Access to 27-Nortomatidine and 27-Norsoladulcidine Derivatives.
Czajkowska-Szczykowska, Dorota; Corona Díaz, Alejandro; Aleksiejczuk, Grzegorz; López Castro, Yliana; Morzycki, Jacek W.; The Journal of organic chemistry 84 (2019) 4104–4111; doi:10.1021/acs.joc.9b00103

data_4034243
_publ_section_title
;
 Access to 27-Nortomatidine and 27-Norsoladulcidine Derivatives.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4104
_journal_page_last               4111
_journal_paper_doi               10.1021/acs.joc.9b00103
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C40 H62 N2 O6 Si'
_chemical_formula_sum            'C40 H62 N2 O6 Si'
_chemical_formula_weight         695.01
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-24
_audit_creation_method           SHELXL-2016/6
_cell_angle_alpha                93.23(4)
_cell_angle_beta                 91.35(3)
_cell_angle_gamma                116.106(17)
_cell_formula_units_Z            2
_cell_length_a                   6.6499(14)
_cell_length_b                   7.472(2)
_cell_length_c                   43.076(10)
_cell_measurement_reflns_used    17125
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.4170
_cell_measurement_theta_min      3.0430
_cell_volume                     1916.2(8)
_computing_cell_refinement       'CrysAlis PRO (Agilent Technologies, 2011)'
_computing_data_collection       'CrysAlis PRO (Agilent Technologies, 2011)'
_computing_data_reduction        'CrysAlis PRO (Agilent Technologies, 2011)'
_computing_molecular_graphics    'OLEX2 (Dolomanov <i>et al.</i>, 2009)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_solution    'SHELXD-2016(Sheldrick, 2016)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4052
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -50.00  17.00   1.00    4.97    --    0.00 104.00  87.00   67
  2  \w   -147.00 -79.00   1.00   19.88    --  -59.00-104.00 -13.00   68
  3  \w    -88.00  17.00   1.00   19.88    --  -59.00 104.00  87.00  105
  4  \w      4.00 109.00   1.00   19.88    --   59.00-104.00 -13.00  105
  5  \w     30.00 113.00   1.00   19.86    --  118.00-104.00 -13.00   83
  6  \w    101.00 178.00   1.00   19.86    --  118.00 104.00  87.00   77
  7  \w      1.00  47.00   1.00    4.97    --    0.00 -99.00-150.00   46
  8  \w      1.00  47.00   1.00    4.97    --    0.00 -99.00-180.00   46
  9  \w      1.00  47.00   1.00    4.97    --    0.00 -99.00 -90.00   46
 10  \w      1.00  47.00   1.00    4.97    --    0.00 -99.00  90.00   46
 11  \w   -148.00 -79.00   1.00   19.88    --  -59.00 -99.00-180.00   69
 12  \w   -148.00 -79.00   1.00   19.88    --  -59.00 -99.00 120.00   69
 13  \w   -148.00 -79.00   1.00   19.88    --  -59.00 -99.00 -90.00   69
 14  \w     94.00 143.00   1.00   19.88    --   59.00 125.00 -90.00   49
 15  \w     81.00 178.00   1.00   19.86    --  118.00  38.00  90.00   97
 16  \w     32.00 116.00   1.00   19.86    --  118.00-111.00  60.00   84
 17  \w     32.00 155.00   1.00   19.86    --  118.00 -64.00   0.00  123
 18  \w     34.00 154.00   1.00   19.86    --  118.00 -50.00 -60.00  120
 19  \w    100.00 178.00   1.00   19.86    --  118.00 111.00   0.00   78
 20  \w     32.00 116.00   1.00   19.86    --  118.00-111.00-180.00   84
 21  \w     81.00 178.00   1.00   19.86    --  118.00  57.00-163.81   97
 22  \w    100.00 178.00   1.00   19.86    --  118.00 111.00 120.00   78
 23  \w     32.00 116.00   1.00   19.86    --  118.00-111.00 -30.00   84
 24  \w     32.00 116.00   1.00   19.86    --  118.00-111.00 120.00   84
 25  \w     32.00 116.00   1.00   19.86    --  118.00-111.00-120.00   84
 26  \w     82.00 178.00   1.00   19.86    --  118.00  50.00   0.00   96
 27  \w     26.00 157.00   1.00   19.86    --  118.00 -77.00 120.00  131
 28  \w     57.00 118.00   1.00   19.86    --  118.00 178.00 150.00   61
 29  \w    101.00 172.00   1.00   19.86    --  118.00 111.00-120.00   71
 30  \w    139.00 165.00   1.00   19.86    --  118.00  64.00 -30.00   26
 31  \w    101.00 127.00   1.00   19.86    --  118.00 -92.00 -60.00   26
 32  \w     83.00 149.00   1.00   19.86    --  118.00  50.00-180.00   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0781288000
_diffrn_orient_matrix_UB_12      -0.1604375000
_diffrn_orient_matrix_UB_13      0.0215196000
_diffrn_orient_matrix_UB_21      0.0008542000
_diffrn_orient_matrix_UB_22      -0.1212018000
_diffrn_orient_matrix_UB_23      -0.0315590000
_diffrn_orient_matrix_UB_31      0.2215690000
_diffrn_orient_matrix_UB_32      0.0569734000
_diffrn_orient_matrix_UB_33      -0.0065258000
_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  0.0599
_diffrn_reflns_av_unetI/netI     0.0458
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            37317
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.813
_diffrn_reflns_theta_min         3.087
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.916
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73077
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_description       prism
_exptl_crystal_F_000             756
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.096
_refine_diff_density_min         -0.595
_refine_diff_density_rms         0.103
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.13(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     900
_refine_ls_number_reflns         13920
_refine_ls_number_restraints     106
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0975
_refine_ls_R_factor_gt           0.0963
_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^)+(0.0867P)^2^+7.9218P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2566
_refine_ls_wR_factor_ref         0.2574
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.967
_reflns_number_gt                13755
_reflns_number_total             13920
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00103_si_002.cif
_cod_data_source_block           2
_cod_database_code               4034243
_shelx_shelxl_version_number     2016/6
_oxdiff_exptl_absorpt_empirical_full_min 0.580
_oxdiff_exptl_absorpt_empirical_full_max 2.914
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.87(7)
 0.13(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C37B-C38B
 0.005 with sigma of 1.54
 C29A-C34A
 0.005 with sigma of 1.395
 C29B-C34B
 0.005 with sigma of 1.395
 C29A-C34A
 0.005 with sigma of 1.395
 C29B-C34B
 0.005 with sigma of 1.395
4. Rigid bond restraints
 Si1B, C35B, C36B, C37B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C37B, C38B, C39B, C40B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O5A, N2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Si1B \\sim C35B \\sim C36B \\sim C37B: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C37B \\sim C38B \\sim C39B \\sim C40B: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(O5A) \\sim Ueq, Uanis(O5B) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(Si1B)
\\sim Ueq, Uanis(C35B) \\sim Ueq, Uanis(C36B) \\sim Ueq, Uanis(C37B) \\sim Ueq,
Uanis(C38B) \\sim Ueq, Uanis(C39B) \\sim Ueq, Uanis(C40B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
6.a Ternary CH refined with riding coordinates:
 C3A(H3A), C5A(H5A), C8A(H8A), C9A(H9A), C14A(H14A), C16A(H16A), C17A(H17A),
 C20A(H20A), C3B(H3B), C5B(H5B), C8B(H8B), C9B(H9B), C14B(H14B), C16B(H16B),
 C17B(H17B), C20B(H20B)
6.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C2A(H2AA,H2AB), C4A(H4AA,H4AB), C6A(H6AA,H6AB), C7A(H7AA,
 H7AB), C11A(H11A,H11B), C12A(H12A,H12B), C15A(H15A,H15B), C23A(H23A,H23B),
 C24A(H24A,H24B), C25A(H25A,H25B), C26A(H26A,H26B), C28A(H28A,H28B), C1B(H1BA,
 H1BB), C2B(H2BA,H2BB), C4B(H4BA,H4BB), C6B(H6BA,H6BB), C7B(H7BA,H7BB),
 C11B(H11C,H11D), C12B(H12C,H12D), C15B(H15C,H15D), C23B(H23C,H23D), C24B(H24C,
 H24D), C25B(H25C,H25D), C26B(H26C,H26D), C28B(H28C,H28D)
6.c Aromatic/amide H refined with riding coordinates:
 C30A(H30A), C31A(H31A), C33A(H33A), C34A(H34A), C30B(H30B), C31B(H31B),
 C33B(H33B), C34B(H34B)
6.d Idealised Me refined as rotating group:
 C18A(H18A,H18B,H18C), C19A(H19A,H19B,H19C), C21A(H21A,H21B,H21C), C35A(H35A,
 H35B,H35C), C36A(H36A,H36B,H36C), C38A(H38A,H38B,H38C), C39A(H39A,H39B,H39C),
 C40A(H40A,H40B,H40C), C18B(H18D,H18E,H18F), C19B(H19D,H19E,H19F), C21B(H21D,
 H21E,H21F), C35B(H35D,H35E,H35F), C36B(H36D,H36E,H36F), C38B(H38D,H38E,H38F),
 C39B(H39D,H39E,H39F), C40B(H40D,H40E,H40F)
;
_shelx_res_checksum              45263
_shelx_hkl_checksum              9821
_olex2_submission_special_instructions 'No special instructions were received'