A Two-Directional Synthesis of (+)-β-Isosparteine.
Al-Saffar, Firas M; Brown, Richard C. D.; Organic letters 19 (2017) 3502–3504; doi:10.1021/acs.orglett.7b01475

data_1546317
_publ_section_title
;
 A Two-Directional Synthesis of (+)-\b-Isosparteine.
;
_journal_issue                   13
_journal_name_full               'Organic letters'
_journal_page_first              3502
_journal_page_last               3504
_journal_paper_doi               10.1021/acs.orglett.7b01475
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H34 Cl N O5 S'
_chemical_formula_sum            'C26 H34 Cl N O5 S'
_chemical_formula_weight         508.05
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_symmetry_space_group_name_Hall  'P 65'
_symmetry_space_group_name_H-M   'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-12-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   29.3480(19)
_cell_length_b                   29.3480(19)
_cell_length_c                   5.4131(4)
_cell_measurement_reflns_used    4937
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.5090
_cell_measurement_theta_min      2.1450
_cell_volume                     4037.7(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.9329
_diffrn_measured_fraction_theta_max 0.9102
_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    -80.00  59.00   1.00   25.00    --  -19.00  18.00   0.00  139
  2  \w    -60.00  15.00   1.00   25.00    --  -19.00 -72.00  60.00   75
  3  \w    -56.00  -9.00   1.00   25.00    --  -19.00  72.00 150.00   47
  4  \w    -80.00 -69.00   1.00   25.00    --  -19.00  18.00  90.00   11
;
_diffrn_measurement_device       'four-circle \k diffractometer'
_diffrn_measurement_device_type  'Rigaku AFC12 FRE-VHF'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroMesh'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0221922000
_diffrn_orient_matrix_UB_12      0.0256625000
_diffrn_orient_matrix_UB_13      0.0102693000
_diffrn_orient_matrix_UB_21      0.0168445000
_diffrn_orient_matrix_UB_22      -0.0108153000
_diffrn_orient_matrix_UB_23      -0.0021702000
_diffrn_orient_matrix_UB_31      0.0015141000
_diffrn_orient_matrix_UB_32      0.0021750000
_diffrn_orient_matrix_UB_33      -0.1306400000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.1557
_diffrn_reflns_av_unetI/netI     0.2085
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            27278
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.697
_diffrn_reflns_theta_min         3.674
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.254
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31574
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       needle
_exptl_crystal_F_000             1620
_exptl_crystal_recrystallization_method
'The material was recrystallised from THF by slow evaporation'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.694
_refine_diff_density_min         -0.910
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 870 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         6945
_refine_ls_number_restraints     367
_refine_ls_restrained_S_all      0.992
_refine_ls_R_factor_all          0.2199
_refine_ls_R_factor_gt           0.1018
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1202P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2070
_refine_ls_wR_factor_ref         0.2642
_reflns_Friedel_coverage         0.817
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3222
_reflns_number_total             6945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01475_si_003.cif
_cod_data_source_block           2016sot0091_r1_100k
_cod_depositor_comments
'Adding full bibliography for 1546317--1546319.cif.'
_cod_original_cell_volume        4037.7(6)
_cod_database_code               1546317
_shelx_shelxl_version_number     2016/6
_diffrn_measurement_device_type2 'Rigaku AFC12 (Right)'
_reflns_odcompleteness_completeness 93.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.87
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C26B-Cl1B
 1.7 with sigma of 0.02
 C23B-C18
 1.54 with sigma of 0.02
 Cl1A-C26A \\sim Cl1B-C26A
 with sigma of 0.02
 C23B-C18 \\sim C23A-C18 \\sim C24B-C23B \\sim C24A-C23A \\sim C25B-C24B \\sim
C25A-C24A \\sim C26B-
 C25B \\sim C26A-C25A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C24B) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C23B) \\sim Ueq,
Uanis(C23A) \\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C25B) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C26B) \\sim Ueq, Uanis(Cl1B) \\sim Ueq,
Uanis(Cl1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl1A) = Uanis(Cl1B)
Uanis(C26A) = Uanis(C26B)
Uanis(C23A) = Uanis(C23B)
Uanis(C24A) = Uanis(C24B)
Uanis(C25A) = Uanis(C25B)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl1A(0.7) H18(0.7) H18A(0.3) C23A(0.7) H23A(0.7) H23B(0.7)
 C24A(0.7) H24A(0.7) H24B(0.7) C25A(0.7) H25A(0.7) H25B(0.7) C26A(0.7)
 H26A(0.7) H26B(0.7) Cl1B(0.3) C26B(0.3) H26C(0.3) H26D(0.3) C25B(0.3)
 H25C(0.3) H25D(0.3) C24B(0.3) H24C(0.3) H24D(0.3) C23B(0.3) H23C(0.3) H23D(0.3)
6.a Ternary CH refined with riding coordinates:
 C10(H10), C18(H18), C18(H18A)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C23A(H23A,H23B), C24A(H24A,H24B), C25A(H25A,H25B),
 C26A(H26A,H26B), C26B(H26C,H26D), C25B(H25C,H25D), C24B(H24C,H24D), C23B(H23C,
 H23D)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C14(H14), C15(H15),
  C16(H16), C17(H17)
6.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_olex2_date_sample_submission    2016-12-05
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a glass fibre silicon oil'
_olex2_submission_original_sample_id 'fals/7902/21.P5 '
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.931
_oxdiff_exptl_absorpt_empirical_full_min 0.591