Synthesis and stereochemistry of chiral aza-boraspirobifluorenes with tetrahedral boron-stereogenic centers
Yoshigoe, Yusuke; Hashizume, Keiichiro; Saito, Shinichi; Dalton Transactions  (2022) –; doi:10.1039/D2DT03303H

data_7711607
_publ_section_title
;
 Synthesis and stereochemistry of chiral aza-boraspirobifluorenes with
 tetrahedral boron-stereogenic centers
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT03303H
_journal_year                    2022
_chemical_formula_moiety
'C6.639 H5.161 B0.268 N0.268 O0.268, 1.728(C25 H20 B N O), 0.12(O1)'
_chemical_formula_sum            'C49.85 H39.53 B2 N2 O2.03'
_chemical_formula_weight         720.65
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-08-23 deposited with the CCDC.	2022-10-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.703(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.1041(15)
_cell_length_b                   8.6562(9)
_cell_length_c                   36.508(4)
_cell_measurement_reflns_used    5735
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      25.831
_cell_measurement_theta_min      2.234
_cell_volume                     3820.9(7)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      273.15
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0764
_diffrn_reflns_av_unetI/netI     0.0703
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            40071
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         1.977
_diffrn_source                   'sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.075
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.6607
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1167 before and 0.0768 after correction.
The Ratio of minimum to maximum transmission is 0.8854.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             1515
_exptl_crystal_preparation       diffusion
_exptl_crystal_recrystallization_method diffusion
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.240
_refine_diff_density_min         -0.221
_refine_diff_density_rms         0.057
_refine_ls_extinction_coef       0.0042(7)
_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   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     925
_refine_ls_number_reflns         6976
_refine_ls_number_restraints     474
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0723
_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^)+(0.0515P)^2^+5.1634P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1812
_refine_ls_wR_factor_ref         0.1943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5249
_reflns_number_total             6976
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03303h2.cif
_cod_data_source_block           220623_ysg_hashizume_01_0m_a
_cod_original_cell_volume        3820.8(8)
_cod_database_code               7711607
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.998
_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
 C1-O2
 1.377 with sigma of 0.02
 C75-C2
 1.508 with sigma of 0.02
 C25-C24
 1.508 with sigma of 0.02
 C78-C77
 1.474 with sigma of 0.01
 C56-C47
 1.474 with sigma of 0.01
3. Rigid bond restraints
 C75, C2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O2, C1, C3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C75) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C14) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C2, C75
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C75, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C70, C62, N15, C98, B14
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 B15, N54, C81, C41, C43
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O2, C3, C1
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N6, C3, C4, C8, C5, C7
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C27, C22, C28, C23, C26, C24
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C16, C21, C17, C20, C18, C19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C9, C14, C10, C13, C11, C12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N36, C37, C40, C39, C38, C35
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C30, C33, C29, C31, C34, C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C69, C70, C71, C73, C72, C74
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C64, C68, C67, C65, C66, N15
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C25, C24
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C62, C57, C61, C58, C60, C59
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C2, C99, C6, C98, C88, C15
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1, O2, C3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(C5)=Sof(H5)=Sof(C4)=Sof(H4)=Sof(C3)=Sof(C8)=Sof(H8)=Sof(C7)=Sof(N6)=
 Sof(C14)=Sof(C9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=
 Sof(C13)=Sof(H13)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C22)=Sof(C27)=
 Sof(C28)=Sof(H28)=Sof(C26)=Sof(H26)=Sof(C24)=Sof(C23)=Sof(H23)=Sof(C21)=
 Sof(C20)=Sof(H20)=Sof(C19)=Sof(H19)=Sof(C18)=Sof(H18)=Sof(C17)=Sof(H17)=
 Sof(C16)=1-FVAR(1)
 Sof(O55)=Sof(N54)=Sof(C92)=Sof(C93)=Sof(C86)=Sof(H86)=Sof(C84)=Sof(H84)=
 Sof(C83)=Sof(H83)=Sof(C85)=Sof(H85)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C81)=Sof(C41)=Sof(C79)=Sof(H79)=Sof(C43)=Sof(C36)=Sof(C82)=Sof(C78)=
 Sof(C94)=Sof(H94)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C95)=Sof(C87)=
 Sof(H87)=Sof(C97)=Sof(H97)=Sof(C63)=Sof(H63)=Sof(C91)=Sof(H91)=Sof(C80)=
 Sof(H80)=Sof(C89)=Sof(H89)=Sof(C96)=Sof(H96)=Sof(C90)=Sof(H90)=FVAR(1)
 Sof(C69)=Sof(C70)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=
 Sof(C74)=Sof(H74)=Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(C57)=
 Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=
 Sof(O27)=Sof(N15)=Sof(C68)=Sof(C67)=Sof(H67)=Sof(C66)=Sof(C65)=Sof(H65)=
 Sof(C64)=Sof(H64)=Sof(C98)=Sof(C88)=Sof(H88)=Sof(C15)=Sof(H15)=Sof(C2)=
 Sof(C99)=Sof(H99)=Sof(C6)=Sof(B14)=1-FVAR(2)
 Sof(O41)=Sof(N36)=Sof(C30)=Sof(C37)=Sof(H37)=Sof(C53)=Sof(H53)=Sof(C54)=
 Sof(H54)=Sof(C47)=Sof(C44)=Sof(C49)=Sof(B43)=Sof(C50)=Sof(C40)=Sof(H40)=
 Sof(C51)=Sof(C39)=Sof(C33)=Sof(H33)=Sof(C38)=Sof(H38)=Sof(C29)=Sof(H29)=
 Sof(C46)=Sof(H46)=Sof(C31)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C35)=Sof(C45)=Sof(H45)=Sof(C52)=Sof(H52)=
 Sof(C55)=Sof(H55)=Sof(C48)=Sof(H48)=Sof(C34)=Sof(H34)=Sof(C32)=Sof(H32)=FVAR(2)
 Fixed Sof: C75(0.2) H75A(0.2) H75B(0.2) H75C(0.2) O2(0.18) C1(0.18) H1A(0.18)
 H1B(0.18) H1C(0.18)
7.a Aromatic/amide H refined with riding coordinates:
 C71(H71), C72(H72), C73(H73), C74(H74), C37(H37), C53(H53), C54(H54),
 C60(H60), C61(H61), C58(H58), C59(H59), C67(H67), C65(H65), C64(H64), C88(H88),
  C15(H15), C99(H99), C40(H40), C33(H33), C38(H38), C29(H29), C46(H46),
 C45(H45), C52(H52), C55(H55), C48(H48), C34(H34), C32(H32), C86(H86), C84(H84),
  C83(H83), C85(H85), C79(H79), C5(H5), C4(H4), C8(H8), C94(H94), C10(H10),
 C11(H11), C12(H12), C13(H13), C87(H87), C97(H97), C63(H63), C28(H28), C26(H26),
  C23(H23), C91(H91), C20(H20), C19(H19), C18(H18), C17(H17), C80(H80),
 C89(H89), C96(H96), C90(H90)
7.b Fitted hexagon refined as free rotating group:
 C69(C70,C71,C72,C73,C74), C60(C61,C62,C57,C58,C59), N15(C68,C67,C66,C65,C64),
 C98(C88,C15,C2,C99,C6), C5(C4,C3,C8,C7,N6), C14(C9,C10,C11,C12,C13), C22(C27,
 C28,C26,C24,C23), C21(C20,C19,C18,C17,C16)
7.c Idealised Me refined as rotating group:
 C76(H76A,H76B,H76C), C75(H75A,H75B,H75C), C56(H56A,H56B,H56C), C42(H42A,H42B,
 H42C), C100(H10A,H10B,H10C), C1(H1A,H1B,H1C), C77(H77A,H77B,H77C), C25(H25A,
 H25B,H25C)
;
_shelx_res_checksum              76088
_olex2_exptl_crystal_mounting_method cryoroop
_olex2_submission_special_instructions 'No special instructions were received'