Hydrogen-Bond-Induced Selectivity of a Head-to-Head Photo- Dimerization of Dialkynylanthracene ‒ Access to Tetra Lewis Acids
Niermeier, Philipp; Maibom, Kristina; Lamm, Jan-Hendrik; Neumann, Beate; Stammler, Georg; Mitzel, Norbert Werner; Chemical Science  (2021) –; doi:10.1039/D1SC02065J

data_1562399
_publ_section_title
;
 Hydrogen-Bond-Induced Selectivity of a Head-to-Head Photo- Dimerization
 of Dialkynylanthracene -- Access to Tetra Lewis Acids
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02065J
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C84 H72 B4 N8, 3.33(C H2 Cl2)'
_chemical_formula_sum            'C87.33 H78.66 B4 Cl6.66 N8'
_chemical_formula_weight         1519.63
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-18
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2019-09-09 deposited with the CCDC.	2021-05-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.0669(4)
_cell_length_b                   22.8536(4)
_cell_length_c                   15.3750(4)
_cell_measurement_reflns_used    39794
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2340
_cell_measurement_theta_min      2.6740
_cell_volume                     8105.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.54a (Rigaku OD, 2019)'
_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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.975
_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    -32.00  33.00   1.00   11.00    --  -38.50  38.00 150.00   65
  2  \w   -116.00  -6.00   1.00   11.00    --  -38.50 -19.00 -30.00  110
  3  \w    -72.00  22.00   1.00   11.00    --  -38.50  19.00 120.00   94
  4  \w      2.00  63.00   1.00   11.00    --   42.70 -99.00 -90.00   61
  5  \w     13.00  68.00   1.00   11.00    --   42.70  77.00   0.00   55
  6  \w     13.00  42.00   1.00   11.00    --   42.70  77.00  90.00   29
  7  \w     67.00  93.00   1.00   11.00    --   42.70  57.00  90.00   26
  8  \w     13.00  62.00   1.00   11.00    --   42.70  77.00-120.00   49
  9  \w     10.00  65.00   1.00   11.00    --   42.70 -99.00-150.00   55
 10  \w     13.00  59.00   1.00   11.00    --   42.70  77.00 -60.00   46
 11  \w     19.00  85.00   1.00   11.00    --   42.70  57.00-180.00   66
 12  \w    -27.00  44.00   1.00   11.00    --   42.70 -38.00 -60.00   71
 13  \w     46.00  96.00   1.00   11.00    --   42.70-125.00  90.00   50
 14  \w     15.00  55.00   1.00   11.00    --   42.70  77.00 120.00   40
 15  \w      9.00  34.00   1.00   11.00    --   42.70  86.00-176.10   25
 16  \w     18.00  57.00   1.00   11.00    --   42.70  57.00  90.00   39
 17  \w     22.00  87.00   1.00   11.00    --   42.70  38.00 150.00   65
 18  \w     53.00 104.00   1.00   27.50    --  111.00 -94.00 -90.00   51
 19  \w     31.00 109.00   1.00   27.50    --  111.00 -94.00  90.00   78
 20  \w    129.00 173.00   1.00   27.50    --  111.00  60.00 -14.24   44
 21  \w     89.00 115.00   1.00   27.50    --  111.00  45.00-150.00   26
 22  \w     85.00 178.00   1.00   27.50    --  111.00  61.00 -60.00   93
 23  \w     85.00 111.00   1.00   27.50    --  111.00  61.00  90.00   26
 24  \w     81.00 175.00   1.00   27.50    --  111.00  77.00  30.00   94
 25  \w     43.00  71.00   1.00   27.50    --  111.00 -94.00  30.00   28
 26  \w     85.00 144.00   1.00   27.50    --  111.00  61.00-120.00   59
 27  \w     85.00 111.00   1.00   27.50    --  111.00  61.00 -30.00   26
 28  \w     81.00 131.00   1.00   27.50    --  111.00  77.00 150.00   50
 29  \w     81.00 111.00   1.00   27.50    --  111.00  77.00 -90.00   30
 30  \w    115.00 166.00   1.00   27.50    --  111.00  77.00 -90.00   51
 31  \w     85.00 124.00   1.00   27.50    --  111.00  60.00 -14.24   39
 32  \w     82.00 108.00   1.00   27.50    --  111.00  71.00-153.10   26
 33  \w     85.00 111.00   1.00   27.50    --  111.00  61.00-150.00   26
 34  \w     81.00 108.00   1.00   27.50    --  111.00  77.00  90.00   27
 35  \w    106.00 140.00   1.00   27.50    --  111.00 -77.00 -60.00   34
 36  \w     49.00  86.00   1.00   27.50    --  111.00 -77.00 -60.00   37
 37  \w     81.00 175.00   1.00   27.50    --  111.00  77.00-120.00   94
 38  \w     81.00 107.00   1.00   27.50    --  111.00  77.00   0.00   26
 39  \w     85.00 111.00   1.00   27.50    --  111.00  61.00 150.00   26
 40  \w     43.00 126.00   1.00   27.50    --  111.00-136.00  56.84   83
 41  \w     81.00 106.00   1.00   27.50    --  111.00  77.00  60.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0029110000
_diffrn_orient_matrix_UB_12      0.0672737000
_diffrn_orient_matrix_UB_13      -0.0018002000
_diffrn_orient_matrix_UB_21      0.0483477000
_diffrn_orient_matrix_UB_22      -0.0012959000
_diffrn_orient_matrix_UB_23      0.0691551000
_diffrn_orient_matrix_UB_31      0.0460647000
_diffrn_orient_matrix_UB_32      -0.0028584000
_diffrn_orient_matrix_UB_33      -0.0724921000
_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  0.0592
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            91890
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.553
_diffrn_reflns_theta_min         2.722
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.518
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.756
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.54a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.245
_exptl_crystal_description       block
_exptl_crystal_F_000             3168
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.191
_exptl_crystal_size_min          0.111
_refine_diff_density_max         0.834
_refine_diff_density_min         -0.443
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 5642 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(7)
_refine_ls_extinction_coef       0.00132(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1126
_refine_ls_number_reflns         16668
_refine_ls_number_restraints     261
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0724
_refine_ls_R_factor_gt           0.0605
_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^)+(0.0894P)^2^+5.7809P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1554
_refine_ls_wR_factor_ref         0.1723
_reflns_Friedel_coverage         0.888
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                14362
_reflns_number_total             16668
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02065j2.cif
_cod_data_source_block           11
_cod_original_cell_volume        8105.2(3)
_cod_database_code               1562399
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C84H76B4N10 Cl4'
_diffrn_oxdiff_digest_frames
;
01256eeacb8a8a7093da01f43322aa5d21032919c66
;
_diffrn_oxdiff_digest_hkl
;
01491ca4df2ba6d1c60b6f529ab5436a7a25ba
;
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl5-C87 \\sim Cl6-C87 \\sim Cl2-C85 \\sim Cl1-C85 \\sim Cl3_$1-C86_$1 \\sim
Cl4_$1-C86_$1 ~
 Cl11_$1-C90_$1 \\sim Cl12_$1-C90_$1 \\sim Cl13_$1-C91_$1 \\sim Cl14_$1-C91_$1
\\sim Cl10_$1-
 C89_$1 \\sim Cl9_$1-C89_$1 \\sim Cl8_$1-C88_$1 \\sim Cl7_$1-C88_$1
 with sigma of 0.02
 N6-H6A \\sim N6-H6B \\sim N5-H5A \\sim N5-H5B \\sim N7-H7A \\sim N7-H7B \\sim
N8-H8A \\sim N8-H8B \\sim N2-
 H2A \\sim N2-H2B \\sim N1-H1B \\sim N1-H1A \\sim N3-H3B \\sim N3-H3A \\sim
N4-H4A \\sim N4-H4B
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 Cl1, Cl2, C85, Cl3, Cl4, C86, Cl5, Cl6, C87, Cl7, Cl8, C88, Cl9, Cl10, C89,
 Cl11, Cl12, C90, Cl13, Cl14, C91
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(Cl1)=Sof(Cl2)=Sof(C85)=Sof(H85A)=Sof(H85B)=FVAR(1)
 Sof(Cl3)=Sof(Cl4)=Sof(C86)=Sof(H86A)=Sof(H86B)=FVAR(2)
 Sof(Cl5)=Sof(Cl6)=Sof(C87)=Sof(H87A)=Sof(H87B)=FVAR(3)
 Sof(Cl7)=Sof(Cl8)=Sof(C88)=Sof(H88A)=Sof(H88B)=FVAR(4)
 Sof(Cl9)=Sof(Cl10)=Sof(C89)=Sof(H89A)=Sof(H89B)=FVAR(5)
 Sof(Cl11)=Sof(Cl12)=Sof(C90)=Sof(H90A)=Sof(H90B)=FVAR(6)
 Sof(Cl13)=Sof(Cl14)=Sof(C91)=Sof(H91A)=Sof(H91B)=FVAR(7)
5.a Ternary CH refined with riding coordinates:
 C3(H3), C10(H10), C45(H45), C52(H52)
5.b Secondary CH2 refined with riding coordinates:
 C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,
 H89B), C90(H90A,H90B), C91(H91A,H91B)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
 C40(H40), C41(H41), C42(H42), C48(H48), C49(H49), C50(H50), C54(H54), C55(H55),
  C56(H56), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C66(H66),
 C67(H67), C68(H68), C69(H69), C70(H70), C74(H74), C75(H75), C76(H76), C77(H77),
  C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84)
;
_shelx_res_checksum              93691
_shelx_hkl_checksum              81570
_olex2_date_sample_data_collection 2019-06-14
_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 1.800
_oxdiff_exptl_absorpt_empirical_full_min 0.558