# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2003

data_global

_journal_coden_Cambridge         182

loop_
_publ_author_name
'Jieping Zhu'
'Angela Chiaroni'
'Michael De Paolis'

_publ_contact_author_name        'Dr Jieping Zhu'
_publ_contact_author_address     
;
Institut de Chimie des Substances Naturelles
Bat 27
Gif-sur-Yvette
91198
FRANCE
;

_publ_contact_author_email       ZHU@ICSN.CNRS-GIF.FR

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
Synthetic Studies on Ecteinascidine 743: Rapid
Access to the Fully Functionalized  Tetrahydroisoquinoline with a
Bridged 10-member Sulfur Containing Macrocycle
;

data_paol
_database_code_CSD               217803

_audit_creation_method           SHELXL
_chemical_absolute_configuration known
_chemical_name_systematic        
;
?
;
_chemical_name_common            Paol02
_chemical_formula_moiety         'C18 H23 N O7'
_chemical_formula_structural     'C18 H23 N O7'
_chemical_formula_analytical     ?
_chemical_formula_sum            'C18 H23 N O7'
_chemical_formula_weight         365.37
_chemical_melting_point          ?
_chemical_compound_source        'chemical synthesis'

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'
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'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'P 212121'

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'

_cell_length_a                   5.513(6)
_cell_length_b                   12.528(14)
_cell_length_c                   26.192(23)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1809.0(32)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    3152
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       Needle
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.80
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.075
_exptl_crystal_density_meas      none
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             776
_exptl_absorpt_coefficient_mu    0.104
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?

_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       'Nonius kappaCCD aera-detctor diffractometer'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6899/4196
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_sigmaI/netI    0.0470
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         1.55
_diffrn_reflns_theta_max         31.35
_reflns_number_total             2554
_reflns_number_gt                2135
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       
;
'DENZO (Otwinowski & Minor, 1997)  COLLECT (Hooft, 1998)'
;
_computing_cell_refinement       
;
'DENZO (Otwinowski & Minor, 1997)  COLLECT (Hooft, 1998)'
;
_computing_data_reduction        'HKL package (Otwinowski & Minor, 1997)'
_computing_structure_solution    'SHELXS-86 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-93 (Sheldrick, 1993)'
_computing_molecular_graphics    'R3M (Riche, 1983) ORTEP (Johnson, 1965)'
_computing_publication_material  'SHELXL-93 (Sheldrick, 1993)'

_refine_special_details          
;
Refinement on F^2^ for ALL reflections except for 2 with very negative F^2^
or flagged by the user for potential systematic errors.  Weighted R-factors
wR and all goodnesses 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 observed criterion
of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.0437P)^2^+0.4271P] 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    riding
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.23(163)
_refine_ls_number_reflns         2552
_refine_ls_number_parameters     239
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0620
_refine_ls_R_factor_gt           0.0457
_refine_ls_wR_factor_all         0.1441
_refine_ls_wR_factor_ref         0.1042
_refine_ls_goodness_of_fit_all   1.072
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_restrained_S_all      1.380
_refine_ls_restrained_S_obs      1.101
_refine_ls_shift/su_max          -0.030
_refine_ls_shift/esd_mean        0.002

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_thermal_displace_type
_atom_site_occupancy
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_group
N1 N 0.1113(5) 0.8155(2) 0.90636(9) 0.0564(7) Uani 1 d . .
HN1 H -0.0200 0.7800 0.9302 0.068 Uiso 1 d . .
C2 C 0.3111(5) 0.8544(2) 0.93811(12) 0.0547(8) Uani 1 d . .
H2 H 0.3975(5) 0.7933(2) 0.95278(12) 0.066 Uiso 1 calc R .
C3 C 0.4845(5) 0.9178(2) 0.90455(10) 0.0452(7) Uani 1 d . .
H3 H 0.6347(5) 0.9319(2) 0.92335(10) 0.054 Uiso 1 calc R .
C4 C 0.5428(5) 0.8626(2) 0.85520(10) 0.0418(7) Uani 1 d . .
C5 C 0.7316(5) 0.9003(2) 0.82500(10) 0.0441(7) Uani 1 d . .
C6 C 0.7820(6) 0.8599(2) 0.77639(11) 0.0521(8) Uani 1 d . .
C7 C 0.6329(7) 0.7774(2) 0.76151(11) 0.0579(8) Uani 1 d . .
C8 C 0.4527(6) 0.7366(2) 0.79110(12) 0.0571(8) Uani 1 d . .
C9 C 0.3998(5) 0.7763(2) 0.83855(11) 0.0476(7) Uani 1 d . .
C10 C 0.1919(5) 0.7350(2) 0.87041(12) 0.0544(8) Uani 1 d . .
H10 H 0.0565(5) 0.7220(2) 0.84697(12) 0.065 Uiso 1 calc R .
C11 C 0.2137(7) 0.9224(3) 0.98044(12) 0.0705(10) Uani 1 d . .
H11A H 0.0865(7) 0.8838(3) 0.99811(12) 0.085 Uiso 1 calc R .
H11B H 0.3424(7) 0.9366(3) 1.00477(12) 0.085 Uiso 1 calc R .
O12 O 0.1186(4) 1.0216(2) 0.96225(8) 0.0593(6) Uani 1 d . .
O13 O 0.3700(3) 1.01802(14) 0.89089(6) 0.0467(5) Uani 1 d . .
C14 C 0.2892(5) 1.0812(2) 0.93295(12) 0.0531(8) Uani 1 d . .
C15 C 0.1494(7) 1.1721(2) 0.90963(13) 0.0642(9) Uani 1 d . .
H15A H 0.2537(11) 1.2118(9) 0.8873(6) 0.080 Uiso 1 calc R .
H15B H 0.0906(29) 1.2181(9) 0.93620(13) 0.080 Uiso 1 calc R .
H15C H 0.0147(21) 1.1444(3) 0.8906(6) 0.080 Uiso 1 calc R .
C16 C 0.5003(7) 1.1200(3) 0.96535(14) 0.0786(11) Uani 1 d . .
H16A H 0.6049(22) 1.1640(14) 0.9450(3) 0.098 Uiso 1 calc R .
H16B H 0.5898(23) 1.0598(3) 0.9779(7) 0.098 Uiso 1 calc R .
H16C H 0.4394(7) 1.1608(15) 0.9936(5) 0.098 Uiso 1 calc R .
O17 O 0.8724(4) 0.9836(2) 0.84232(7) 0.0574(5) Uani 1 d . .
HO17 H 1.0125 0.9400 0.8640 0.072 Uiso 1 d . .
C18 C 0.9777(7) 0.9044(3) 0.74287(13) 0.0754(10) Uani 1 d . .
H18A H 1.1299(10) 0.9019(16) 0.7606(3) 0.094 Uiso 1 calc R .
H18B H 0.9399(21) 0.9771(6) 0.7343(7) 0.094 Uiso 1 calc R .
H18C H 0.9885(28) 0.8628(11) 0.7122(4) 0.094 Uiso 1 calc R .
O19 O 0.6391(6) 0.7265(2) 0.71508(8) 0.0887(8) Uani 1 d . .
O20 O 0.3314(5) 0.6569(2) 0.76523(9) 0.0855(8) Uani 1 d . .
C21 C 0.4656(10) 0.6427(3) 0.7196(2) 0.103(2) Uani 1 d . .
H21A H 0.3570(10) 0.6437(3) 0.6905(2) 0.124 Uiso 1 calc R .
H21B H 0.5478(10) 0.5742(3) 0.7203(2) 0.124 Uiso 1 calc R .
C22 C 0.2449(7) 0.6288(2) 0.89735(14) 0.0628(9) Uani 1 d . .
O23 O 0.1694(6) 0.6076(2) 0.93830(13) 0.1159(12) Uani 1 d . .
O24 O 0.3846(5) 0.5664(2) 0.87197(11) 0.0947(9) Uani 1 d . .
C25 C 0.4316(9) 0.4608(3) 0.8925(2) 0.105(2) Uani 1 d . .
H25A H 0.4352(9) 0.4638(3) 0.9295(2) 0.126 Uiso 1 calc R .
H25B H 0.3033(9) 0.4123(3) 0.8823(2) 0.126 Uiso 1 calc R .
C26 C 0.6506(10) 0.4244(4) 0.8744(3) 0.146(2) Uani 1 d . .
H26A H 0.6818(34) 0.3545(13) 0.8879(12) 0.182 Uiso 1 calc R .
H26B H 0.7772(13) 0.4722(17) 0.8850(12) 0.182 Uiso 1 calc R .
H26C H 0.6457(25) 0.4212(29) 0.8378(3) 0.182 Uiso 1 calc R .

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
N1 0.052(2) 0.0533(14) 0.063(2) 0.0044(13) 0.0007(14) 0.0023(13)
C2 0.059(2) 0.058(2) 0.048(2) 0.0079(15) -0.0028(15) 0.008(2)
C3 0.048(2) 0.045(2) 0.043(2) -0.0020(13) -0.0093(13) 0.0080(14)
C4 0.046(2) 0.0391(14) 0.040(2) -0.0029(12) -0.0091(12) 0.0076(13)
C5 0.048(2) 0.0385(14) 0.046(2) -0.0020(13) -0.0076(13) 0.0089(13)
C6 0.059(2) 0.052(2) 0.045(2) 0.0055(15) 0.0003(14) 0.011(2)
C7 0.087(2) 0.044(2) 0.043(2) -0.0052(14) -0.003(2) 0.009(2)
C8 0.084(2) 0.0395(15) 0.048(2) -0.0014(14) -0.007(2) -0.003(2)
C9 0.058(2) 0.0393(14) 0.046(2) 0.0049(13) -0.0046(14) 0.0044(14)
C10 0.056(2) 0.047(2) 0.060(2) 0.007(2) -0.0095(15) -0.0022(15)
C11 0.082(3) 0.078(2) 0.052(2) 0.005(2) 0.001(2) 0.015(2)
O12 0.0620(14) 0.0626(12) 0.0533(12) -0.0056(11) 0.0071(11) 0.0100(12)
O13 0.0550(12) 0.0408(9) 0.0442(10) -0.0080(8) -0.0034(8) 0.0055(10)
C14 0.053(2) 0.053(2) 0.053(2) -0.0161(15) 0.0022(15) 0.0029(15)
C15 0.069(2) 0.048(2) 0.075(2) -0.011(2) 0.004(2) 0.008(2)
C16 0.070(2) 0.094(3) 0.072(2) -0.043(2) -0.008(2) -0.003(2)
O17 0.0513(12) 0.0575(12) 0.0633(13) 0.0016(10) -0.0145(10) -0.0031(10)
C18 0.077(3) 0.082(2) 0.067(2) 0.001(2) 0.014(2) 0.012(2)
O19 0.145(2) 0.0695(15) 0.0517(14) -0.0210(12) 0.0122(15) -0.009(2)
O20 0.134(2) 0.0556(13) 0.067(2) -0.0190(12) -0.005(2) -0.025(2)
C21 0.176(5) 0.069(2) 0.065(3) -0.024(2) 0.004(3) -0.020(3)
C22 0.062(2) 0.047(2) 0.079(3) 0.009(2) 0.001(2) 0.000(2)
O23 0.153(3) 0.078(2) 0.117(2) 0.044(2) 0.060(2) 0.027(2)
O24 0.131(2) 0.0510(12) 0.102(2) 0.0200(13) 0.032(2) 0.029(2)
C25 0.120(4) 0.055(2) 0.139(4) 0.030(2) 0.021(3) 0.021(2)
C26 0.126(4) 0.098(3) 0.213(6) 0.043(4) 0.043(5) 0.035(3)

_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
N1 C10 1.450(4) . ?
N1 C2 1.464(4) . ?
C2 C11 1.498(5) . ?
C2 C3 1.522(4) . ?
C3 O13 1.450(3) . ?
C3 C4 1.500(4) . ?
C4 C5 1.390(4) . ?
C4 C9 1.407(4) . ?
C5 O17 1.378(3) . ?
C5 C6 1.398(4) . ?
C6 C7 1.377(4) . ?
C6 C18 1.499(5) . ?
C7 C8 1.360(5) . ?
C7 O19 1.373(4) . ?
C8 C9 1.370(4) . ?
C8 O20 1.380(4) . ?
C9 C10 1.509(4) . ?
C10 C22 1.533(4) . ?
C11 O12 1.430(4) . ?
O12 C14 1.425(4) . ?
O13 C14 1.427(3) . ?
C14 C15 1.505(4) . ?
C14 C16 1.520(4) . ?
O19 C21 1.425(5) . ?
O20 C21 1.417(5) . ?
C22 O23 1.181(4) . ?
C22 O24 1.284(4) . ?
O24 C25 1.451(4) . ?
C25 C26 1.374(6) . ?

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
C10 N1 C2 111.7(2) . . ?
N1 C2 C11 109.9(3) . . ?
N1 C2 C3 108.5(2) . . ?
C11 C2 C3 110.9(3) . . ?
O13 C3 C4 106.2(2) . . ?
O13 C3 C2 108.7(2) . . ?
C4 C3 C2 113.1(3) . . ?
C5 C4 C9 120.3(3) . . ?
C5 C4 C3 119.6(3) . . ?
C9 C4 C3 120.1(3) . . ?
O17 C5 C4 119.5(3) . . ?
O17 C5 C6 117.5(3) . . ?
C4 C5 C6 123.0(3) . . ?
C7 C6 C5 114.3(3) . . ?
C7 C6 C18 122.9(3) . . ?
C5 C6 C18 122.8(3) . . ?
C8 C7 O19 110.4(3) . . ?
C8 C7 C6 123.8(3) . . ?
O19 C7 C6 125.8(3) . . ?
C7 C8 C9 122.4(3) . . ?
C7 C8 O20 110.3(3) . . ?
C9 C8 O20 127.2(3) . . ?
C8 C9 C4 116.2(3) . . ?
C8 C9 C10 122.6(3) . . ?
C4 C9 C10 121.2(3) . . ?
N1 C10 C9 110.7(2) . . ?
N1 C10 C22 111.3(3) . . ?
C9 C10 C22 114.0(3) . . ?
O12 C11 C2 112.3(2) . . ?
C14 O12 C11 113.1(2) . . ?
C14 O13 C3 115.2(2) . . ?
O12 C14 O13 109.3(2) . . ?
O12 C14 C15 106.1(2) . . ?
O13 C14 C15 105.4(2) . . ?
O12 C14 C16 111.9(3) . . ?
O13 C14 C16 111.7(2) . . ?
C15 C14 C16 112.1(3) . . ?
C7 O19 C21 104.6(3) . . ?
C8 O20 C21 104.6(3) . . ?
O20 C21 O19 109.2(3) . . ?
O23 C22 O24 123.0(3) . . ?
O23 C22 C10 123.1(3) . . ?
O24 C22 C10 113.9(3) . . ?
C22 O24 C25 118.1(3) . . ?
C26 C25 O24 109.4(4) . . ?

_refine_diff_density_max         0.121
_refine_diff_density_min         -0.128
_refine_diff_density_rms         0.028