Development of electronically tuneable N-heterocyclic borates.
Huerfano, I. J.; Gorobets, Evgueni; Zhou, Wen; Piers, Warren E.; Van Humbeck, Jeffrey F.; Derksen, Darren J.; Chemical communications (Cambridge, England) 61 (2025) 10610–10613; doi:10.1039/d5cc01578b

data_7134734
_publ_section_title
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 Development of electronically tuneable N-heterocyclic borates.
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_journal_issue                   57
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10610
_journal_page_last               10613
_journal_paper_doi               10.1039/d5cc01578b
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C52 H81 B N4, C51 H81 B2 N4, C H2 Cl2'
_chemical_formula_sum            'C104 H164 B3 Cl2 N8'
_chemical_formula_weight         1629.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-04-29
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
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2025-04-30 deposited with the CCDC.	2025-06-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.244(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.1177(9)
_cell_length_b                   18.5164(13)
_cell_length_c                   20.8008(14)
_cell_measurement_reflns_used    9866
_cell_measurement_temperature    173.15
_cell_measurement_theta_max      72.49
_cell_measurement_theta_min      3.23
_cell_volume                     5270.3(6)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0842
_diffrn_reflns_av_unetI/netI     0.0875
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            59525
_diffrn_reflns_point_group_measured_fraction_full 0.911
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.511
_diffrn_reflns_theta_min         2.386
_diffrn_source_current           0.64
_diffrn_source_power             0.0285824
_diffrn_source_voltage           44.66
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.890
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6243
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1124 before and 0.0831 after correction.
The Ratio of minimum to maximum transmission is 0.8284.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.027
_exptl_crystal_description       Block
_exptl_crystal_F_000             1786
_exptl_crystal_size_max          0.178
_exptl_crystal_size_mid          0.117
_exptl_crystal_size_min          0.046
_refine_diff_density_max         1.239
_refine_diff_density_min         -0.337
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 4151 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.106(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1280
_refine_ls_number_reflns         18637
_refine_ls_number_restraints     420
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1178
_refine_ls_R_factor_gt           0.0907
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2581
_refine_ls_wR_factor_ref         0.2905
_reflns_Friedel_coverage         0.793
_reflns_Friedel_fraction_full    0.822
_reflns_Friedel_fraction_max     0.789
_reflns_number_gt                13385
_reflns_number_total             18637
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01578b2.cif
_cod_data_source_block           20240428hbpyr4_0m_a
_cod_depositor_comments
'Adding full bibliography for 7134731--7134734.cif.'
_cod_original_sg_symbol_H-M      Pc
_cod_database_code               7134734
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.858
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C109-Cl5 = C109-Cl6 = C110-Cl8
 1.75 with sigma of 0.02
 Cl5-Cl6
 3 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl4 \\sim Cl9 \\sim Cl3 \\sim Cl1 \\sim Cl5 \\sim Cl6 \\sim Cl2 \\sim Cl8 \\sim
C109 \\sim C108 \\sim C107 \\sim C110: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C79 \\sim C80 \\sim C81 \\sim C82 \\sim C97 \\sim C98 \\sim C29 \\sim C30 \\sim
C12 \\sim C110 \\sim C111 \\sim C112 \\sim C113: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C65 \\sim C85 \\sim C86 \\sim C114 \\sim C115 \\sim C116: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Cl4) \\sim Ueq, Uanis(Cl9) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl1)
\\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(Cl2) \\sim Ueq,
Uanis(Cl8) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(C107)
\\sim Ueq, Uanis(C110) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C82)
\\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C111)
\\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C113) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C65) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C114)
\\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C116) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=
 Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=1-FVAR(1)
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=
 Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(H97C)=FVAR(1)
 Sof(Cl5)=Sof(C109)=Sof(H10Z)=Sof(H)=Sof(Cl6)=0.5*(1-FVAR(3))
 Sof(Cl4)=Sof(Cl9)=Sof(C108)=Sof(H10V)=Sof(H10W)=0.5*FVAR(3)
 Sof(Cl2)=Sof(C110)=Sof(H11Y)=Sof(HA)=Sof(Cl8)=0.5*(1-FVAR(4))
 Sof(Cl3)=Sof(C107)=Sof(H10X)=Sof(H10Y)=Sof(Cl1)=0.5*FVAR(4)
 Sof(C111)=Sof(H11M)=Sof(H11N)=Sof(H11O)=Sof(C112)=Sof(C113)=Sof(H11V)=
 Sof(H11W)=Sof(H11X)=1-FVAR(4)
 Sof(H11P)=Sof(H11Q)=Sof(H11R)=Sof(H11S)=Sof(H11T)=Sof(H11U)=0.5*(1-FVAR(5))
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(4)
 Sof(H4)=1-FVAR(5)
 Sof(H3)=FVAR(5)
 Sof(H6)=Sof(H7)=0.5*(1-FVAR(7))
 Sof(H5)=Sof(H8)=0.5*FVAR(7)
 Sof(C114)=Sof(C115)=Sof(H11G)=Sof(H11H)=Sof(H11I)=Sof(C116)=Sof(H11J)=
 Sof(H11K)=Sof(H11L)=1-FVAR(7)
 Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(H11D)=Sof(H11E)=Sof(H11F)=0.5*(1-FVAR(8))
 Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H85C)=Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=FVAR(7)
5.a Secondary CH2 refined with riding coordinates:
 C108(H10V,H10W), C107(H10X,H10Y), C109(H10Z,H), C110(H11Y,HA)
5.b Aromatic/amide H refined with riding coordinates:
 N3(H3), N4(H4), N5(H5), N6(H6), N7(H7), N8(H8), C2(H2), C5(H5A), C7(H7A),
 C10(H10), C16(H16), C19(H19), C21(H21), C24(H24), C54(H54), C57(H57), C59(H59),
  C62(H62), C67(H67), C70(H70), C72(H72), C75(H75)
5.c Disordered Me refined with riding coordinates:
 C112(H11P,H11Q,H11R,H11S,H11T,H11U), C114(H11A,H11B,H11C,H11D,H11E,H11F)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C38(H38A,
 H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C64(H64A,H64B,H64C),
 C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C65(H65A,H65B,H65C), C77(H77A,H77B,
 H77C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C88(H88A,H88B,H88C), C90(H90A,
 H90B,H90C), C92(H92A,H92B,H92C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C),
 C96(H96A,H96B,H96C), C81(H81A,H81B,H81C), C79(H79A,H79B,H79C), C97(H97A,H97B,
 H97C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C12(H12A,H12B,H12C), C82(H82A,
 H82B,H82C), C80(H80A,H80B,H80C), C98(H98A,H98B,H98C), C111(H11M,H11N,H11O),
 C113(H11V,H11W,H11X), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C), C101(H10D,
 H10E,H10F), C102(H10G,H10H,H10I), C103(H10J,H10K,H10L), C104(H10M,H10N,H10O),
 C105(H10P,H10Q,H10R), C106(H10S,H10T,H10U), C115(H11G,H11H,H11I), C116(H11J,
 H11K,H11L)
;
_shelx_res_checksum              22952
_shelx_hkl_checksum              72391
_olex2_submission_special_instructions 'No special instructions were received'