Cascade reactions of indigo with oxiranes and aziridines: efficient access to dihydropyrazinodiindoles and spiro-oxazocinodiindoles.
Butler, Nicholas M.; Hendra, Rudi; Bremner, John B.; Willis, Anthony C.; Lucantoni, Leonardo; Avery, Vicky M.; Keller, Paul A.; Organic & biomolecular chemistry 16 (2018) 6006–6016; doi:10.1039/c8ob00865e

data_7156350
_publ_section_title
;
 Cascade reactions of indigo with oxiranes and aziridines: efficient
 access to dihydropyrazinodiindoles and spiro-oxazocinodiindoles.
;
_journal_issue                   33
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6006
_journal_page_last               6016
_journal_paper_doi               10.1039/c8ob00865e
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_compound_source        ' from U of Wollongong'
_chemical_formula_moiety
'2(C20 H16 N2 O4), 1.85(C H2 Cl2), 0.15(C H Cl3)'
_chemical_formula_sum            'C42 H35.85 Cl4.15 N4 O8'
_chemical_formula_weight         871.73
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             16-10-20
_audit_creation_method           CRYSTALS_ver_14.40
_audit_update_record
;
2017-12-10 deposited with the CCDC.
2018-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.5565(2)
_cell_length_b                   14.9406(2)
_cell_length_c                   25.9563(4)
_cell_measurement_reflns_used    11874
_cell_measurement_temperature    150
_cell_measurement_theta_max      64
_cell_measurement_theta_min      3
_cell_volume                     4093.84(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2016)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2016)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2016)'
_computing_molecular_graphics    'PLATON (Spek, 2008)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.056
_diffrn_reflns_av_sigmaI/netI    0.0767
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            61022
_diffrn_reflns_theta_full        71.949
_diffrn_reflns_theta_max         71.949
_diffrn_reflns_theta_min         3.405
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.205
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.80
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro version 1.171.38.43 (Rigaku Oxford Diffraction, 2016)
(Release 29 April 2016; compiled 27 May 2016,16:53)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       lath
_exptl_crystal_F_000             1801.264
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.53
_refine_diff_density_min         -0.40
_refine_ls_abs_structure_details 'Flack (1983), 3498 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.05(3)
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9821
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         7971
_refine_ls_number_restraints     66
_refine_ls_R_factor_all          0.0769
_refine_ls_R_factor_gt           0.0684
_refine_ls_shift/su_max          0.0028496
_refine_ls_shift/su_mean         0.0001198
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 0.156E+04 0.244E+04 0.141E+04 512. 46.6 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1506
_refine_ls_wR_factor_gt          0.1456
_refine_ls_wR_factor_ref         0.1506
_reflns_limit_h_max              13
_reflns_limit_h_min              -12
_reflns_limit_k_max              18
_reflns_limit_k_min              0
_reflns_limit_l_max              31
_reflns_limit_l_min              0
_reflns_number_gt                6934
_reflns_number_total             7974
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   4.29
_oxford_diffrn_Wilson_scale      0.13
_oxford_refine_ls_r_factor_ref   0.0769
_oxford_refine_ls_scale          2.97(2)
_oxford_reflns_number_all        7971
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title
'Z:\kel1611SNQ\Tony_kel1611SNQ_da At 12:23 on'
_cod_data_source_file            c8ob00865e2.cif
_cod_data_source_block           kel1611SNQ
_cod_depositor_comments
'Adding full bibliography for 7156347--7156351.cif.'
_cod_original_sg_symbol_H-M      'P 21 21 21 '
_cod_database_code               7156350
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, CL(1,U'S) UNTIL CL(2) 
CONT CL(11,U'S,OCC) UNTIL CL(32) 
CONT O(1,U'S) UNTIL O(8) 
CONT N(1,U'S) UNTIL C(41) C(91,U'S,OCC) UNTIL C(93) 
CONT ENANTIO 
EQUIV CL(11,OCC) CL(12,OCC) C(91,OCC) 
EQUIV CL(21,OCC) CL(22,OCC) CL(23,OCC) C(92,OCC) 
EQUIV CL(31,OCC) CL(32,OCC) C(93,OCC) 
RIDE CL(11,X'S) CL(21,X'S) 
EQUIV CL(11,U[11]) CL(21,U[11]) 
EQUIV CL(11,U[22]) CL(21,U[22]) 
EQUIV CL(11,U[33]) CL(21,U[33]) 
EQUIV CL(11,U[12]) CL(21,U[12]) 
EQUIV CL(11,U[13]) CL(21,U[13]) 
EQUIV CL(11,U[23]) CL(21,U[23]) 
RIDE C   (   2,X'S) H   (  21,X'S) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  17,X'S) H   ( 171,X'S) H   ( 172,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) H   ( 202,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) 
RIDE C   (  34,X'S) H   ( 341,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) H   ( 372,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) H   ( 402,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) H   ( 412,X'S) 
RIDE C(91,X'S) H(911,X'S) H(912,X'S) 
RIDE C(92,X'S) H(921,X'S) 
RIDE C(93,X'S) H(931,X'S) H(932,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
REM U(IJ) 0.0, .01 = CL(3) TO CL(4) 
U(IJ) 0.0, .02 = CL(12) TO CL(11) 
U(IJ) 0.0, .02 = CL(12) TO CL(22) 
U(IJ) 0.0, .02 = CL(12) TO CL(23) 
U(IJ) 0.0, .02 = CL(12) TO CL(31) 
U(IJ) 0.0, .02 = CL(12) TO CL(32) 
REM 
U(IJ) 0.0, .01 = CL(11) TO C(91) 
DIST 1.75, .01 = C(91) TO CL(11) 
DIST 1.75, .01 = C(91) TO CL(12) 
ANGLE 109 2 = CL(11) TO C(91) TO CL(12) 
DIST 2.8, .02 = CL(11) TO CL(12) 
REM 
U(IJ) 0.0, .01 = CL(21) TO C(92) 
DIST 1.75, .01 = C(92) TO CL(21) 
DIST 1.75, .01 = C(92) TO CL(22) 
DIST 1.75, .01 = C(92) TO CL(23) 
ANGLE 109 2 = CL(21) TO C(92) TO CL(22) 
ANGLE 109 2 = CL(21) TO C(92) TO CL(23) 
ANGLE 109 2 = CL(22) TO C(92) TO CL(23) 
DIST 2.8, .02 = CL(21) TO CL(22) 
DIST 2.8, .02 = CL(21) TO CL(23) 
DIST 2.8, .02 = CL(22) TO CL(23) 
REM 
U(IJ) 0.0, .01 = CL(31) TO C(93) 
DIST 1.75, .01 = C(93) TO CL(31) 
DIST 1.75, .01 = C(93) TO CL(32) 
ANGLE 109 2 = CL(31) TO C(93) TO CL(32) 
DIST 2.8, .02 = CL(31) TO CL(32) 
REM 
REM 
SUM  .0001 FOR CL(12,OCC) CL(22,OCC) CL(32,OCC) 
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
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