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_7708613
_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         'C34 H52 B Cu N2 O3'
_chemical_formula_sum            'C34 H52 B Cu N2 O3'
_chemical_formula_weight         611.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-13
_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                 99.7840(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.13010(10)
_cell_length_b                   17.33930(10)
_cell_length_c                   15.07540(10)
_cell_measurement_reflns_used    17482
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.8990
_cell_measurement_theta_min      2.9630
_cell_volume                     3382.25(4)
_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_temperature      150.00(10)
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0172
_diffrn_reflns_av_unetI/netI     0.0139
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25199
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.038
_diffrn_reflns_theta_min         3.918
_exptl_absorpt_coefficient_mu    1.166
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78017
_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    1.200
_exptl_crystal_description       block
_exptl_crystal_F_000             1312
_exptl_crystal_size_max          0.348
_exptl_crystal_size_mid          0.253
_exptl_crystal_size_min          0.209
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.532
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     463
_refine_ls_number_reflns         6726
_refine_ls_number_restraints     155
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0372
_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^)+(0.0507P)^2^+1.8088P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.0993
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6429
_reflns_number_total             6726
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03540a2.cif
_cod_data_source_block           s20djl01-cpd2
_cod_database_code               7708613
_shelxl_version_number           2014-3
_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
 C24A-C23A \\sim C24-C23 \\sim C25A-C23A \\sim C25-C23
 with sigma of 0.005
 C23A-C18 \\sim C23-C18
 with sigma of 0.005
 C31A-C29 \\sim C31-C29 \\sim C32A-C29 \\sim C32-C29 \\sim C34-C30 \\sim
C34A-C30 \\sim C33A-C30 \\sim C33-
 C30
 with sigma of 0.005
 C33-C34 \\sim C33A-C34A \\sim C31-C32 \\sim C31A-C32A
 with sigma of 0.01
 O2-B1 \\sim O2A-B1 \\sim O3A-B1 \\sim O3-B1
 with sigma of 0.005
 O2-C29 \\sim O2A-C29 \\sim O3A-C30 \\sim O3-C30
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C23 \\sim C24 \\sim C25 \\sim C23A \\sim C24A \\sim C25A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.01
O2 \\sim O2A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
C33 \\sim C34 \\sim C33A \\sim C34A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.01
O3 \\sim O3A: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
C31 \\sim C32 \\sim C31A \\sim C32A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.01
Uanis(C23A) = Uanis(C23)
4. Others
 Fixed Sof: O2(0.75) O3(0.75) C23(0.75) H23(0.75) C24(0.75) H24A(0.75)
 H24B(0.75) H24C(0.75) C25(0.75) H25A(0.75) H25B(0.75) H25C(0.75) C31(0.75)
 H31A(0.75) H31B(0.75) H31C(0.75) C32(0.75) H32A(0.75) H32B(0.75) H32C(0.75)
 C33(0.75) H33A(0.75) H33B(0.75) H33C(0.75) C34(0.75) H34A(0.75) H34B(0.75)
 H34C(0.75) O2A(0.25) O3A(0.25) C23A(0.25) H23A(0.25) C24A(0.25) H24D(0.25)
 H24E(0.25) H24F(0.25) C25A(0.25) H25D(0.25) H25E(0.25) H25F(0.25) C31A(0.25)
 H31D(0.25) H31E(0.25) H31F(0.25) C32A(0.25) H32D(0.25) H32E(0.25) H32F(0.25)
 C33A(0.25) H33D(0.25) H33E(0.25) H33F(0.25) C34A(0.25) H34D(0.25) H34E(0.25)
 H34F(0.25)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C26(H26), C23(H23), C23A(H23A)
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:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21)
5.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F), C31A(H31D,
 H31E,H31F), C32A(H32D,H32E,H32F), C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F)
;