(5) 0.0266(8) Uani 1 1 d . . . . .
H11 H 0.6289 0.9964 0.1366 0.032 Uiso 1 1 calc R U . . .
C18 C 0.4940(6) 0.80056(18) 0.8828(7) 0.0482(12) Uani 1 1 d . . . . .
H18A H 0.4248 0.8162 0.8078 0.058 Uiso 1 1 calc R U . . .
H18B H 0.4656 0.8047 1.0040 0.058 Uiso 1 1 calc R U . . .
C16 C 0.8712(6) 0.8902(3) 0.9901(7) 0.0654(17) Uani 1 1 d . U . . .
H16A H 0.8631 0.8556 1.0378 0.078 Uiso 1 1 calc R U . . .
H16B H 0.8479 0.9147 1.0818 0.078 Uiso 1 1 calc R U . . .
C1 C 0.4731(4) 0.93762(15) 0.6444(5) 0.0307(8) Uani 1 1 d . . . . .
H1A H 0.4433 0.9502 0.5365 0.037 Uiso 1 1 calc R U . . .
H1B H 0.4301 0.9483 0.7473 0.037 Uiso 1 1 calc R U . . .
C5 C 0.4562(4) 0.82914(15) 0.4053(6) 0.0308(8) Uani 1 1 d . . . . .
H5 H 0.3959 0.8564 0.4266 0.037 Uiso 1 1 calc R U . . .
C9 C 0.6797(5) 0.79609(16) 0.3969(6) 0.0337(9) Uani 1 1 d . . . . .
H9 H 0.7743 0.8006 0.4111 0.040 Uiso 1 1 calc R U . . .
C10 C 0.7047(4) 0.96904(14) 0.3614(5) 0.0228(7) Uani 1 1 d . . . . .
C12 C 0.7427(4) 1.05226(16) 0.2404(5) 0.0302(9) Uani 1 1 d . . . . .
H12 H 0.7257 1.0765 0.1530 0.036 Uiso 1 1 calc R U . . .
C7 C 0.4939(6) 0.74273(16) 0.3187(6) 0.0394(11) Uani 1 1 d . . . . .
H7 H 0.4602 0.7109 0.2814 0.047 Uiso 1 1 calc R U . . .
C4 C 0.5938(4) 0.83587(13) 0.4301(4) 0.0238(7) Uani 1 1 d . . . . .
C6 C 0.4055(5) 0.78267(16) 0.3492(5) 0.0358(9) Uani 1 1 d . . . . .
H6 H 0.3112 0.7784 0.3320 0.043 Uiso 1 1 calc R U . . .
N1 N 0.6428(4) 0.92274(12) 0.3512(4) 0.0268(7) Uani 1 1 d . . . . .
H1 H 0.5980 0.9149 0.2572 0.032 Uiso 1 1 calc R U . . .
C13 C 0.8261(4) 1.06393(15) 0.3771(6) 0.0289(8) Uani 1 1 d . . . . .
C2 C 0.5744(4) 0.90522(14) 0.6512(5) 0.0248(7) Uani 1 1 d . . . . .
C19 C 0.5096(9) 0.7452(2) 0.8401(8) 0.0612(16) Uani 1 1 d . . . . .
H19A H 0.5311 0.7415 0.7178 0.092 Uiso 1 1 calc R U . . .
H19B H 0.4250 0.7275 0.8656 0.092 Uiso 1 1 calc R U . . .
H19C H 0.5828 0.7308 0.9093 0.092 Uiso 1 1 calc R U . . .
C17 C 1.0059(9) 0.8989(4) 0.9316(11) 0.093(2) Uani 1 1 d . U . . .
H17A H 1.0188 0.8824 0.8199 0.139 Uiso 1 1 calc R U . . .
H17B H 1.0701 0.8848 1.0149 0.139 Uiso 1 1 calc R U . . .
H17C H 1.0214 0.9353 0.9197 0.139 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 C13 1.900(4) . ?
P1 O1 1.466(4) . ?
P1 O2 1.566(4) . ?
P1 O3 1.571(3) . ?
P1 C2 1.775(4) . ?
O3 C18 1.471(7) . ?
O2 C16 1.411(6) . ?
C3 N1 1.451(5) . ?
C3 C4 1.513(5) . ?
C3 C2 1.535(5) . ?
C3 H3 1.0000 . ?
C14 C15 1.382(6) . ?
C14 C13 1.384(6) . ?
C14 H14 0.9500 . ?
C8 C7 1.377(8) . ?
C8 C9 1.385(6) . ?
C8 H8 0.9500 . ?
C15 C10 1.405(5) . ?
C15 H15 0.9500 . ?
C11 C12 1.384(6) . ?
C11 C10 1.394(5) . ?
C11 H11 0.9500 . ?
C18 C19 1.508(7) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C16 C17 1.427(11) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C1 C2 1.319(6) . ?
C1 H1A 0.9500 . ?
C1 H1B 0.9500 . ?
C5 C4 1.386(6) . ?
C5 C6 1.397(6) . ?
C5 H5 0.9500 . ?
C9 C4 1.376(6) . ?
C9 H9 0.9500 . ?
C10 N1 1.371(5) . ?
C12 C13 1.380(6) . ?
C12 H12 0.9500 . ?
C7 C6 1.391(7) . ?
C7 H7 0.9500 . ?
C6 H6 0.9500 . ?
N1 H1 0.8800 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 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
O1 P1 O2 116.2(2) . . ?
O1 P1 O3 113.71(19) . . ?
O2 P1 O3 102.3(2) . . ?
O1 P1 C2 114.46(19) . . ?
O2 P1 C2 101.09(18) . . ?
O3 P1 C2 107.64(17) . . ?
C18 O3 P1 115.9(3) . . ?
C16 O2 P1 123.8(3) . . ?
N1 C3 C4 109.9(3) . . ?
N1 C3 C2 111.8(3) . . ?
C4 C3 C2 111.6(3) . . ?
N1 C3 H3 107.8 . . ?
C4 C3 H3 107.8 . . ?
C2 C3 H3 107.8 . . ?
C15 C14 C13 120.1(4) . . ?
C15 C14 H14 120.0 . . ?
C13 C14 H14 120.0 . . ?
C7 C8 C9 120.3(4) . . ?
C7 C8 H8 119.9 . . ?
C9 C8 H8 119.9 . . ?
C14 C15 C10 120.3(4) . . ?
C14 C15 H15 119.9 . . ?
C10 C15 H15 119.9 . . ?
C12 C11 C10 121.4(4) . . ?
C12 C11 H11 119.3 . . ?
C10 C11 H11 119.3 . . ?
O3 C18 C19 107.1(5) . . ?
O3 C18 H18A 110.3 . . ?
C19 C18 H18A 110.3 . . ?
O3 C18 H18B 110.3 . . ?
C19 C18 H18B 110.3 . . ?
H18A C18 H18B 108.5 . . ?
O2 C16 C17 108.4(5) . . ?
O2 C16 H16A 110.0 . . ?
C17 C16 H16A 110.0 . . ?
O2 C16 H16B 110.0 . . ?
C17 C16 H16B 110.1 . . ?
H16A C16 H16B 108.4 . . ?
C2 C1 H1A 120.0 . . ?
C2 C1 H1B 120.0 . . ?
H1A C1 H1B 120.0 . . ?
C4 C5 C6 120.6(4) . . ?
C4 C5 H5 119.7 . . ?
C6 C5 H5 119.7 . . ?
C4 C9 C8 121.2(4) . . ?
C4 C9 H9 119.4 . . ?
C8 C9 H9 119.4 . . ?
N1 C10 C11 119.9(3) . . ?
N1 C10 C15 121.8(3) . . ?
C11 C10 C15 118.3(3) . . ?
C13 C12 C11 119.2(4) . . ?
C13 C12 H12 120.4 . . ?
C11 C12 H12 120.4 . . ?
C8 C7 C6 119.5(4) . . ?
C8 C7 H7 120.3 . . ?
C6 C7 H7 120.3 . . ?
C9 C4 C5 118.8(4) . . ?
C9 C4 C3 120.6(4) . . ?
C5 C4 C3 120.6(4) . . ?
C7 C6 C5 119.7(5) . . ?
C7 C6 H6 120.1 . . ?
C5 C6 H6 120.1 . . ?
C10 N1 C3 122.2(3) . . ?
C10 N1 H1 118.9 . . ?
C3 N1 H1 118.9 . . ?
C12 C13 C14 120.7(4) . . ?
C12 C13 Br1 120.6(3) . . ?
C14 C13 Br1 118.7(3) . . ?
C1 C2 C3 122.9(3) . . ?
C1 C2 P1 117.9(3) . . ?
C3 C2 P1 119.3(3) . . ?
C18 C19 H19A 109.5 . . ?
C18 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C18 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C16 C17 H17A 109.5 . . ?
C16 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C16 C17 H17C 109.4 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 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
O1 P1 O3 C18 46.3(4) . . . . ?
O2 P1 O3 C18 172.4(3) . . . . ?
C2 P1 O3 C18 -81.6(4) . . . . ?
O1 P1 O2 C16 49.7(6) . . . . ?
O3 P1 O2 C16 -74.7(5) . . . . ?
C2 P1 O2 C16 174.2(5) . . . . ?
C13 C14 C15 C10 0.4(6) . . . . ?
P1 O3 C18 C19 168.8(3) . . . . ?
P1 O2 C16 C17 173.1(5) . . . . ?
C7 C8 C9 C4 1.2(7) . . . . ?
C12 C11 C10 N1 178.6(4) . . . . ?
C12 C11 C10 C15 -1.2(6) . . . . ?
C14 C15 C10 N1 -179.6(4) . . . . ?
C14 C15 C10 C11 0.1(6) . . . . ?
C10 C11 C12 C13 1.8(6) . . . . ?
C9 C8 C7 C6 -0.2(7) . . . . ?
C8 C9 C4 C5 -1.3(6) . . . . ?
C8 C9 C4 C3 179.4(4) . . . . ?
C6 C5 C4 C9 0.6(6) . . . . ?
C6 C5 C4 C3 179.8(4) . . . . ?
N1 C3 C4 C9 105.8(4) . . . . ?
C2 C3 C4 C9 -129.6(4) . . . . ?
N1 C3 C4 C5 -73.4(5) . . . . ?
C2 C3 C4 C5 51.2(5) . . . . ?
C8 C7 C6 C5 -0.5(7) . . . . ?
C4 C5 C6 C7 0.3(6) . . . . ?
C11 C10 N1 C3 -173.2(4) . . . . ?
C15 C10 N1 C3 6.5(6) . . . . ?
C4 C3 N1 C10 -169.7(3) . . . . ?
C2 C3 N1 C10 65.8(5) . . . . ?
C11 C12 C13 C14 -1.3(6) . . . . ?
C11 C12 C13 Br1 179.3(3) . . . . ?
C15 C14 C13 C12 0.2(7) . . . . ?
C15 C14 C13 Br1 179.7(3) . . . . ?
N1 C3 C2 C1 27.1(5) . . . . ?
C4 C3 C2 C1 -96.4(4) . . . . ?
N1 C3 C2 P1 -151.7(3) . . . . ?
C4 C3 C2 P1 84.8(4) . . . . ?
O1 P1 C2 C1 -1.0(4) . . . . ?
O2 P1 C2 C1 -126.7(3) . . . . ?
O3 P1 C2 C1 126.4(3) . . . . ?
O1 P1 C2 C3 177.8(3) . . . . ?
O2 P1 C2 C3 52.1(3) . . . . ?
O3 P1 C2 C3 -54.7(3) . . . . ?

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
C17 H17B Br1 0.98 2.96 3.745(8) 137.9 4_776
N1 H1 O1 0.88 2.05 2.899(4) 160.4 1_554
C15 H15 O2 0.95 2.61 3.541(5) 165.6 .
C3 H3 O2 1.00 2.61 3.101(5) 110.6 .
C17 H17B Br1 0.98 2.96 3.745(8) 137.9 4_776
N1 H1 O1 0.88 2.05 2.899(4) 160.4 1_554
C15 H15 O2 0.95 2.61 3.541(5) 165.6 .
C3 H3 O2 1.00 2.61 3.101(5) 110.6 .

_refine_diff_density_max         1.535
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.087

_shelxl_version_number           2013-4



