# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is (c) The Royal Society of Chemistry 2009



data_global
_journal_name_full               Org.Biomol.Chem.

_journal_coden_Cambridge         0177

_publ_contact_author_name        'Huanfeng Jiang'
_publ_contact_author_email       JIANGHF@SCUT.EDU.CN

_publ_section_title              
;
L-Proline-Catalyzed Synthesis of Highly
Functionalized Multisubstituted 1,4-Dihydropyridines
;
loop_
_publ_author_name
'Huanfeng Jiang'
'Hua Cao'
'Xiaohang Liu'
'Ronghuan Mai'
'Qiuhua Zhu'

# Attachment '5ckaa.cif'

data_1
_database_code_depnum_ccdc_archive 'CCDC 744016'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H20 Cl N O2'
_chemical_formula_sum            'C22 H20 Cl N O2'
_chemical_formula_weight         365.84

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'
Cl Cl 0.1484 0.1585 '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'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pbca
_symmetry_space_group_name_Hall  '-P 2ac 2ab '

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

_cell_length_a                   17.530(3)
_cell_length_b                   14.759(3)
_cell_length_c                   14.559(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3766.8(13)
_cell_formula_units_Z            8
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4520
_cell_measurement_theta_min      1.36
_cell_measurement_theta_max      28

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.22
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1536
_exptl_absorpt_coefficient_mu    0.218
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.951
_exptl_absorpt_correction_T_max  0.964
_exptl_absorpt_process_details   '(Jacobson, 1998)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  'Rigaku/MSC Mercury CCD'
_diffrn_measurement_method       \w
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            26778
_diffrn_reflns_av_R_equivalents  0.0524
_diffrn_reflns_av_sigmaI/netI    0.0338
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.03
_diffrn_reflns_theta_max         25.20
_reflns_number_total             3357
_reflns_number_gt                1942
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'RAPID-AUTO (Rigaku, 1998)'
_computing_cell_refinement       RAPID-AUTO
_computing_data_reduction        'CrystalStructure (Rigaku/MSC, 2002)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'ORTEPII (Johnson, 1976)'
_computing_publication_material  SHELXL97

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ 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/[\s^2^(Fo^2^)+(0.1303P)^2^+0.2046P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3357
_refine_ls_number_parameters     232
_refine_ls_number_restraints     7
_refine_ls_R_factor_all          0.1059
_refine_ls_R_factor_gt           0.0663
_refine_ls_wR_factor_ref         0.2385
_refine_ls_wR_factor_gt          0.2090
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_restrained_S_all      1.146
_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
Cl1 Cl 0.49948(7) 0.71496(7) 1.05398(9) 0.0989(5) Uani 1 1 d . . .
O1 O 0.56610(13) 0.64277(14) 0.8152(2) 0.0819(9) Uani 1 1 d . . .
C22 C 0.7122(2) 0.9185(3) 0.8484(4) 0.1011(11) Uani 1 1 d U . .
H22A H 0.7535 0.9608 0.8535 0.152 Uiso 1 1 calc R . .
H22B H 0.7071 0.8995 0.7857 0.152 Uiso 1 1 calc R . .
H22C H 0.7223 0.8667 0.8864 0.152 Uiso 1 1 calc R . .
N1 N 0.43360(13) 0.91737(15) 0.8398(2) 0.0590(7) Uani 1 1 d . . .
C1 C 0.45704(16) 0.62308(17) 0.9027(2) 0.0558(8) Uani 1 1 d . . .
C2 C 0.45144(18) 0.62979(19) 0.9967(3) 0.0635(9) Uani 1 1 d . . .
C3 C 0.4103(2) 0.5682(2) 1.0469(3) 0.0825(12) Uani 1 1 d . . .
H3 H 0.4083 0.5732 1.1105 0.099 Uiso 1 1 calc R . .
C4 C 0.3723(2) 0.4996(2) 1.0042(4) 0.0891(14) Uani 1 1 d . . .
H4 H 0.3441 0.4583 1.0384 0.107 Uiso 1 1 calc R . .
C5 C 0.3758(2) 0.4917(2) 0.9115(4) 0.0836(12) Uani 1 1 d . . .
H5 H 0.3490 0.4457 0.8821 0.100 Uiso 1 1 calc R . .
C6 C 0.41864(17) 0.5514(2) 0.8610(3) 0.0717(10) Uani 1 1 d . . .
H6 H 0.4221 0.5438 0.7978 0.086 Uiso 1 1 calc R . .
C7 C 0.50942(16) 0.6807(2) 0.8472(3) 0.0587(8) Uani 1 1 d . . .
C8 C 0.49926(15) 0.77740(19) 0.8343(3) 0.0560(8) Uani 1 1 d . . .
C9 C 0.43261(15) 0.82349(19) 0.8419(2) 0.0564(8) Uani 1 1 d . . .
C10 C 0.50094(15) 0.9640(2) 0.8618(3) 0.0573(8) Uani 1 1 d . . .
C11 C 0.56870(16) 0.92118(19) 0.8517(3) 0.0586(8) Uani 1 1 d . . .
C12 C 0.56874(18) 0.8301(2) 0.8058(3) 0.0699(10) Uani 1 1 d . . .
H12A H 0.6144 0.7969 0.8229 0.084 Uiso 1 1 calc R . .
H12B H 0.5689 0.8378 0.7396 0.084 Uiso 1 1 calc R . .
C13 C 0.35614(16) 0.78090(18) 0.8505(3) 0.0635(10) Uani 1 1 d . . .
C14 C 0.3118(2) 0.7956(2) 0.9265(4) 0.0831(13) Uani 1 1 d . . .
H14 H 0.3309 0.8291 0.9756 0.100 Uiso 1 1 calc R . .
C15 C 0.2386(2) 0.7607(3) 0.9303(5) 0.116(2) Uani 1 1 d . . .
H15 H 0.2083 0.7711 0.9816 0.139 Uiso 1 1 calc R . .
C16 C 0.2110(3) 0.7111(3) 0.8587(6) 0.125(3) Uani 1 1 d . . .
H16 H 0.1615 0.6884 0.8613 0.150 Uiso 1 1 calc R . .
C17 C 0.2537(3) 0.6946(3) 0.7853(5) 0.116(2) Uani 1 1 d . . .
H17 H 0.2344 0.6594 0.7377 0.140 Uiso 1 1 calc R . .
C18 C 0.3272(2) 0.7296(2) 0.7792(4) 0.0881(13) Uani 1 1 d . . .
H18 H 0.3567 0.7186 0.7273 0.106 Uiso 1 1 calc R . .
C19 C 0.36359(18) 0.9686(2) 0.8221(3) 0.0756(11) Uani 1 1 d . . .
H19A H 0.3436 0.9911 0.8790 0.113 Uiso 1 1 calc R . .
H19B H 0.3266 0.9297 0.7936 0.113 Uiso 1 1 calc R . .
H19C H 0.3747 1.0185 0.7820 0.113 Uiso 1 1 calc R . .
C20 C 0.49033(18) 1.0580(2) 0.8964(3) 0.0690(10) Uani 1 1 d . . .
H20A H 0.5364 1.0782 0.9256 0.104 Uiso 1 1 calc R . .
H20B H 0.4493 1.0591 0.9400 0.104 Uiso 1 1 calc R . .
H20C H 0.4784 1.0974 0.8459 0.104 Uiso 1 1 calc R . .
C21 C 0.6412(2) 0.9619(3) 0.8785(4) 0.1011(11) Uani 1 1 d U . .
O2 O 0.64906(17) 1.0309(3) 0.9192(4) 0.173(2) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Cl1 0.1438(11) 0.0798(7) 0.0731(9) -0.0142(5) -0.0215(6) -0.0093(5)
O1 0.0794(16) 0.0637(13) 0.102(2) -0.0056(13) 0.0303(14) 0.0063(11)
C22 0.0662(16) 0.113(2) 0.124(3) -0.033(2) -0.0015(16) -0.0098(14)
N1 0.0548(14) 0.0478(12) 0.074(2) 0.0014(12) -0.0024(12) -0.0012(10)
C1 0.0563(16) 0.0510(15) 0.060(3) -0.0034(14) 0.0031(14) 0.0062(12)
C2 0.0700(19) 0.0551(17) 0.065(3) -0.0038(15) -0.0001(17) 0.0086(13)
C3 0.101(3) 0.075(2) 0.071(3) 0.012(2) 0.018(2) 0.016(2)
C4 0.088(3) 0.064(2) 0.115(5) 0.013(2) 0.027(2) -0.0013(17)
C5 0.082(2) 0.062(2) 0.106(4) -0.003(2) 0.007(2) -0.0080(16)
C6 0.074(2) 0.0627(19) 0.078(3) -0.0109(17) 0.0056(18) -0.0078(15)
C7 0.0589(17) 0.0556(17) 0.061(2) -0.0087(15) 0.0022(15) 0.0014(12)
C8 0.0546(18) 0.0525(17) 0.061(2) -0.0049(14) 0.0032(14) -0.0049(11)
C9 0.0555(17) 0.0534(15) 0.060(2) -0.0020(13) -0.0036(14) -0.0058(12)
C10 0.0643(19) 0.0531(16) 0.055(2) -0.0002(14) 0.0004(14) -0.0070(12)
C11 0.0549(17) 0.0571(16) 0.064(2) -0.0025(14) 0.0051(15) -0.0093(12)
C12 0.0663(19) 0.0615(17) 0.082(3) -0.0083(17) 0.0165(17) -0.0085(14)
C13 0.0495(16) 0.0486(16) 0.092(3) 0.0052(16) -0.0084(17) -0.0001(11)
C14 0.0569(19) 0.067(2) 0.126(4) 0.011(2) 0.008(2) -0.0034(15)
C15 0.062(2) 0.077(2) 0.209(7) 0.020(3) 0.023(3) -0.001(2)
C16 0.060(3) 0.073(3) 0.242(9) 0.022(4) -0.016(4) -0.011(2)
C17 0.087(3) 0.068(2) 0.195(7) 0.002(3) -0.063(4) -0.010(2)
C18 0.081(2) 0.067(2) 0.117(4) -0.001(2) -0.036(2) -0.0064(16)
C19 0.067(2) 0.0608(18) 0.099(4) 0.0145(18) -0.0132(18) 0.0022(14)
C20 0.081(2) 0.0518(17) 0.075(3) -0.0065(16) 0.0003(17) -0.0039(13)
C21 0.0662(16) 0.113(2) 0.124(3) -0.033(2) -0.0015(16) -0.0098(14)
O2 0.084(2) 0.140(3) 0.294(6) -0.117(4) -0.011(3) -0.0237(18)

_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
Cl1 C2 1.728(3) . ?
O1 C7 1.232(3) . ?
C22 C21 1.465(5) . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?
N1 C9 1.386(4) . ?
N1 C10 1.404(3) . ?
N1 C19 1.464(4) . ?
C1 C2 1.376(5) . ?
C1 C6 1.393(4) . ?
C1 C7 1.490(4) . ?
C2 C3 1.372(5) . ?
C3 C4 1.362(6) . ?
C3 H3 0.9300 . ?
C4 C5 1.355(6) . ?
C4 H4 0.9300 . ?
C5 C6 1.371(5) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C7 C8 1.450(4) . ?
C8 C9 1.357(4) . ?
C8 C12 1.503(4) . ?
C9 C13 1.486(4) . ?
C10 C11 1.353(4) . ?
C10 C20 1.488(4) . ?
C11 C21 1.459(5) . ?
C11 C12 1.502(4) . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
C13 C14 1.369(6) . ?
C13 C18 1.381(5) . ?
C14 C15 1.385(5) . ?
C14 H14 0.9300 . ?
C15 C16 1.363(8) . ?
C15 H15 0.9300 . ?
C16 C17 1.327(9) . ?
C16 H16 0.9300 . ?
C17 C18 1.390(6) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 O2 1.187(5) . ?

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
C21 C22 H22A 109.5 . . ?
C21 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C21 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C9 N1 C10 119.7(2) . . ?
C9 N1 C19 120.6(2) . . ?
C10 N1 C19 119.5(2) . . ?
C2 C1 C6 116.9(3) . . ?
C2 C1 C7 122.8(3) . . ?
C6 C1 C7 119.7(3) . . ?
C3 C2 C1 121.3(3) . . ?
C3 C2 Cl1 118.8(3) . . ?
C1 C2 Cl1 119.9(2) . . ?
C4 C3 C2 120.4(4) . . ?
C4 C3 H3 119.8 . . ?
C2 C3 H3 119.8 . . ?
C5 C4 C3 119.8(4) . . ?
C5 C4 H4 120.1 . . ?
C3 C4 H4 120.1 . . ?
C4 C5 C6 120.2(4) . . ?
C4 C5 H5 119.9 . . ?
C6 C5 H5 119.9 . . ?
C5 C6 C1 121.3(4) . . ?
C5 C6 H6 119.3 . . ?
C1 C6 H6 119.3 . . ?
O1 C7 C8 119.8(3) . . ?
O1 C7 C1 116.2(3) . . ?
C8 C7 C1 123.8(3) . . ?
C9 C8 C7 126.1(3) . . ?
C9 C8 C12 117.5(3) . . ?
C7 C8 C12 116.4(2) . . ?
C8 C9 N1 119.3(2) . . ?
C8 C9 C13 124.9(3) . . ?
N1 C9 C13 115.9(2) . . ?
C11 C10 N1 119.0(3) . . ?
C11 C10 C20 125.6(3) . . ?
N1 C10 C20 115.4(2) . . ?
C10 C11 C21 122.9(3) . . ?
C10 C11 C12 117.8(3) . . ?
C21 C11 C12 119.1(3) . . ?
C11 C12 C8 109.9(3) . . ?
C11 C12 H12A 109.7 . . ?
C8 C12 H12A 109.7 . . ?
C11 C12 H12B 109.7 . . ?
C8 C12 H12B 109.7 . . ?
H12A C12 H12B 108.2 . . ?
C14 C13 C18 119.1(3) . . ?
C14 C13 C9 120.8(3) . . ?
C18 C13 C9 120.0(4) . . ?
C13 C14 C15 119.9(5) . . ?
C13 C14 H14 120.0 . . ?
C15 C14 H14 120.0 . . ?
C16 C15 C14 120.0(5) . . ?
C16 C15 H15 120.0 . . ?
C14 C15 H15 120.0 . . ?
C17 C16 C15 120.9(5) . . ?
C17 C16 H16 119.6 . . ?
C15 C16 H16 119.6 . . ?
C16 C17 C18 120.4(5) . . ?
C16 C17 H17 119.8 . . ?
C18 C17 H17 119.8 . . ?
C13 C18 C17 119.7(5) . . ?
C13 C18 H18 120.1 . . ?
C17 C18 H18 120.1 . . ?
N1 C19 H19A 109.5 . . ?
N1 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
N1 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C10 C20 H20A 109.5 . . ?
C10 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C10 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
O2 C21 C11 126.0(4) . . ?
O2 C21 C22 115.2(3) . . ?
C11 C21 C22 118.7(4) . . ?

_diffrn_measured_fraction_theta_max 0.989
_diffrn_reflns_theta_full        25.20
_diffrn_measured_fraction_theta_full 0.989
_refine_diff_density_max         0.768
_refine_diff_density_min         -0.634
_refine_diff_density_rms         0.049