Brightly phosphorescent tetranuclear copper(i) pyrazolates.
Dias, H. V. Rasika; Diyabalanage, Himashinie V. K.; Ghimire, Mukunda M.; Hudson, Joshua M.; Parasar, Devaborniny; Palehepitiya Gamage, Chammi S.; Li, Shan; Omary, Mohammad A.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 14979–14983; doi:10.1039/c9dt03402a

data_7701251
_publ_section_title
;
 Brightly phosphorescent tetranuclear copper(i) pyrazolates.
;
_journal_issue                   40
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14979
_journal_page_last               14983
_journal_paper_doi               10.1039/c9dt03402a
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C32 H40 Cu4 F12 N8'
_chemical_formula_sum            'C32 H40 Cu4 F12 N8'
_chemical_formula_weight         1018.88
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-12-05
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2019-09-12 deposited with the CCDC.    2019-09-25 downloaded from the CCDC.
;
_cell_angle_alpha                90.2780(10)
_cell_angle_beta                 92.8550(10)
_cell_angle_gamma                107.1450(10)
_cell_formula_units_Z            2
_cell_length_a                   9.7771(4)
_cell_length_b                   11.5138(4)
_cell_length_c                   18.9800(7)
_cell_measurement_reflns_used    9734
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.45
_cell_measurement_theta_min      2.38
_cell_volume                     2038.70(13)
_computing_cell_refinement       'SAINT v7.06A (Bruker, 2003)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT v7.06A (Bruker, 2003)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0670
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            27043
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.503
_diffrn_reflns_theta_min         1.851
_exptl_absorpt_coefficient_mu    2.147
_exptl_absorpt_correction_T_max  0.8139
_exptl_absorpt_correction_T_min  0.7827
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   TWINABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.660
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       blocks
_exptl_crystal_F_000             1024
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.048
_refine_diff_density_min         -0.554
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     615
_refine_ls_number_reflns         27043
_refine_ls_number_restraints     1976
_refine_ls_restrained_S_all      0.973
_refine_ls_R_factor_all          0.0784
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0586P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1138
_refine_ls_wR_factor_ref         0.1263
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19910
_reflns_number_total             27043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt03402a2.cif
_cod_data_source_block           dias158t
_cod_depositor_comments
'Adding full bibliography for 7701251--7701253.cif.'
_cod_database_code               7701251
_shelx_estimated_absorpt_t_max   0.814
_shelx_estimated_absorpt_t_min   0.783
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5147(9) 0.4853(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Shared sites
{C1, C1', C1"}
{C9, C9', C9"}
{C17, C17', C17"}
{C25, C25', C25"}
{C29, C29'}
4. Restrained distances
 C1-F1 \\sim C1-F2 \\sim C1-F3
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F2-F3
 with sigma of 0.02
5. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim F1' \\sim F2' \\sim F3' \\sim F1" \\sim F2" \\sim
F3" \\sim F4 \\sim F5 \\sim F6 \\sim F4' \\sim F5' \\sim F6' \\sim F4" \\sim
F5" \\sim F6" \\sim F7 \\sim F8 \\sim F9 \\sim F7' \\sim F8' \\sim F9' \\sim
F7" \\sim F8" \\sim F9" \\sim F10 \\sim F11 \\sim F12 \\sim F10' \\sim F11'
\\sim F12' \\sim F10" \\sim F11" \\sim F12": within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.1 and sigma
for terminal atoms of 0.2
Uanis(C1) = Uanis(C1') = Uanis(C1")
Uanis(F1) = Uanis(F1') = Uanis(F1")
Uanis(F2) = Uanis(F2') = Uanis(F2")
Uanis(F3) = Uanis(F3') = Uanis(F3")
Uanis(C9) = Uanis(C9') = Uanis(C9")
Uanis(F4) = Uanis(F4') = Uanis(F4")
Uanis(F5) = Uanis(F5') = Uanis(F5")
Uanis(F6) = Uanis(F6') = Uanis(F6")
Uanis(C17) = Uanis(C17') = Uanis(C17")
Uanis(F7) = Uanis(F7') = Uanis(F7")
Uanis(F8) = Uanis(F8') = Uanis(F8")
Uanis(F9) = Uanis(F9') = Uanis(F9")
Uanis(C25) = Uanis(C25') = Uanis(C25")
Uanis(F10) = Uanis(F10') = Uanis(F10")
Uanis(F11) = Uanis(F11') = Uanis(F11")
Uanis(F12) = Uanis(F12') = Uanis(F12")
Uanis(C29) = Uanis(C29')
Uanis(C30) = Uanis(C30')
Uanis(C31) = Uanis(C31')
Uanis(C32) = Uanis(C32')
7. Same fragment restrains
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C1', F1', F2', F3'}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C1", F1", F2", F3"}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C9, F4, F5, F6}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C9', F4', F5', F6'}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C9", F4", F5", F6"}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C17, F7, F8, F9}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C17', F7', F8', F9'}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C17", F7", F8", F9"}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C25, F10, F11, F12}
{C1, F1, F2, F3} sigma for 1-2: 0.02, 1-3: 0.04
as
{C25", F10", F11", F12"}
{C29, C30, C31, C32} sigma for 1-2: 0.02, 1-3: 0.04
as
{C29', C30', C31', C32'}
8. Others
 1*[Sof(C1)+Sof(F1)+Sof(F2)+Sof(F3)]+1*[Sof(C1')+Sof(F1')+Sof(F2')+Sof(F3')]+1*
 [Sof(C1")+Sof(F1")+Sof(F2")+Sof(F3")]=1 with esd of 0.001
 1*[Sof(C9)+Sof(F4)+Sof(F5)+Sof(F6)]+1*[Sof(C9')+Sof(F4')+Sof(F5')+Sof(F6')]+1*
 [Sof(C9")+Sof(F4")+Sof(F5")+Sof(F6")]=1 with esd of 0.001
 1*[Sof(C17)+Sof(F7)+Sof(F8)+Sof(F9)]+1*[Sof(C17')+Sof(F7')+Sof(F8')+Sof(F9')]+
 1*[Sof(C17")+Sof(F7")+Sof(F8")+Sof(F9")]=1 with esd of 0.001
 1*[Sof(C25)+Sof(F10)+Sof(F11)+Sof(F12)]+1*[Sof(C25')+Sof(F10')+Sof(F11')+
 Sof(F12')]+1*[Sof(C25")+Sof(F10")+Sof(F11")+Sof(F12")]=1 with esd of 0.001
 Sof(C1)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(C1')=Sof(F1')=Sof(F2')=Sof(F3')=FVAR(2)
 Sof(C1")=Sof(F1")=Sof(F2")=Sof(F3")=FVAR(3)
 Sof(C9)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(4)
 Sof(C9')=Sof(F4')=Sof(F5')=Sof(F6')=FVAR(5)
 Sof(C9")=Sof(F4")=Sof(F5")=Sof(F6")=FVAR(6)
 Sof(C17)=Sof(F7)=Sof(F8)=Sof(F9)=FVAR(7)
 Sof(C17')=Sof(F7')=Sof(F8')=Sof(F9')=FVAR(8)
 Sof(C17")=Sof(F7")=Sof(F8")=Sof(F9")=FVAR(9)
 Sof(C25)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(10)
 Sof(C25')=Sof(F10')=Sof(F11')=Sof(F12')=FVAR(11)
 Sof(C25")=Sof(F10")=Sof(F11")=Sof(F12")=FVAR(12)
 Sof(C29')=Sof(C30')=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31')=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=Sof(C32')=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(13)
 Sof(C29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(13)
9.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C11(H11), C19(H19), C27(H27)
9.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C30'(H30D,H30E,H30F), C31'(H31D,H31E,H31F), C32'(H32D,H32E,H32F)
;
_shelx_res_checksum              20904
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'