A Stable Ring-Expanded NHC-Supported Copper Boryl and its Reactivity towards Heterocumulenes
Horsley Downie, Thomas Mardale; Charman, Rex S. C.; Hall, Jonathan W.; Mahon, Mary F.; Lowe, John P.; Liptrot, David Jonathan; Dalton Transactions  (2021) –; doi:10.1039/D1DT03540A

data_7708614
_publ_section_title
;
 A Stable Ring-Expanded NHC-Supported Copper Boryl and its Reactivity
 towards Heterocumulenes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT03540A
_journal_year                    2021
_chemical_formula_moiety         'C46 H66 B Cu N4 O3'
_chemical_formula_sum            'C46 H66 B Cu N4 O3'
_chemical_formula_weight         797.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-10-19 deposited with the CCDC.	2021-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.4325(2)
_cell_length_b                   21.3202(4)
_cell_length_c                   25.9216(5)
_cell_measurement_reflns_used    12777
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      28.6360
_cell_measurement_theta_min      3.1140
_cell_volume                     9081.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1468
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0621
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            78752
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.130
_diffrn_reflns_theta_min         2.935
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.523
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87044
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.166
_exptl_crystal_description       block
_exptl_crystal_F_000             3424
_exptl_crystal_size_max          0.401
_exptl_crystal_size_mid          0.282
_exptl_crystal_size_min          0.162
_refine_diff_density_max         0.719
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     623
_refine_ls_number_reflns         11957
_refine_ls_number_restraints     293
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0996
_refine_ls_R_factor_gt           0.0512
_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^)+(0.0389P)^2^+7.7073P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1032
_refine_ls_wR_factor_ref         0.1241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7591
_reflns_number_total             11957
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03540a2.cif
_cod_data_source_block           e20djl04-cpd5
_cod_database_code               7708614
_shelxl_version_number           2014-3
_chemical_oxdiff_usercomment     'pale yellow blocks'
_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
 N1-C5 \\sim N1-C5A
 with sigma of 0.005
 C6-C5 \\sim C7-C6 \\sim C8-C7 \\sim C9-C8 \\sim C9-C10 \\sim C5-C10 \\sim
C6A-C5A \\sim C7A-C6A \\sim C8A-C7A
 \\sim C9A-C8A \\sim C9A-C10A \\sim C5A-C10A
 with sigma of 0.005
 C6-C11 \\sim C6A-C11A \\sim C14A-C10A \\sim C14-C10
 with sigma of 0.005
 C13-C11 \\sim C13A-C11A \\sim C12A-C11A \\sim C12-C11 \\sim C16A-C14A \\sim
C16-C14 \\sim C15A-C14A ~
 C15-C14
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C10A \\sim C10 \\sim C9A \\sim C9 \\sim C8A \\sim C8 \\sim C7A \\sim C6A \\sim
C5A \\sim C5 \\sim C6: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.01
C14A \\sim C14 \\sim C11A \\sim C11: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.01
C15A \\sim C15 \\sim C16A \\sim C16 \\sim C13A \\sim C13 \\sim C12 \\sim C12A:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: C5(0.63) C6(0.63) C7(0.63) H7(0.63) C8(0.63) H8(0.63) C9(0.63)
 H9(0.63) C10(0.63) C11(0.63) H11(0.63) C12(0.63) H12A(0.63) H12B(0.63)
 H12C(0.63) C13(0.63) H13A(0.63) H13B(0.63) H13C(0.63) C14(0.63) H14(0.63)
 C15(0.63) H15A(0.63) H15B(0.63) H15C(0.63) C16(0.63) H16A(0.63) H16B(0.63)
 H16C(0.63) C5A(0.37) C6A(0.37) C7A(0.37) H7A(0.37) C8A(0.37) H8A(0.37)
 C9A(0.37) H9A(0.37) C10A(0.37) C11A(0.37) H11A(0.37) C12A(0.37) H12D(0.37)
 H12E(0.37) H12F(0.37) C13A(0.37) H13D(0.37) H13E(0.37) H13F(0.37) C14A(0.37)
 H14A(0.37) C15A(0.37) H15D(0.37) H15E(0.37) H15F(0.37) C16A(0.37) H16D(0.37)
 H16E(0.37) H16F(0.37)
5.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C11(H11), C14(H14), C11A(H11A), C14A(H14A)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
5.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C7(H7), C8(H8), C9(H9), C7A(H7A), C8A(H8A), C9A(H9A)
5.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C12A(H12D,H12E,H12F), C13A(H13D,H13E,H13F), C15A(H15D,H15E,H15F),
 C16A(H16D,H16E,H16F)
;