Heteroleptic copper(i) complexes bearing functionalized 1H-pyrazole-bipyridine ligands: synthesis, photophysical properties, crystal structures, and applications in halogen sensing
Tong, Jin; Zhao, Li-Rong; Zhang, Jin; Wang, Xia-Yan; Yu, Yan-Min; Yu, Shu-Yan; New Journal of Chemistry 47 (2023) 4374–4385; doi:10.1039/D2NJ05408F

data_7062330
_publ_section_title
;
 Heteroleptic copper(i) complexes bearing functionalized
 1H-pyrazole-bipyridine ligands: synthesis, photophysical properties,
 crystal structures, and applications in halogen sensing
;
_journal_issue                   9
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              4374
_journal_page_last               4385
_journal_paper_doi               10.1039/D2NJ05408F
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety         'C52 H40 Cu N6 O P2, B F4, C2 H3 N'
_chemical_formula_sum            'C54 H43 B Cu F4 N7 O P2'
_chemical_formula_weight         1018.24
_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             2023-01-12
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-01-12 deposited with the CCDC.	2023-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                87.336(4)
_cell_angle_beta                 77.073(4)
_cell_angle_gamma                69.958(4)
_cell_formula_units_Z            2
_cell_length_a                   11.5294(10)
_cell_length_b                   12.5413(12)
_cell_length_c                   22.969(2)
_cell_measurement_reflns_used    9904
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      60.30
_cell_measurement_theta_min      3.27
_cell_volume                     3039.3(5)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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      193.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0746
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            45815
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         60.823
_diffrn_reflns_theta_min         1.718
_diffrn_source_current           2.86
_diffrn_source_power             0.19937059999999998
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.537
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.6031
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1171 before and 0.0865 after correction.
The Ratio of minimum to maximum transmission is 0.8021.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.113
_exptl_crystal_description       block
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_refine_diff_density_max         1.051
_refine_diff_density_min         -0.518
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     706
_refine_ls_number_reflns         13845
_refine_ls_number_restraints     235
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0624
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1256P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1890
_refine_ls_wR_factor_ref         0.2031
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9911
_reflns_number_total             13845
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj05408f2.cif
_cod_data_source_block           tj_CCDC1
_cod_database_code               7062330
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 B1-F2 = B1-F3 = B1-F4 = B1-F1
 1.42 with sigma of 0.02
 N7-C54
 1.14 with sigma of 0.02
 C54-N7
 1.137 with sigma of 0.01
 C54-C53
 1.456 with sigma of 0.01
 C53-N7
 2.593 with sigma of 0.02
 C55-N8
 2.593 with sigma of 0.02
 N8-C56
 1.14 with sigma of 0.02
 C56-N8
 1.137 with sigma of 0.01
 C56-C55
 1.456 with sigma of 0.01
 B2-F8 = B2-F5 = B2-F7 = B2-F6
 1.42 with sigma of 0.02
 N8-C55
 2.59 with sigma of 0.04
 N7-C53
 2.59 with sigma of 0.04
 B1-F2 \\sim B1-F3 \\sim B1-F4 \\sim B1-F1
 with sigma of 0.02
 F2-F3 \\sim F3-F4 \\sim F4-F1 \\sim F1-F2 \\sim F3-F1 \\sim F2-F4
 with sigma of 0.04
 B2-F8 \\sim B2-F5 \\sim B2-F7 \\sim B2-F6
 with sigma of 0.02
 F8-F5 \\sim F5-F7 \\sim F7-F6 \\sim F6-F8 \\sim F5-F6 \\sim F8-F7
 with sigma of 0.04
3. Rigid bond restraints
 C22, C21, C20, C19, C18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
N8 \\sim C55 \\sim C56: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N7 \\sim C53 \\sim C54: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
F1 \\sim F2 \\sim F3 \\sim F4 \\sim B1: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
F5 \\sim F6 \\sim F7 \\sim F8 \\sim B2: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(B2) \\sim Ueq, Uanis(F5) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 N8, C55, C56
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, C53, C54
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F2, F3, F4, B1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F5, F6, F7, F8, B2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(B2)=Sof(N8)=Sof(C55)=Sof(H55A)=Sof(H55B)=
 Sof(H55C)=Sof(C56)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=Sof(N7)=Sof(C53)=Sof(H53A)=Sof(H53B)=
 Sof(H53C)=Sof(C54)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 N3(H3), N5(H5), C1(H1), C2(H2), C4(H4), C7(H7), C9(H9), C10(H10), C11(H11),
 C13(H13), C14(H14), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
  C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C30(H30), C31(H31),
 C32(H32), C33(H33), C36(H36), C37(H37), C38(H38), C39(H39), C42(H42), C43(H43),
  C44(H44), C45(H45), C46(H46), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52)
7.b Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C55(H55A,H55B,H55C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              44871
_shelx_fab_checksum              99383
_olex2_submission_special_instructions 'No special instructions were received'