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_7062332
_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
'C43 H38 Cu N6 P2, B F4, 0.25(C6 H14 O), 0.25(H2 O)'
_chemical_formula_sum            'C44.5 H42 B Cu F4 N6 O0.5 P2'
_chemical_formula_weight         881.13
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-01-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-01-08 deposited with the CCDC.	2023-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.9590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.1862(6)
_cell_length_b                   20.5002(7)
_cell_length_c                   25.9562(8)
_cell_measurement_reflns_used    9952
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      27.41
_cell_measurement_theta_min      2.30
_cell_volume                     9304.0(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0705
_diffrn_reflns_av_unetI/netI     0.0676
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            76244
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.987
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.592
_exptl_absorpt_correction_T_max  0.0949
_exptl_absorpt_correction_T_min  0.0663
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1495 before and 0.0588 after correction.
The Ratio of minimum to maximum transmission is 0.6986.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.258
_exptl_crystal_description       block
_exptl_crystal_F_000             3640
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.17
_refine_diff_density_max         1.129
_refine_diff_density_min         -0.726
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1042
_refine_ls_number_reflns         18247
_refine_ls_number_restraints     263
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1583
_refine_ls_R_factor_gt           0.0947
_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^)+(0.1897P)^2^+19.0238P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2728
_refine_ls_wR_factor_ref         0.3482
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10018
_reflns_number_total             18247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj05408f2.cif
_cod_data_source_block           20210701li_lidz7493_0m
_cod_original_formula_sum        'C44.50 H42 B Cu F4 N6 O0.50 P2'
_cod_database_code               7062332
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.901
_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 O(H,H) groups
2. Restrained distances
 C88-C87 = C89-C87
 1.55 with sigma of 0.02
 O1-C87
 1.41 with sigma of 0.02
 C39-C38 = C40-C39 = C41-C40 = C42-C41 = C43-C42 = C43-C38
 1.38 with sigma of 0.02
 C76-C75 = C77-C76 = C78-C77 = C79-C78 = C80-C79 = C80-C75
 1.38 with sigma of 0.02
 C88-C89
 2.55 with sigma of 0.04
 C88-O1 \\sim O1-C89
 with sigma of 0.02
 C39-C38 \\sim C40-C39 \\sim C41-C40 \\sim C42-C41 \\sim C43-C42 \\sim C43-C38
 with sigma of 0.01
 C76-C75 \\sim C77-C76 \\sim C78-C77 \\sim C79-C78 \\sim C80-C79 \\sim C80-C75
 with sigma of 0.02
3. Rigid bond restraints
 C60, C61, C62, C63, C64, C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C66, C67, C68, C69, C70, C71
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1 \\sim C87 \\sim C88 \\sim C89: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 1.7A
Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Others
 Fixed Sof: O2(0.25) H2A(0.25) H2B(0.25) O3(0.25) H3A(0.25) H3B(0.25)
6.a Riding coordinates:
 C87(H87), O2(H2A,H2B), O3(H3A,H3B)
6.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C72(H72A,H72B), C73(H73A,
 H73B), C74(H74A,H74B)
6.c Me refined with riding coordinates:
 C88(H88A,H88B,H88C), C89(H89A,H89B,H89C)
6.d Aromatic/amide H refined with riding coordinates:
 N3(H3), N5(H5), C1(H1), C2(H2), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10),
 C12(H12), C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
  C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C33(H33), C34(H34),
 C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43),
  N10(H10A), N12(H12A), C44(H44), C45(H45), C47(H47), C50(H50), C51(H51),
 C52(H52), C53(H53), C55(H55), C58(H58), C59(H59), C61(H61), C62(H62), C63(H63),
  C64(H64), C65(H65), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71),
 C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C82(H82), C83(H83), C84(H84),
  C85(H85), C86(H86)
6.e Fitted hexagon refined as free rotating group:
 C60(C61,C62,C63,C64,C65), C66(C67,C68,C69,C70,C71), C81(C82,C83,C84,C85,C86)
;
_shelx_res_checksum              58279
_olex2_submission_special_instructions 'No special instructions were received'