BNN-1,3-dipoles: isolation and intramolecular cycloaddition with unactivated arenes
Guo, Rui; Jiang, Jingxing; Hu, Chenyang; Liu, Liu Leo; Cui, Ping; Zhao, Meihua; Ke, Zhuofeng; Tung, Chen-Ho; Kong, Lingbing; Chemical Science  (2020) –; doi:10.1039/D0SC02162H

data_1558373
_publ_section_title
;
 BNN-1,3-dipoles: isolation and intramolecular cycloaddition with
 unactivated arenes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02162H
_journal_year                    2020
_chemical_formula_moiety         'C47 H78 B2 N4, 1.5(C7 H8)'
_chemical_formula_sum            'C57.5 H90 B2 N4'
_chemical_formula_weight         858.95
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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             2020-05-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-25 deposited with the CCDC.	2020-06-19 downloaded from the CCDC.
;
_cell_angle_alpha                102.637(2)
_cell_angle_beta                 99.834(2)
_cell_angle_gamma                105.896(3)
_cell_formula_units_Z            2
_cell_length_a                   11.7577(4)
_cell_length_b                   13.9324(4)
_cell_length_c                   18.6526(5)
_cell_measurement_reflns_used    10907
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.0120
_cell_measurement_theta_min      3.3950
_cell_volume                     2779.50(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_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     35.00  66.00   1.00    5.00    --  106.49 -57.00  30.00   31
  2  \w     43.00 106.00   1.00    5.00    --  106.49 -99.00 -30.00   63
  3  \w     50.00 106.00   1.00    5.00    --  106.49 -99.00-120.00   56
  4  \w     80.00 109.00   1.00    5.00    --  106.49-125.00-180.00   29
  5  \w     73.00 104.00   1.00    5.00    --  106.49-102.00-146.00   31
  6  \w     35.00 103.00   1.00    5.00    --  106.49 -99.00-180.00   68
  7  \w     38.00  77.00   1.00    5.00    --  106.49-125.00-180.00   39
  8  \w     14.00  56.00   1.00    0.50    --   48.45-102.00-146.00   42
  9  \w    -24.00  23.00   1.00    0.50    --   48.45 -19.00 -60.00   47
 10  \w     93.00 139.00   1.00    5.00    --  106.49  38.00-120.00   46
 11  \w    141.00 176.00   1.00    5.00    --  106.49  38.00-120.00   35
 12  \w    106.00 168.00   1.00    5.00    --  106.49 102.00 -43.00   62
 13  \w     94.00 178.00   1.00    5.00    --  106.49  38.00  30.00   84
 14  \w     97.00 171.00   1.00    5.00    --  106.49  19.00 -30.00   74
 15  \w     96.00 178.00   1.00    5.00    --  106.49  19.00 -60.00   82
 16  \w     34.00 103.00   1.00    5.00    --  106.49 -99.00 120.00   69
 17  \w     34.00 106.00   1.00    5.00    --  106.49 -99.00  30.00   72
 18  \w     40.00 103.00   1.00    5.00    --  106.49 -77.00  30.00   63
 19  \w    -43.00  25.00   1.00    0.50    --  -48.45  38.00-120.00   68
 20  \w    -66.00 -14.00   1.00    5.00    --  -86.25  57.00 -60.00   52
 21  \w    -79.00   8.00   1.00    0.50    --  -48.45 102.00 -43.00   87
 22  \w   -117.00 -74.00   1.00    0.50    --  -48.45-125.00  30.00   43
 23  \w   -119.00 -35.00   1.00    0.50    --  -48.45 -77.00 120.00   84
 24  \w    -43.00 -15.00   1.00    5.00    --  -86.25  38.00 150.00   28
 25  \w    -42.00 -16.00   1.00    5.00    --  -86.25  38.00 120.00   26
 26  \w    -81.00 -33.00   1.00    5.00    --  -86.25 102.00 -43.00   48
 27  \w   -138.00 -85.00   1.00    5.00    --  -86.25-102.00-146.00   53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1302567000
_diffrn_orient_matrix_UB_12      0.0701727000
_diffrn_orient_matrix_UB_13      0.0070595000
_diffrn_orient_matrix_UB_21      0.0095847000
_diffrn_orient_matrix_UB_22      0.0535145000
_diffrn_orient_matrix_UB_23      0.0833643000
_diffrn_orient_matrix_UB_31      0.0519161000
_diffrn_orient_matrix_UB_32      -0.0809728000
_diffrn_orient_matrix_UB_33      0.0250170000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0543
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26375
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        66.595
_diffrn_reflns_theta_max         66.595
_diffrn_reflns_theta_min         2.504
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.432
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96091
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.026
_exptl_crystal_description       block
_exptl_crystal_F_000             946
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     706
_refine_ls_number_reflns         9658
_refine_ls_number_restraints     475
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0845
_refine_ls_R_factor_gt           0.0595
_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^)+(0.0421P)^2^+1.7653P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1426
_refine_ls_wR_factor_ref         0.1519
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7728
_reflns_number_total             9658
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02162h2.cif
_cod_data_source_block           klb-6
_cod_original_cell_volume        2779.50(15)
_cod_original_formula_sum        'C57.50 H90 B2 N4'
_cod_database_code               1558373
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         CBN
_shelx_estimated_absorpt_t_max   0.881
_shelx_estimated_absorpt_t_min   0.813
_diffrn_oxdiff_digest_frames
;
013c0db2bc851586cca7c1b59c25d34f62000266b7e
;
_diffrn_oxdiff_digest_hkl
;
0180f37593be9cfd47ff2d316b20c2ad4b1483
;
_reflns_odcompleteness_completeness 98.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C60-C61
 1.53 with sigma of 0.02
 C49A-C48A \\sim C48A-C53A \\sim C52B-C53A \\sim C51A-C52B \\sim C51A-C50A
\\sim C50A-C49A
 with sigma of 0.02
 C23-C21 \\sim C24B-C21 \\sim C24A-C21 \\sim C22-C21
 with sigma of 0.02
 C60-C59 \\sim C55-C56 \\sim C57-C58
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C24A \\sim C24B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C48A \\sim C48B \\sim C49A \\sim C49B \\sim C50A \\sim C50B \\sim C51A \\sim
C51B \\sim C52A \\sim C52B \\sim C53A \\sim C53B \\sim C54A \\sim C54B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24B) \\sim Ueq, Uanis(C24A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C51B) \\sim Ueq, Uanis(C48A) \\sim Ueq, Uanis(C49A) \\sim Ueq,
Uanis(C53A) \\sim Ueq, Uanis(C50A) \\sim Ueq, Uanis(C52B) \\sim Ueq,
Uanis(C54A) \\sim Ueq, Uanis(C53B) \\sim Ueq, Uanis(C48B) \\sim Ueq,
Uanis(C50B) \\sim Ueq, Uanis(C49B) \\sim Ueq, Uanis(C51A) \\sim Ueq,
Uanis(C54B) \\sim Ueq, Uanis(C52A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C57) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C61) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C55, C56, C57, C58, C59, C60
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C24B)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=
 Sof(H51A)=Sof(C52B)=Sof(H52B)=Sof(C53A)=Sof(C54A)=Sof(H54A)=Sof(H54B)=
 Sof(H54C)=1-FVAR(2)
 Sof(C48B)=Sof(H48B)=Sof(C49B)=Sof(H49B)=Sof(C50B)=Sof(H50B)=Sof(C51B)=
 Sof(H51B)=Sof(C52A)=Sof(H52A)=Sof(C53B)=Sof(C54B)=Sof(H54D)=Sof(H54E)=
 Sof(H54F)=FVAR(2)
 Fixed Sof: C55(0.5) H55(0.5) C56(0.5) H56(0.5) C57(0.5) H57(0.5) C58(0.5)
 H58(0.5) C59(0.5) H59(0.5) C60(0.5) C61(0.5) H61A(0.5) H61B(0.5) H61C(0.5)
6.a Ternary CH refined with riding coordinates:
 C40(H40), C43(H43)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C11(H11), C48A(H48A), C48B(H48B), C49A(H49A),
 C49B(H49B), C50A(H50A), C50B(H50B), C51A(H51A), C51B(H51B), C52A(H52A),
 C52B(H52B), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F), C26(H26A,H26B,H26C),
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C54A(H54A,H54B,
 H54C), C54B(H54D,H54E,H54F), C61(H61A,H61B,H61C)
;
_shelx_res_checksum              77898
_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 1.335
_oxdiff_exptl_absorpt_empirical_full_min 0.444