Synthesis and Isolation of Dinuclear N,C-Chelate Organoboron Compounds Bridged by Neutral, Anionic, and Dianionic 4,4’-Bipyridine via Reductive Coupling of Pyridines
Li, Hai-Jun; Feng, Rui; Shi, Xianghui; Wei, Junnian; Xi, Zhenfeng; Dalton Transactions  (2022) –; doi:10.1039/D2DT02650C

data_7711331
_publ_section_title
;
 Synthesis and Isolation of Dinuclear N,C-Chelate Organoboron Compounds
 Bridged by Neutral, Anionic, and Dianionic 4,4&#x2019;-Bipyridine via
 Reductive Coupling of Pyridines
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02650C
_journal_year                    2022
_chemical_formula_moiety         '2(C20 H40 K O8), C58 H58 B2 N2, 2(C4 H8 O1)'
_chemical_formula_sum            'C106 H154 B2 K2 N2 O18'
_chemical_formula_weight         1844.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-02-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-06-22 deposited with the CCDC.	2022-09-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.889(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.8072(17)
_cell_length_b                   12.8637(7)
_cell_length_c                   26.0895(14)
_cell_measurement_reflns_used    8757
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      20.0350
_cell_measurement_theta_min      2.4090
_cell_volume                     10516.1(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -69.00  24.00   0.50   24.44    --   -5.70 -37.00   0.00  186
  2  \w    -32.00  82.00   0.50   24.44    --   -5.70  19.00-150.00  228
  3  \w    -30.00  32.00   0.50   24.44    --    5.70  77.00 150.00  124
  4  \w    -20.00  12.00   0.50   24.44    --    5.70  57.00  30.00   64
  5  \w     49.00  75.00   0.50   24.44    --    5.70  57.00  30.00   52
  6  \w    -62.00  35.00   0.50   24.44    --    5.70 -37.00 -60.00  194
  7  \w      2.00  91.00   0.50   24.44    --    5.70  57.00-120.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0207829000
_diffrn_orient_matrix_UB_12      -0.0119300000
_diffrn_orient_matrix_UB_13      -0.0046669000
_diffrn_orient_matrix_UB_21      0.0086603000
_diffrn_orient_matrix_UB_22      0.0384171000
_diffrn_orient_matrix_UB_23      0.0183186000
_diffrn_orient_matrix_UB_31      0.0022577000
_diffrn_orient_matrix_UB_32      -0.0376830000
_diffrn_orient_matrix_UB_33      0.0201246000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0962
_diffrn_reflns_av_unetI/netI     0.0539
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            77775
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.255
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.154
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70359
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.165
_exptl_crystal_description       needle
_exptl_crystal_F_000             3984
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.509
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     838
_refine_ls_number_reflns         9220
_refine_ls_number_restraints     829
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.1535
_refine_ls_R_factor_gt           0.0999
_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^)+(0.1499P)^2^+12.1029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2527
_refine_ls_wR_factor_ref         0.2909
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5580
_reflns_number_total             9220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02650c2.cif
_cod_data_source_block           exp_6335
_cod_database_code               7711331
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N B K'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.968
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. 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
2. Restrained distances
 O13-C60 = O13-C61 = O14-C62 = O14-C63 = O15-C64 = O15-C65 = O10-C66 = O10-C55
 = O11-C56 = O12-C59
 1.46 with sigma of 0.01
 C61-C62 = C60-C59 = C56-C55 = C66-C65
 1.51 with sigma of 0.01
 C64-C63
 1.51 with sigma of 0.01
 C58-C57
 1.54 with sigma of 0.01
 O12-C58 = O11-C57
 1.46 with sigma of 0.01
 O7-C70 = O7-C67 = C68-C67 = C68-C69
 1.54 with sigma of 0.01
 C69-C70
 1.54 with sigma of 0.01
 O9-C47 = C48-C47 = C49-C48 = C49-C50 = O9-C50
 1.54 with sigma of 0.01
 O16-C71 = O9-C47 = C48-C47 = C72-C71 = C73-C72 = C49-C48 = C49-C50 = C73-C74 =
  O16-C74 = O9-C50
 1.46 with sigma of 0.01
 C66-O15
 2.5 with sigma of 0.04
 C65-O10
 2.5 with sigma of 0.04
 C55-C66
 2.5 with sigma of 0.04
 O10-C56
 2.5 with sigma of 0.04
 C55-O11
 2.5 with sigma of 0.04
 O12-C60
 2.5 with sigma of 0.04
 C59-O13
 2.5 with sigma of 0.04
 O11-C58
 2.5 with sigma of 0.04
 O12-C57
 2.5 with sigma of 0.04
 C56-C57
 2.5 with sigma of 0.04
 C58-C59
 2.5 with sigma of 0.04
 O7-C68
 2.5 with sigma of 0.02
 C70-C67
 2.5 with sigma of 0.02
 C69-O7
 2.5 with sigma of 0.02
 C70-C68
 2.5 with sigma of 0.02
 C67-C69
 2.5 with sigma of 0.02
 O9-C49
 2.5 with sigma of 0.02
 C50-C48
 2.5 with sigma of 0.02
 C49-C47
 2.5 with sigma of 0.02
 C48-O9
 2.5 with sigma of 0.02
 C47-C50
 2.5 with sigma of 0.02
3. Rigid bond restraints
 K1, O5, O7, O6, O1, O4, O3, O2, O8, C40, C38, C36, C34, C32, C37, C41, C42,
 C35, C51, C31, C54, C30, C53, C44, C52, C43, C45, C39, C46, C67, C68, C70, C69,
  O14, O15, O13, O11, O10, O12, C56, C55, C62, C63, C64, C61, C59, C66, C60,
 C65, C58, C57
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O9, C47, C48, C49, C50
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C48 \\sim C50 \\sim C49 \\sim C47 \\sim O9 \\sim C71 \\sim C72 \\sim C73 \\sim
C74 \\sim O16: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(K1) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(O6) \\sim
Ueq, Uanis(O1) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O2)
\\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C51) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C52) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C70) \\sim Ueq,
Uanis(C69) \\sim Ueq, Uanis(O14) \\sim Ueq, Uanis(O15) \\sim Ueq, Uanis(O13)
\\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(O12) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C59) \\sim Ueq,
Uanis(C66) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C57) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
Uanis(C59) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C57) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C50) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
Uanis(C48) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq,
Uanis(C73) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(O16) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C48, C50, C49, C47, O9, C71, C72, C73, C74, O16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(C70)=Sof(H70A)=
 Sof(H70B)=Sof(C69)=Sof(H69A)=Sof(H69B)=1-FVAR(1)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C45)=Sof(H45A)=
 Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=FVAR(1)
 Sof(O14)=Sof(O15)=Sof(O13)=Sof(O11)=Sof(O10)=Sof(O12)=Sof(C56)=Sof(H56A)=
 Sof(H56B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=
 Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(C61)=Sof(H61A)=Sof(H61B)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(C60)=Sof(H60A)=
 Sof(H60B)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C57)=
 Sof(H57A)=Sof(H57B)=1-FVAR(2)
 Sof(O5)=Sof(O6)=Sof(O1)=Sof(O4)=Sof(O3)=Sof(O2)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C41)=
 Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C35)=Sof(H35A)=Sof(H35B)=
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=FVAR(2)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(O16)=1-FVAR(3)
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C49)=Sof(H49A)=
 Sof(H49B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(O9)=FVAR(3)
7.a Secondary CH2 refined with riding coordinates:
 C40(H40A,H40B), C38(H38A,H38B), C36(H36A,H36B), C34(H34A,H34B), C32(H32A,
 H32B), C37(H37A,H37B), C41(H41A,H41B), C42(H42A,H42B), C35(H35A,H35B),
 C51(H51A,H51B), C31(H31A,H31B), C54(H54A,H54B), C30(H30A,H30B), C53(H53A,H53B),
  C44(H44A,H44B), C52(H52A,H52B), C43(H43A,H43B), C45(H45A,H45B), C39(H39A,
 H39B), C46(H46A,H46B), C67(H67A,H67B), C68(H68A,H68B), C70(H70A,H70B),
 C69(H69A,H69B), C56(H56A,H56B), C55(H55A,H55B), C62(H62A,H62B), C63(H63A,H63B),
  C64(H64A,H64B), C61(H61A,H61B), C59(H59A,H59B), C66(H66A,H66B), C60(H60A,
 H60B), C65(H65A,H65B), C58(H58A,H58B), C57(H57A,H57B), C48(H48A,H48B),
 C50(H50A,H50B), C49(H49A,H49B), C47(H47A,H47B), C71(H71A,H71B), C72(H72A,H72B),
  C73(H73A,H73B), C74(H74A,H74B)
7.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C14(H14), C9(H9), C16(H16), C8(H8), C7(H7), C1(H1), C25(H25),
 C4(H4), C23(H23), C2(H2)
7.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C27(H27A,H27B,H27C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              83289
_shelx_hkl_checksum              12979
_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 1.365
_oxdiff_exptl_absorpt_empirical_full_min 0.641