General Approach to Spiro Indole-3,1′-naphthalen Tetracyclic System: Stereoselective Pseudo Four-component Reaction of Isatins and Cyclic Ketones with two Molecules of Malononitrile
Elinson, Michail N.; Vereshchagin, Anatoly N.; Nasybullin, Ruslan; Bobrovsky, Sergey; Ilovaisky, Alexey; Merkulova, Valentina; Bushmarinov, Ivan S.; Egorov, Mikhail; RSC Adv.  (2015) –; doi:10.1039/C5RA03452C

data_7220619
_publ_section_title
;
 General Approach to Spiro Indole-3,1&#x2032;-naphthalen Tetracyclic
 System: Stereoselective Pseudo Four-component Reaction of Isatins and
 Cyclic Ketones with two Molecules of Malononitrile
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C5RA03452C
_journal_year                    2015
_chemical_formula_moiety         'C20 H15 N5 O, 1.5(C2 H6 O)'
_chemical_formula_sum            'C23 H24 N5 O2.5'
_chemical_formula_weight         410.47
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-02-22 deposited with the CCDC.
2015-05-29 downloaded from the CCDC.
;
_cell_angle_alpha                77.760(6)
_cell_angle_beta                 83.288(7)
_cell_angle_gamma                70.811(6)
_cell_formula_units_Z            2
_cell_length_a                   7.4809(18)
_cell_length_b                   11.265(3)
_cell_length_c                   13.576(3)
_cell_measurement_reflns_used    1422
_cell_measurement_temperature    150
_cell_measurement_theta_max      0.000
_cell_measurement_theta_min      0.000
_cell_volume                     1054.6(4)
_computing_cell_refinement       'SAINT v6.45A (Bruker, 2003)'
_computing_data_reduction        'SAINT v6.45A (Bruker, 2003)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 1K area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0575
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            9729
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         1.537
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.087
_exptl_absorpt_correction_T_max  0.986
_exptl_absorpt_correction_T_min  0.7459
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       prism
_exptl_crystal_F_000             434
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Ethanol'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.223
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.998
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     358
_refine_ls_number_reflns         4309
_refine_ls_number_restraints     122
_refine_ls_restrained_S_all      0.994
_refine_ls_R_factor_all          0.1417
_refine_ls_R_factor_gt           0.0631
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0903P)^2^+0.6337P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1538
_refine_ls_wR_factor_ref         0.2092
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2102
_reflns_number_total             4309
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ra03452c2.cif
_cod_data_source_block           a
_cod_original_formula_sum        'C23 H24 N5 O2.50'
_cod_database_code               7220619
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups, All
  O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
O1S \\sim C2S \\sim C3S' \\sim O1S' \\sim C2S' \\sim C3S: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
O2S \\sim C4S \\sim C5S \\sim O2S' \\sim C4S' \\sim C5S': within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
3. Same fragment restrains
{O2S, C4S, C5S} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1S, C2S, C3S}
{C5S, O2S, C4S} sigma for 1-2: 0.02, 1-3: 0.04
as
{C3S', O1S', C2S'}
{O2S, C4S, C5S} sigma for 1-2: 0.02, 1-3: 0.04
as
{O2S', C4S', C5S'}
4. Others
 Sof(C3S)=Sof(H3SD)=Sof(H3SE)=Sof(H3SF)=Sof(O1S')=Sof(H1S')=Sof(C2S')=
 Sof(H2SC)=Sof(H2SD)=1-FVAR(1)
 Sof(O1S)=Sof(H1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S')=Sof(H3SA)=Sof(H3SB)=
 Sof(H3SC)=FVAR(1)
 Sof(O2S')=Sof(H2S')=Sof(C4S')=Sof(H4SC)=Sof(H4SD)=Sof(C5S')=Sof(H5SD)=
 Sof(H5SE)=Sof(H5SF)=0.5*(1-FVAR(3))
 Sof(O2S)=Sof(H2S)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=
 Sof(H5SC)=0.5*FVAR(3)
5.a Riding coordinates:
 O1S(H1S), O1S'(H1S')
5.b Ternary CH refined with riding coordinates:
 C8A'(H8A')
5.c Secondary CH2 refined with riding coordinates:
 C6'(H6'A,H6'B), C7'(H7'A,H7'B), C8'(H8'A,H8'B), C2S(H2SA,H2SB), C2S'(H2SC,
 H2SD), C4S(H4SA,H4SB), C4S'(H4SC,H4SD)
5.d Me refined with riding coordinates:
 C5S(H5SA,H5SB,H5SC), C5S'(H5SD,H5SE,H5SF)
5.e Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C5'(H5'), C6(H6), C7(H7)
5.f Idealised Me refined as rotating group:
 C3S(H3SD,H3SE,H3SF), C3S'(H3SA,H3SB,H3SC)
5.g Idealised tetrahedral OH refined as rotating group:
 O2S(H2S), O2S'(H2S')
;
_shelx_res_checksum              56361
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method 'mounted on a needle'
_olex2_submission_special_instructions 'No special instructions were received'