Filling the gap with a bulky diaryl boron group: fluorinated and non-fluorinated copper pyrazolates fitted with a dimesityl boron moiety on the backbone
Vanga, Mukundam; Diroll, Benjamin T.; Muñoz-Castro, Alvaro; Dias, Rasika; Dalton Transactions  (2023) –; doi:10.1039/D3DT03167E

data_7714134
_publ_section_title
;
 Filling the gap with a bulky diaryl boron group: fluorinated and
 non-fluorinated copper pyrazolates fitted with a dimesityl boron moiety
 on the backbone
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT03167E
_journal_year                    2023
_chemical_formula_moiety         'C69 H66 B3 Cu3 F18 N6, 1.5(C7 H16)'
_chemical_formula_sum            'C79.5 H90 B3 Cu3 F18 N6'
_chemical_formula_weight         1694.62
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-08-09 deposited with the CCDC.	2023-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                72.604(2)
_cell_angle_beta                 69.820(2)
_cell_angle_gamma                60.055(2)
_cell_formula_units_Z            2
_cell_length_a                   16.9215(7)
_cell_length_b                   16.9436(7)
_cell_length_c                   17.6659(8)
_cell_measurement_reflns_used    9802
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      30.47
_cell_measurement_theta_min      2.41
_cell_volume                     4069.1(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Photon II 7 CPAD'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest Photon II 7'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    '0.6 mm double-pinhole'
_diffrn_radiation_detector       'Photon II 7 CPAD'
_diffrn_radiation_monochromator  'curved graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0269
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            68277
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.532
_diffrn_reflns_theta_min         2.559
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'KFF MO-2KC-90'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.864
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6784
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0458 before and 0.0384 after correction.
The Ratio of minimum to maximum transmission is 0.9093.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plates
_exptl_crystal_F_000             1746
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.866
_refine_diff_density_min         -0.715
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1134
_refine_ls_number_reflns         24572
_refine_ls_number_restraints     441
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0617
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0470P)^2^+3.8326P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1014
_refine_ls_wR_factor_ref         0.1093
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19360
_reflns_number_total             24572
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03167e2.cif
_cod_data_source_block           hrd85_0m_a
_cod_original_formula_sum        'C79.50 H90 B3 Cu3 F18 N6'
_cod_database_code               7714134
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.846
_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
 C83-C82 = C82-C81 = C81-C80 = C80-C79 = C79-C78 = C78-C77
 1.52 with sigma of 0.02
 C1A-C1B = C1B-C1C = C1C-C1D = C1D-C1E = C1E-C1F = C1F-C1G
 1.52 with sigma of 0.02
 C1H-C1I = C1I-C1J = C1J-C1K = C1K-C1L = C1L-C1M = C1M-C1N
 1.52 with sigma of 0.02
 C83-C81
 2.53 with sigma of 0.04
 C82-C80 = C80-C78
 2.55 with sigma of 0.04
 C81-C79 = C79-C77
 2.54 with sigma of 0.04
 C1A-C1C
 2.53 with sigma of 0.04
 C1B-C1D = C1D-C1F
 2.55 with sigma of 0.04
 C1C-C1E = C1E-C1G
 2.54 with sigma of 0.04
 C1H-C1J
 2.53 with sigma of 0.04
 C1I-C1K = C1K-C1M
 2.55 with sigma of 0.04
 C1J-C1L = C1L-C1N
 2.54 with sigma of 0.04
 C83-C82 \\sim C82-C81 \\sim C81-C80 \\sim C80-C79 \\sim C79-C78 \\sim C78-C77
 with sigma of 0.02
 C83-C81 \\sim C81-C79 \\sim C82-C80 \\sim C80-C78 \\sim C79-C77
 with sigma of 0.02
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F \\sim C1F-C1G
 with sigma of 0.02
 C1A-C1C \\sim C1C-C1E \\sim C1B-C1D \\sim C1D-C1F \\sim C1E-C1G
 with sigma of 0.02
 C1H-C1I \\sim C1I-C1J \\sim C1J-C1K \\sim C1K-C1L \\sim C1L-C1M \\sim C1M-C1N
 with sigma of 0.02
 C1H-C1J \\sim C1J-C1L \\sim C1I-C1K \\sim C1K-C1M \\sim C1L-C1N
 with sigma of 0.02
 F16-C51 \\sim F16A-C51
 with sigma of 0.02
 F17-C51 \\sim F17A-C51
 with sigma of 0.02
 F18-C51 \\sim F18A-C51
 with sigma of 0.02
 F16A-F18A \\sim F16A-F17A \\sim F18A-F17A \\sim F16-F17 \\sim F16-F18 \\sim
F17-F18
 with sigma of 0.04
 C51-F16A \\sim C51-F18A \\sim C51-F17A \\sim C51-F16 \\sim C51-F17 \\sim
C51-F18
 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F \\sim C1G: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C1H \\sim C1I \\sim C1J \\sim C1K \\sim C1L \\sim C1M \\sim C1N: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
F16A \\sim F16 \\sim F18A \\sim F18 \\sim F17A \\sim F17: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.005 within 2A
4. Rigid body (RIGU) restrains
 C77, C78, C79, C80, C81, C82, C83
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C1B, C1C, C1D, C1E, C1F, C1G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1H, C1I, C1J, C1K, C1L, C1M, C1N
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C49, C51, F18, F17, F16
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 F16A, F17A, F18A, C49, C51
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(C1H)=Sof(H1HA)=Sof(H1HB)=Sof(H1HC)=Sof(C1I)=Sof(H1IA)=Sof(H1IB)=Sof(C1J)=
 Sof(H1JA)=Sof(H1JB)=Sof(C1K)=Sof(H1KA)=Sof(H1KB)=Sof(C1L)=Sof(H1LA)=Sof(H1LB)=
 Sof(C1M)=Sof(H1MA)=Sof(H1MB)=Sof(C1N)=Sof(H1NA)=Sof(H1NB)=Sof(H1NC)=1-FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C1C)=
 Sof(H1CA)=Sof(H1CB)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=
 Sof(C1F)=Sof(H1FA)=Sof(H1FB)=Sof(C1G)=Sof(H1GA)=Sof(H1GB)=Sof(H1GC)=FVAR(1)
 Sof(F16A)=Sof(F18A)=Sof(F17A)=1-FVAR(2)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(2)
 Fixed Sof: C77(0.5) H77A(0.5) H77B(0.5) H77C(0.5) C78(0.5) H78A(0.5)
 H78B(0.5) C79(0.5) H79A(0.5) H79B(0.5) C80(0.5) H80A(0.5) H80B(0.5) C81(0.5)
 H81A(0.5) H81B(0.5) C82(0.5) H82A(0.5) H82B(0.5) C83(0.5) H83A(0.5) H83B(0.5)
 H83C(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,
 H82B), C1B(H1BA,H1BB), C1C(H1CA,H1CB), C1D(H1DA,H1DB), C1E(H1EA,H1EB),
 C1F(H1FA,H1FB), C1I(H1IA,H1IB), C1J(H1JA,H1JB), C1K(H1KA,H1KB), C1L(H1LA,H1LB),
  C1M(H1MA,H1MB)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C17(H17), C19(H19), C31(H31), C33(H33), C40(H40), C42(H42),
 C54(H54), C56(H56), C63(H63), C65(H65)
6.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C77(H77A,
 H77B,H77C), C83(H83A,H83B,H83C), C1A(H1AA,H1AB,H1AC), C1G(H1GA,H1GB,H1GC),
 C1H(H1HA,H1HB,H1HC), C1N(H1NA,H1NB,H1NC)
;
_shelx_res_checksum              9008
_olex2_submission_special_instructions 'No special instructions were received'