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
'Hans-Joachim Knolker'
'Olga Kataeva'
'Micha P. Krahl'

_publ_contact_author_name        'ProfD Hans-Joachim Knolker'
_publ_contact_author_address     
;
Institut fur Organische Chemie
Technische Universitat Dresden
Bergstrasse 66
Dresden
01069
GERMANY
;

_publ_contact_author_email       HANS-JOACHIM.KNOELKER@CHEMIE.TU-DRESDEN.DE

_publ_requested_journal          'Organic & Biomolecular Chemistry'

_publ_section_title              
;
First total synthesis of the biologically active
2,7-dioxygenated tricyclic carbazole alkaloids
7-methoxy-O-methylmukonal, clausine H (clauszoline-C), clausine K
(clauszoline-J) and clausine O
;

data_compound2
_database_code_depnum_ccdc_archive 'CCDC 273763'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            'clausine H'
_chemical_melting_point          '191-192 C'
_chemical_formula_moiety         ?
_chemical_formula_sum            'C16 H15 N O4'
_chemical_formula_weight         285.29

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'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Pca2(1)

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

_cell_length_a                   23.051(1)
_cell_length_b                   7.509(1)
_cell_length_c                   7.739(1)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1339.5(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    198(2)
_cell_measurement_reflns_used    34
_cell_measurement_theta_min      4.17
_cell_measurement_theta_max      19.52

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.415
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             600
_exptl_absorpt_coefficient_mu    0.102
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9506
_exptl_absorpt_correction_T_max  0.9898
_exptl_absorpt_process_details   'SADABS 2.03.(Sheldrick,Bruker AXS Inc.,2002)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      198(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  KappaCCD
_diffrn_measurement_method       CCD
_diffrn_detector_area_resol_mean 9
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            15467
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_sigmaI/netI    0.0286
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         3.17
_diffrn_reflns_theta_max         25.40
_reflns_number_total             2198
_reflns_number_gt                1835
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Collect (Nonius BV, 1997-2000)'
_computing_cell_refinement       'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)'
_computing_data_reduction        'EvalCCD (Duisenberg & Schreurs 1990-2000)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Schakal-99 (E.Keller 1999)'
_computing_publication_material  'XCIF 6.12 (Sheldrick, 1997)'

_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^)+(0.0475P)^2^+0.0043P] 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    'refined as riding atoms'
_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   0.3(10)
_refine_ls_number_reflns         2198
_refine_ls_number_parameters     193
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0324
_refine_ls_wR_factor_ref         0.0740
_refine_ls_wR_factor_gt          0.0693
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_restrained_S_all      1.053
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.30212(8) 0.5939(3) -0.0101(2) 0.0251(4) Uani 1 1 d . . .
C2 C 0.25146(9) 0.6863(3) -0.0649(3) 0.0268(4) Uani 1 1 d . . .
C3 C 0.25505(8) 0.8520(3) -0.1428(3) 0.0295(5) Uani 1 1 d . . .
H3 H 0.2211 0.9127 -0.1800 0.035 Uiso 1 1 calc R . .
C4 C 0.30985(8) 0.9270(2) -0.1649(2) 0.0243(4) Uani 1 1 d . . .
C5 C 0.36056(8) 0.8402(3) -0.1110(2) 0.0236(4) Uani 1 1 d . . .
C6 C 0.35613(8) 0.6738(3) -0.0346(2) 0.0234(4) Uani 1 1 d . . .
H6 H 0.3903 0.6134 0.0014 0.028 Uiso 1 1 calc R . .
N7 N 0.32435(6) 1.0889(2) -0.2363(2) 0.0286(4) Uani 1 1 d . . .
H7 H 0.2997 1.1659 -0.2807 0.034 Uiso 1 1 calc R . .
C8 C 0.38408(8) 1.1110(3) -0.2270(2) 0.0244(4) Uani 1 1 d . . .
C9 C 0.41709(7) 1.2576(2) -0.2778(3) 0.0251(4) Uani 1 1 d . . .
H9 H 0.3999 1.3598 -0.3287 0.030 Uiso 1 1 calc R . .
C10 C 0.47642(7) 1.2459(3) -0.2498(3) 0.0254(4) Uani 1 1 d . . .
C11 C 0.50172(8) 1.0964(3) -0.1733(3) 0.0268(5) Uani 1 1 d . . .
H11 H 0.5425 1.0934 -0.1554 0.032 Uiso 1 1 calc R . .
C12 C 0.46830(8) 0.9533(3) -0.1236(2) 0.0251(4) Uani 1 1 d . . .
H12 H 0.4858 0.8520 -0.0717 0.030 Uiso 1 1 calc R . .
C13 C 0.40844(8) 0.9590(2) -0.1503(2) 0.0220(4) Uani 1 1 d . . .
C14 C 0.29881(9) 0.4204(3) 0.0802(3) 0.0265(5) Uani 1 1 d . . .
O14 O 0.25659(6) 0.3279(2) 0.0977(2) 0.0412(4) Uani 1 1 d . . .
O15 O 0.35081(6) 0.37435(17) 0.14595(19) 0.0356(4) Uani 1 1 d . . .
C16 C 0.35169(10) 0.2123(3) 0.2444(3) 0.0454(6) Uani 1 1 d . . .
H16A H 0.3242 0.2216 0.3405 0.068 Uiso 1 1 calc R . .
H16B H 0.3908 0.1924 0.2899 0.068 Uiso 1 1 calc R . .
H16C H 0.3407 0.1124 0.1699 0.068 Uiso 1 1 calc R . .
O17 O 0.19953(6) 0.60460(19) -0.0355(2) 0.0370(4) Uani 1 1 d . . .
C18 C 0.14816(8) 0.7065(3) -0.0671(3) 0.0383(6) Uani 1 1 d . . .
H18A H 0.1484 0.8131 0.0059 0.057 Uiso 1 1 calc R . .
H18B H 0.1139 0.6342 -0.0400 0.057 Uiso 1 1 calc R . .
H18C H 0.1469 0.7418 -0.1890 0.057 Uiso 1 1 calc R . .
O19 O 0.51544(5) 1.37760(16) -0.29237(19) 0.0314(3) Uani 1 1 d . . .
C20 C 0.49325(9) 1.5356(3) -0.3682(3) 0.0369(5) Uani 1 1 d . . .
H20A H 0.4739 1.5064 -0.4773 0.055 Uiso 1 1 calc R . .
H20B H 0.5252 1.6186 -0.3905 0.055 Uiso 1 1 calc R . .
H20C H 0.4653 1.5910 -0.2892 0.055 Uiso 1 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
C1 0.0237(10) 0.0283(11) 0.0233(11) 0.0000(9) 0.0007(8) -0.0026(8)
C2 0.0211(9) 0.0327(10) 0.0266(11) -0.0007(9) 0.0004(8) -0.0027(9)
C3 0.0212(10) 0.0353(11) 0.0322(11) 0.0028(9) -0.0034(9) 0.0048(9)
C4 0.0239(10) 0.0252(11) 0.0239(10) 0.0030(8) -0.0010(8) 0.0008(8)
C5 0.0223(10) 0.0263(11) 0.0223(10) -0.0002(9) 0.0004(8) 0.0011(8)
C6 0.0193(10) 0.0259(11) 0.0248(10) 0.0005(9) -0.0007(8) 0.0030(8)
N7 0.0213(8) 0.0301(9) 0.0343(9) 0.0082(8) -0.0007(7) 0.0042(7)
C8 0.0211(10) 0.0297(11) 0.0223(10) -0.0022(9) 0.0011(8) 0.0013(8)
C9 0.0271(9) 0.0229(10) 0.0254(11) 0.0038(8) 0.0006(8) 0.0015(8)
C10 0.0268(10) 0.0262(10) 0.0231(10) -0.0030(8) 0.0024(8) -0.0049(9)
C11 0.0201(9) 0.0293(11) 0.0311(11) 0.0015(9) -0.0019(8) 0.0000(9)
C12 0.0274(10) 0.0228(9) 0.0250(10) 0.0039(9) -0.0022(8) 0.0035(9)
C13 0.0238(9) 0.0231(10) 0.0191(9) 0.0015(9) 0.0018(8) 0.0021(8)
C14 0.0245(10) 0.0292(11) 0.0259(10) -0.0025(9) 0.0033(8) -0.0033(9)
O14 0.0332(8) 0.0398(8) 0.0507(9) 0.0113(8) -0.0013(7) -0.0127(8)
O15 0.0312(8) 0.0291(8) 0.0464(9) 0.0123(7) -0.0028(6) -0.0010(6)
C16 0.0444(13) 0.0356(13) 0.0564(16) 0.0172(13) -0.0026(13) -0.0007(10)
O17 0.0202(7) 0.0398(9) 0.0510(9) 0.0081(8) -0.0009(6) -0.0047(7)
C18 0.0197(11) 0.0485(15) 0.0468(14) 0.0031(11) 0.0011(9) -0.0010(10)
O19 0.0278(7) 0.0282(7) 0.0382(8) 0.0076(6) 0.0007(6) -0.0042(6)
C20 0.0382(12) 0.0300(12) 0.0427(13) 0.0068(10) 0.0028(10) -0.0053(10)

_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 C6 1.395(3) . ?
C1 C2 1.423(3) . ?
C1 C14 1.480(3) . ?
C2 O17 1.364(2) . ?
C2 C3 1.385(3) . ?
C3 C4 1.394(3) . ?
C4 N7 1.376(2) . ?
C4 C5 1.402(3) . ?
C5 C6 1.386(3) . ?
C5 C13 1.452(3) . ?
N7 C8 1.389(2) . ?
C8 C9 1.394(3) . ?
C8 C13 1.404(3) . ?
C9 C10 1.387(2) . ?
C10 O19 1.377(2) . ?
C10 C11 1.397(3) . ?
C11 C12 1.377(3) . ?
C12 C13 1.396(3) . ?
C14 O14 1.203(2) . ?
C14 O15 1.347(2) . ?
O15 C16 1.436(2) . ?
O17 C18 1.431(3) . ?
O19 C20 1.419(2) . ?

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
C6 C1 C2 118.81(18) . . ?
C6 C1 C14 119.26(17) . . ?
C2 C1 C14 121.85(17) . . ?
O17 C2 C3 121.94(18) . . ?
O17 C2 C1 116.81(17) . . ?
C3 C2 C1 121.25(18) . . ?
C2 C3 C4 118.09(18) . . ?
N7 C4 C3 128.78(17) . . ?
N7 C4 C5 109.14(15) . . ?
C3 C4 C5 122.07(17) . . ?
C6 C5 C4 119.00(17) . . ?
C6 C5 C13 134.40(17) . . ?
C4 C5 C13 106.59(16) . . ?
C5 C6 C1 120.77(17) . . ?
C4 N7 C8 109.00(15) . . ?
N7 C8 C9 128.38(17) . . ?
N7 C8 C13 108.72(16) . . ?
C9 C8 C13 122.87(16) . . ?
C10 C9 C8 116.37(17) . . ?
O19 C10 C9 124.14(17) . . ?
O19 C10 C11 113.96(15) . . ?
C9 C10 C11 121.90(17) . . ?
C12 C11 C10 120.81(17) . . ?
C11 C12 C13 119.18(17) . . ?
C12 C13 C8 118.88(17) . . ?
C12 C13 C5 134.56(17) . . ?
C8 C13 C5 106.53(15) . . ?
O14 C14 O15 121.93(18) . . ?
O14 C14 C1 127.07(19) . . ?
O15 C14 C1 111.00(16) . . ?
C14 O15 C16 115.50(15) . . ?
C2 O17 C18 117.21(16) . . ?
C10 O19 C20 117.65(14) . . ?

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 O17 -178.85(17) . . . . ?
C14 C1 C2 O17 -2.1(3) . . . . ?
C6 C1 C2 C3 0.5(3) . . . . ?
C14 C1 C2 C3 177.28(19) . . . . ?
O17 C2 C3 C4 178.84(18) . . . . ?
C1 C2 C3 C4 -0.5(3) . . . . ?
C2 C3 C4 N7 -179.26(19) . . . . ?
C2 C3 C4 C5 -0.1(3) . . . . ?
N7 C4 C5 C6 179.95(17) . . . . ?
C3 C4 C5 C6 0.6(3) . . . . ?
N7 C4 C5 C13 0.9(2) . . . . ?
C3 C4 C5 C13 -178.45(19) . . . . ?
C4 C5 C6 C1 -0.6(3) . . . . ?
C13 C5 C6 C1 178.2(2) . . . . ?
C2 C1 C6 C5 0.0(3) . . . . ?
C14 C1 C6 C5 -176.80(17) . . . . ?
C3 C4 N7 C8 178.2(2) . . . . ?
C5 C4 N7 C8 -1.1(2) . . . . ?
C4 N7 C8 C9 -177.4(2) . . . . ?
C4 N7 C8 C13 0.9(2) . . . . ?
N7 C8 C9 C10 178.47(19) . . . . ?
C13 C8 C9 C10 0.5(3) . . . . ?
C8 C9 C10 O19 179.8(2) . . . . ?
C8 C9 C10 C11 -0.6(3) . . . . ?
O19 C10 C11 C12 -179.95(17) . . . . ?
C9 C10 C11 C12 0.5(3) . . . . ?
C10 C11 C12 C13 0.0(3) . . . . ?
C11 C12 C13 C8 -0.1(3) . . . . ?
C11 C12 C13 C5 -177.6(2) . . . . ?
N7 C8 C13 C12 -178.44(16) . . . . ?
C9 C8 C13 C12 -0.1(3) . . . . ?
N7 C8 C13 C5 -0.3(2) . . . . ?
C9 C8 C13 C5 178.04(18) . . . . ?
C6 C5 C13 C12 -1.5(4) . . . . ?
C4 C5 C13 C12 177.3(2) . . . . ?
C6 C5 C13 C8 -179.2(2) . . . . ?
C4 C5 C13 C8 -0.3(2) . . . . ?
C6 C1 C14 O14 -172.9(2) . . . . ?
C2 C1 C14 O14 10.4(3) . . . . ?
C6 C1 C14 O15 7.6(2) . . . . ?
C2 C1 C14 O15 -169.07(17) . . . . ?
O14 C14 O15 C16 -2.7(3) . . . . ?
C1 C14 O15 C16 176.79(17) . . . . ?
C3 C2 O17 C18 -8.1(3) . . . . ?
C1 C2 O17 C18 171.29(17) . . . . ?
C9 C10 O19 C20 0.6(3) . . . . ?
C11 C10 O19 C20 -178.99(18) . . . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        25.40
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.137
_refine_diff_density_min         -0.172
_refine_diff_density_rms         0.038