Modulation of Chiroptical Properties in a Series of Helicene-like Compounds.
Guy, Laure; Mosser, Maëlle; Pitrat, Delphine; Mulatier, Jean-Christophe; Kukułka, Mercedes; Srebro-Hooper, Monika; Jeanneau, Erwann; Bensalah-Ledoux, Amina; Baguenard, Bruno; Guy, Stéphan; The Journal of organic chemistry 84 (2019) 10870–10876; doi:10.1021/acs.joc.9b01465

data_4033795
_publ_section_title
;
 Modulation of Chiroptical Properties in a Series of Helicene-like
 Compounds.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10870
_journal_page_last               10876
_journal_paper_doi               10.1021/acs.joc.9b01465
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C43 H27 N2 O2, C3 H6 O'
_chemical_formula_sum            'C46 H33 N2 O3'
_chemical_formula_weight         661.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.838(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.9582(4)
_cell_length_b                   19.5408(8)
_cell_length_c                   21.7073(13)
_cell_measurement_reflns_used    20085
_cell_measurement_temperature    100.00(14)
_cell_measurement_theta_max      66.9120
_cell_measurement_theta_min      4.3460
_cell_volume                     3363.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4685
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -43.00 -16.00   1.00    4.26    --  -41.64 -57.00  30.00   27
  2  \w    -95.00 -47.00   1.00    4.26    --  -41.64 125.00 150.00   48
  3  \w     32.00 118.00   1.00    4.26    --   41.64  77.00  60.00   86
  4  \w     10.00  85.00   1.00    4.26    --   41.64  77.00   0.00   75
  5  \w    -31.00  -4.00   1.00    4.26    --   41.64 -57.00  90.00   27
  6  \w     -3.00  92.00   1.00    4.26    --   41.64-125.00-150.00   95
  7  \w    117.00 162.00   1.00   17.07    --   92.50  77.00 -60.00   45
  8  \w     60.00  86.00   1.00   17.07    --   92.50  77.00 -60.00   26
  9  \w     64.00 164.00   1.00   17.07    --   92.50  59.00  48.78  100
 10  \w     63.00 162.00   1.00   17.07    --   92.50  61.00  30.00   99
 11  \w     60.00  89.00   1.00   17.07    --   92.50  77.00 -30.00   29
 12  \w    117.00 143.00   1.00   17.07    --   92.50  77.00 -30.00   26
 13  \w     76.00 102.00   1.00   17.07    --   92.50 125.00-120.00   26
 14  \w    140.00 165.00   1.00   17.07    --   92.50 125.00-120.00   25
 15  \w     25.00  92.00   1.00   17.07    --   92.50-125.00  30.00   67
 16  \w     20.00  91.00   1.00   17.07    --   92.50-125.00-180.00   71
 17  \w     74.00 164.00   1.00   17.07    --   92.50 125.00  60.00   90
 18  \w     31.00  57.00   1.00   17.07    --   92.50 -94.00  60.00   26
 19  \w     67.00 109.00   1.00   17.07    --   92.50  61.00 -30.00   42
 20  \w     45.00  76.00   1.00   17.07    --   92.50 -88.00 -43.34   31
 21  \w     84.00 109.00   1.00   17.07    --   92.50 -88.00 -43.34   25
 22  \w     32.00  69.00   1.00   17.07    --   92.50-140.00  60.00   37
 23  \w     60.00  86.00   1.00   17.07    --   92.50  77.00  30.00   26
 24  \w    102.00 128.00   1.00   17.07    --   92.50  77.00  30.00   26
 25  \w     69.00 141.00   1.00   17.07    --   92.50  45.00 -30.00   72
 26  \w     73.00 165.00   1.00   17.07    --   92.50 125.00 150.00   92
 27  \w     74.00 100.00   1.00   17.07    --   92.50 125.00  90.00   26
 28  \w    113.00 149.00   1.00   17.07    --   92.50 125.00  90.00   36
 29  \w     11.00  50.00   1.00   17.07    --   92.50 -94.00  90.00   39
 30  \w    123.00 151.00   1.00   17.07    --   92.50 125.00-180.00   28
 31  \w     26.00  64.00   1.00   17.07    --   92.50 -45.00 120.00   38
 32  \w     48.00  74.00   1.00   17.07    --   92.50 -19.00  53.16   26
 33  \w     83.00 116.00   1.00   17.07    --   92.50  61.00  60.00   33
 34  \w    145.00 170.00   1.00   17.07    --   92.50  15.00   0.00   25
 35  \w     78.00 112.00   1.00   17.07    --   92.50 -45.00 120.00   34
 36  \w     63.00  89.00   1.00   17.07    --   92.50  61.00 -60.00   26
 37  \w     66.00  99.00   1.00   17.07    --   92.50  15.00   0.00   33
 38  \w     60.00  93.00   1.00   17.07    --   92.50  77.00   0.00   33
 39  \w     60.00 129.00   1.00   17.07    --   92.50  77.00  60.00   69
 40  \w     58.00  84.00   1.00   17.07    --   92.50 -83.00  -0.10   26
 41  \w     10.00  86.00   1.00   17.07    --   92.50 -87.00-167.47   76
 42  \w     22.00  71.00   1.00   17.07    --   92.50 -90.00-106.30   49
 43  \w    103.00 145.00   1.00   17.07    --   92.50 -15.00 150.00   42
 44  \w     61.00  87.00   1.00   17.07    --   92.50  71.00  -9.89   26
 45  \w     84.00 116.00   1.00   17.07    --   92.50  45.00  30.00   32
 46  \w     28.00  54.00   1.00   17.07    --   92.50 -45.00  60.00   26
 47  \w     68.00  94.00   1.00   17.07    --   92.50 -45.00  60.00   26
 48  \w     83.00 109.00   1.00   17.07    --   92.50 -57.00 -82.15   26
 49  \w     68.00 165.00   1.00   17.07    --   92.50  44.00  10.03   97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1808568000
_diffrn_orient_matrix_UB_12      -0.0278935000
_diffrn_orient_matrix_UB_13      0.0007680000
_diffrn_orient_matrix_UB_21      -0.0210164000
_diffrn_orient_matrix_UB_22      0.0030904000
_diffrn_orient_matrix_UB_23      -0.0712091000
_diffrn_orient_matrix_UB_31      0.0669237000
_diffrn_orient_matrix_UB_32      -0.0736969000
_diffrn_orient_matrix_UB_33      -0.0032972000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            22070
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        66.895
_diffrn_reflns_theta_max         66.895
_diffrn_reflns_theta_min         3.048
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.644
_exptl_absorpt_correction_T_max  0.887
_exptl_absorpt_correction_T_min  0.784
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_description       block
_exptl_crystal_F_000             1388
_exptl_crystal_recrystallization_method
'The material was recrystallised from methanol by ---'
_exptl_crystal_size_max          0.445
_exptl_crystal_size_mid          0.342
_exptl_crystal_size_min          0.193
_refine_diff_density_max         0.741
_refine_diff_density_min         -0.455
_refine_diff_density_rms         0.070
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.2(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     924
_refine_ls_number_reflns         22070
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      6.498
_refine_ls_R_factor_all          0.0831
_refine_ls_R_factor_gt           0.0767
_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^)+(0.1749P)^2^+0.6522P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2080
_refine_ls_wR_factor_ref         0.2205
_reflns_Friedel_coverage         0.910
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                20186
_reflns_number_total             22070
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01465_si_001.cif
_cod_data_source_block           heli4_acetone_twin1_hklf4
_cod_depositor_comments
;

2020-06-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C92 H66 N4 O6'
_cod_original_formula_weight         1323.48
_cod_original_formula_moiety         '2(C43 H27 N2 O2), 2(C3 H6 O)'
_cod_original_formula_units_Z            2
_cod_database_code               4033795
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C92 H70 N4 O6'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6152(16)
 0.3848(16)
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
 C91-C90 \\sim C92-C87 \\sim C88-C89
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(O6) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C91)
\\sim Ueq, Uanis(O5) \\sim Ueq: with sigma of 0.001 and sigma for terminal
atoms of 0.005
5.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C38(H38A,H38B), C39(H39A,H39B), C49(H49A,H49B),
 C50(H50A,H50B), C81(H81A,H81B), C82(H82A,H82B)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15),
 C16(H16), C17(H17), C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34),
  C36(H36), C41(H41), C42(H42), C44(H44), C46(H46), C47(H47), C52(H52),
 C54(H54), C55(H55), C57(H57), C58(H58), C59(H59), C60(H60), C71(H71), C72(H72),
  C73(H73), C74(H74), C76(H76), C77(H77), C79(H79), C84(H84), C85(H85)
5.c Idealised Me refined as rotating group:
 C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C88(H88A,H88B,H88C), C89(H89A,H89B,
 H89C)
;
_shelx_res_checksum              19094
_shelx_hkl_checksum              47415
_olex2_submission_original_sample_id Heli4_acetone
_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 4.483
_oxdiff_exptl_absorpt_empirical_full_min 0.509
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 179.9067\% 
 around [1.00 -0.00 -0.00] (reciprocal) or [1.00 0.00 0.03] (direct)
;