# Electronic Supplementary Material (ESI) for Organic & Biomolecular 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_tcd239
_database_code_depnum_ccdc_archive 'CCDC 1448170'
_audit_update_record             
;
2016-01-18 deposited with the CCDC.
2016-02-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
'(2R,3R)-dimethyl 2-cyano-3-phenyl-2-(pyridin-4-yl)cyclopropane-1,1-dicarboxylate '
_chemical_name_common            ?
_chemical_melting_point          102-105
_chemical_formula_moiety         'C19 H16 N2 O4'
_chemical_formula_sum            'C19 H16 N2 O4'
_chemical_formula_weight         336.34

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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   9.5857(4)
_cell_length_b                   10.4800(5)
_cell_length_c                   16.9107(8)
_cell_angle_alpha                90
_cell_angle_beta                 100.4013(12)
_cell_angle_gamma                90
_cell_volume                     1670.90(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9919
_cell_measurement_theta_min      2.45
_cell_measurement_theta_max      30.09

_exptl_crystal_description       needle
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_F_000             704
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.090
_exptl_absorpt_coefficient_mu    0.095
_shelx_estimated_absorpt_T_min   0.970
_shelx_estimated_absorpt_T_max   0.991
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7166
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_process_details   'SADABS-2014/5 (Bruker, 2014)'

_exptl_absorpt_special_details   ?
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.258
_diffrn_reflns_number            32841
_diffrn_reflns_av_unetI/netI     0.0089
_diffrn_reflns_av_R_equivalents  0.0182
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         2.160
_diffrn_reflns_theta_max         27.510
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3841
_reflns_number_gt                3459
_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       'APEX2 Ver. 2014.11-0 (Bruker-AXS, 2014)'
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2013)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2013)'
_computing_structure_solution    'SHELXT-2014/4 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'SHELXTL (Bruker-AXS, 2008-2014)'
_computing_publication_material  'SHELXTL (Bruker-AXS, 2008-2014)'

_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)+(0.0552P)²+0.5066P] 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_number_reflns         3841
_refine_ls_number_parameters     228
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0327
_refine_ls_wR_factor_ref         0.0961
_refine_ls_wR_factor_gt          0.0920
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_restrained_S_all      1.051
_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_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
C1 C -0.05878(11) 0.14998(10) 0.05370(6) 0.0207(2) Uani 1 1 d . . . . .
H1 H 0.0271 0.1629 0.0342 0.025 Uiso 1 1 calc R U . . .
C2 C -0.18440(11) 0.12905(11) -0.00037(6) 0.0235(2) Uani 1 1 d . . . . .
H2 H -0.1838 0.1265 -0.0565 0.028 Uiso 1 1 calc R U . . .
C3 C -0.31068(11) 0.11196(11) 0.02769(7) 0.0234(2) Uani 1 1 d . . . . .
H3 H -0.3969 0.1001 -0.0093 0.028 Uiso 1 1 calc R U . . .
C4 C -0.31072(11) 0.11222(11) 0.10971(7) 0.0233(2) Uani 1 1 d . . . . .
H4 H -0.3969 0.0998 0.1290 0.028 Uiso 1 1 calc R U . . .
C5 C -0.18437(10) 0.13065(10) 0.16385(6) 0.0191(2) Uani 1 1 d . . . . .
H5 H -0.1844 0.1285 0.2200 0.023 Uiso 1 1 calc R U . . .
C6 C -0.05798(10) 0.15217(9) 0.13625(6) 0.01556(19) Uani 1 1 d . . . . .
C7 C 0.08120(10) 0.16655(9) 0.19241(6) 0.01499(19) Uani 1 1 d . . . . .
H7 H 0.1392 0.0867 0.1979 0.018 Uiso 1 1 calc R U . . .
C8 C 0.17033(9) 0.28632(9) 0.19726(6) 0.01465(19) Uani 1 1 d . . . . .
C9 C 0.10034(9) 0.24421(9) 0.26916(6) 0.01427(19) Uani 1 1 d . . . . .
C10 C -0.02108(10) 0.31643(9) 0.28544(6) 0.01547(19) Uani 1 1 d . . . . .
N11 N -0.11720(9) 0.36432(8) 0.30445(5) 0.01911(18) Uani 1 1 d . . . . .
C12 C 0.19980(9) 0.20475(9) 0.34478(6) 0.01529(19) Uani 1 1 d . . . . .
C13 C 0.22312(10) 0.28690(10) 0.41056(6) 0.0190(2) Uani 1 1 d . . . . .
H13 H 0.1711 0.3641 0.4099 0.023 Uiso 1 1 calc R U . . .
C14 C 0.32380(11) 0.25389(11) 0.47717(6) 0.0234(2) Uani 1 1 d . . . . .
H14 H 0.3384 0.3104 0.5218 0.028 Uiso 1 1 calc R U . . .
N15 N 0.40153(10) 0.14715(9) 0.48214(6) 0.0255(2) Uani 1 1 d . . . . .
C16 C 0.37613(11) 0.06807(10) 0.41904(7) 0.0233(2) Uani 1 1 d . . . . .
H16 H 0.4293 -0.0088 0.4216 0.028 Uiso 1 1 calc R U . . .
C17 C 0.27647(10) 0.09171(10) 0.34984(6) 0.0189(2) Uani 1 1 d . . . . .
H17 H 0.2613 0.0318 0.3070 0.023 Uiso 1 1 calc R U . . .
C18 C 0.32935(10) 0.26566(9) 0.21007(6) 0.01585(19) Uani 1 1 d . . . . .
O19 O 0.38490(7) 0.17521(7) 0.18454(5) 0.02100(17) Uani 1 1 d . . . . .
O20 O 0.39690(7) 0.35891(7) 0.25474(4) 0.02052(17) Uani 1 1 d . . . . .
C21 C 0.55023(10) 0.34756(11) 0.27257(7) 0.0272(2) Uani 1 1 d . . . . .
H21A H 0.5767 0.2728 0.3068 0.041 Uiso 1 1 calc R U . . .
H21B H 0.5910 0.4245 0.3006 0.041 Uiso 1 1 calc R U . . .
H21C H 0.5865 0.3377 0.2223 0.041 Uiso 1 1 calc R U . . .
C22 C 0.11739(10) 0.40344(9) 0.14997(6) 0.01699(19) Uani 1 1 d . . . . .
O23 O 0.00217(8) 0.44923(8) 0.14636(5) 0.0314(2) Uani 1 1 d . . . . .
O24 O 0.21722(8) 0.44625(7) 0.11146(5) 0.02457(18) Uani 1 1 d . . . . .
C25 C 0.18541(13) 0.56133(11) 0.06403(7) 0.0286(2) Uani 1 1 d . . . . .
H25A H 0.1221 0.5406 0.0134 0.043 Uiso 1 1 calc R U . . .
H25B H 0.2736 0.5980 0.0525 0.043 Uiso 1 1 calc R U . . .
H25C H 0.1390 0.6233 0.0941 0.043 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
C1 C2 1.3917(14) . ?
C1 C6 1.3949(14) . ?
C1 H1 0.9500 . ?
C2 C3 1.3892(15) . ?
C2 H2 0.9500 . ?
C3 C4 1.3871(15) . ?
C3 H3 0.9500 . ?
C4 C5 1.3936(14) . ?
C4 H4 0.9500 . ?
C5 C6 1.3930(13) . ?
C5 H5 0.9500 . ?
C6 C7 1.4990(12) . ?
C7 C8 1.5122(13) . ?
C7 C9 1.5148(13) . ?
C7 H7 1.0000 . ?
C8 C22 1.5023(13) . ?
C8 C18 1.5159(12) . ?
C8 C9 1.5550(13) . ?
C9 C10 1.4556(13) . ?
C9 C12 1.5083(12) . ?
C10 N11 1.1451(13) . ?
C12 C17 1.3886(14) . ?
C12 C13 1.3925(14) . ?
C13 C14 1.3883(14) . ?
C13 H13 0.9500 . ?
C14 N15 1.3383(15) . ?
C14 H14 0.9500 . ?
N15 C16 1.3383(15) . ?
C16 C17 1.3928(14) . ?
C16 H16 0.9500 . ?
C17 H17 0.9500 . ?
C18 O19 1.2047(12) . ?
C18 O20 1.3298(12) . ?
O20 C21 1.4509(12) . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 O23 1.1956(12) . ?
C22 O24 1.3290(12) . ?
O24 C25 1.4500(12) . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 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
C2 C1 C6 120.53(9) . . ?
C2 C1 H1 119.7 . . ?
C6 C1 H1 119.7 . . ?
C3 C2 C1 119.99(10) . . ?
C3 C2 H2 120.0 . . ?
C1 C2 H2 120.0 . . ?
C4 C3 C2 119.93(9) . . ?
C4 C3 H3 120.0 . . ?
C2 C3 H3 120.0 . . ?
C3 C4 C5 120.00(10) . . ?
C3 C4 H4 120.0 . . ?
C5 C4 H4 120.0 . . ?
C6 C5 C4 120.51(9) . . ?
C6 C5 H5 119.7 . . ?
C4 C5 H5 119.7 . . ?
C5 C6 C1 118.99(9) . . ?
C5 C6 C7 122.17(9) . . ?
C1 C6 C7 118.63(8) . . ?
C6 C7 C8 123.18(8) . . ?
C6 C7 C9 123.58(8) . . ?
C8 C7 C9 61.82(6) . . ?
C6 C7 H7 113.0 . . ?
C8 C7 H7 113.0 . . ?
C9 C7 H7 113.0 . . ?
C22 C8 C7 121.06(8) . . ?
C22 C8 C18 115.28(8) . . ?
C7 C8 C18 115.65(8) . . ?
C22 C8 C9 119.74(8) . . ?
C7 C8 C9 59.17(6) . . ?
C18 C8 C9 114.36(7) . . ?
C10 C9 C12 112.76(8) . . ?
C10 C9 C7 117.65(8) . . ?
C12 C9 C7 122.64(8) . . ?
C10 C9 C8 118.23(8) . . ?
C12 C9 C8 116.41(7) . . ?
C7 C9 C8 59.01(6) . . ?
N11 C10 C9 172.92(10) . . ?
C17 C12 C13 118.13(9) . . ?
C17 C12 C9 122.19(9) . . ?
C13 C12 C9 119.57(9) . . ?
C14 C13 C12 118.81(10) . . ?
C14 C13 H13 120.6 . . ?
C12 C13 H13 120.6 . . ?
N15 C14 C13 123.83(10) . . ?
N15 C14 H14 118.1 . . ?
C13 C14 H14 118.1 . . ?
C14 N15 C16 116.65(9) . . ?
N15 C16 C17 123.93(10) . . ?
N15 C16 H16 118.0 . . ?
C17 C16 H16 118.0 . . ?
C12 C17 C16 118.60(10) . . ?
C12 C17 H17 120.7 . . ?
C16 C17 H17 120.7 . . ?
O19 C18 O20 125.48(9) . . ?
O19 C18 C8 124.00(9) . . ?
O20 C18 C8 110.50(8) . . ?
C18 O20 C21 115.39(8) . . ?
O20 C21 H21A 109.5 . . ?
O20 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
O20 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
O23 C22 O24 125.43(9) . . ?
O23 C22 C8 125.12(9) . . ?
O24 C22 C8 109.43(8) . . ?
C22 O24 C25 116.98(8) . . ?
O24 C25 H25A 109.5 . . ?
O24 C25 H25B 109.5 . . ?
H25A C25 H25B 109.5 . . ?
O24 C25 H25C 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 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
C6 C1 C2 C3 0.92(16) . . . . ?
C1 C2 C3 C4 -1.80(17) . . . . ?
C2 C3 C4 C5 0.52(17) . . . . ?
C3 C4 C5 C6 1.65(16) . . . . ?
C4 C5 C6 C1 -2.51(15) . . . . ?
C4 C5 C6 C7 -177.18(9) . . . . ?
C2 C1 C6 C5 1.23(15) . . . . ?
C2 C1 C6 C7 176.08(9) . . . . ?
C5 C6 C7 C8 -118.85(10) . . . . ?
C1 C6 C7 C8 66.47(12) . . . . ?
C5 C6 C7 C9 -42.92(14) . . . . ?
C1 C6 C7 C9 142.39(9) . . . . ?
C6 C7 C8 C22 5.18(14) . . . . ?
C9 C7 C8 C22 -108.36(9) . . . . ?
C6 C7 C8 C18 -142.21(9) . . . . ?
C9 C7 C8 C18 104.25(9) . . . . ?
C6 C7 C8 C9 113.54(10) . . . . ?
C6 C7 C9 C10 -4.98(13) . . . . ?
C8 C7 C9 C10 107.95(9) . . . . ?
C6 C7 C9 C12 143.68(9) . . . . ?
C8 C7 C9 C12 -103.39(9) . . . . ?
C6 C7 C9 C8 -112.93(10) . . . . ?
C22 C8 C9 C10 3.58(13) . . . . ?
C7 C8 C9 C10 -106.98(9) . . . . ?
C18 C8 C9 C10 146.57(8) . . . . ?
C22 C8 C9 C12 -135.61(9) . . . . ?
C7 C8 C9 C12 113.83(9) . . . . ?
C18 C8 C9 C12 7.38(12) . . . . ?
C22 C8 C9 C7 110.55(9) . . . . ?
C18 C8 C9 C7 -106.45(9) . . . . ?
C10 C9 C12 C17 147.51(9) . . . . ?
C7 C9 C12 C17 -2.52(14) . . . . ?
C8 C9 C12 C17 -71.14(12) . . . . ?
C10 C9 C12 C13 -36.48(12) . . . . ?
C7 C9 C12 C13 173.50(8) . . . . ?
C8 C9 C12 C13 104.88(10) . . . . ?
C17 C12 C13 C14 1.51(14) . . . . ?
C9 C12 C13 C14 -174.67(9) . . . . ?
C12 C13 C14 N15 0.41(16) . . . . ?
C13 C14 N15 C16 -1.56(16) . . . . ?
C14 N15 C16 C17 0.81(16) . . . . ?
C13 C12 C17 C16 -2.19(14) . . . . ?
C9 C12 C17 C16 173.89(9) . . . . ?
N15 C16 C17 C12 1.06(16) . . . . ?
C22 C8 C18 O19 -117.14(11) . . . . ?
C7 C8 C18 O19 32.16(13) . . . . ?
C9 C8 C18 O19 98.17(11) . . . . ?
C22 C8 C18 O20 64.51(10) . . . . ?
C7 C8 C18 O20 -146.19(8) . . . . ?
C9 C8 C18 O20 -80.18(10) . . . . ?
O19 C18 O20 C21 0.31(14) . . . . ?
C8 C18 O20 C21 178.63(8) . . . . ?
C7 C8 C22 O23 47.41(15) . . . . ?
C18 C8 C22 O23 -165.08(10) . . . . ?
C9 C8 C22 O23 -22.42(15) . . . . ?
C7 C8 C22 O24 -131.16(9) . . . . ?
C18 C8 C22 O24 16.34(12) . . . . ?
C9 C8 C22 O24 159.01(8) . . . . ?
O23 C22 O24 C25 2.88(16) . . . . ?
C8 C22 O24 C25 -178.55(9) . . . . ?

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
C16 H16 N15 0.95 2.54 3.3371(14) 142 3_656


_refine_diff_density_max         0.344
_refine_diff_density_min         -0.185
_refine_diff_density_rms         0.039


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: methanol'
