Designing luminescent diimine-Cu(i)–phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra
Sun, Zhen-Zhou; Zhu, Ning; Pan, Xun; Hu, Fu-Zhen; Wang, Guo; Yang, Yu-Ping; Qiu, Qi-Ming; Li, Zhong-Feng; Xin, Xiu-Lan; Liu, Jian-Ming; Li, Xiao-Qi; Jin, Qiong-Hua; Ren, Zhi-Gang; Zhou, Qing-Li; CrystEngComm  (2022) –; doi:10.1039/D1CE01574E

data_7244259
_publ_section_title
;
 Designing luminescent diimine-Cu(i)--phosphine complexes by tuning
 N-ligand and counteranions: correlation of weak interactions,
 luminescence and THz absorption spectra
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D1CE01574E
_journal_year                    2022
_chemical_formula_moiety         'C61 H52 Cu2 N8 P2, 2(C H3 O), C H4 O'
_chemical_formula_sum            'C64 H62 Cu2 N8 O3 P2'
_chemical_formula_weight         1180.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-11-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-04-02 deposited with the CCDC.	2022-01-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.466(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7324(2)
_cell_length_b                   20.7132(3)
_cell_length_c                   23.3587(4)
_cell_measurement_reflns_used    20599
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.614
_cell_measurement_theta_min      3.845
_cell_volume                     5650.72(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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    'SHELXL-2018/3 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            22763
_diffrn_reflns_point_group_measured_fraction_full 0.911
_diffrn_reflns_point_group_measured_fraction_max 0.874
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.130
_diffrn_reflns_theta_min         3.802
_exptl_absorpt_coefficient_mu    1.896
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.09738
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             2456
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.855
_refine_diff_density_min         -0.777
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.06(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     716
_refine_ls_number_reflns         10043
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0827
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1854P)^2^+5.2003P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2124
_refine_ls_wR_factor_ref         0.2129
_reflns_Friedel_coverage         0.790
_reflns_Friedel_fraction_full    0.823
_reflns_Friedel_fraction_max     0.772
_reflns_number_gt                9905
_reflns_number_total             10043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ce01574e2.cif
_cod_data_source_block           1_a
_cod_original_cell_volume        5650.71(16)
_cod_depositor_comments
;
It seems clear that the carbon and nitrogen atoms of cyanide
anions are missasigned, monodentate cyanide always bind via the
carbon atom.
miguel.
;
_cod_database_code               7244259
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.703
_shelx_estimated_absorpt_t_min   0.600
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C35(H35A,H35B)
2.b Me refined with riding coordinates:
 C60(H60A,H60B,H60C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C61(H61A,H61B,
 H61C)
2.c Aromatic/amide H refined with riding coordinates:
 C49(H49), C31(H31), C9(H9), C50(H50), C23(H23), C24(H24), C26(H26), C2(H2),
 C27(H27), C53(H53), C57(H57), C28(H28), C32(H32), C18(H18), C34(H34), C11(H11),
  C46(H46), C47(H47), C58(H58), C44(H44), C41(H41), C10(H10), C45(H45), C8(H8),
 C52(H52), C37(H37), C38(H38), C40(H40), C43(H43), C3(H3), C21(H21), C33(H33),
 C22(H22), C39(H39), C20(H20), C19(H19)
2.d Idealised Me refined as rotating group:
 C64(H64A,H64B,H64C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              36520
_shelx_hkl_checksum              15284
_olex2_submission_special_instructions 'No special instructions were received'