# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2005


data_global

_journal_coden_Cambridge         177

loop_
_publ_author_name
'K. Jorgensen'
'Pompiliu S. Aburel'
'Rita G. Hazell'
'Wei Zhuang.'

_publ_contact_author_name        'Prof Karl Anker Jorgensen'
_publ_contact_author_address     
;
Department of Chemistry
Aarhus University
Aarhus
DK 8000
DENMARK
;

_publ_contact_author_email       KAJ@CHEM.AU.DK

_publ_requested_journal          'Organic & Biomolecular Chemistry'

_publ_section_title              
;
Catalytic and enantioselective aza-ene and
hetero-Diels-Alder reactions of alkenes and dienes with
azodicarboxylates
;

_publ_section_references         
;

Altomare,A., Cascarano,G., Giacovazzo,C., Guagliardi,A.,
Moliterni,.A,G,G., Burla,M.C., Polidori,G., Camalli,M.
& Spagna,R. (1997). SIR97. University of Bari, Italy.

Burnett,M.N. & Johnson,C.K. (1996). ORTEP-III. Report ORNL-6895.
Oak Ridge National Laboratory, Tennessee, USA.

Busing,W.R., Martin,K.O. & Levy,H.A. (1962). ORFLS. Report
ORNL-TM-305. Oak Ridge National Laboratory, Tennessee, USA.

Hazell,A. (1995). KRYSTAL, An integrated system of
crystallographic programs. Aarhus University, Denmark.

Siemens (1995) SMART, SAINT and XPREP Area-Detector Control and
Integration Software. Siemens Analytical X-ray Instruments Inc.
Madison, Wisconsin, USA.

;

#==============================================================================

data_sorin
_database_code_depnum_ccdc_archive 'CCDC 268562'

#===================================

# 5. CHEMICAL DATA

_chemical_name_systematic        
;
N'-Cyclopent-2-enyl-N'-(2-oxo-oxazolidine-3-carbonyl)-
hydrazinecarboxylic acid 2,2,2-tricloro-ethyl ester
;
_chemical_formula_sum            'C12 H14 Cl3 N3 O5'
_chemical_formula_moiety         'C12 H14 Cl3 N3 O5'
_chemical_formula_weight         386.61
_chemical_melting_point          ?
_chemical_compound_source        ?

#===================================
# 6. CRYSTAL DATA

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'

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

_cell_length_a                   11.4775(5)
_cell_length_b                   11.1987(5)
_cell_length_c                   24.918(1)
_cell_angle_alpha                90.000
_cell_angle_beta                 90.000
_cell_angle_gamma                90.000
_cell_volume                     3202.8(2)
_cell_formula_units_Z            8
_cell_measurement_temperature    120
_cell_measurement_reflns_used    14220
_cell_measurement_theta_min      2.41
_cell_measurement_theta_max      29.82
_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_diffrn    1.604
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1584
_exptl_absorpt_coefficient_mu    0.600
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'XPREP, 1995 '
_exptl_absorpt_correction_T_min  0.773
_exptl_absorpt_correction_T_max  0.942

#===================================

# 7. EXPERIMENTAL DATA

_diffrn_ambient_temperature      120
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_source         'x-ray tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'Siemens SMART CCD diffractometer'
_diffrn_measurement_method       '\w rotation scans with narrow frames'
_diffrn_standards_decay_%        0
_diffrn_reflns_number            49125
_diffrn_reflns_av_R_equivalents  0.055
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_theta_min         2.41
_diffrn_reflns_theta_max         29.82
_diffrn_reflns_reduction_process 49125
_reflns_number_total             4589
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_theta_full        29.82
_reflns_number_gt                3283
_reflns_threshold_expression     I>3\s(I)
_computing_data_collection       'SMART (Siemens, 1995)'
_computing_cell_refinement       'SAINT (Siemens, 1995)'
_computing_data_reduction        'SAINT (Siemens, 1995)'
_computing_structure_solution    
;
SIR97 (Altomare et al., 1997 ), KRYSTAL
;
_computing_structure_refinement  'modified ORFLS(1962), KRYSTAL'
_computing_molecular_graphics    
;
ORTEP-III (Burnett & Johnson, 1996), KRYSTAL
;
_computing_publication_material  KRYSTAL
_atom_type_scat_source           IntTabIV

#===================================

# 8. REFINEMENT DATA

_refine_special_details          
;The cyclopentene ring is disordered (rotated around the
N2 - C5 bond) and C7 and C8 are split into two each with
occupancies consrained to add up to 1.0. The hydrogen
atoms on this ring are constrained accordingly. The
residual density is found near Cl or this ring.
;
_refine_ls_structure_factor_coef F
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
w= 1/{[\s~cs~(F^2^)+B+(1+A)F^2^]^1/2^- |F|}^2^
where A = 0.03 and B = 1.00
;
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_number_reflns         3283
_refine_ls_number_parameters     205
_refine_ls_number_restraints     0
_refine_ls_number_constraints    17
_refine_ls_R_factor_gt           0.048
_refine_ls_wR_factor_ref         0.054
_refine_ls_goodness_of_fit_ref   1.54
_refine_ls_shift/su_max          0.0060
_refine_ls_shift/su_mean         0.0015
_refine_diff_density_max         0.95(9)
_refine_diff_density_min         -1.11(9)

#==========================================

# 9. ATOMIC COORDINATES AND THERMAL PARAMETERS

loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_thermal_displace_type
_atom_site_occupancy
Cl1 0.81801(6) -0.23430(9) 0.58637(3) 0.0419(4) Uij 1.00
Cl2 0.62617(7) -0.34599(7) 0.64009(4) 0.0382(4) Uij 1.00
Cl3 0.68851(8) -0.10702(8) 0.66789(3) 0.0464(5) Uij 1.00
O1 0.5256(2) 0.0425(2) 0.76146(7) 0.0229(9) Uij 1.00
O2 0.3718(2) -0.0656(2) 0.73454(7) 0.0225(9) Uij 1.00
O3 0.2760(1) 0.2420(1) 0.66473(7) 0.0199(8) Uij 1.00
O4 0.4782(2) 0.0484(2) 0.57447(7) 0.0242(9) Uij 1.00
O5 0.4837(2) -0.1525(2) 0.59063(7) 0.0230(9) Uij 1.00
N1 0.4178(2) 0.1180(2) 0.69546(7) 0.0149(9) Uij 1.00
N2 0.2736(2) 0.0510(2) 0.63497(8) 0.0152(9) Uij 1.00
N3 0.3393(2) -0.0493(2) 0.62407(8) 0.0148(9) Uij 1.00
C1 0.4890(2) 0.2196(2) 0.71349(10) 0.0198(12) Uij 1.00
C2 0.5811(2) 0.1537(2) 0.74538(11) 0.0258(13) Uij 1.00
C3 0.4316(2) 0.0218(2) 0.73043(9) 0.0172(11) Uij 1.00
C4 0.3179(2) 0.1419(2) 0.66473(9) 0.0144(11) Uij 1.00
C5 0.1669(2) 0.0684(2) 0.60239(9) 0.0163(11) Uij 1.00
C6 0.0927(2) -0.0441(2) 0.60263(10) 0.0210(12) Uij 1.00
C9 0.1934(2) 0.0867(2) 0.54306(10) 0.0259(14) Uij 1.00
C10 0.4374(2) -0.0397(2) 0.59435(9) 0.0179(12) Uij 1.00
C11 0.5990(2) -0.1618(3) 0.57043(10) 0.0246(13) Uij 1.00
C12 0.6785(2) -0.2090(2) 0.61442(10) 0.0230(13) Uij 1.00
C8a 0.1679(5) -0.0366(8) 0.5155(2) 0.0232(8) Uiso 0.58(2)
C8b 0.1668(7) -0.0020(11) 0.5142(3) 0.0232 Uiso 0.42
C7a 0.0977(6) -0.1035(6) 0.5575(3) 0.0224(8) Uiso 0.58
C7b 0.1129(8) -0.1001(8) 0.5458(4) 0.0224 Uiso 0.42
H3n 0.3157 -0.1248 0.6373 0.018 Uiso 1.00
H1a 0.4459 0.2733 0.7353 0.024 Uiso 1.00
H1b 0.5220 0.2620 0.6841 0.024 Uiso 1.00
H2a 0.6476 0.1384 0.7238 0.031 Uiso 1.00
H2b 0.6035 0.1988 0.7760 0.031 Uiso 1.00
H5 0.1234 0.1340 0.6158 0.020 Uiso 1.00
H11a 0.6255 -0.0853 0.5592 0.029 Uiso 1.00
H11b 0.6003 -0.2151 0.5408 0.029 Uiso 1.00
H6 0.0473 -0.0686 0.6326 0.025 Uiso 0.58
H6a 0.0128 -0.0248 0.6077 0.025 Uiso 0.42
H6b 0.1174 -0.0971 0.6301 0.025 Uiso 0.42
H9 0.2262 0.1580 0.5290 0.031 Uiso 0.42
H9a 0.2726 0.1086 0.5381 0.031 Uiso 0.58
H9b 0.1444 0.1470 0.5284 0.031 Uiso 0.58
H8aa 0.2381 -0.0786 0.5076 0.043 Uiso 0.58
H8ab 0.1240 -0.0273 0.4834 0.043 Uiso 0.58
H8b 0.1802 -0.0072 0.4765 0.043 Uiso 0.42
H7a 0.0612 -0.1786 0.5520 0.038 Uiso 0.58
H7ba 0.0404 -0.1247 0.5306 0.038 Uiso 0.42
H7bb 0.1630 -0.1677 0.5483 0.038 Uiso 0.42

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_12
_atom_site_aniso_U_13
_atom_site_aniso_U_23
Cl1 0.0174(3) 0.0787(6) 0.0296(4) 0.0065(4) 0.0042(3) 0.0114(4)
Cl2 0.0269(4) 0.0298(4) 0.0579(5) -0.0002(3) 0.0006(3) 0.0143(4)
Cl3 0.0563(5) 0.0531(5) 0.0297(4) -0.0182(4) -0.0029(4) -0.0163(4)
O1 0.0283(10) 0.0228(9) 0.0177(8) 0.0029(8) -0.0094(8) -0.0007(7)
O2 0.0294(10) 0.0202(9) 0.0180(8) -0.0024(8) -0.0006(8) 0.0055(7)
O3 0.0216(8) 0.0139(8) 0.0242(9) 0.0025(7) 0.0002(7) 0.0005(7)
O4 0.0249(10) 0.0233(9) 0.0245(9) -0.0034(8) 0.0048(8) 0.0024(8)
O5 0.0191(9) 0.0205(9) 0.0293(10) 0.0028(7) 0.0069(8) -0.0042(8)
N1 0.0188(10) 0.0124(9) 0.0135(9) -0.0013(8) -0.0016(8) 0.0000(7)
N2 0.0146(10) 0.0139(9) 0.0171(9) 0.0032(8) -0.0008(8) -0.0007(8)
N3 0.0150(10) 0.0126(9) 0.0167(9) 0.0018(8) 0.0017(8) -0.0001(8)
C1 0.0237(13) 0.0164(12) 0.0193(11) -0.0032(10) -0.0040(10) -0.0036(10)
C2 0.0265(14) 0.0250(13) 0.0261(13) -0.0029(11) -0.0083(11) -0.0050(11)
C3 0.0209(12) 0.0201(12) 0.0105(10) 0.0046(10) 0.0008(9) 0.0004(9)
C4 0.0158(11) 0.0151(11) 0.0122(10) -0.0011(9) 0.0018(9) 0.0034(9)
C5 0.0159(11) 0.0192(12) 0.0138(10) 0.0016(9) -0.0022(9) 0.0001(9)
C6 0.0178(12) 0.0199(12) 0.0253(12) 0.0013(10) 0.0000(10) -0.0009(10)
C9 0.0253(14) 0.0329(15) 0.0196(12) 0.0004(12) -0.0039(11) 0.0074(11)
C10 0.0189(12) 0.0193(12) 0.0154(11) -0.0001(10) -0.0009(10) -0.0036(9)
C11 0.0188(13) 0.0348(15) 0.0203(12) 0.0039(11) 0.0048(10) -0.0023(11)
C12 0.0180(12) 0.0305(14) 0.0204(12) -0.0052(11) 0.0048(10) -0.0005(10)

#=================================

# 10. MOLECULAR GEOMETRY

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
Cl1 C12 1.770(3)
Cl2 C12 1.768(3)
Cl3 C12 1.758(3)
O1 C3 1.347(3)
O1 C2 1.455(3)
O2 C3 1.200(3)
O3 C4 1.219(3)
O4 C10 1.199(3)
O5 C10 1.373(3)
O5 C11 1.419(3)
N1 C3 1.394(3)
N1 C4 1.405(3)
N1 C1 1.471(3)
N2 C4 1.358(3)
N2 N3 1.380(3)
N2 C5 1.482(3)
N3 C10 1.352(3)
C1 C2 1.515(4)
C5 C6 1.520(3)
C5 C9 1.523(3)
C6 C7a 1.309(7)
C6 C7b 1.567(10)
C9 C8b 1.263(11)
C9 C8a 1.570(8)
C11 C12 1.520(4)
C8a C7a 1.517(8)
C8b C7b 1.487(11)
N3 H3n 0.95
C1 H1a 0.95
C1 H1b 0.95
C2 H2a 0.95
C2 H2b 0.95
C5 H5 0.95
C6 H6 0.95
C7a H7a 0.95
C8a H8aa 0.95
C8a H8ab 0.95
C9 H9a 0.95
C9 H9b 0.95
C6 H6a 0.95
C6 H6b 0.95
C7b H7ba 0.95
C7b H7bb 0.95
C8b H8b 0.95
C9 H9 0.95
C11 H11b 0.95
C11 H11a 0.95

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
C2 O1 C3 109.9(2)
C11 O5 C10 116.9(2)
C4 N1 C3 125.5(2)
C1 N1 C3 110.1(2)
C1 N1 C4 118.2(2)
N3 N2 C4 120.9(2)
C5 N2 C4 120.6(2)
C5 N2 N3 116.8(2)
N2 N3 C10 119.9(2)
C2 C1 N1 99.8(2)
C1 C2 O1 104.8(2)
O1 C3 O2 123.3(2)
N1 C3 O2 128.2(2)
N1 C3 O1 108.5(2)
N2 C4 O3 122.8(2)
N1 C4 O3 119.8(2)
N1 C4 N2 117.4(2)
C6 C5 N2 110.6(2)
C9 C5 N2 112.6(2)
C9 C5 C6 103.1(2)
C5 C6 C7a 113.2(4)
C5 C6 C7b 104.2(4)
C6 C7a C8a 111.4(5)
C6 C7b C8b 104.1(6)
C9 C8a C7a 103.4(5)
C9 C8b C7b 112.4(7)
C5 C9 C8b 113.4(5)
C5 C9 C8a 105.6(3)
N3 C10 O4 128.1(2)
O5 C10 O4 125.3(2)
O5 C10 N3 106.6(2)
C12 C11 O5 109.2(2)
Cl3 C12 C11 111.1(2)
Cl2 C12 C11 111.0(2)
Cl1 C12 C11 108.3(2)
Cl2 C12 Cl3 108.2(1)
Cl1 C12 Cl3 110.1(1)
Cl1 C12 Cl2 108.1(2)
C10 N3 H3n 120.0
N2 N3 H3n 120.1
H1b C1 H1a 109.4
N1 C1 H1a 112.0
C2 C1 H1a 111.9
N1 C1 H1b 111.8
C2 C1 H1b 111.7
H2b C2 H2a 109.5
O1 C2 H2a 110.7
C1 C2 H2a 110.6
O1 C2 H2b 110.6
C1 C2 H2b 110.5
N2 C5 H5 110.1
C6 C5 H5 110.2
C9 C5 H5 110.0
C7a C6 H6 123.5
C5 C6 H6 123.4
C6 C7a H7a 123.6
C8a C7a H7a 125.0
H8aa C8a H8ab 109.1
C7a C8a H8ab 110.6
C9 C8a H8ab 111.7
C7a C8a H8aa 110.4
C9 C8a H8aa 111.6
H9b C9 H9a 109.5
C5 C9 H9a 110.6
C8a C9 H9a 110.4
C5 C9 H9b 110.5
C8a C9 H9b 110.3
C5 C6 H6a 110.7
C7b C6 H6a 110.7
H6a C6 H6b 109.4
C5 C6 H6b 110.8
C7b C6 H6b 110.9
H7ba C7b H7bb 108.9
C8b C7b H7bb 111.8
C6 C7b H7bb 110.3
C8b C7b H7ba 111.5
C6 C7b H7ba 110.2
C9 C8b H8b 124.7
C8b C9 H9 123.1
C5 C9 H9 123.4
H11a C11 H11b 109.5
O5 C11 H11b 109.6
C12 C11 H11b 109.5
O5 C11 H11a 109.6
C12 C11 H11a 109.4

loop_
_geom_bond_atom_site_label_D
_geom_bond_atom_site_label_H
_geom_contact_atom_site_label_A
_geom_bond_distance_DH
_geom_contact_distance_HA
_geom_contact_distance_DA
_geom_angle_DHA
_geom_contact_site_symmetry_A
N3 H3n O3 0.947(2) 1.950(2) 2.871(3) 163.7(1) 8_545